Catalytic systems for olefin polymerization and their applications

Abstract

The present invention discloses a catalyst system for olefin polymerization and its application. The catalyst system comprises a main catalyst and a cocatalyst, where the cocatalyst comprises a 12-membered ring compound represented by formula (M). The catalyst system provided by the present invention is particularly suitable for producing polypropylene products with high stereoregularity and low ash content, and the melt index of the product can be adjusted over a wide range by adjusting the amount of hydrogenation. The catalyst system provided by the present invention can also be applied to copolymerization systems, improving copolymerization productivity. [Formula 1] JPEG2022542156000031.jpg105169

Description

Detailed Description of the Invention

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to application documents filed on July 26, 2019. 1. Chinese patent application CN201910684095.6 entitled "12-membered ring compounds and their applications". 2. Chinese patent application CN201910684053.2, entitled “Catalyst system for olefin polymerization and its application.” 3. Chinese patent application CN201910684239.8 entitled “Catalyst for olefin polymerization and method for olefin polymerization”. 4. Chinese patent application CN201910684103.7, entitled "Catalyst system and prepolymerization catalyst composition for olefin polymerization reaction". The contents of all of the above documents are incorporated herein by reference.

[0002] [Technical field] The present invention is in the field of petrochemical industry, and in particular relates to catalyst systems used in olefin polymerization and to methods for olefin polymerization.

[0003] [Background technology] As is well known, when a solid titanium-based catalyst component based on magnesium, titanium, halogen and an electron donor compound is used in an olefin polymerization reaction, it has different properties according to the electron donor, so some catalyst systems have high catalytic activity, some catalyst systems have high hydrogen modulation sensitivity, and some catalyst systems have high stereospecificity. In the industrial production of polyolefins, a catalyst with excellent overall performance, especially high activity, high hydrogen modulation sensitivity, and high stereospecificity is required. The stereospecificity of the catalyst determines the isotacticity index of the polymer, and the isotacticity index is one of the important performance indicators of a polymer. The higher the isotacticity index of polypropylene, the higher its regularity and crystallinity, and the mechanical properties such as hardness, stiffness, modulus, break and yield strength of the product are all increased, and the melting point, thermal stability, aging resistance and radiation resistance are also correspondingly improved. Therefore, in order to improve the stereospecificity of the catalyst, researchers are constantly conducting a large amount of research work. In some studies, two (or more) kinds of electron donors are mixed together to make up for the deficiency of a single electron donor, thereby improving the performance of the catalyst. However, the effect of the mixed combination is not simply the superposition of the performance of multiple electron donors. For example, WO03002617 discloses a catalyst component and catalyst for olefin polymerization obtained by mixing monocarboxylic acid ester and dicarboxylic acid ester, and although the hydrogen adjustment sensitivity of the catalyst is high, the stereospecificity and polymerization activity are still not high.

[0004] Therefore, the development of a catalyst having excellent overall performance, i.e., a catalyst which maintains high activity while having high stereospecificity, and which produces olefin polymers having high isotacticity index and low ash content, remains a problem to be solved.

[0005] Summary of the Invention The present inventors have found that by introducing a 12-membered ring compound having a specific structure as a cocatalyst in an olefin polymerization process and blending it with a Ziegler-Natta type main catalyst, the polymerization activity and stereospecificity of the catalyst can be significantly improved. Based on this finding, the present invention is provided.

[0006] In a first aspect, the present invention provides a catalyst system for use in olefin polymerization, comprising a main catalyst and a cocatalyst, the cocatalyst comprising a 12-membered ring compound represented by formula (M):

[0007] [ka]

[0008] In formula (M), R1 to R 16 are the same or different and are each independently selected from hydrogen, a hydroxyl group, a halogen, a cyano group, a nitro group, an amino group, an amine group, an aldehyde group, a carboxyl group, a ketone group, a hydrocarbyloxy group, and a hydrocarbon group; when two adjacent groups in a benzene ring are each selected from a hydrocarbyloxy group and a hydrocarbon group, the two adjacent groups can be optionally cyclized with each other, and the rings are selected from a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof; R 17 ~R 24 are the same or different, and each independently represents hydrogen and C1 to C 10 wherein the amine, aldehyde, carboxyl, ketone, hydrocarbyloxy and hydrocarbon groups may be optionally substituted with one or more substituents.

[0009] In this application, "optional" or "optionally" means that the object it describes is either present or absent.

[0010] According to an embodiment of the catalyst system described in the present invention, the main catalyst comprises (i) a solid catalyst component containing magnesium, titanium, a halogen and an internal electron donor compound, and (ii) an organoaluminum compound, and optionally (iii) an external electron donor compound. "Optionally (iii) an external electron donor compound" means that "(iii) an external electron donor compound" may or may not be present in the main catalyst.

[0011] According to some embodiments of the catalyst system described herein, the main catalyst comprises the external electron donor compound. According to other embodiments of the catalyst system described herein, the main catalyst does not comprise the external electron donor compound.

[0012] According to an embodiment of the catalyst system according to the present invention, in formula (M), R 16 are the same or different, and each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amino group, or a mono-C 10 Alkylamine group, bis-C1-C 10 Alkylamine groups, C1-C 10 Aldehyde groups, C1-C 10 Carboxyl group, R a C(O)-, R a O-, C1~C 20 Alkyl groups, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 aralkyl groups, 4-12 membered heterocycloalkyl groups and C5-C 20 and each of the adjacent two groups on the benzene ring is selected from the group consisting of heteroaryl groups represented by R a C(O)-, R a O-, C1~C 20 Alkyl groups, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C20 aralkyl groups, 4-12 membered heterocycloalkyl groups and C5-C 20 When the heteroaryl group is selected from the heteroaryl groups listed above, the two adjacent groups may be optionally cyclized with each other, and the ring may be selected from a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and a combination thereof.

[0013] According to an embodiment of the catalyst system according to the invention, in formula (M), R a is C1~C 20 Alkyl groups, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 aralkyl groups, 4-12 membered heterocycloalkyl groups and C5-C 20 The heteroaryl group is selected from the following:

[0014] According to an embodiment of the catalyst system according to the invention, in formula (M), R 17 ~R 24 are the same or different, and each independently represents hydrogen, C1 to C 10 Alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups of C3 to C8, cycloalkyl groups of C6 to C 10 Aryl groups, C7-C 20 aralkyl groups, 4-12 membered heterocycloalkyl groups and C5-C 20 The heteroaryl group is selected from the following:

[0015] According to an embodiment of the catalyst system described in the present invention, in formula (M), any one of the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, aralkyl group, heterocycloalkyl group and heteroaryl group may be optionally substituted with one or more substituents.

[0016] According to an embodiment of the catalyst system described in the present invention, in formula (M), the substituent is selected from an alkyl group, an alkoxy group, a hydroxy group, a halogen, a cyano group, a nitro group, an amino group, an amino group substituted with an alkyl group, an aldehyde group, a carboxyl group and a heteroatom-containing group, and preferably, the substituent is a C1-C 10 Alkyl groups, C1-C 10 Alkoxy groups, hydroxy groups, halogens, cyano groups, nitro groups, amino groups, mono-C1 to C 10 Alkylamine group, bis-C1-C 10 Alkylamine groups, C1-C 10 Aldehyde groups, C1-C 10 and a heteroatom-containing group, and more preferably, the substituent is selected from a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a hydroxy group, fluorine, chlorine, bromine, iodine, a cyano group, a nitro group, an amino group, a mono-C1 to C6 alkylamine group, a bis-C1 to C6 alkylamine group, a C1 to C6 aldehyde group, and a C1 to C6 carboxyl group.

[0017] According to an embodiment of the catalyst system according to the present invention, in formula (M), R 16 are the same or different, and each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amino group, a mono-C1 to C6 alkylamine group, a bis-C1 to C6 alkylamine group, a C1 to C6 aldehyde group, a C1 to C6 carboxyl group, R a C(O)-, R a O-, C1-C6 alkyl group, C2-C6 alkenyl group, C2-C6 alkynyl group, C3-C6 cycloalkyl group, C6-C 10 Aryl groups, C7-C 10 aralkyl groups, 4-6 membered heterocycloalkyl groups and C5-C 10 wherein R a is an alkyl group having C1 to C6, an alkenyl group having C2 to C6, an alkynyl group having C2 to C6, a cycloalkyl group having C3 to C6, or a cycloalkyl group having C6 to C 10 Aryl groups, C7-C 10aralkyl groups, 4-6 membered heterocycloalkyl groups and C5-C 10 The heteroaryl group is selected from the following:

[0018] According to an embodiment of the catalyst system according to the present invention, in formula (M), R 16 are the same or different and each independently selected from hydrogen, a hydroxyl group, an amino group, a halogen, a C1 to C6 aldehyde group, a C1 to C6 alkoxy group, and a C1 to C6 alkoxy group substituted with a halogen.

[0019] According to an embodiment of the catalyst system according to the present invention, in formula (M), R 16 is not hydrogen at the same time.

[0020] According to an embodiment of the catalyst system according to the present invention, in formula (M), R1, R4, R5, R8, R9, R 12 , R 13 and R 16 are each independently selected from hydrogen and C1 to C6 alkyl groups; R2, R3, R6, R7, R 10 , R 11 , R 14 and R 15 are each independently selected from a hydroxy group, an amino group, a halogen, a C1 to C6 aldehyde group, a C1 to C6 alkoxy group, and a C1 to C6 alkoxy group substituted with a halogen.

[0021] According to an embodiment of the catalyst system according to the invention, in formula (M), R 17 ~R 24 are each independently hydrogen and C1 to C 10 is preferably selected from hydrogen and C1 to C6 alkyl groups, and more preferably selected from hydrogen and C1 to C4 alkyl groups.

[0022] According to some embodiments, in formula (M), R 17 ~R 24 are all hydrogen, and the general formula is:

[0023] [ka]

[0024] According to an embodiment of the catalyst system described in the present invention, the 12-membered ring compound shown in formula (M) is as shown in formula (N).

[0025] [ka]

[0026] Specifically, the 12-membered ring compound represented by formula (M) may be one or more selected from the following compounds: Compound A: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OCH3 Compound B: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OCH2CH3 Compound C: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OCH2CH2CH3 Compound D: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OCH(CH3)2 Compound E: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OCH2CH2CH2CH3 Compound F: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =OCH2CH3 Compound G: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =OCH2CH2CH3 Compound H: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =OCH2CH2CH2CH3 Compound I: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OH Compound J: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =OH Compound K: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =NH2 Compound L: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =Cl Compound M: In formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =Br Compound N: In the formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =I Compound O: In the formula (N), R2=R6=R 10 =R 14 =OCH3, R3=R7=R 11 =R 15 =CHO Compound P: In formula (N), R2=R6=R 10=R 14 =OCH3, R3=R7=R 11 =R 15 =OCH2CH2CH2Br Compound Q: In formula (N), R2=R3=R6=R7=R 10 =R 11 =R 14 =R 15 =OCH2CH2Cl Compound R: In formula (N), R2=R6=R 10 =R 14 =OH, R3=R7=R 11 =R 15 =OCH2CH3 According to an embodiment of the catalyst system described in the present invention, the internal electron donor compound is one or more selected from the group consisting of aromatic carboxylic acid ester compounds, diether compounds, alcohol ester compounds, succinic acid ester compounds and ketone compounds.

[0027] According to an embodiment of the catalyst system described in the present invention, the internal electron donor compound includes an alcohol ester compound and one or more compounds selected from a diether compound, an aromatic carboxylate compound, a succinate compound, or a ketone compound. According to an embodiment of the catalyst system described in the present invention, the molar ratio of the alcohol ester compound to one or more compounds selected from a diether compound, an aromatic carboxylate compound, a succinate compound, or a ketone compound is 1:(0.02-50).

[0028] According to an embodiment of the catalyst system described in the present invention, the internal electron donor compound comprises a succinic acid ester compound and one or more compounds selected from a diether compound, an aromatic carboxylic acid ester compound, an alcohol ester compound, or a ketone compound. According to some embodiments, the molar ratio of the succinic acid ester compound to one or more compounds selected from a diether compound, an aromatic carboxylic acid ester compound, an alcohol ester compound, or a ketone compound is 1:(0.02-50).

[0029] According to an embodiment of the catalyst system described in the present invention, the alcohol ester compound is a glycol ester compound as shown in formula B,

[0030] [ka]

[0031] In formula B, R1 and R2 are the same or different and each independently represents C1 to C 20 Alkyl groups, C2-C 20 Alkenyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 Alkylaryl groups, C7-C 20 Aralkyl groups of C 10 ~C 20 Preferably, each independently represents a C1 to C 10 Alkyl groups, C2-C 10 Alkenyl groups, C3-C 10 Cycloalkyl groups of C6 to C 10 Aryl groups, C7-C 10 Alkylaryl groups, C7-C 10 Aralkyl groups of C 10 ~C 15 The alkyl group, the alkenyl group, the cycloalkyl group, the aryl group, the alkylaryl group, the aralkyl group and the fused ring aryl group are selected from the group consisting of C1 to C 10 Alkyl groups, C1-C 10 is optionally substituted with one or more substituents selected from an alkoxy group, a hydroxy group, a halogen, a cyano group, a nitro group, an amino group, a mono-C1 to C6 alkylamine group, a bis-C1 to C6 alkylamine group, an aldehyde group, a carboxyl group, and a hetero atom; M is a divalent linking group, preferably a C1 to C 20 Alkylene group, C3-C 20 Cycloalkylene groups and C6-C 20 The alkylene group, the cycloalkylene group and / or the arylene group are selected from the group consisting of C1 to C 20Alkyl groups, C1-C 20 and halogen, and the substituents are optionally bonded to one or more rings, and the carbon and / or hydrogen atoms in M ​​are optionally substituted with nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.

[0032] According to some preferred embodiments of the present invention, in formula B, R1 and R2 are the same or different and each independently represent C1 to C 10 Alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 Aralkyl groups and C7-C 20 The alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group is selected from the group consisting of halogen, C1 to C 10 Alkyl groups of C1 to C 10 The alkoxy group is optionally substituted with one or more substituents selected from the group consisting of the alkoxy groups listed above.

[0033] According to some preferred embodiments of the present invention, in formula B, M is C1-C 10 Alkylene group, C3-C 10 Cycloalkylene groups and C6-C 10 The alkylene group, the cycloalkylene group and / or the arylene group are selected from the group consisting of C1 to C 10 Alkyl groups, C1-C 10 and halogen. According to some embodiments, R1 is a phenyl group or a substituted phenyl group, for example a phenyl group substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxy group, or a halogen.

[0034] According to some embodiments, R2 is a phenyl group or a substituted phenyl group, for example a phenyl group substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxy group, or a halogen.

[0035] According to some embodiments, M is C1 to C 10 or a substituted C1-C 10 and the like, for example, an alkylene group of C1 to C6, an alkoxy group of C1 to C6, or an alkylene group substituted with hydroxy or halogen.

[0036] According to some embodiments, M is a benzylidene group, a substituted phenylene group, a naphthylene group, or a substituted naphthylene group, such as a phenylene group or a naphthylene group substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a hydroxyl group, or a halogen.

[0037] According to some preferred embodiments of the present invention, the alcohol ester compound is a glycol ester compound represented by formula C:

[0038] [ka]

[0039] In formula C, R1 and R2 are the same or different, and each independently represents C1 to C 10 Alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 Aralkyl groups and C7-C 20 The alkyl group, the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group or the alkylaryl group is optionally substituted with one or more substituents selected from halogen, an alkyl group having C1 to C6, and an alkoxy group having C1 to C6; R3, R4, R5, R6 and R1 ~R 2n are the same or different, and each independently represents hydrogen, halogen, C1 to C 20 Alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C3-C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 Alkylaryl groups, C7-C 20 Aralkyl groups of C 10 ~C 20 The alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the aryl group, the alkylaryl group, the aralkyl group and the fused ring aryl group are optionally substituted with one or more substituents selected from halogen, an alkyl group having C1 to C6 and an alkoxy group having C1 to C6, and R3, R4, R5, R6 and R 1 ~R 2n optionally containing heteroatoms, said heteroatoms being one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus, or R, R, R, R and R 1 ~R 2n two or more of these are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring, where n is an integer from 0 to 10, preferably an integer from 1 to 8, and more preferably an integer from 2 to 6, and when n is 0, the carbon atoms of the substituents R3 and R4 are bonded to the carbon atoms of the substituents R5 and R6. As will be understood by those skilled in the art, the bracketed moieties

[0040] [ka]

[0041] represents a bond of n carbon atoms, where each carbon atom has two substituents, namely R 1 , R 2 , R 3 …R 2n The parts consisting of are connected.

[0042] As will be appreciated by one of ordinary skill in the art, when n is 0, formula C is as shown below:

[0043] [ka]

[0044] As will be appreciated by those skilled in the art, when n is 1, 2, 3, 4, 5, 6,

[0045] [ka]

[0046] are as shown below.

[0047] [ka]

[0048] According to some preferred embodiments of the present invention, the alcohol ester compound is 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate. , 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate Acid ester, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate 2-Methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-Methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-Methyl-4-propyl-3,5-heptanediol dibenzoate, 4-Methyl-4-propyl-3,5-heptanediol dibenzoate, 6-Methyl-2,4-heptanediol di(p-chlorobenzoate), 6-Methyl-2,4-heptanediol di(p-methylbenzoate), 6-Methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-Tetramethyl-3,5-heptanediol dibenzoate, 4-Methyl-3,5-octanediol dibenzoate, 4-Ethyl-3,5-octanediol dibenzoate, 4-Propyl-3,5-octanediol dibenzoate, 4-Butyl-3,5-octanediol dibenzoate, 4,4-Dimethyl-3,5-octanediol dibenzoate, 4-Methyl-4-ethyl-3,5-octanediol dibenzoate, 2-Methyl-4-ethyl-3,5-octanediol dibenzoate, 2-Methyl-6 -ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6-nonanediol dibenzoate, 5-ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4 -Butyl-3,5-heptanediol dibenzoate, 1,2-phenylenedibenzoate, 3-methyl-5-t-butyl-1,2-phenylenedibenzoate, 3,5-diisopropyl-1,2-phenylenedibenzoate, 3,6-dimethyl-1,2-phenylenedibenzoate, 4-t-butyl-1,2-phenylenedibenzoate, 1,2-naphthalenedibenzoate, 2,3-naphthalenedibenzoate, 1,8-naphthyl dibenzoate, 1,8-naphthyl di-4-methylbenzoate, 3-methylbenzoate -1,8-naphthyl, di-2-methylbenzoate-1,8-naphthyl, di-4-ethylbenzoate-1,8-naphthyl, di-4-n-propylbenzoate-1,8-naphthyl, di-4-isopropylbenzoate-1,8-naphthyl, di-4-n-butylbenzoate-1,8-naphthyl, di-4-isobutylbenzoate-1,8-naphthyl, di-4-t-butylbenzoate-1,8-naphthyl, di-4-phenylbenzoate-1,8-naphthyl, di-4-fluorobenzoate-1,8-naphthyl, di-3-fluorobenzoate-1,8-naphthyl and di-2-fluorobenzoate-1,8-naphthyl.

[0049] According to an embodiment of the catalyst system described in the present invention, the structure of the aromatic carboxylic acid ester compound is as shown in Formula F:

[0050] [ka]

[0051] In formula F, each R3 is the same or different and is independently a C1 to C8 alkyl group, a C5 to C 10 Cycloalkyl groups of C6 to C 15 Aryl groups, C7-C 15 or an alkylaryl group of C7 to C 15 The alkyl group having C1 to C8 and the alkyl group having C3 to C 10 Branched chain alkyl groups, C5-C 10 Cycloalkyl groups of C6 to C 15 Aryl groups, C7-C 15 or an alkylaryl group of C7 to C 15 The hydrogen on the carbon of the aralkyl group may be arbitrarily substituted with a substituent selected from an alkane and a halogen atom, and is preferably substituted with one or more substituents selected from a C1 to C6 alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and R4 to R7 may be the same or different and are each selected from hydrogen, a halogen, a C1 to C6 alkyl group, a C5 to C 10 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 or an alkylaryl group of C7 to C 20 The alkyl group having C1 to C8, the alkyl group having C5 to C 10 Cycloalkyl groups of C6 to C 15 Aryl groups, C7-C 15 or an alkylaryl group of C7 to C 15The hydrogen on the carbon in the aralkyl group can be arbitrarily substituted with a substituent selected from an alkane and a halogen atom, and is preferably substituted with one or more substituents selected from a C1 to C6 alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0052] According to a preferred embodiment of the present invention, the aromatic carboxylic acid ester compound is a phthalic acid ester.

[0053] According to a preferred embodiment of the present invention, the aromatic carboxylate compound is at least one selected from diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, and dioctyl phthalate.

[0054] According to an embodiment of the catalyst system described in the present invention, the structure of the succinate compound is as shown in formula G:

[0055] [ka]

[0056] In formula G, R1 and R2 are the same or different and each independently represents C1 to C 20 Alkyl groups of C3 to C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 or C7-C 20 R3, R4, R5 and R6 are the same or different and each independently represent hydrogen, C1-C 20 The alkyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups may optionally contain heteroatoms and the groups may be connected together in a ring.

[0057] According to a preferred embodiment of the present invention, in formula G, R1 and R2 are the same or different and each independently represent C1 to C 10 Alkyl groups of C3 to C 10 Cycloalkyl groups of C6 to C 10 Aryl groups, C7-C 10 or C7-C 10 R3, R4, R5 and R6 are the same or different and each independently represent hydrogen, C1-C 10 Alkyl groups of C3 to C 10 Cycloalkyl groups of C6 to C 10 Aryl groups, C6-C 10 or C6-C 10 The alkylaryl groups are selected from the group consisting of:

[0058] According to a preferred embodiment of the present invention, the succinic acid ester compound is 2,3-bis(2-ethylbutyl)succinic acid diethyl ester, 2,3-diethyl-2-isopropyl succinic acid diethyl ester, 2,3-diisopropyl succinic acid diethyl ester, 2,3-di-tert-butyl succinic acid diethyl ester, 2,3-diisobutyl succinic acid diethyl ester, 2,3-(bistrimethylsilyl)succinic acid diethyl ester, 2-(3,3,3-trifluoropropyl)-3-methyl succinic acid diethyl ester, 2,3-dineopentyl succinic acid diethyl ester, acid diethyl ester, 2,3-diisoamyl succinic acid diethyl ester, 2,3-(1-trifluoromethyl-ethyl) succinic acid diethyl ester, 2-isopropyl-3-isobutyl succinic acid diethyl ester, 2-tert-butyl-3-isopropyl succinic acid diethyl ester, 2-isopropyl-3-cyclohexyl succinic acid diethyl ester, 2-isoamyl-3-cyclohexyl succinic acid diethyl ester, 2,2,3,3-tetramethyl succinic acid diethyl ester, 2,2,3,3-tetraethyl succinic acid diethyl ester, 2,2,3 ,3-tetrapropyl succinic acid diethyl ester, 2,3-diethyl-2,3-diisopropyl disuccinic acid diethyl ester, 2,3-bis(2-ethylbutyl) succinic acid diisobutyl ester, 2,3-diethyl-2-isopropyl succinic acid diisobutyl ester, 2,3-diisopropyl succinic acid diisobutyl ester, 2,3-di-tert-butyl succinic acid diisobutyl ester, 2,3-diisobutyl succinic acid diisobutyl ester, 2,3-(bistrimethylsilyl) succinic acid diisobutyl ester, 2-(3,3,3-trifluoroprop 2,3-(1-trifluoromethyl-ethyl)succinic acid diisobutyl ester, 2-isopropyl-3-isobutylsuccinic acid diisobutyl ester, 2-tert-butyl-3-isopropylsuccinic acid diisobutyl ester, 2-isopropyl-3-cyclohexylsuccinic acid diisobutyl ester, 2-isoamyl-3-cyclohexylsuccinic acid diisobutyl ester, 2,2,3,It is selected from 3-tetramethylsuccinic acid diisobutyl ester, 2,2,3,3-tetraethylsuccinic acid diisobutyl ester, 2,2,3,3-tetrapropylsuccinic acid diisobutyl ester, and 2,3-diethyl-2,3-diisopropyldisuccinic acid diisobutyl ester, and is preferably selected from 2,3-diisopropylsuccinic acid diethyl ester, 2,3-di-tert-butylsuccinic acid diethyl ester, 2,3-diisobutylsuccinic acid diethyl ester, and 2,3-diisopropylsuccinic acid diisobutyl ester.

[0059] According to some embodiments, the external electron donor compound is one or more selected from silane-based compounds, ester-based compounds, ether-based compounds, preferably diether-based compounds or ketone-based compounds.

[0060] According to an embodiment of the catalyst system described in the present invention, the structure of the silane-based compound is as shown in Formula D,

[0061] [ka]

[0062] In formula D, R1 to R4 are the same or different and each independently represents hydrogen, C1 to C 10 Alkyl groups, C2-C 10 Alkenyl groups, C1-C 10 Alkoxy groups, C2-C 10 Alkenyloxy groups, C2-C 10 Alkynyl groups, C2-C 10 Alkynyloxy groups, C3-C 10 Cycloalkyl groups of C6 to C 15 Aryl groups, C3-C 10 Cycloalkoxy groups, C6-C 15and an amino group, and the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group, the alkenyloxy group, the alkynyloxy group, the cycloalkyl group, the aryl group, the cycloalkoxy group, the aryloxy group and the amino group are selected from halogen, a C1 to C6 alkyl group, a C3 to C6 cycloalkyl group, a C6 to C 10 It may be optionally substituted with one or more substituents selected from an aryl group and an amino group.

[0063] According to a preferred embodiment of the present invention, in formula D, R1 to R4 are the same or different and each independently represent hydrogen, a C1 to C6 alkyl group, a C3 to C6 cycloalkyl group, a C6 to C 10 The alkyl group, the cycloalkyl group, the aryl group and the amino group are selected from halogen, an alkyl group having C1 to C6, a cycloalkyl group having C3 to C6, a cycloalkyl group having C6 to C 10 It may be optionally substituted with one or more substituents selected from an aryl group and an amino group.

[0064] According to a preferred embodiment of the present invention, the silane-based compound is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-tert-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, At least one selected from vinyltriethoxysilane, vinyltrippropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrippropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-n-butylsilane, aminotriisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane, and ethylaminotriisobutylsilane.

[0065] According to an embodiment of the catalyst system described in the present invention, the diether-based compound that can be used as the internal electron donor compound and / or the external electron donor compound is a 1,3-diether compound as shown in formula E,

[0066] [ka]

[0067] In formula E, R I , R II , R III , R IV , R V and R VI are the same or different, and each independently represents hydrogen, halogen, C1 to C 20 Alkyl groups of C3 to C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 Aralkyl groups and C7-C 20 R VII and R VIII are the same or different, and each independently represents C1 to C 20 Alkyl groups of C3 to C 20 Cycloalkyl groups of C6 to C 20 Aryl groups, C7-C 20 Aralkyl groups and C7-C 20 wherein any one of the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, aralkyl group, and alkylaryl group may be optionally substituted with one or more substituents, and the one or more substituents may be a hydroxy group, a halogen, a cyano group, a nitro group, an amino group, a mono-C1 to C4 10 Alkylamine group, bis-C1-C 10 or R I , R II , R III , R IV , R V and R VI two or more of these are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring, such as a fluorene ring.

[0068] According to a preferred embodiment of the present invention, in formula E, R I , R II , R III , R IV , R V and R VIare the same or different, and each independently represents hydrogen, halogen, C1 to C 18 Alkyl groups of C3 to C 18 Cycloalkyl groups of C6 to C 18 Aryl groups, C7-C 18 Aralkyl groups and C7-C 18 The alkylaryl groups are selected from the group consisting of:

[0069] According to a preferred embodiment of the present invention, in formula E, R I , R II , R III , R IV , R V and R VI are the same or different, and each independently represents hydrogen, halogen, C1 to C 10 Alkyl groups of C3 to C 10 Cycloalkyl groups of C6 to C 10 Aryl groups, C7-C 10 Aralkyl groups and C7-C 10 The alkylaryl groups are selected from the group consisting of:

[0070] According to a preferred embodiment of the present invention, in formula E, R VII and R VIII are the same or different, and each independently represents hydrogen, halogen, C1 to C 10 Alkyl groups of C3 to C 10 Cycloalkyl groups of C6 to C 10 Aryl groups, C7-C 10 Aralkyl groups and C7-C 10 The alkylaryl groups are selected from the group consisting of:

[0071] According to a preferred embodiment of the present invention, in formula E, R VII and R VIII are each independently hydrogen, halogen, or C1-C 10 Alkyl groups of C3 to C 10 Cycloalkyl groups of C6 to C 10 Aryl groups, C7-C 10 Aralkyl groups and C7-C 10 The alkylaryl groups are selected from the group consisting of:

[0072] According to a preferred embodiment of the present invention, in formula E, R III and R IV are linked to each other to form a saturated or unsaturated monocyclic or polycyclic ring.

[0073] According to a preferred embodiment of the present invention, in formula E, R VII and R VIII are C1 to C 10 is an alkyl group.

[0074] According to a preferred embodiment of the present invention, the diether compound is 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl) -1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(2-fluorophenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexyl) 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-Dimethoxypropane, 2-(1-methylbutyl)-2-sec-butyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-di Methoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene, 1,1-bis( 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene, 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene, 1,1-bis(methoxymethyl)indene, 1,1-bis(methoxymethyl)-2,3-dimethoxyindene , 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,5,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,7-dimethylindene, 1,1-bis(methoxymethyl)-3,6-dimethylindene, 1,1-bis(methoxymethyl)-4-phenylindene, 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene, 1,1-bis(methoxymethyl)-4-tetracyclohexylindene, 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)phenylindene, 1,1-bis(methoxymethyl)-7-cyclopentylindene, 1,1-bis(methoxymethyl)-7-isopropylindene, 1,1-bis(methoxymethyl)-7-cyclohexylindene, 1,1-bis(methoxymethyl)-7-tert-butylindene, 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene, 1,1-bis(methoxymethyl)-7-phenylindene, 1,1-bis(methoxymethyl)-2-phenylindene, 9,9-di(methoxymethyl)fluorene, 9,9-di(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-di(methoxymethyl)-1,8-dichlorofluorene, 9,9-di(methoxymethyl)-1,8-difluorofluorene, 9,9-di(methoxymethyl)-1,2,3,4-tetrafluorofluorene At least one selected from hydrofluorene, 9,9-di(methoxymethyl)-4-tert-butylfluorene, 1,1-bis-(methoxymethyl)-2,5-cyclohexadiene, 1,1-bis-(methoxymethyl)-benzonaphthalene, 7,7-bis-(methoxymethyl)-2,5-norbornadiene, 9,9-bis-(methoxymethyl)-1,4-methanedihydronaphthalene, 9,9-bis-(methoxymethyl)-1,4-methanedihydroanthracene, 4,4-bis-(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene, 4,4-bis-(methoxymethyl)-1-phenyl-3,4-dihydronaphthalene, 5,5-bis-(methoxymethyl)-1,3,6-cycloheptatriene, and 1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene.

[0075] According to an embodiment of the catalyst system described in the present invention, the molar ratio of the 12-membered ring compound represented by formula (M) to the external electron donor compound is 1:100-100:1, preferably 1:50-50:1, and more preferably 1:20-20:1.

[0076] According to an embodiment of the catalyst system described in the present invention, the organoaluminum compound is an alkylaluminum compound. According to a preferred embodiment of the present invention, the alkylaluminum compound has the general formula AlR3, where each R is independently hydrogen, halogen, C1-C 20 Alkyl groups, C1-C 20 Alkoxy group or halogenated C1-C 20 At least one of the three R's is selected from the alkyl groups C1-C 20 Alkyl group or halogenated C1-C 20 According to a preferred embodiment of the present invention, the alkylaluminum compound has a general formula of AlR3, where each R is independently hydrogen, halogen, C1-C 10 Alkyl groups, C1-C 10 Alkoxy group or halogenated C1-C 10 At least one of the three R's is selected from the alkyl groups C1-C 10 Alkyl group or halogenated C1-C 10 Specifically, the organoaluminum compound is preferably one or more selected from the group consisting of trialkylaluminum, dialkylaluminum chloride, monoalkylaluminum dichloride, and alkylaluminoxane. According to a preferred embodiment of the present invention, the alkylaluminum compound is selected from the group consisting of triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, monohydrodiethylaluminum, monohydrodiisobutylaluminum, monochlorodiethylaluminum, monochlorodiisobutylaluminum, dichloroethylaluminum, Al(n-CH 13 )3 and Al(n-CH 17 ) 3 is one or more of the above.

[0077] According to an embodiment of the catalyst system described in the present invention, the molar ratio of the 12-membered ring compound represented by the formula (M) to the organoaluminum compound calculated in terms of aluminum is 1:(0.1 to 500), and preferably 1:(1 to 200).

[0078] According to an embodiment of the catalyst system described in the present invention, the molar ratio of the solid catalyst component calculated in terms of titanium element to the organoaluminum compound calculated in terms of aluminum is 1:(5-5000), preferably 1:(20-2000).

[0079] According to some embodiments of the catalyst system described in the present invention, the molar ratio of the external electron donor compound to the titanium element in the solid catalyst component is (0-500):1, preferably (0.01-200):1, more preferably (0.1-100):1.

[0080] According to an embodiment of the catalyst system described in the present invention, the weight ratio of titanium element, magnesium element and internal electron donor compound in the solid catalyst component is 1:(5-25):(2-15). According to the present invention, the solid catalyst component comprises titanium, magnesium and an internal electron donor and is a reaction product of a titanium compound, a magnesium compound and an internal electron donor.

[0081] In the present invention, the method for preparing the solid catalyst component may be carried out according to the general method used in this field, for example, the methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, etc. may be referred to, and the present invention incorporates the disclosed contents thereof herein by reference.

[0082] In the present invention, the method for producing the solid catalyst component includes, but is not limited to, the following methods. Method 1: Add a magnesium compound to an inert solvent, then add an organic epoxy compound and an organic phosphorus compound, dissolve them, then add a deposition aid and a titanium compound to deposit a solid, add an internal electron donor, attach it to the solid, and then treat with titanium tetrahalide and an inert diluent to obtain the product. Method 2: In an inert solvent such as decane or toluene, a solid magnesium compound is dissolved in an organic alcohol compound such as 2-ethylhexanol, and after dissolution, a precipitating agent and a titanium compound are added to precipitate the solid material, and an internal electron donor is added to adhere to the solid material, and then the solid material is treated with a titanium compound and an inert diluent to obtain the product. Method 3: A magnesium halide alcoholate is dispersed in a titanium compound at a low temperature (e.g., −5° C. or lower), and the temperature is further increased to a high temperature (e.g., 50° C. or higher). During the temperature increase process, an internal electron donor compound is added, filtered, and the resulting precipitate is treated with a titanium compound and washed to obtain the solid catalyst component. Method 4: Prepare an alkoxy magnesium carrier and an inert diluent into a suspension, then react with a mixture formed by a titanium compound and an inert diluent, filter, contact the resulting precipitate with a titanium compound and an internal electron donor compound, wash the precipitate, and obtain the solid catalyst component.

[0083] According to some embodiments of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (e.g., an inert solvent such as hexane, heptane, octane, decane, toluene, etc.) pre-cooled to -15°C to 40°C is mixed with a magnesium compound, the temperature of the mixture is gradually increased to 90 to 110°C and maintained for 0.1 to 2 hours, and an internal electron donor is added during the temperature increase process. Then, solid-liquid separation is performed, and the obtained solid phase is treated again at least twice with a titanium compound, washed with a solvent, and finally dried in vacuum to obtain the solid catalyst component.

[0084] According to the present invention, the magnesium compound may be any of various magnesium compounds commonly used in the field of olefin polymerization catalyst preparation, for example, the magnesium compound may be at least one selected from magnesium dihalide, alkoxy magnesium, alkyl magnesium, magnesium dihalide hydrate, magnesium dihalide alcoholate, and derivatives in which one halogen atom in the magnesium dihalide molecule is replaced with a hydrocarbyloxy group or hydrocarbyloxy halide. According to a preferred embodiment of the present invention, the magnesium compound is magnesium dihalide alcoholate.

[0085] According to a preferred embodiment of the present invention, the magnesium dihalide alcoholate has the spherical magnesium alcoholate of formula (I), MgX2 m(R'OH) nE qH2O Formula (I) In formula (I), X is chlorine or bromine, R' is a C1-C4 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), m is 0.5-4.0, E is an ether or ester electron donor compound, n is 0-1.0, where the ether or ester may be any ether or ester known in the art that can be an electron donor, or may be an internal electron donor and / or an external electron donor used in the present invention, and q is 0-0.8.

[0086] According to a preferred embodiment of the present invention, in formula (I), X is chlorine or bromine, R' is a C1-C4 alkyl group, m is 1.5-3.5, and n and q are both 0. According to a preferred embodiment of the present invention, the magnesium compound is MgCl2·m(CH3CH2OH), where m is 1.5 to 3.5.

[0087] According to some embodiments of the present invention, the preparation method of the magnesium dihalide alcoholate can be carried out according to a method known in the art, for example, the method disclosed in CN1330086A.

[0088] According to a preferred embodiment of the present invention, the method for producing the alcoholate of magnesium dihalide includes: (1) mixing anhydrous magnesium dihalide and an alcohol compound (R'OH) and reacting them at 90 to 140°C to obtain an alcoholate of magnesium halide; and (2) shearing the alcoholate of magnesium halide in a dispersion medium, and cooling the sheared alcoholate in an inert medium to obtain the spherical alcoholate of magnesium halide. Here, the mixing ratio of the anhydrous magnesium dihalide and the alcohol compound can be determined according to the ratio of the alcohol compound supported on the anhydrous magnesium dihalide according to actual needs. Here, the dispersion medium can be a hydrocarbon-based inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc. Here, the shearing refers to shearing the magnesium halide alcoholate by external shearing force, such as high speed stirring method (e.g. CN1330086), spray method (e.g. US6020279), super gravity rotating bed (e.g. CN1580136A) and emulsifier method (CN1463990A), etc.

[0089] According to a preferred embodiment of the present invention, the obtained spherical magnesium halide alcoholate is further subjected to washing and drying steps in order to further improve the purity of the magnesium compound.

[0090] The alkoxy magnesium according to the present invention is prepared by reacting metallic magnesium, ethanol, isooctanol (2-ethylhexanol) and a mixed halogenating agent under an inert atmosphere. The mixed halogenating agent is a combination of a halogen and a halogen compound, and the halogen and the halogen compound are selected from, but not limited to, iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide, ethoxy magnesium iodide, methoxy magnesium iodide, isopropyl magnesium iodide, hydrogen chloride, chloroacetyl chloride, etc.

[0091] According to the present invention, the titanium compound is a variety of titanium compounds commonly used in the preparation of olefin polymerization catalysts in the field. According to a preferred embodiment of the present invention, the titanium compound has a structure as shown in formula (II): Ti(OR'') 4-k X k Formula (II) In formula (II), R″ is C1 to C 20 wherein X is F, Cl or Br, and k is an integer of 0 to 4.

[0092] According to a preferred embodiment of the present invention, in formula (II), R″ is a C1-C 10 is an alkyl group.

[0093] According to a preferred embodiment of the present invention, in formula (II), R'' is a C1 to C5 alkyl group.

[0094] According to a preferred embodiment of the present invention, for example, in formula (II), R'' is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isoamyl, neopentyl.

[0095] According to a preferred embodiment of the present invention, in formula (II), X is Cl.

[0096] According to a preferred embodiment of the present invention, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, monochlorotributoxytitanium, dichlorodibutoxytitanium, trichloromonobutoxytitanium, monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, and titanium trichloride.

[0097] According to a preferred embodiment of the present invention, the titanium compound is titanium tetrachloride. In a second aspect, the present invention further provides a prepolymerized catalyst composition for use in the polymerization of olefins, comprising the catalyst system according to the first aspect and a prepolymer obtained by prepolymerizing an olefin.

[0098] According to some embodiments of the present invention, the prepolymer has a prepolymerization ratio of 0.1 to 1000 g of olefin polymer / g of solid catalyst component. According to some preferred embodiments of the present invention, the prepolymer has a prepolymerization ratio of 0.2 to 500 g of olefin polymer / g of solid catalyst component.

[0099] According to some preferred embodiments of the present invention, the prepolymer has a prepolymerization ratio of 0.5 to 20 g of olefin polymer / g of solid catalyst component.

[0100] According to some embodiments of the present invention, the prepolymerization temperature is −20 to 80° C., and the polymerization pressure is preferably 0 to 5 MPa.

[0101] According to some preferred embodiments of the present invention, the temperature of the prepolymerization is 0 to 50°C.

[0102] According to some embodiments of the present invention, the prepolymerization is carried out in liquid or gas phase. In a third aspect, the present invention further provides a process for use in the polymerization of olefins, comprising polymerizing olefins in the presence of a catalyst system according to the first aspect and / or a pre-polymerized catalyst composition according to the second aspect.

[0103] According to an embodiment of the method for olefin polymerization of the present invention, the olefin has a general formula of CH2=CHR, where R is hydrogen or an alkyl group of C1-C8, preferably hydrogen or an alkyl group of C1-C6. Preferably, the olefin is one or more selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. According to some embodiments, the olefin is ethylene, propylene or a mixture of ethylene and propylene.

[0104] According to the present invention, the catalyst system described in the present invention can be directly introduced into a reactor for use in the polymerization process, or can be prepolymerized with an olefin to obtain a prepolymerized catalyst, which can then be introduced into a reactor for polymerization reaction.

[0105] According to the present invention, the olefin polymerization reaction may be carried out according to known polymerization methods, may be carried out in liquid phase or gas phase, may be carried out by a combination of liquid phase and gas phase polymerization steps, or may employ conventional techniques such as slurry method, gas phase fluidized bed, etc.

[0106] According to some preferred embodiments of the present invention, the polymerization conditions include a temperature of 0 to 150° C., a time of 0.2 to 5 hours, and a pressure of 0.01 to 10 MPa.

[0107] According to some preferred embodiments of the present invention, the polymerization conditions include a temperature of 50 to 90° C., a time of 0.3 to 2 hours, and a pressure of 0.02 to 5 MPa.

[0108] According to the present invention, the polymerization may be carried out in the presence of a solvent, where the concentration of the catalyst system in the solvent is 0.1×10 relative to the titanium element in the solid catalyst component. -5~5×10 -5 It may also be in moles / liter.

[0109] According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent is 0.2×10 relative to the titanium element in the solid catalyst component. -5 ~2×10 -5 It may also be in moles / liter.

[0110] In the present invention, the hydrocarbon group may be selected from an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and an alkylaryl group.

[0111] In the present invention, the alkyl group means a straight-chain alkyl group or a branched-chain alkyl group, and non-limiting examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 1-ethylpropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-methylpentyl group, a 3-methyl These include pentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-icosyl groups.

[0112] In the present invention, examples of alkenyl groups include, but are not limited to, vinyl, propenyl, butenyl, pentenyl, and octenyl groups.

[0113] In the present invention, illustrative examples of alkynyl groups include, but are not limited to, ethynyl and propargyl groups.

[0114] In the present invention, examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, and cyclododecyl groups.

[0115] In the present invention, examples of halogen include, but are not limited to, fluorine, chlorine, bromine and iodine.

[0116] In the present invention, illustrative examples of aryl groups include, but are not limited to, phenyl, methylphenyl, ethylphenyl, 4-t-butylphenyl, and naphthyl.

[0117] As used herein, an aralkyl group refers to an alkyl group having an aryl substituent, and examples include, but are not limited to, phenylmethyl, phenylethyl, phenyl n-propyl, phenyl n-butyl, phenyl t-butyl, and phenylisopropyl groups.

[0118] In the present invention, an alkylaryl group means an aryl group having 7 to 20 carbon atoms and having an alkyl substituent, and examples thereof include, but are not limited to, a methylphenyl group and an ethylphenyl group.

[0119] In the present invention, examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and hexyloxy groups.

[0120] In the present invention, examples of fused ring aryl groups include, but are not limited to, naphthyl, anthryl, phenanthryl, and pyrenyl groups. In the present invention, the heteroatom means an atom generally contained in a molecular structure other than a halogen atom, a carbon atom, and a hydrogen atom, such as O, N, S, P, Si, and B. The beneficial effects of the present invention are as follows:

[0121] When the catalyst system provided by the present invention is used in olefin polymerization, it has good stereospecificity, catalytic activity and hydrogen adjustment sensitivity. According to the above characteristics of the catalyst provided by the present invention, the catalyst system provided by the present invention is particularly suitable for producing polypropylene products with high stereoregularity and low ash content, and the melt index of the product can be adjusted in a wide range by adjusting the amount of hydrogen added. The catalyst system provided by the present invention can also be applied to copolymerization systems to improve copolymerization productivity.

[0122] [Mode for carrying out the invention] Hereinafter, the embodiments of the present invention will be described in detail with reference to the examples. However, as will be understood by those skilled in the art, the following examples are merely used to illustrate the present invention and should not be considered as limiting the scope of the present invention. In the examples, the specific conditions are not specified, but are carried out according to the usual conditions or the conditions suggested by the manufacturer. The reagents or equipment used, unless the manufacturer is specified, are all commercially available as usual products.

[0123] (Test Method) 1. Polymerization activity of catalyst: The amount of polymer obtained in a certain time (calculated in kg) divided by the amount of catalyst added (calculated in g). 2. Weight average molecular weight: measured by high temperature gel permeation chromatography in accordance with standard GB / T36214.4-2018. 3. Polymer isotacticity index: according to standard GB / T 2412-2008. 4. Ethylene content: measured by Fourier infrared spectrometer VERTEX70.

[0124] (Production Example 1) A mixed solution of 3,4-dimethoxybenzyl alcohol (5 g) / dichloromethane (20 mL) is dropped into a solution of trifluoroacetic acid (25 mL) in dichloromethane (200 mL), and after the dropwise addition is completed, the mixture is allowed to react in an ice bath for 4 hours. The reaction solution is neutralized with sodium hydroxide solution, and the organic phase is separated and completely extracted. The resulting product is washed several times with water and an organic solvent, and recrystallized from chloroform (80 mL) / benzene (30 mL) to obtain 2.5 g of compound A.

[0125] [ka]

[0126] (Production Example 2) This preparation example is used to illustrate the preparation of magnesium compounds. Anhydrous magnesium chloride and ethanol are mixed in a molar ratio of 1:2.6, heated to 120°C, and reacted to produce a magnesium chloride alcoholate melt. This is then stirred at high speed with the dispersion media of white oil and silicone oil, and then added to cooled hexane to form spherical magnesium chloride alcoholate particles. After washing and drying, the spherical magnesium chloride alcoholate carrier is obtained.

[0127] (Production Example 3) This preparation example is used to illustrate the preparation of a solid catalyst component.

[0128] In a 300ml glass reaction flask with stirring, which is fully purged with high-purity nitrogen gas, add 100ml of titanium tetrachloride, cool to -20℃, add 8g of the spherical magnesium chloride alcoholate prepared in Preparation Example 2, gradually heat to 110℃, add 6mmol of 2-isopropyl-2-isoamyl-1,3-dimethoxypropane as an internal electron donor during the heating process, keep at 110℃ for 0.5h, filter off the liquid, add titanium tetrachloride and treat twice, then wash with hexane 5 times, and vacuum dry to obtain titanium-containing solid catalyst component Z1, with a titanium content of 2.4wt%.

[0129] (Production Example 4) This preparation example is used to illustrate the preparation of a solid catalyst component.

[0130] In a 300ml glass reaction flask with stirring, which is fully purged with high-purity nitrogen gas, add 100ml titanium tetrachloride, cool to -20℃, add 8g of the spherical magnesium chloride alcoholate prepared in Preparation Example 2, and gradually heat to 110℃. During the heating process, add 3mmol of 2,4-pentanediol dibenzoate and 3mmol of 2-isopropyl-2-isoamyl-1,3-dimethoxypropane as internal electron donors. After keeping the temperature at 110℃ for 0.5h, filter off the liquid, add titanium tetrachloride and treat twice, then wash with hexane 5 times, and vacuum dry to obtain titanium-containing solid catalyst component Z2, with a titanium content of 2.7wt%.

[0131] (Production Example 5) This preparation example is used to illustrate the preparation of a solid catalyst component.

[0132] In a reactor that has been fully purged with high-purity nitrogen gas, 6.0 g of magnesium chloride, 119 ml of toluene, 5 ml of epichlorohydrin, and 15.6 ml of tributyl phosphate (TBP) are added in that order, and the temperature is raised to 50°C while stirring and maintained for 2.5 hours to completely dissolve the solid. 1.7 g of phthalic anhydride is added and maintained for another hour. The solution is cooled to below -25°C, and 70 ml of TiCl4 is added dropwise over an hour to gradually raise the temperature to 80°C, and solid matter is gradually precipitated during the temperature rise process. 6 mmol of 3-methyl-2,4-pentanediol dibenzoate is added as an internal electron donor, the temperature is maintained for 1 hour, and after filtration, 80 ml of toluene is added and washed twice to obtain a solid precipitate. Then, add 60ml toluene and 40ml TiCl4, heat to 100℃, process for 2 hours, drain the filtrate, add another 60ml toluene and 40ml TiCl4, heat to 100℃, process for 2 hours, drain the filtrate, add 60ml toluene and wash three times at boiling, add 60ml hexane and wash twice at boiling, add 60ml hexane and wash twice at room temperature, and obtain solid catalyst component Z3, with a titanium content of 2.5wt%.

[0133] (Production Example 6) This preparation is used to illustrate the preparation of alkoxymagnesium.

[0134] After thoroughly replacing the atmosphere in a 16L pressure-resistant reactor equipped with a stirrer with nitrogen gas, add 10L of ethanol, 300mL of 2-ethylhexanol, 11.2g of iodine, 8g of magnesium chloride, and 640g of magnesium powder to the reactor. The system is heated to 75°C while stirring, and the reaction is refluxed until no more hydrogen is released. The reaction is stopped, washed with 3L of ethanol, filtered, and dried to obtain alkoxy magnesium.

[0135] (Production Example 7) This preparation example is used to illustrate the preparation of a solid catalyst component.

[0136] 10g of the alkoxy magnesium compound of Preparation Example 6, 50mL of toluene, 3mmol of 2,3-diisopropyl succinic acid diethyl ester and 3mmol of 3,5-heptanediol dibenzoate are prepared into a suspension. 40mL of toluene and 60mL of titanium tetrachloride are added to a 300mL reaction vessel that has been repeatedly replaced with high-purity nitrogen gas, and the temperature is raised to 80°C. Then, the suspension prepared is put into the vessel, and the temperature is kept constant for 1 hour, the temperature is gradually raised to 110°C, and the temperature is kept constant for 2 hours. After pressure filtration, 78mL of toluene and 52mL of titanium tetrachloride mixture are added and stirred at 110°C for 1 hour, and this process is repeated three times. After pressure filtration, the mixture is washed with hexane four times, each time 150mL, pressure filtration, and drying to obtain solid catalyst component Z4, with a titanium content of 2.5wt%.

[0137] (Production Example 8) A mixed solution of 3,4-diethoxybenzyl alcohol (5.8 g) / dichloromethane (20 mL) is dropped into a solution of trifluoroacetic acid (25 mL) in dichloromethane (200 mL), and after the dropwise addition is completed, the mixture is allowed to react in an ice bath for 4 hours. The reaction solution is neutralized with sodium hydroxide solution, and the organic phase is separated and completely extracted. The resulting product is washed several times with water and an organic solvent, and recrystallized from chloroform (80 mL) / benzene (30 mL) to obtain 1.5 g of compound B.

[0138] [ka]

[0139] (Production Example 9) A mixed solution of 3-methoxy-4-bromopropoxybenzyl alcohol (7 g) / dichloromethane (20 mL) is added dropwise to a solution of trifluoroacetic acid (25 mL) in dichloromethane (200 mL), and after the addition is completed, the mixture is allowed to react in an ice bath for 4 hours. The reaction solution is neutralized with sodium hydroxide solution, and the organic phase is separated and completely extracted. The resulting product is washed several times with water and an organic solvent, and recrystallized from chloroform (80 mL) / benzene (30 mL) to obtain 1.7 g of compound P.

[0140] [ka]

[0141] (Production Example 10) Drop 100 mL of ethyl ether solution containing PO (57.5 g) into 23 g of 3-iodo-4-methoxybenzyl alcohol / ethyl ether solution with stirring, reflux, stop stirring, and spin-dry the ethyl ether after 3 days. Dissolve the product in dichloromethane and pass it through a column. Spin-dry the filtrate and recrystallize it with 95 / 5 ethyl ether mixture to obtain 1.3 g of compound N.

[0142] [ka]

[0143] (Production Example 11) To 25 mL of THF solution (containing 0.5 g of compound N) at -80°C, 2 mL of toluene solution containing n-BuLi (where n-BuLi is 5 mmol) is added, the reaction is warmed to 0°C after 1 h, stirred at room temperature for 1 h, then quickly cooled to -70°C and 2 mL of ethyl chloroformate is added. The reaction is warmed to room temperature and stirred for 3 h. The remaining n-BuLi is neutralized with NH4Cl. The organic phase is extracted with ethyl acetate and after drying, 0.14 g of compound O is obtained.

[0144] [ka]

[0145] Example 1 Add 4 mNL (mNL means millistandard liter) of hydrogen gas to a 48-channel parallel pressure reactor (reaction volume 20 ml). Fill with propylene gas until the pressure reaches 1 mPa, and add 5 ml of liquid propylene. Add triethylaluminum (calculated in aluminum element): compound A: solid catalyst component Z1 (calculated in titanium element) in a molar ratio of 500:20:1 in a heptane solution of triethylaluminum, compound A, and solid catalyst component Z1 in sequence to prepare a mixed solution. Take a certain amount of the mixed solution (containing 0.02 mg of solid catalyst component) and inject it into the reactor. Allow to react at 70°C for 1 hour.

[0146] The reaction product was discharged, the weight of the polymer was weighed, and the catalytic activity was calculated. At the same time, the isotacticity index of the polymer was measured, and the results are shown in Table 1.

[0147] Example 2 The results are basically the same as in Example 1, except that the amount of hydrogen added was 20 mNL. The results are shown in Table 1.

[0148] Example 3 The experiment was basically the same as in Example 1, with the only difference being that compound A was replaced with an equimolar amount of compound P. The results are shown in Table 1.

[0149] Example 4 The procedure was basically the same as in Example 2, with the only difference being that compound A was replaced with an equimolar amount of compound N. The results are shown in Table 1.

[0150] Comparative Example 1 The experiment was basically the same as in Example 1, with the only difference being that no compound A was added. The results are shown in Table 1.

[0151] Comparative Example 2 The experiment was basically the same as in Example 2, with the only difference being that no compound A was added. The results are shown in Table 1.

[0152] Comparative Example 3 The experiment was basically the same as in Example 2, except that Compound A was replaced with an equimolar amount of C-Donor. The results are shown in Table 1.

[0153] Example 5 The procedure was basically the same as in Comparative Example 3, with the only difference being that an equimolar amount of compound A to C-Donor was additionally added. The results are shown in Table 1.

[0154] Comparative Example 4 The experiment was basically the same as in Example 1, with the only difference being that Compound A was replaced with an equimolar amount of Donor 1. The results are shown in Table 1.

[0155] Example 6 The procedure was basically the same as in Comparative Example 4, with the only difference being that an equimolar amount of Compound B to Donor 1 was additionally added. The results are shown in Table 1.

[0156] Example 7 The procedure is basically the same as in Example 6, except that the solid catalyst component Z1 is replaced by Z2, and Donor 1 is replaced by an equimolar C-Donor. The results are shown in Table 1.

[0157] Comparative Example 5 The experiment was basically the same as in Example 7, except that no compound B was added. The results are shown in Table 1.

[0158] Example 8 The procedure was basically the same as in Example 7, with the only difference being that the solid catalyst component Z2 was replaced with Z4 and the amount of hydrogen added was changed to 20 mNL. The results are shown in Table 1.

[0159] Comparative Example 6 The experiment was basically the same as in Example 8, except that no compound B was added. The results are shown in Table 1.

[0160] [Table 1]

[0161] remarks: C-Donor Cyclohexylmethyldimethoxysilane Donor 1 2-Isopropyl-2-isoamyl-1,3-dimethoxypropane As can be seen from Table 1, when the catalyst system without external electron donor or without external electron donor is used for propylene polymerization, adding the 12-membered ring compound represented by formula (M) as a cocatalyst can significantly improve the activity of the catalyst, and the isotacticity index of the polymerization product can also be improved.

[0162] Example 9 The experiment was basically the same as in Example 1, with the only difference being that compound A was replaced with an equimolar amount of compound B. The results are shown in Table 2.

[0163] Comparative Example 7 The experiment was basically the same as in Example 1, except that Compound A was replaced with an equimolar amount of C-Donor. The results are shown in Table 2.

[0164] Example 10 The experiment is basically the same as that in Example 2, except that a part of Compound A is replaced with an equimolar amount of C-Donor. In this example, the molar ratio of Compound A to C-Donor is 1:1. The results are shown in Table 2.

[0165] Example 11 The experiment is basically the same as that in Example 2, except that a part of Compound A is replaced with an equimolar amount of C-Donor. In this example, the molar ratio of Compound A to C-Donor is 1:9. The results are shown in Table 2.

[0166] Example 12 The procedure was basically the same as in Example 10, with the only difference being that compound A was replaced with an equimolar amount of compound B. The results are shown in Table 2.

[0167] (Example 13) The procedure was basically the same as in Example 12, with the only difference being that C-Donor was replaced with an equimolar amount of Donor 1 and the amount of hydrogen added was changed to 4 mNL. The results are shown in Table 2.

[0168] Example 14 The procedure is basically the same as in Example 2, except that the solid catalyst component Z1 is replaced by Z2. The results are shown in Table 2.

[0169] Example 15 The procedure is basically the same as in Example 10, except that the solid catalyst component Z1 is replaced with Z2. The results are shown in Table 2.

[0170] Example 16 The procedure is basically the same as in Example 9, except that the solid catalyst component Z1 is replaced with Z2. The results are shown in Table 2.

[0171] (Example 17) The procedure was basically the same as in Example 16, with the only difference being that the amount of hydrogen added was changed to 20 mNL. The results are shown in Table 2.

[0172] (Example 18) The procedure is basically the same as in Example 13, except that the solid catalyst component Z1 is replaced by Z2, and Donor 1 is replaced by an equimolar C-Donor. The results are shown in Table 2.

[0173] (Example 19) The procedure was basically the same as in Example 18, with the only difference being that the amount of hydrogen added was changed to 20 mNL. The results are shown in Table 2.

[0174] Comparative Example 8 The results are basically the same as those of Comparative Example 5, except that the amount of hydrogen added was changed to 20 mNL. The results are shown in Table 2.

[0175] (Example 20) The procedure is basically the same as in Example 9, except that the solid catalyst component Z1 is replaced with Z3. The results are shown in Table 2.

[0176] Example 21 The procedure was basically the same as in Example 20, with the only difference being that the amount of hydrogen added was changed to 20 mNL. The results are shown in Table 2.

[0177] Example 22 The procedure was basically the same as in Example 21, except that compound B was replaced with an equimolar amount of compound O. The results are shown in Table 2.

[0178] Comparative Example 9 The procedure was basically the same as in Example 20, except that compound B was replaced with an equimolar amount of C-Donor. The results are shown in Table 2.

[0179] Comparative Example 10 The results are basically the same as those in Comparative Example 9, except that the amount of hydrogen added was changed to 20 mNL. The results are shown in Table 2.

[0180] (Example 23) The procedure is basically the same as in Example 21, except that the solid catalyst component Z3 is replaced with Z4. The results are shown in Table 2.

[0181] Example 24 The procedure is basically the same as in Example 12, except that the solid catalyst component Z1 is replaced with Z4. The results are shown in Table 2.

[0182] [Table 2]

[0183] remarks: C-Donor Cyclohexylmethyldimethoxysilane Donor 1 2-Isopropyl-2-isoamyl-1,3-dimethoxypropane As can be seen from Table 2, when the catalyst system provided by the present invention is used in olefin polymerization, especially propylene polymerization, the stereospecificity, catalytic activity and hydrogen adjustment sensitivity are all good. Compared with the catalyst system containing a silane-based compound or a diether-based compound as an external electron donor, the catalyst system containing a 12-membered ring compound represented by formula (M) as a cocatalyst has improved hydrogen adjustment sensitivity, obviously improved polymerization activity, and good isotacticity index of the polymer. When a silane-based compound or a diether-based compound is added to the catalyst system as an external electron donor, the isotacticity index of the product is further improved. According to the above characteristics of the catalyst provided by the present invention, the catalyst system provided by the present invention is particularly suitable for producing polypropylene products with high stereoregularity and low ash content, and the melt index of the product can be adjusted in a wide range by adjusting the amount of hydrogen added.

[0184] (Example 25) In a 48-channel parallel pressure reactor (reaction volume 20 ml), replace the reactor with hydrogen gas. Fill with propylene gas to 1 mPa, and add 5 ml of liquid propylene. Prepare a mixed solution by sequentially adding triethylaluminum, compound A, and heptane solution of solid catalyst component Z1 in a molar ratio of triethylaluminum (calculated in aluminum element): compound A: solid catalyst component (calculated in titanium element) of 250:25:1. Take a certain amount of the mixed solution (containing 0.02 mg of solid catalyst component) and inject it into the reactor. React at 70°C for 40 minutes. Replace the system with ethylpropylene mixed gas (volume ratio of ethylene and propylene is 1:1), and react at 80°C for 20 minutes with the pressure controlled at 0.7 MPa.

[0185] The reaction product was discharged, the weight of the polymer was weighed, and the catalytic activity was calculated. At the same time, the ethylene content of the polymer was measured, and the results are shown in Table 3.

[0186] Comparative Example 11 The procedure was basically the same as in Example 25, except that compound A was replaced with an equimolar C-donor. The results are shown in Table 3.

[0187] (Example 26) The same as in Example 25, the only difference is that a part of compound A is replaced with equimolar C-Donor. In this example, the molar ratio of compound A to C-Donor is 1:1. The results are shown in Table 3.

[0188] Example 27 The procedure was basically the same as in Example 26, except that the molar ratio of Compound A to C-Donor was 1:9. The results are shown in Table 3.

[0189] (Example 28) The procedure is basically the same as in Example 25, except that the solid catalyst component Z1 is replaced with the solid catalyst component Z2. The results are shown in Table 3.

[0190] (Example 29) The only difference from Example 28 is that compound A was replaced with an equimolar amount of compound B. The results are shown in Table 3.

[0191] Comparative Example 12 The only difference from Example 28 is that compound A was replaced with an equimolar C-donor. The results are shown in Table 3.

[0192] [Table 3]

[0193] remarks: C-Donor Cyclohexylmethyldimethoxysilane The ethylene content means the content of -CH2CH2- units derived from ethylene monomers in a polymer.

[0194] As can be seen from Table 3, when the catalyst system provided by the present invention is used for olefin copolymerization, particularly the copolymerization of ethylene and propylene, the copolymer obtained by the catalyst system using the 12-membered ring compound represented by formula (M) as a cocatalyst has a comparable ethylene content and improved polymerization activity compared to the case where C-Donor is used as an external electron donor. According to the above characteristics of the catalyst provided by the present invention, the catalyst system provided by the present invention can also be applied to copolymerization systems to improve copolymerization productivity.

[0195] It should be noted that the above-described examples are only used to explain the present invention, and do not limit the present invention in any way. The present invention can be modified within the scope of the claims of the present invention as specified, and the present invention can be modified without departing from the scope and spirit of the present invention. Although the present invention described relates to specific methods, materials and examples, the present invention is not limited to the specific examples disclosed therein, and on the contrary, the present invention can be extended to all other methods and applications having similar functions.

Claims

1. A catalyst system for use in olefin polymerization, comprising a main catalyst and a cocatalyst, the cocatalyst comprising a 12-membered ring compound represented by formula (M): 【Chemistry 1】 In formula (M), R １ , R ４ , R ５ , R ８ , R ９ , R １２ , R １３ and R １６ are each independently hydrogen, halogen, or C １ ~C ６ R ２ , R ３ , R ６ , R ７ , R １０ , R １１ , R １４ and R １５ are each independently a hydroxy group, an amino group, a halogen, or C １ ~C ６ Aldehyde group of C １ ~C ６ C substituted with alkoxy groups and halogens １ ~C ６ R １７ ~R ２４ are each independently hydrogen and C １ ~C １０ and selected from the alkyl groups 1. A catalyst system, characterized in that the main catalyst comprises (i) a solid catalyst component containing magnesium, titanium, a halogen and an internal electron donor compound, and (ii) an organoaluminum compound, and optionally (iii) an external electron donor compound.

2. 2. The catalytic system according to claim 1, wherein the molar ratio of said external electron donor compound to titanium element in said solid catalyst component is (0-500):

1.

3. 2. The catalytic system according to claim 1, wherein the molar ratio of said external electron donor compound to titanium element in said solid catalyst component is (0.01-200):

1.

4. 2. The catalytic system according to claim 1, wherein the molar ratio of said external electron donor compound to titanium element in said solid catalyst component is (0.1-100):

1.

5. In formula (M), R １７ ~R ２４ are each independently hydrogen and C １ ~C ６ 5. The catalytic system according to claim 1, wherein the alkyl group is selected from the group consisting of:

6. In formula (M), R １７ ~R ２４ are each independently hydrogen and C １ ~C ４ 5. The catalytic system according to claim 1, wherein the alkyl group is selected from the group consisting of:

7. The 12-membered ring compound represented by formula (M) is represented by formula (N): 【Chemistry 2】 In formula (N), R ２ , R ３ , R ６ , R ７ , R １０ , R １１ , R １４ and R １５ are each independently a hydroxy group, an amino group, a halogen, or C １ ~C ６ Aldehyde group of C １ ~C ６ C substituted with alkoxy groups and halogens １ ~C ６ 7. The catalytic system according to claim 1, characterized in that the alkoxy group is selected from the group consisting of

8. 8. The catalyst system according to claim 7, wherein the 12-membered ring compound represented by formula (M) is one or more selected from the following compounds: Compound A: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ = OCH ３ Compound B: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ = OCH ２ CH ３ Compound C: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ = OCH ２ CH ２ CH ３ Compound D: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ = OCH(CH ３ ) ２ Compound E: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ = OCH ２ CH ２ CH ２ CH ３ Compound F: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ = OCH ２ CH ３ Compound G: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ = OCH ２ CH ２ CH ３ Compound H: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ = OCH ２ CH ２ CH ２ CH ３ Compound I: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ =OH Compound J: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ =OH Compound K: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ =NH ２ Compound L: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ = Cl Compound M: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ =Br Compound N: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ = I Compound O: In the formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ =CHO Compound P: In formula (N), R ２ = R ６ = R １０ = R １４ = OCH ３ , R ３ = R ７ = R １１ = R １５ = OCH ２ CH ２ CH ２ B Compound Q: In formula (N), R ２ = R ３ = R ６ = R ７ = R １０ = R １１ = R １４ = R １５ = OCH ２ CH ２ C Compound R: In formula (N), R ２ = R ６ = R １０ = R １４ =OH, R ３ = R ７ = R １１ = R １５ = OCH ２ CH ３

9. The catalyst system according to any one of claims 1 to 8, characterized in that the internal electron donor compound is one or more selected from the group consisting of diether compounds, alcohol ester compounds, aromatic carboxylic acid ester compounds, succinic acid ester compounds and ketone compounds.

10. The alcohol ester compound is a glycol ester compound represented by formula B, 【Chemistry 3】 In formula B, R １ and R ２ are the same or different, and each independently represents C １ ~C ２０ Alkyl groups of C ２ ~C ２０ an alkenyl group of C ３ ~C ２０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ an alkylaryl group of C ７ ~C ２０ Aralkyl groups of C １０ ~C ２０ M is a divalent linking group; The diether compound is a 1,3-diether compound represented by formula E, 【Chemistry 4】 In formula E, R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , R Ｖ and R ＶＩ are the same or different, and each independently represents hydrogen, halogen, C １ ~C ２０ Alkyl groups of C ３ ~C ２０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ Aralkyl groups of C ７ ~C ２０ R ＶＩＩ and R ＶＩＩＩ are the same or different, and each independently represents C １ ~C ２０ Alkyl groups of C ３ ~C ２０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ Aralkyl groups of C ７ ~C ２０ wherein any one of the C 1 -C 20 alkyl group, the C 3 -C 20 cycloalkyl group, the C 6 -C 20 aryl group, the C 7 -C 20 aralkyl group, and the C 7 -C 20 alkylaryl group may be optionally substituted with one or more substituents, and the one or more substituents may be a hydroxy group, a halogen, a cyano group, a nitro group, an amino group, a mono-C １ ~C １０ Alkylamino group of bis-C １ ~C １０ or R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , R Ｖ and R ＶＩ two or more of the following are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring: The structure of the aromatic carboxylic acid ester compound is as shown in Formula F: 【Chemistry 5】 In formula F, each R ３ are the same or different, and independently C １ ~C ８ Alkyl groups of C ５ ~C １０ a cycloalkyl group of C ６ ~C １５ an aryl group of C ７ ~C １５ or an alkylaryl group of C ７ ~C １５ is an aralkyl group represented by the formula C １ ~C ８ Alkyl groups of C ５ ~C １０ a cycloalkyl group of C ６ ~C １５ an aryl group of C ７ ~C １５ or an alkylaryl group of C ７ ~C １５ The hydrogen on the carbon of the aralkyl group of R can be optionally substituted with a substituent selected from an alkane and a halogen atom; ４ ~R ７ may be the same or different, and are hydrogen, halogen, C １ ~C ６ Alkyl groups of C ５ ~C １０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ or an alkylaryl group of C ７ ~C ２０ is an aralkyl group represented by the formula C １ C to C6 alkyl groups, ５ Cycloalkyl groups of C to C ６ Aryl groups of C to C ７ to C20 alkylaryl group or C ７ The hydrogen on the carbon in the C to C 20 aralkyl group can be optionally substituted with a substituent selected from an alkane and a halogen atom; The structure of the succinate compound is as shown in Formula G, 【Chemistry 6】 In formula G, R １ and R ２ are the same or different, and each independently represents C １ ~C ２０ Alkyl groups of C ３ ~C ２０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ or an arylalkyl group of ７ ~C ２０ R ３ , R ４ , R ５ and R ６ are the same or different, and each independently represents hydrogen, C １ ~C ２０ 10. The catalytic system according to claim 9, characterized in that the alkyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups are selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups, optionally containing heteroatoms, and the groups can be connected as a ring.

11. In formula B, R １ and R ２ are the same or different, and each independently represents C １ ~C １０ Alkyl groups of C ２ ~C １０ an alkenyl group of C ３ ~C １０ a cycloalkyl group of C ６ ~C １０ an aryl group of C ７ ~C １０ an alkylaryl group of C ７ ~C １０ Aralkyl groups of C １０ ~C １５ The alkyl group, the alkenyl group, the cycloalkyl group, the aryl group, the alkylaryl group, the aralkyl group and the fused ring aryl group are selected from the group consisting of C １ ~C １０ Alkyl groups of C １ ~C １０ Alkoxy groups, hydroxy groups, halogens, cyano groups, nitro groups, amino groups, mono-C １ ~C ６ Alkylamino group of bis-C １ ~C ６ is optionally substituted with one or more substituents selected from an alkylamino group, an aldehyde group, a carboxyl group, and a heteroatom; Or / and M is C １ ~C ２０ an alkylene group of C ３ ~C ２０ and a cycloalkylene group of C ６ ~C ２０ The alkylene group, the cycloalkylene group and / or the arylene group are selected from the group consisting of C １ ~C ２０ Alkyl groups of C １ ~C ２０ and halogen, and the substituents are optionally bonded to one or more rings; carbon and / or hydrogen atoms in M ​​are optionally substituted with nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms; and / or in formula F, each R ３ In C １ ~C ８ Alkyl groups of C ５ ~C １０ a cycloalkyl group of C ６ ~C １５ an aryl group of C ７ ~C １５ or an alkylaryl group of C ７ ~C １５ The hydrogen on the carbon of the aralkyl group is C １ ~C ６ substituted with one or more substituents selected from an alkyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; R ４ ~R ７ In C １ C to C6 alkyl groups, ５ ~C １０ a cycloalkyl group of C ６ Aryl groups of C to C ７ to C20 alkylaryl group or C ７ The hydrogen on the carbon in the aralkyl group of C to C １ ~C ６ 11. The catalyst system according to claim 10, characterized in that the aryl group is substituted with one or more substituents selected from the group consisting of an alkyl group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

12. 12. The catalyst system according to claim 1, wherein the external electron donor compound is one or more selected from the group consisting of silane-based compounds, ester-based compounds, ether-based compounds and ketone-based compounds.

13. The structure of the silane-based compound is as shown in Formula D, 【Chemistry 7】 In formula D, R １ ~R ４ are the same or different, and each independently represents hydrogen, C １ ~C １０ Alkyl groups of C ２ ~C １０ an alkenyl group of C １ ~C １０ an alkoxy group of C ２ ~C １０ an alkenyloxy group of C ２ ~C １０ an alkynyl group of C ２ ~C １０ an alkynyloxy group of C ３ ~C １０ a cycloalkyl group of C ６ ~C １５ an aryl group of C ３ ~C １０ a cycloalkoxy group of C ６ ~C １５ and an amino group, and the C 1 -C 10 alkyl group, the C 2 -C 10 alkenyl group, the C 1 -C 10 alkoxy group, the C 2 -C 10 alkenyloxy group, the C 2 -C 10 alkynyl group, the C 2 -C 10 alkynyloxy group, the C 3 -C 10 cycloalkyl group, the C 6 -C 15 aryl group, the C 3 -C 10 cycloalkoxy group, the C 6 -C 15 aryloxy group and the amino group are selected from halogen, １ ~C ６ Alkyl groups of C ３ ~C ６ a cycloalkyl group of C ６ ~C １０ and an amino group, The ether compound is a 1,3-diether compound represented by formula E, 【Chemistry 8】 In formula E, R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , R Ｖ and R ＶＩ are the same or different, and each independently represents hydrogen, halogen, C １ ~C ２０ Alkyl groups of C ３ ~C ２０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ Aralkyl groups of C ７ ~C ２０ R ＶＩＩ and R ＶＩＩＩ are the same or different, and each independently represents C １ ~C ２０ Alkyl groups of C ３ ~C ２０ a cycloalkyl group of C ６ ~C ２０ an aryl group of C ７ ~C ２０ Aralkyl groups of C ７ ~C ２０ wherein any one of the C 1 -C 20 alkyl group, the C 3 -C 20 cycloalkyl group, the C 6 -C 20 aryl group, the C 7 -C 20 aralkyl group, and the C 7 -C 20 alkylaryl group may be optionally substituted with one or more substituents, and the one or more substituents may be a hydroxy group, a halogen, a cyano group, a nitro group, an amino group, a mono-C １ ~C １０ Alkylamino group of bis-C １ ~C １０ or R Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ , R Ｖ and R ＶＩ 13. The catalyst system of claim 12, characterized in that two or more of: are linked to each other to form a saturated or unsaturated monocyclic or polycyclic ring.

14. 14. The catalytic system according to any one of claims 1 to 13, characterized in that the molar ratio of the 12-membered ring compound represented by formula (M) to the external electron donor compound is 1:100 to 100:

1.

15. the molar ratio of the 12-membered ring compound represented by formula (M) to the external electron donor compound is 1:50 to 50:1; And / or a catalyst system according to any one of claims 1 to 14, characterized in that the organoaluminium compound is an alkylaluminium compound.

16. the molar ratio of the 12-membered ring compound represented by formula (M) to the external electron donor compound is 1:20 to 20:1; And / or the general formula of the alkylaluminum compound is AlR ３ where each R is independently hydrogen, halogen, C １ ~C ２０ Alkyl groups of C １ ~C ２０ Alkoxy group or halogenated C １ ~C ２０ At least one of the three R's is selected from the alkyl groups represented by the formula: １ ~C ２０ 16. The catalyst system according to claim 15, characterized in that the alkyl group is:

17. The general formula of the alkylaluminum compound is AlR ３ where each R is independently hydrogen, halogen, C １ ~C １０ Alkyl groups of C １ ~C １０ Alkoxy group or halogenated C １ ~C １０ At least one of the three R's is selected from the alkyl groups represented by the formula: １ ~C １０ 16. The catalyst system according to claim 15, characterized in that the alkyl group is:

18. The alkylaluminum compound may be triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, monohydrodiethylaluminum, monohydrodiisobutylaluminum, monochlorodiethylaluminum, monochlorodiisobutylaluminum, dichloroethylaluminum, Al(n-C ６ H １３ ) ３ and Al(n-C ８ H １７ ) ３ 16. The catalyst system according to claim 15, characterized in that it is one or more of:

19. The catalyst system according to any one of claims 1 to 18, characterized in that the molar ratio of the 12-membered ring compound represented by the formula (M) to the organoaluminum compound calculated in terms of aluminum is 1: (0.1 to 500), and the molar ratio of the solid catalyst component calculated in terms of titanium element to the organoaluminum compound calculated in terms of aluminum is 1: (5 to 5000).

20. The catalyst system according to claim 19, characterized in that the molar ratio of the 12-membered ring compound represented by the formula (M) to the organoaluminum compound calculated in terms of aluminum is 1:(1-200), and / or the molar ratio of the solid catalyst component calculated in terms of titanium element to the organoaluminum compound calculated in terms of aluminum is 1:(20-2000).

21. A prepolymerized catalyst composition for use in olefin polymerization, comprising the catalyst system according to any one of claims 1 to 20 and a prepolymer obtained by prepolymerizing an olefin.

22. The prepolymerization ratio of the prepolymer is 0.1 to 1000 g of olefin polymer / g of solid catalyst component, according to claim 21.

23. Polymerizing an olefin in the presence of a catalyst system according to any one of claims 1 to 20 and / or a pre-polymerized catalyst composition according to claim 21 or 22, wherein the olefin has the general formula CH ２ =CHR, where R is hydrogen or C １ ~C ８ The method used in olefin polymerization is as follows:

24. 24. The method of claim 23, wherein the olefin is one or more selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.

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