CN113754803A - Catalyst system and application thereof as catalyst for olefin polymerization - Google Patents

Catalyst system and application thereof as catalyst for olefin polymerization Download PDF

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CN113754803A
CN113754803A CN202010507244.4A CN202010507244A CN113754803A CN 113754803 A CN113754803 A CN 113754803A CN 202010507244 A CN202010507244 A CN 202010507244A CN 113754803 A CN113754803 A CN 113754803A
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dimethoxypropane
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CN113754803B (en
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林洁
张晓帆
郭子芳
张军辉
黄庭
李昌秀
孙竹芳
周俊领
赵惠
张纪贵
齐琳
王宇
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a catalyst system for olefin polymerization, which comprises the following components or the reaction product of the following components: 1) a solid catalyst component comprising a magnesium element, a titanium element, a halogen element, and an internal electron donor; 2) a cocatalyst component selected from the group consisting of alkylaluminum compounds; 3) an external electron donor comprising a columnar aromatic compound represented by formula (I). According to the invention, the column arene or the derivative thereof with special properties is introduced into the Ziegler-Natta type polyolefin catalyst system as an external electron donor, so that the molecular weight and the isotactic index of the polymerization product can be improved, and the molecular weight distribution of the polymerization product is widened.

Description

Catalyst system and application thereof as catalyst for olefin polymerization
Technical Field
The invention relates to the field of olefin polymerization, in particular to a catalyst system and application thereof as a catalyst for olefin polymerization.
Background
It is well known that in order to meet the demands of industrial production and produce polyolefin products with excellent properties, the stereospecificity of the Ziegler-Natta type polyolefin catalyst, the molecular weight and molecular weight distribution of the polymer are important technical parameters. Catalyst systems with excellent overall performance have been the subject of efforts of polyolefin resin production enterprises and research and development institutions.
The Ziegler-Natta catalyst used as the core of polyolefin technology mainly comprises magnesium element, titanium element and internal electron donor, and the catalyst is often used together with alkyl aluminum and external electron donor to form a complete catalyst system. The external electron donor has the obvious characteristics of rich varieties, flexible and controllable addition, large influence on various performances of the catalyst and the like, so that the regulation of the overall performance of the catalyst system by selecting a proper external electron donor is an important direction for catalyst research and development.
Disclosure of Invention
In view of the above problems of the prior art, it is an object of the present invention to provide a catalyst system for olefin polymerization, which can increase the molecular weight and isotactic index of a polymerization product and broaden the molecular weight distribution of the polymerization product by introducing a pillar aromatic hydrocarbon or a derivative thereof having specific properties as an external electron donor into a Ziegler-Natta type polyolefin catalyst system.
It is a further object of the present invention to provide a prepolymerized catalyst composition for olefin polymerization.
It is a further object of the present invention to provide a catalyst system and the use of a prepolymerized catalyst composition corresponding to the first and second object.
The fourth object of the present invention is to provide a process for the polymerization of olefins corresponding to the above object.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
a catalyst system for the polymerization of olefins comprising the following components or the reaction product of the following components:
1) a solid catalyst component comprising a magnesium element, a titanium element, a halogen element, and an internal electron donor;
2) a cocatalyst component selected from the group consisting of alkylaluminum compounds;
3) an external electron donor comprising a columnar aromatic compound selected from those represented by the formula (I),
Figure BDA0002526975850000021
in the formula (I), the compound is shown in the specification,
Figure BDA0002526975850000022
is a basic unit, wherein M1、M2、M3、M4、R1And R2The same or different, each independently selected from hydrogen, hydroxy, cyano, nitro, amino, -CHO, -R3CHO、-C(O)R4、-C(O)OH、-R3C(O)OH、-C(O)OR4、-R3C(O)OR4、-OR4、-R3OR4Halogen atom, C with or without substituents1-C10Alkyl and C with or without substituents1-C10Alkoxy, wherein R3Is C with or without substituents1-C6Alkylene radical, R4Is C with or without substituents1-C6Alkyl, the substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen, C1-C6Alkyl radical, C1-C6Alkoxy and heteroatoms;
n represents the number of basic units and is an integer of 3-20;
when the adjacent groups within or between adjacent base units are-C (O) R4、-C(O)OR4、-R3C(O)OR4、-OR4、-R3OR4C with or without substituents1-C10Hydrocarbyl and C with or without substituents1-C10Hydrocarbyloxy, two adjacent groups are optionally linked to each other to form a cyclic structure selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof.
According to the present invention, the base unit may also be head-to-head connected as shown in the following formula (a), thereby forming an isomer. Said isomers are also intended to be within the scope of the present invention.
Figure BDA0002526975850000031
The inventors of the present application have found that by introducing a column aromatic hydrocarbon or a derivative thereof having a specific property as an external electron donor into a Ziegler-Natta type polyolefin catalyst system, the molecular weight and isotactic index of the polymerization product can be increased, and the molecular weight distribution of the polymerization product can be broadened.
According to the invention, M on different base units1、M2、M3、M4、R1And R2May be the same or different.
In some preferred embodiments of the invention, in formula (I), M1、M2、M3And M4The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C1-C10Alkyl, halogen atom substituted C1-C10Alkyl radical, C1-C10Alkoxy and halogen substituted C1-C10An alkoxy group.
In some preferred embodiments of the invention, R1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C10Alkyl and C with or without substituents1-C10An alkoxy group.
In some preferred embodiments of the invention, n is an integer from 4 to 10, such as 4,5,6,7, 8, 9, 10. In some preferred embodiments of the invention, n is an integer from 4 to 7.
In some preferred embodiments of the invention, in formula (I), M1、M2、M3And M4The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C1-C6Alkoxy and halogen substituted C1-C6An alkoxy group.
In some preferred embodiments of the invention, R1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C6Alkyl and C with or without substituents1-C6An alkoxy group.
In some preferred embodiments of the invention, in formula (I), M1And M2Are the same or different and are each independently selected from C1-C6An alkoxy group.
In some preferred embodiments of the inventionIn the embodiment of (I), M3And M4Are all hydrogen.
In some preferred embodiments of the present invention, the column arene compound represented by formula (I) is selected from one or more of the following compounds:
compound a 1: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound a 2: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound a 3: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound B1: m1＝M2＝OCH2CH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound B2: m1＝M2＝OCH2CH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound B3: m1＝M2＝OCH2CH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound C1: m1＝M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound C2: m1＝M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound C3: m1＝M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound D1: m1＝M2＝OCH(CH3)2；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound D2: m1＝M2＝OCH(CH3)2；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound D3: m1＝M2＝OCH(CH3)2；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound E1: m1＝OCH3；M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound E2: m1＝OCH3；M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound E3: m1＝OCH3；M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound F1: m1＝OCH3；M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound F2: m1＝OCH3；M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound F3: m1＝OCH3；M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound G1: m1＝OCH3；M2＝OCH2CH2Cl；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound G2: m1＝OCH3；M2＝OCH2CH2Cl；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound G3: m1＝OCH3；M2＝OCH2CH2Cl；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound H1: m1＝OCH3；M2＝I；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound H2: m1＝OCH3；M2＝I；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound H3: m1＝OCH3；M2＝I；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound I1: m1＝M3＝OCH3；M2＝M4＝H；R1＝R2＝H；n＝5；
Compound I2: m1＝M3＝OCH3；M2＝M4＝H；R1＝R2＝H；n＝6；
Compound I3: m1＝M3＝OCH3；M2＝M4＝H；R1＝R2＝H；n＝7；
Compound J1: m1＝M2＝OCH3；M3＝M4＝OCH2CH2CH3；R1＝R2＝H；n＝5；
Compound J2: m1＝M2＝OCH3；M3＝M4＝OCH2CH2CH3；R1＝R2＝H；n＝6；
Compound J3: m1＝M2＝OCH3；M3＝M4＝OCH2CH2CH3；R1＝R2＝H；n＝7；
Compound K1: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝CH3；n＝5；
Compound K2: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝CH3；n＝6；
Compound K3: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝CH3；n＝7；
Compound L1: m1＝OH；M3＝H；M2＝M4＝Br；R1＝R2＝H；n＝5；
Compound L2: m1＝OH；M3＝H；M2＝M4＝Br；R1＝R2＝H；n＝6；
Compound L3: m1＝OH；M3＝H；M2＝M4＝Br；R1＝R2＝H；n＝7；
Compound M1: m1＝M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound M2: m1＝M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound M3: m1＝M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound N1: m1＝OCH3；M2＝M3＝M4＝H；R1＝R2＝H；n＝5；
Compound N2: m1＝OCH3；M2＝M3＝M4＝H；R1＝R2＝H；n＝6；
Compound N3: m1＝OCH3；M2＝M3＝M4＝H；R1＝R2＝H；n＝7；
Compound O1: m1＝OH；M2＝M3＝M4＝H；R1＝R2＝H；n＝5；
Compound O2: m1＝OH；M2＝M3＝M4＝H；R1＝R2＝H；n＝6；
Compound O3: m1＝OH；M2＝M3＝M4＝H；R1＝R2＝H；n＝7；
Compound P1: m1＝OCH3；M2＝OH；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound P2: m1＝OCH3；M2＝OH；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound P3: m1＝OCH3；M2＝OH；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound Q1: m1＝OCH3；M2＝CH3COO；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound Q2: m1＝OCH3；M2＝CH3COO；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound Q3: m1＝OCH3；M2＝CH3COO；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound R1: m1＝OCH3；M2＝Ph；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound R2: m1＝OCH3；M2＝Ph；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound R3: m1＝OCH3；M2＝Ph；M3＝M4＝H；R1＝R2＝H；n＝7。
In some preferred embodiments of the invention, the alkyl aluminum compound is selected from compounds of formula (II),
AlR3a compound of the formula (II),
in the formula (II), R is C with or without halogen atom substituent1-C20Alkyl, preferably C with or without halogen substituents1-C6An alkyl group.
In some preferred embodiments of the invention, the alkyl aluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al (n-C)6H13)3And Al (n-C)8H17)3One or more of (a).
In some preferred embodiments of the present invention, the molar ratio of the external electron donor to the aluminum element in the alkylaluminum compound is 1 (0.1-5000), preferably 1 (1-1000).
In some preferred embodiments of the present invention, the internal electron donor is selected from one or more of an alcohol ester compound, an aromatic carboxylic acid ester compound, and a diether compound.
In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (III),
Figure BDA0002526975850000061
in the formula (III), R1And R2The same or different, each being independentSelected from C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents2-C20Alkynyl, C with or without substituents3-C20Cycloalkyl, C with or without substituents6-C20Aryl, C with or without substituents7-C20Alkylaryl, C with or without substituents7-C20Aralkyl and C with or without substituents10-C20The condensed ring aromatic groups are preferably each independently selected from C having or not having a substituent1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents3-C10Cycloalkyl, C with or without substituents6-C10Aryl, C with or without substituents7-C10Alkylaryl, C with or without substituents7-C10Aralkyl and C with or without substituents10-C15A condensed ring aryl group, the substituent is selected from hydroxyl, halogen atom, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is a divalent linking group, preferably selected from C with or without substituents1-C20Alkylene, C with or without substituents3-C20Cycloalkylene and C with or without substituents6-C20Arylene group, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C1-C20Alkyl when the substituent is multiple C1-C20When alkyl, the substituents are optionally bonded to one or more rings.
In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (b),
Figure BDA0002526975850000071
r 'in the formula (b)'1And R'2Are the same or different and are each independently selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20Alkylaryl, preferably selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl and C7-C10Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and C1-C6One or more substituents in alkoxy; r'3、R’4、R’5、R’6And R’1-R’2nThe same or different, each is independently selected from hydrogen, halogen and C1-C20Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20Aralkyl and C10-C20Condensed ring aryl, preferably selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl group, C7-C10Aralkyl and C10-C15A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C1-C6Alkyl and C1-C6One or more substituents in alkoxy; r'3、R’4、R’5、R’6And R’1-R’2nOptionally containing heteroatoms of one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus(ii) a Or, R'3、R’4、R’5、R’6And R’1-R’2nTwo or more of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and when n is 0, the substituent is R'3And R'4Is R 'to carbon atom and substituent'5And R'6Is bonded to the carbon atom(s) of (a).
According to the invention, in formula (b) the bracketed moiety indicates that n carbon atoms are bonded in sequence and that each carbon atom is further bonded to 2 substituents, i.e. there are a total of n carbon atoms and R 'in the bracketed moiety'1、R’2、R’3…R’2nAnd 2n substituents.
In some preferred embodiments of the present invention, the aromatic carboxylic acid ester compound is selected from compounds represented by formula (IV),
Figure BDA0002526975850000081
in the formula (IV), each R3Identical or different, each independently selected from the group consisting of1-C6C of substituents of alkyl radicals and halogen atoms1-C8Alkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms5-C10Cycloalkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms6-C15Aryl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C15Alkylaryl or with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C15Aralkyl group of (1); r4-R7Can be the same or different, and are independently selected from hydrogen, halogen, with or without C1-C6C of substituents of alkyl radicals and halogen atoms1-C8Alkyl, with or without C1-C6Alkyl and halogenC of a substituent of an atom5-C10Cycloalkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms6-C20Aryl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C20Alkylaryl or with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C20An aralkyl group.
In some preferred embodiments of the present invention, the diether compound is selected from 1, 3-diether compounds, more preferably from 1, 3-diether compounds represented by formula (V),
Figure BDA0002526975850000082
r 'in the formula (V)'1、R'2、R'3、R'4、R'5And R'6The same or different, each independently selected from hydrogen, halogen, C with or without substituent1-C20Alkyl, C with or without substituents3-C20Cycloalkyl, C with or without substituents6-C20Aryl, C with or without substituents7-C20Aralkyl and C with or without substituents7-C20An alkaryl group; r'7And R'8Identical or different, each independently selected from C with or without substituents1-C20Alkyl, C with or without substituents3-C20Cycloalkyl, C with or without substituents6-C20Aryl, C with or without substituents7-C20Aralkyl and C with or without substituents7-C20Alkylaryl, said substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; optionally, R'1、R'2、R'3、R'4、R'5And R'6Are bonded to each other to form saturatedOr unsaturated monocyclic or polycyclic.
In some preferred embodiments of the present invention, the glycol ester compound is selected from the group consisting of 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, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 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-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-4-heptanediol di (p-methylbenzoic acid) ester, 2, 5-heptanediol dibenzoate, 2-methyl-4-heptanediol di (p-methylbenzoic acid) ester, 4-methylbenzoic acid, 4-methyl ester, 4-heptanediol di (m-methylbenzoic acid) ester, 4-methylbenzoic acid, and mixtures thereof, 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-dimethyl-3, 5-octanediol dibenzoate, 4-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-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-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-dibenzoate, 2-phenylene dibenzoate, and mixtures thereof, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-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, 8-naphthyl ester, 1, 8-naphthyl bis-4-isobutylbenzoate, 1, 8-naphthyl bis-4-tert-butylbenzoate, 1, 8-naphthyl bis-4-phenylbenzoate, 1, 8-naphthyl bis-4-fluorobenzoate, 1, 8-naphthyl bis-3-fluorobenzoate, 1, 8-naphthyl bis-2-fluorobenzoate.
In some preferred embodiments of the present invention, the aromatic carboxylic acid ester-based compound is preferably a phthalic acid carboxylic acid ester-based compound; more preferably, the aromatic carboxylic acid ester compound is one or more selected from the group consisting of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate, and still more preferably, the aromatic carboxylic acid ester compound is diisobutyl phthalate.
In some preferred embodiments of the invention the diether compound is selected from the group consisting of 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-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-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-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-phenyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 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-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene, 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-bis (methoxymethyl) -4-phenylindene, 2-methylindene, 2-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -2-dimethylindene, and the like, 1, 1-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylindene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 2-phenylindene, 1-bis (methoxymethyl) indene, 1-bis (methoxymethyl) -7-phenylindene, and, 9, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.
According to the invention, the solid catalyst component comprises a titanium element, a magnesium element and an internal electron donor, and is a reaction product of a titanium compound, a magnesium compound and the internal electron donor. Since the present invention improves the performance of the olefin polymerization catalyst by changing the external electron donor, the method of preparing the solid catalyst component by the reaction as described above in the present invention may be performed according to a method conventionally used in the art, for example, methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, and the like, the disclosure of which is incorporated herein by reference.
The preparation method of the solid catalyst component in the present invention includes, but is not limited to, the following methods:
the method comprises the following steps: adding an inert solvent into a magnesium compound, adding an organic epoxy compound and an organic phosphorus compound, dissolving, adding a precipitation aid and a titanium compound, and precipitating a solid; adding an internal electron donor to make it be carried on the solid, and treating with titanium tetrahalide and inert diluent.
The method 2 comprises the following steps: dissolving solid magnesium compound in organic alcohol compound such as 2-ethylhexanol in inert solvent such as decane or toluene, adding precipitation assistant and titanium compound after dissolving, and precipitating solid; adding an internal electron donor to make it be carried on the solid, and treating with titanium compound and inert diluent.
The method 3 comprises the following steps: dispersing a magnesium halide alcohol compound into a titanium compound at a low temperature (such as below-5 ℃), heating to a high temperature (such as above 50 ℃), adding an internal electron donor compound during heating, filtering, treating the obtained precipitate with a titanium compound, and washing the precipitate to obtain the solid catalyst component.
The method 4 comprises the following steps: preparing an alkoxy magnesium carrier and an inert diluent into a suspension, then reacting with a mixture formed by a titanium compound and the inert diluent, filtering, carrying out contact reaction on the obtained precipitate, the titanium compound and an internal electron donor compound, and washing the precipitate to obtain the solid catalyst component.
According to a preferred embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.) precooled to-15 to-40 ℃ is mixed with a magnesium compound, and the temperature of the mixture is raised to 90 to 110 ℃ in stages and maintained for 0.1 to 2 hours, and an internal electron donor is added during the raising of the temperature. Then solid-liquid separation is carried out, the obtained solid phase is treated for at least 2 times by using the titanium compound again, and is washed by using a solvent, and finally, the solid catalyst component is obtained by vacuum drying.
According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, and for example, the magnesium compound may be selected from at least one of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the molecule of magnesium dihalide is substituted with hydrocarbyloxy group or halohydrocarbyloxy group. According to a preferred embodiment of the invention, the magnesium compound is an alcoholate of magnesium dihalide.
According to a preferred embodiment of the invention, the alcoholate of magnesium dihalide has a spherical magnesium alcoholate of formula (VI),
MgX2·m(R’OH)·nE·qH2o type (VI)
In the formula (VI), X is chlorine or bromine; r' is C1-C4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), m is 0.5 to 4.0; e is an ether or ester electron donor compound, n is 0-1.0, wherein the ether or ester can be an ether or ester which can be used as an electron donor and is known in the art, and can also be an internal electron donor and/or an external electron donor used in the invention; q is 0 to 0.8.
According to a preferred embodiment of the invention, in formula (VI), X is chlorine or bromine; r' is C1-C4 alkyl, m is 1.5-3.5; n and q are both 0.
According to a preferred embodiment of the invention, the magnesium compound is MgCl2·m(CH3CH2OH), m is 1.5-3.5.
According to some embodiments of the present invention, the preparation of said alcoholate of magnesium dihalide can be carried out according to methods known in the art, for example with reference to the method disclosed in CN 1330086A.
According to a preferred embodiment of the invention, the preparation process of the alcoholate of magnesium dihalide comprises: (1) mixing anhydrous magnesium dihalide with alcohol compound (R' OH), and reacting at 90-140 deg.C to obtain magnesium halide alcohol compound; (2) shearing the magnesium halide alcohol compound in a dispersion medium, and cooling in an inert medium after shearing to obtain the spherical magnesium halide alcohol compound. The mixing ratio of the anhydrous magnesium dihalide and the alcohol compound may be determined according to the actual need of the alcohol compound supported on the anhydrous magnesium dihalide. Wherein, the dispersion medium can adopt hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, and the like. Wherein the shearing means shearing the alcoholic product of the magnesium halide by external shearing force, for example, high-speed stirring method (e.g. CN1330086), spraying method (e.g. US6020279) and super-gravity rotating bed (e.g. CN1580136A) and emulsifier method (CN1463990A) and the like.
According to a preferred embodiment of the present invention, in order to further increase the purity of the magnesium compound, the obtained alcohol hydrate of spherical magnesium halide is further subjected to washing and drying steps.
The alkoxy magnesium is prepared by reacting metal magnesium, ethanol, isooctyl alcohol (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, a non-limiting selection of which are: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, ethoxymagnesium iodide, methoxymagnesium iodide, isopropylmagnesium iodide, hydrogen chloride, chloroacetyl chloride, and the like.
According to the present invention, the titanium compound may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. According to a preferred embodiment of the present invention, the titanium compound has a structure represented by formula (VII),
Ti(OR”)4-kXkformula (VII)
In formula (VII): r' is C1-C20 alkyl, and X is F, Cl or Br; k is an integer of 0 to 4.
According to a preferred embodiment of the invention, in formula (VII): r' is C1-C10 alkyl.
According to a preferred embodiment of the invention, in formula (VII): r' is C1-C5 alkyl.
According to a preferred embodiment of the invention, for example, in formula (VII): r' is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.
According to a preferred embodiment of the invention, in formula (VII): and X is Cl.
According to a preferred embodiment of the present invention, the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride.
According to a preferred embodiment of the invention, the titanium compound is titanium tetrachloride.
According to some embodiments of the present invention, the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1 (5-25) to (2-15).
According to the invention, in the catalyst system, the molar ratio of the solid catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1 (5-5000), preferably 1 (20-2000).
In order to achieve the second purpose, the invention adopts the following technical scheme:
a prepolymerized catalyst composition for the polymerization of olefins comprising:
a) the catalyst system of any one of claims 1 to 7 subjected to a prepolymerization step of an olefin;
b) the olefin prepolymerization step is carried out to obtain a prepolymer.
In some preferred embodiments of the present invention, the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of prepolymer per g of solid catalyst component, preferably 0.2 to 500g of prepolymer per g of solid catalyst component, and more preferably 0.5 to 20g of prepolymer per g of solid catalyst component.
According to the invention, the term "prepolymerized catalyst" refers to a catalyst which has undergone a polymerization step with a relatively low degree of conversion. In the present invention, the prepolymerization can be carried out using the same α -olefin as the olefin used for the polymerization.
According to some preferred embodiments of the invention, the olefin to be prepolymerized is propylene.
According to some preferred embodiments of the invention, the prepolymerization is carried out with propylene or a mixture thereof with one or more alpha-olefins in a molar amount of up to 20%.
According to some embodiments of the invention, the temperature of the prepolymerization is in the range of-20 to 80 ℃ and the polymerization pressure is preferably in the range of 0 to 5 MPa.
According to some preferred embodiments of the invention, the temperature of the prepolymerization is between 0 and 50 ℃.
According to some embodiments of the invention, the prepolymerization is carried out in a liquid or in the gas phase.
According to some embodiments of the invention, the prepolymerization step can be carried out in-line as part of a continuous polymerization process, or independently in a batch operation.
According to some preferred embodiments of the present invention, the prepolymerization of the catalyst of the present invention with an olefin is carried out independently in a batch operation at a polymerization pressure of 0 to 5MPa, for the preparation of a polymer of 0.1 to 1000g of olefin prepolymer per g of solid catalyst component.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
use of a catalyst system as described above or a prepolymerized catalyst composition as described above in the field of olefin polymerization, especially propylene polymerization.
According to the invention, the olefin has the general formula CH2＝CHR5Wherein R is5Is hydrogen or C1-C6And the olefin polymerization can be homopolymerization of a single olefin or copolymerization of a plurality of olefins, and can also be a combination of a single olefin homopolymerization process and a plurality of olefin copolymerization processes.
According to some preferred embodiments of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
According to some preferred embodiments of the invention, the olefin is ethylene, propylene and/or 1-butene.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
an olefin polymerization process comprising: the olefin is polymerized in the presence of the above-mentioned catalyst system and/or the above-mentioned prepolymerized catalyst composition.
In some preferred embodiments of the present invention, the polymerization conditions include: the temperature is 0-150 ℃, preferably 50-90 ℃; the pressure is 0.01MPa-10MPa, preferably 0.1MPa-5 MPa; the time is 0.1h to 5h, preferably 0.2h to 3 h.
According to some embodiments of the invention, both the catalyst system and the prepolymerized catalyst composition may be used in the polymerization of olefins.
According to some preferred embodiments of the present invention, both the catalyst system and the prepolymerized catalyst composition may be used in the homopolymerization of propylene or in the copolymerization with other olefins.
According to the present invention, the catalyst system of the present invention may be directly added to a reactor for use in a polymerization process, or the catalyst system and a prepolymerized catalyst composition obtained by prepolymerizing an olefin may be added to the reactor for polymerization.
According to the invention, the olefin polymerization can be carried out according to known polymerization methods, in liquid or gas phase, or in a combination of liquid and gas phase polymerization stages, or using conventional techniques such as slurry processes, gas phase fluidized beds, etc.
According to the invention, the polymerization can be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X 10 in terms of the titanium element in the solid catalyst component-5-5×10-5Mol/l.
According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent may be 0.2 expressed in terms of titanium element in the solid catalyst component10-5-2×10-5Mol/l.
In the present invention, the hydrocarbon group may be selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl and alkaryl groups.
In the present invention, alkyl means a straight or branched alkyl group, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 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-eicosyl.
In the present invention, examples of the alkenyl group may include, but are not limited to: ethenyl, propenyl, butenyl, pentenyl, octenyl.
In the present invention, examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.
In the present invention, examples of the cycloalkyl group may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl and cyclododecyl.
In the present invention, examples of the halogen include, but are not limited to, fluorine, chlorine, bromine and iodine.
In the present invention, examples of the aryl group may include, but are not limited to: phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, naphthyl.
In the present invention, aralkyl means an alkyl group having an aryl substituent, and examples may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.
In the present invention, the alkylaryl group means an aryl group having an alkyl substituent group with a carbon number of 7 to 20, and examples thereof may include, but are not limited to: methylphenyl, ethylphenyl.
In the present invention, examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and hexoxy.
In the present invention, examples of the condensed ring aryl group may include, but are not limited to: naphthyl, anthryl, phenanthryl, pyrenyl. In the present invention, the hetero atom means an atom usually contained in a molecular structure other than a halogen atom, a carbon atom and a hydrogen atom, for example, O, N, S, P, Si and B, etc.
The present invention has at least the beneficial effect that the polymerization reaction in the presence of the catalyst system and/or the prepolymerized catalyst composition of the present invention results in a product having a higher isotactic index and weight average molecular weight and a broader molecular weight distribution.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
In the present invention, the compounds represented by the formula (I) can be prepared by referring to the existing literature, for example, the compounds F1 and L1 can be prepared by referring to the literature Angew.chem.int.Ed.2020,59,3994-3999(DOI: 10.1002/anie.201913055); compounds Q1, R1 can be prepared according to the document org.Lett.2019,21,3976-3980(DOI: 10.1021/acs.orglett.9b01123).
In the following examples, the test methods involved are as follows:
1. weight average molecular weight and molecular weight distribution: high temperature sol gel chromatography, measured with reference to standard GB/T36214.4-2018.
2. Polymer isotactic index: reference is made to the standard GB/T2412-.
Preparation example 1
This preparation example is intended to illustrate the preparation of a magnesium compound.
Mixing anhydrous magnesium chloride and ethanol according to a molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alcoholate melt, stirring at a high speed in white oil and silicone oil serving as dispersion media, then putting into cooled hexane to form spherical magnesium chloride alcoholate particles, and washing and drying to obtain the spherical carrier.
Preparation example 2
This preparation example is intended to illustrate the preparation of the solid catalyst component.
Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, which is fully replaced by high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 6mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane as an internal electron donor in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride for treatment twice, washing with hexane for five times, and drying in vacuum to obtain a titanium-containing solid catalyst component Z1.
Preparation example 3
This preparation example is intended to illustrate the preparation of the solid catalyst component.
Sequentially adding 6.0g of magnesium chloride, 119mL of toluene, 5mL of epichlorohydrin and 15.6mL of tributyl phosphate (TBP) into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, and maintaining for 2.5 hours until the solid is completely dissolved; 1.7g of phthalic anhydride is added and the mixture is maintained for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl within 1 hour4Slowly heating 70mL to 80 ℃, and gradually separating out solids in the heating process; adding 6mmol of 3-methyl-2, 4-pentanediol dibenzoate as an internal electron donor, maintaining the temperature for 1 hour, filtering, adding 80mL of toluene, and washing twice to obtain a solid precipitate. Then 60mL of toluene and TiCl were added440mL, heating to 100 ℃, treating for 2 hours, discharging the filtrate, then adding 60mL of toluene and TiCl440mL, heating to 100 ℃, treating for 2 hours, and discharging the filtrate; adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, washing for two times in a boiling state, adding 60mL of hexane, and washing for two times at normal temperature to obtain a solid catalyst component Z2.
Preparation example 4
This preparation example is intended to illustrate the preparation of the solid catalyst component.
Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with stirring, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 6mmol of diisobutyl phthalate as an internal electron donor in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for two times, washing with hexane for five times, and drying in vacuum to obtain the titanium-containing solid catalyst component Z3.
Preparation example 5
This preparation example is intended to illustrate the preparation of the solid catalyst component.
Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, which is fully replaced by high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 3mmol of 2, 4-pentanediol dibenzoate and 3mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane as internal electron donors in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for two times, washing with hexane five times, and drying in vacuum to obtain a titanium-containing solid catalyst component Z4.
Preparation example 6
This preparation serves to illustrate the preparation of compound B3.
Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-diethoxybenzene, and stirred uniformly, 9mmol of paraformaldehyde and 0.45mmol of ferric chloride were added to the mixture, and the mixture was reacted at 30 ℃ for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate ═ 30: 1) to obtain compound B3.
Preparation example 7
This preparation serves to illustrate the preparation of compound C1.
Compound C1 was prepared in the manner of preparation 6. Except that 1, 4-di-n-propoxybenzene was used in place of 1, 4-diethoxybenzene in preparation example 6, as in preparation example 6.
Preparation example 8
Compound G1 was prepared in the manner of preparation 6. Except that 1-methoxy-4-2-chloroethoxybenzene in preparation example 6 was replaced with 1, 4-diethoxybenzene in preparation example 6.
Preparation example 9
This preparation serves to illustrate the preparation of mixture J.
Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-dimethoxy-2, 5-diethoxybenzene, and stirred uniformly, 9mmol of paraformaldehyde and 0.45mmol of ferric chloride were added to the mixture, and the mixture was reacted at 30 ℃ for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate ═ 30: 1) to obtain a mixture J containing compound J1, compound J2, and compound J3. Nuclear magnetic analysis revealed that the molar ratio of J1: J2: J3 in mixture J was 1: 0.68: 0.04.
examples 1 to 12 and comparative examples 1 to 5
Examples 1-12 and comparative examples 1-5 are provided to illustrate the catalyst systems provided by the present invention and their applications.
A 48-channel parallel pressure reactor (reaction volume 20mL) was charged with a quantity of hydrogen; filling propylene gas to about 1MPa, and adding 5mL of liquid propylene; based on triethyl aluminum (calculated by aluminum element): external electron donor: sequentially adding triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component according to the molar ratio of the solid catalyst component (calculated by titanium element) of 500:2:1 to prepare a mixed solution; a certain amount of the mixed solution (containing 0.02mg of the solid catalyst component) was injected into the reactor and reacted at 70 ℃ for 1 hour.
The polymer was discharged and the isotactic index, weight average molecular weight and molecular weight distribution of the polymer were determined, the results are shown in Table 1.
TABLE 1
Figure BDA0002526975850000201
Figure BDA0002526975850000211
As can be seen from Table 1, when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the weight average molecular weight of the polymer is obviously improved, the molecular weight distribution is widened, the isotactic index is improved, and the processability is improved.
Examples 13 to 15 and comparative examples 6 to 7
Examples 13-15 and comparative examples 6-7 are provided to illustrate the catalyst systems provided by the present invention and their applications.
A 48-channel parallel pressure reactor (reaction volume 20mL) was charged with a quantity of hydrogen; filling propylene gas to about 1MPa, and adding 5mL of liquid propylene; adding triethyl aluminum, an external electron donor and a heptane solution of a solid catalyst component according to a certain proportion to prepare a mixed solution; injecting a certain amount of mixed liquid (containing 0.02mg of solid catalyst component) into a reactor; the reaction was carried out at 70 ℃ for 1 hour.
The polymer was discharged and the isotactic index of the polymer was determined and the results are shown in Table 2.
TABLE 2
Figure BDA0002526975850000212
Figure BDA0002526975850000221
As can be seen from Table 2, when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the isotactic index of a polymerization product can be obviously improved by adding a small amount of a column aromatic compound, and when the dosage of the compound C1 is 10% of the dosage of a common external electron donor C-donor, an effect equivalent to that of the C-donor can be achieved. And, increasing the amount of compound C1 can further increase the isotactic index of the polymerization product.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A catalyst system for the polymerization of olefins comprising the following components or the reaction product of the following components:
1) a solid catalyst component comprising a magnesium element, a titanium element, a halogen element, and an internal electron donor;
2) a cocatalyst component selected from the group consisting of alkylaluminum compounds;
3) an external electron donor comprising a columnar aromatic hydrocarbon compound represented by the formula (I),
Figure FDA0002526975840000011
in the formula (I), the compound is shown in the specification,
Figure FDA0002526975840000012
is a basic unit, wherein M1、M2、M3、M4、R1And R2The same or different, each independently selected from hydrogen, hydroxy, cyano, nitro, amino, -CHO, -R3CHO、-C(O)R4、-C(O)OH、-R3C(O)OH、-C(O)OR4、-R3C(O)OR4、-OR4、-R3OR4Halogen atom, C with or without substituents1-C10Alkyl and C with or without substituents1-C10Alkoxy, wherein R3Is C with or without substituents1-C6Alkylene radical, R4Is C with or without substituents1-C6Alkyl, the substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen, C1-C6Alkyl radical, C1-C6Alkoxy and heteroatoms;
n represents the number of basic units and is an integer of 3-20;
when the adjacent groups within or between adjacent base units are-C (O) R4、-C(O)OR4、-R3C(O)OR4、-OR4、-R3OR4C with or without substituents1-C10Hydrocarbyl and C with or without substituents1-C10Hydrocarbyloxy, two adjacent groups are optionally linked to each other to form a cyclic structure selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof.
2. The catalyst system as claimed in claim 1, wherein in the formula (I), M1、M2、M3And M4The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C1-C10Alkyl, halogen atom substituted C1-C10Alkyl radical, C1-C10Alkoxy and halogen substituted C1-C10An alkoxy group; r1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C10Alkyl and C with or without substituents1-C10An alkoxy group; n is an integer of 4 to 10;
preferably, in formula (I), M1、M2、M3And M4The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C1-C6Alkoxy and halogen substituted C1-C6An alkoxy group; r1And R2The same or different, each independently selected from hydrogen, C with or without substituent1-C6Alkyl and C with or without substituents1-C6An alkoxy group; n is an integer of 4 to 7;
more preferably, in formula (I), M1And M2Are the same or different and are each independently selected fromC1-C6An alkoxy group.
3. Catalyst system according to claim 1 or 2, characterized in that the column aromatic compound of formula (I) is selected from one or more of the following compounds:
compound a 1: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound a 2: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound a 3: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound B1: m1＝M2＝OCH2CH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound B2: m1＝M2＝OCH2CH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound B3: m1＝M2＝OCH2CH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound C1: m1＝M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound C2: m1＝M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound C3: m1＝M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound D1:M1＝M2＝OCH(CH3)2；M3＝M4＝H；R1＝R2＝H；n＝5；
compound D2: m1＝M2＝OCH(CH3)2；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound D3: m1＝M2＝OCH(CH3)2；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound E1: m1＝OCH3；M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound E2: m1＝OCH3；M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound E3: m1＝OCH3；M2＝OCH2CH2CH3；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound F1: m1＝OCH3；M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound F2: m1＝OCH3；M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound F3: m1＝OCH3；M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound G1: m1＝OCH3；M2＝OCH2CH2Cl；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound G2: m1＝OCH3；M2＝OCH2CH2Cl；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound G3: m1＝OCH3；M2＝OCH2CH2Cl；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound H1: m1＝OCH3；M2＝I；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound H2: m1＝OCH3；M2＝I；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound H3: m1＝OCH3；M2＝I；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound I1: m1＝M3＝OCH3；M2＝M4＝H；R1＝R2＝H；n＝5；
Compound I2: m1＝M3＝OCH3；M2＝M4＝H；R1＝R2＝H；n＝6；
Compound I3: m1＝M3＝OCH3；M2＝M4＝H；R1＝R2＝H；n＝7；
Compound J1: m1＝M2＝OCH3；M3＝M4＝OCH2CH2CH3；R1＝R2＝H；n＝5；
Compound J2: m1＝M2＝OCH3；M3＝M4＝OCH2CH2CH3；R1＝R2＝H；n＝6；
Compound J3: m1＝M2＝OCH3；M3＝M4＝OCH2CH2CH3；R1＝R2＝H；n＝7；
Compound K1: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝CH3；n＝5；
Compound K2: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝CH3；n＝6；
Compound K3: m1＝M2＝OCH3；M3＝M4＝H；R1＝R2＝CH3；n＝7；
Compound L1: m1＝OH；M3＝H；M2＝M4＝Br；R1＝R2＝H；n＝5；
Compound L2: m1＝OH；M3＝H；M2＝M4＝Br；R1＝R2＝H；n＝6；
Compound L3: m1＝OH；M3＝H；M2＝M4＝Br；R1＝R2＝H；n＝7；
Compound M1: m1＝M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound M2: m1＝M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound M3: m1＝M2＝CHO；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound N1: m1＝OCH3；M2＝M3＝M4＝H；R1＝R2＝H；n＝5；
Compound N2: m1＝OCH3；M2＝M3＝M4＝H；R1＝R2＝H；n＝6；
Compound N3: m1＝OCH3；M2＝M3＝M4＝H；R1＝R2＝H；n＝7；
Compound O1: m1＝OH；M2＝M3＝M4＝H；R1＝R2＝H；n＝5；
Compound O2: m1＝OH；M2＝M3＝M4＝H；R1＝R2＝H；n＝6；
Compound O3: m1＝OH；M2＝M3＝M4＝H；R1＝R2＝H；n＝7；
Compound P1: m1＝OCH3；M2＝OH；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound P2: m1＝OCH3；M2＝OH；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound P3: m1＝OCH3；M2＝OH；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound Q1: m1＝OCH3；M2＝CH3COO；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound Q2: m1＝OCH3；M2＝CH3COO；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound Q3: m1＝OCH3；M2＝CH3COO；M3＝M4＝H；R1＝R2＝H；n＝7；
Compound R1: m1＝OCH3；M2＝Ph；M3＝M4＝H；R1＝R2＝H；n＝5；
Compound R2: m1＝OCH3；M2＝Ph；M3＝M4＝H；R1＝R2＝H；n＝6；
Compound R3: m1＝OCH3；M2＝Ph；M3＝M4＝H；R1＝R2＝H；n＝7。
4. The catalyst system according to any one of claims 1 to 3, characterized in that the alkylaluminum compound is selected from the compounds of formula (II),
AlR3a compound of the formula (II),
in the formula (II), R is C with or without halogen atom substituent1-C20Alkyl, preferably C with or without halogen substituents1-C6An alkyl group, a carboxyl group,
preferably, the alkylaluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al (n-C)6H13)3And Al (n-C)8H17)3One or more of (a).
5. The catalyst system according to any of claims 1 to 4, wherein the molar ratio of the external electron donor to the aluminum element in the alkylaluminum compound is 1 (0.1-5000), preferably 1 (1-1000).
6. The catalyst system of any of claims 1-5, wherein the internal electron donor is selected from one or more of an alcohol ester compound, an aromatic carboxylate compound, and a diether compound,
preferably, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (III),
Figure FDA0002526975840000041
in the formula (III), R1And R2Identical or different, each independently selected from C with or without substituents1-C20Alkyl, C with or without substituents2-C20Alkenyl, C with or without substituents2-C20Alkynyl, C with or without substituents3-C20Cycloalkyl, C with or without substituents6-C20Aryl, C with or without substituents7-C20Alkylaryl, C with or without substituents7-C20Aralkyl and C with or without substituents10-C20The condensed ring aromatic groups are preferably each independently selected from C having or not having a substituent1-C10Alkyl, C with or without substituents2-C10Alkenyl, C with or without substituents3-C10Cycloalkyl, C with or without substituents6-C10Aryl, C with or without substituents7-C10Alkylaryl, C with or without substituents7-C10Aralkyl and C with or without substituents10-C15A condensed ring aryl group, the substituent is selected from hydroxyl, halogen atom, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is a divalent linking group, preferably selected from C with or without substituents1-C20Alkylene, C with or without substituents3-C20Cycloalkylene and C with or without substituents6-C20Arylene group, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C1-C20Alkyl when the substituent is multiple C1-C20When alkyl, the substituents are optionally bonded to one or more rings;
preferably, the aromatic carboxylic acid ester compound is selected from compounds represented by formula (IV),
Figure FDA0002526975840000051
in the formula (IV), each R3Identical or different, each independently selected from the group consisting of1-C6C of substituents of alkyl radicals and halogen atoms1-C8Alkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms5-C10Cycloalkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms6-C15Aryl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C15Alkylaryl or with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C15Aralkyl group of (1); r4-R7Can be the same or different, and are independently selected from hydrogen, halogen, with or without C1-C6C of substituents of alkyl radicals and halogen atoms1-C8Alkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms5-C10Cycloalkyl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms6-C20Aryl, with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C20Alkylaryl or with or without C1-C6C of substituents of alkyl radicals and halogen atoms7-C20Aralkyl group;
preferably, the diether compound is selected from 1, 3-diether compounds, more preferably from 1, 3-diether compounds represented by formula (V),
Figure FDA0002526975840000052
r 'in the formula (V)'1、R'2、R'3、R'4、R'5And R'6The same or different, each independently selected from hydrogen, halogen, C with or without substituent1-C20Alkyl, C with or without substituents3-C20CycloalkanesRadical, C with or without substituents6-C20Aryl, C with or without substituents7-C20Aralkyl and C with or without substituents7-C20An alkaryl group; r'7And R'8Identical or different, each independently selected from C with or without substituents1-C20Alkyl, C with or without substituents3-C20Cycloalkyl, C with or without substituents6-C20Aryl, C with or without substituents7-C20Aralkyl and C with or without substituents7-C20Alkylaryl, said substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; optionally, R'1、R'2、R'3、R'4、R'5And R'6Two or more of which are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring.
7. The catalyst system according to claim 6,
the diol ester compound is selected from 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, 4-diol dibenzoate, 4-methyl-3, 5-di-p-methylbenzoate, and a, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 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-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2-heptanediol di (p-methylbenzoic acid) ester, and a mixture thereof, 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-dimethyl-3, 5-octanediol dibenzoate, 4-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-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-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-dibenzoate, 2-phenylene dibenzoate, and mixtures thereof, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-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, one or more of 8-naphthyl ester, di-4-isobutylbenzoic acid-1, 8-naphthyl ester, di-4-tert-butylbenzoic acid-1, 8-naphthyl ester, di-4-phenylbenzoic acid-1, 8-naphthyl ester, di-4-fluorobenzoic acid-1, 8-naphthyl ester, di-3-fluorobenzoic acid-1, 8-naphthyl ester and di-2-fluorobenzoic acid-1, 8-naphthyl ester; and/or
The aromatic carboxylic ester compound is preferably a phthalic acid carboxylic ester compound; more preferably, the aromatic carboxylic acid ester compound is one or more selected from diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate, and further preferably, the aromatic carboxylic acid ester compound is diisobutyl phthalate; and/or
The diether compound is selected from the group consisting of 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, di-n-butyl-2-propyl-2-methyl-1, 3-dimethoxypropane, di-n-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-methyl-1, 3-dimethoxypropane, 2-phenyl-methyl-1, 3-dimethoxypropane, 2-propyl-methyl-2-propyl-2-methyl-2-propyl-2-methyl-1, 3-dimethoxypropane, 2-propyl-dimethyl-2-propyl-2-methyl-propyl-2-tert-butyl-tert-butyl-tert-butyl-tert-ethyl-tert-butyl-ethyl-butyl-ethyl-tert-butyl-tert-butyl-ethyl-tert-butyl-tert-butyl-ethyl-butyl-tert-butyl-ethyl-butyl-tert-ethyl-tert-butyl-tert-butyl-tert-ethyl, 2- (1-naphthyl) -1, 3-dimethoxypropane, 2- (2-fluorophenyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-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-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-phenyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 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-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene, 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-bis (methoxymethyl) -4-phenylindene, 2-methylindene, 2-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -2-dimethylindene, and the like, 1, 1-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylindene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 2-phenylindene, 1-bis (methoxymethyl) indene, 1-bis (methoxymethyl) -7-phenylindene, and, 9, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.
8. A prepolymerized catalyst composition for the polymerization of olefins comprising:
a) the catalyst system of any one of claims 1 to 7 subjected to a prepolymerization step of an olefin;
b) the prepolymer obtained in the olefin prepolymerization step,
preferably, the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of the prepolymer per g of the solid catalyst component, preferably 0.2 to 500g of the prepolymer per g of the solid catalyst component, and more preferably 0.5 to 20g of the prepolymer per g of the solid catalyst component.
9. Use of the catalyst system according to any one of claims 1 to 7 or the prepolymerized catalyst composition according to claim 8 in the field of olefin polymerization, especially propylene polymerization.
10. An olefin polymerization process comprising: subjecting an olefin to a polymerization reaction in the presence of the catalyst system of any one of claims 1-7 and/or the prepolymerized catalyst composition of claim 8, preferably the polymerization reaction conditions comprise: the temperature is 0-150 ℃, preferably 50-90 ℃; the pressure is 0.01MPa-10MPa, preferably 0.1MPa-5 MPa; the time is 0.1h to 5h, preferably 0.2h to 3 h.
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