CN113754799B - Solid catalyst component and solid catalyst system comprising same - Google Patents
Solid catalyst component and solid catalyst system comprising same Download PDFInfo
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- CN113754799B CN113754799B CN202010508037.0A CN202010508037A CN113754799B CN 113754799 B CN113754799 B CN 113754799B CN 202010508037 A CN202010508037 A CN 202010508037A CN 113754799 B CN113754799 B CN 113754799B
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention provides a solid catalyst component for olefin polymerization, comprising: magnesium element, titanium element, halogen element, and an internal electron donor comprising a compound selected from the group consisting of aromatic hydrocarbon compounds represented by formula (I). The inventors of the present application have found that the molecular weight of a polymerization product can be increased by introducing a column aromatic hydrocarbon and its derivative as an internal electron donor into a Z-N catalyst.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a solid catalyst component and a solid catalyst system containing the solid catalyst component.
Background
Ultra-high molecular weight polyethylene (Ultra high molecular weight polyethylene, abbreviated as UHMWPE) is a special polyethylene variety with a molecular weight greater than 150 ten thousand. Most of the current commercial UHMWPE is prepared from Ziegler-Natta catalyst (Z-N catalyst for short), and has the comprehensive properties of wear resistance, impact resistance, self-lubrication, corrosion resistance, low temperature resistance, sanitation, no toxicity, difficult adhesion, difficult water absorption, low density and the like which are incomparable with common polyethylene and other engineering plastics.
One key index for UHMWPE products is the molecular weight, and UHMWPE products with higher molecular weight have better mechanical properties and higher added value. Thus, it is desirable to incorporate an electron donor into the Z-N catalyst component to increase the molecular weight of the UHMWPE product.
Disclosure of Invention
In view of the problems in the prior art described above, it is an object of the present invention to provide a use of a column aromatic hydrocarbon and its derivatives as an internal electron donor in a solid catalyst component for olefin polymerization. The inventors of the present application have found that the molecular weight of a polymerization product can be increased by introducing a column aromatic hydrocarbon and its derivative as an internal electron donor into a Z-N catalyst.
It is another object of the present invention to provide a solid catalyst component for olefin polymerization which employs a column aromatic hydrocarbon and its derivatives as an internal electron donor.
It is a further object of the present invention to provide a catalyst system for the polymerization of olefins comprising the solid catalyst component provided for in object two.
It is a fourth object of the present invention to provide the use of a catalyst system corresponding to the third object.
The fifth object of the present invention is to provide a process for polymerizing olefins corresponding to the third object and the fourth object.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
the use of a column aromatic compound of formula (I) as an electron donor in a catalyst system for the polymerization of olefins, in particular as an internal electron donor in a solid catalyst component for the polymerization of olefins,
in the formula (I), the middle bracket part represents a base unit, wherein M 1 、M 2 、M 3 、M 4 、R 1 And R is 2 Identical or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R 3 CHO、-C(O)OH、-R 3 C(O)OH、-C(O)OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C, with or without substituents, halogen atoms 1 -C 10 Alkyl and C with or without substituents 1 -C 10 Alkoxy group, wherein，R 3 Is C with or without substituents 1 -C 6 Alkylene group, R 4 Is C with or without substituents 1 -C 6 Alkyl groups, said substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen atoms, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy and heteroatom;
n represents the number of basic units and is an integer of 4-20;
when the adjacent groups in the base units OR between adjacent base units are-C (O) OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C with or without substituents 1 -C 10 Hydrocarbyl and C with or without substituents 1 -C 10 In hydrocarbyloxy, two adjacent groups are optionally linked to each other to form a cyclic structure.
The inventors of the present application have found that the molecular weight of a polymerization product can be increased by introducing a column aromatic hydrocarbon and its derivative as an internal electron donor into a Z-N catalyst.
According to the invention, the values of n can be cited as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, preferably 4, 5, 6, 7, 8.
According to the invention M on different base units 1 、M 2 、M 3 、M 4 、R 1 And R is 2 May be the same or different.
In the context of the present specification, C 1 ～C 10 The hydrocarbon group may be selected from C 1 ～C 10 Alkyl, C 3 ～C 10 Cycloalkyl, C 2 ～C 10 Alkenyl, C 2 ～C 10 Alkynyl, C 6 ～C 10 Aryl and C 7 ～C 10 Aralkyl groups.
C 1 ～C 10 Alkyl means C 1 ～C 10 Straight-chain alkyl or C 3 ～C 10 Non-limiting examples of branched alkyl groups of (2) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,Tertiary amyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
C 3 ～C 10 Examples of cycloalkyl groups may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C 6 ～C 10 Examples of aryl groups may include, but are not limited to: phenyl, 4-methylphenyl and 4-ethylphenyl.
C 2 ～C 10 Examples of alkenyl groups may include, but are not limited to: vinyl and allyl.
C 2 ～C 10 Examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.
C 7 ～C 10 Examples of aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.
In the context of this specification, "substituted C 1 ～C 10 "hydrocarbon group" means "C 1 ～C 10 The hydrogen atom (preferably one hydrogen atom) or the carbon atom on the hydrocarbon group "of (a) is substituted with the substituent. Wherein the substituent is selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group, and a heteroatom. The hetero atom means an atom commonly contained in the molecular structure of other column aromatic hydrocarbons and derivatives thereof except halogen atoms, carbon atoms and hydrogen atoms, for example O, N, S, P, si and B and the like.
According to the present invention, the compound represented by formula (I) is selected from one or more of the following compounds:
compound A1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound A2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound A3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound B1: m is M 1 ＝M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound B2: m is M 1 ＝M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound B3: m is M 1 ＝M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound C1: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound C2: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound C3: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound D1: m is M 1 ＝M 2 ＝OCH(CH 3 ) 2 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound D2: m is M 1 ＝M 2 ＝OCH(CH 3 ) 2 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound D3: m is M 1 ＝M 2 ＝OCH(CH 3 ) 2 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound E1: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound E2: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound E3: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound F1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound F2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound F3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound G1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound G2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound G3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound H1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound H2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound H3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound I1: m is M 1 ＝M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound I2: m is M 1 ＝M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound I3: m is M 1 ＝M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound J1: m is M 1 ＝OCH 3 ，M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound J2: m is M 1 ＝OCH 3 ，M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound J3: m is M 1 ＝OCH 3 ，M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound K1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 ，R 1 ＝R 2 ＝H，n＝5；
Compound K2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 ，R 1 ＝R 2 ＝H，n＝6；
Compound K3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 ，R 1 ＝R 2 ＝H，n＝7；
Compound L1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl，R 1 ＝R 2 ＝H，n＝5；
Compound L2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl，R 1 ＝R 2 ＝H，n＝6；
Compound L3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl，R 1 ＝R 2 ＝H，n＝7；
Compound M1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br，R 1 ＝R 2 ＝CH 3 ，n＝5；
Compound M2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br，R 1 ＝R 2 ＝CH 3 ，n＝6；
Compound M3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br，R 1 ＝R 2 ＝CH 3 ，n＝7；
Compound N1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝I，R 1 ＝R 2 ＝H，n＝5；
Compound N2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝I，R 1 ＝R 2 ＝H，n＝6；
Compound N3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝I，R 1 ＝R 2 ＝H，n＝7；
Compound O1: m is M 1 ＝OCH 3 ，M 2 ＝CHO，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound O2: m is M 1 ＝OCH 3 ，M 2 ＝CHO，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound O3: m is M 1 ＝OCH 3 ，M 2 ＝CHO，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound P1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 Br，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound P2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 Br，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound P3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 Br，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound Q1: m is M 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 3 ，R 1 ＝R 2 ＝H，n＝5；
Compound Q2: m is M 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 3 ，R 1 ＝R 2 ＝H，n＝6；
Compound Q3: m is M 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 3 ，R 1 ＝R 2 ＝H，n＝7；
Compound R1: m is M 1 ＝OCH 2 CH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝OCH 3 ，n＝5；
Compound R2: m is M 1 ＝OCH 2 CH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝OCH 3 ，n＝6；
Compound R3: m is M 1 ＝OCH 2 CH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝OCH 3 ，n＝7。
In order to achieve the second purpose, the technical scheme adopted by the invention is as follows:
a solid catalyst component for the polymerization of olefins comprising: magnesium element, titanium element, halogen element, and an internal electron donor comprising a compound selected from the group consisting of aromatic hydrocarbon compounds represented by formula (I),
in the formula (I), the middle bracket part represents a base unit, wherein M 1 、M 2 、M 3 、M 4 、R 1 And R is 2 Identical or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R 3 CHO、-C(O)OH、-R 3 C(O)OH、-C(O)OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C, with or without substituents, halogen atoms 1 -C 10 Alkyl and C with or without substituents 1 -C 10 Alkoxy, wherein R is 3 Is C with or without substituents 1 -C 6 Alkylene group, R 4 Is C with or without substituents 1 -C 6 Alkyl groups, said substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen atoms, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy and heteroatom;
n represents the number of basic units and is an integer of 4-20;
when the adjacent groups in the base units OR between adjacent base units are-C (O) OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C with or without substituents 1 -C 10 Hydrocarbyl and C with or without substituents 1 -C 10 In the case of the hydrocarbyloxy group,two adjacent groups are optionally linked to each other to form a cyclic structure.
In some preferred embodiments of the invention, in formula (I), M 1 、M 2 、M 3 And M 4 The same or different are each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C 1 -C 10 C substituted by alkyl or halogen atoms 1 -C 10 Alkyl, C 1 -C 10 Alkoxy and halogen atom substituted C 1 -C 10 An alkoxy group; r is R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 10 Alkyl and C with or without substituents 1 -C 10 An alkoxy group; n is an integer of 4 to 10.
In some preferred embodiments of the invention, in formula (I), M 1 、M 2 、M 3 And M 4 The same or different are each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C 1 -C 6 Alkoxy and halogen atom substituted C 1 -C 6 An alkoxy group; r is R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 6 Alkyl and C with or without substituents 1 -C 6 An alkoxy group; n is an integer of 5 to 7.
In some preferred embodiments of the invention, in formula (I), M 1 And M 2 Identical or different, each independently selected from C 1 -C 6 An alkoxy group.
In some preferred embodiments of the present invention, the aromatic hydrocarbon compound of formula (I) is selected from one or more of the following compounds:
compound A1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound A2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound A3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound B1: m is M 1 ＝M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound B2: m is M 1 ＝M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound B3: m is M 1 ＝M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound C1: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound C2: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound C3: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound D1: m is M 1 ＝M 2 ＝OCH(CH 3 ) 2 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound D2: m is M 1 ＝M 2 ＝OCH(CH 3 ) 2 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound D3: m is M 1 ＝M 2 ＝OCH(CH 3 ) 2 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound E1: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound E2: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound E3: m is M 1 ＝M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound F1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound F2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound F3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound G1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound G2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound G3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound H1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound H2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound H3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound I1: m is M 1 ＝M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound I2: m is M 1 ＝M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound I3: m is M 1 ＝M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound J1: m is M 1 ＝OCH 3 ，M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound J2: m is M 1 ＝OCH 3 ，M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound J3: m is M 1 ＝OCH 3 ，M 2 ＝OH，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound K1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 ，R 1 ＝R 2 ＝H，n＝5；
Compound K2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 ，R 1 ＝R 2 ＝H，n＝6；
Compound K3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝NH 2 ，R 1 ＝R 2 ＝H，n＝7；
Compound L1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl，R 1 ＝R 2 ＝H，n＝5；
Compound L2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl，R 1 ＝R 2 ＝H，n＝6；
Compound L3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Cl，R 1 ＝R 2 ＝H，n＝7；
Compound M1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br，R 1 ＝R 2 ＝CH 3 ，n＝5；
Compound M2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br，R 1 ＝R 2 ＝CH 3 ，n＝6；
Compound M3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝Br，R 1 ＝R 2 ＝CH 3 ，n＝7；
Compound N1: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝I，R 1 ＝R 2 ＝H，n＝5；
Compound N2: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝I，R 1 ＝R 2 ＝H，n＝6；
Compound N3: m is M 1 ＝M 2 ＝OCH 3 ，M 3 ＝M 4 ＝I，R 1 ＝R 2 ＝H，n＝7；
Compound O1: m is M 1 ＝OCH 3 ，M 2 ＝CHO，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound O2: m is M 1 ＝OCH 3 ，M 2 ＝CHO，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound O3: m is M 1 ＝OCH 3 ，M 2 ＝CHO，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound P1: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 Br，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝5；
Compound P2: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 Br，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝6；
Compound P3: m is M 1 ＝OCH 3 ；M 2 ＝OCH 2 CH 2 CH 2 Br，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝H，n＝7；
Compound Q1: m is M 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 3 ，R 1 ＝R 2 ＝H，n＝5；
Compound Q2: m is M 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 3 ，R 1 ＝R 2 ＝H，n＝6；
Compound Q3: m is M 1 ＝M 3 ＝OCH 3 ，M 2 ＝M 4 ＝OCH 3 ，R 1 ＝R 2 ＝H，n＝7；
Compound R1: m is M 1 ＝OCH 2 CH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝OCH 3 ，n＝5；
Compound R2: m is M 1 ＝OCH 2 CH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝OCH 3 ，n＝6；
Compound R3: m is M 1 ＝OCH 2 CH 3 ；M 2 ＝OCH 2 CH 2 CH 3 ，M 3 ＝M 4 ＝H，R 1 ＝R 2 ＝OCH 3 ，n＝7。
In some preferred embodiments of the present invention, the mass content of the column aromatic hydrocarbon compound represented by the formula (I) in the solid catalyst component is 0.1wt% to 20wt%, preferably 1wt% to 15wt%, more preferably 2wt% to 10wt%.
In some preferred embodiments of the present invention, the internal electron donor further comprises one or more selected from the group consisting of organic alcohol compounds, organic acid ester compounds, organic acid halide compounds, organic acid anhydride compounds, ether compounds, ketone compounds, amine compounds, phosphate compounds, amide compounds, carbonate compounds, phenol compounds, pyridine compounds and polar group-bearing polymer compounds, preferably one or more selected from the group consisting of organic alcohol compounds, ether compounds and phosphate compounds, more preferably, the molar ratio of the internal electron donor to the magnesium element is (0.01 to 5): 1, preferably (0.05 to 1): 1, and still more preferably (0.1 to 1): 1.
According to the present invention, the other internal electron donor is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, n-octyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, hexyl benzoate, ethyl p-methylbenzoate, methyl naphthoate, ethyl naphthoate, methyl methacrylate, ethyl acrylate, butyl acrylate, diethyl ether, butyl ether, tetrahydrofuran, 2-dimethyl-1, 3-diethoxypropane, 2-dimethyl-1, 3-dimethoxypropane, phthalmether, phthalyl diethyl ether, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, ethylene oxide, propylene oxide, epichlorohydrin, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate, polymethyl methacrylate, polystyrene, polyepichloropropane and polyethylene oxide.
According to the invention, the solid catalyst component comprises the reaction product of a magnesium-containing compound, a titanium-containing compound, a column aromatic compound of formula (I) and optionally other internal electron donors.
In some preferred embodiments of the present invention, the solid catalyst component comprises a titanium-containing compound having at least one Ti-halogen bond and an internal electron donor represented by formula (I) supported on the magnesium-containing compound, preferably magnesium halide.
In some preferred embodiments of the present invention, the magnesium element is derived from a magnesium-containing compound, preferably from magnesium halide, more preferably from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, further preferably magnesium dichloride; in the solid catalyst component, the molar ratio of the aromatic hydrocarbon compound represented by the formula (I) to the magnesium element is preferably (0.001 to 0.1): 1, more preferably (0.001 to 0.05): 1, and still more preferably (0.002 to 0.05): 1.
In some preferred embodiments of the present invention, the titanium element in the solid catalyst component is derived from TiCl 3 、TiCl 4 、TiBr 4 、TiI 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl、Ti(OC 2 H 5 ) 3 I、Ti(OC 2 H 5 ) 4 、Ti(OC 3 H 7 ) 4 And Ti (OC) 4 H 9 ) 4 One or more of them, more preferably TiCl 3 、TiCl 4 、TiBr 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OC 2 H 5 ) 2 Cl 2 And Ti (OC) 2 H 5 ) 3 One or more of Cl, further preferably TiCl 4 And/or TiCl 3 。
In some preferred embodiments of the present invention, the molar ratio of magnesium element to titanium element in the solid catalyst component is (0.1-50): 1, preferably (1-25): 1.
According to the present invention, the solid catalyst component may further comprise an ultrafine carrier. Preferably, the particle size of the ultra-fine support is 0.01 μm to 10 μm, and the ultra-fine support may be selected from one or more of alumina, activated carbon, clay, silica, titania, polystyrene, and calcium carbonate.
According to the present invention, the solid catalyst component may be prepared according to any one of the methods in the prior art.
According to the present invention, the solid catalyst component may be prepared by the following method:
method 1
1) Mixing and grinding magnesium halide and optional titanium compound under the condition of activating the magnesium halide;
2) Treating the mixed and ground product one or more times with an excess of titanium compound;
3) Washing the treated product with a hydrocarbon solvent, then adding a hydrocarbon solution containing a column aromatic compound represented by formula (I) and carrying out a contact reaction;
4) Washing the reacted product with hydrocarbon solvent to obtain the solid catalyst component.
Method 2
1) Reacting a magnesium halide with an alcohol compound in the presence of an inert solvent;
2) Then adding an organic silicon compound to carry out contact reaction;
3) Carrying out contact reaction on the system in the step 2) and a titanium compound;
4) Removing unreacted materials and solvent, washing the precipitate, then adding a hydrocarbon solution containing a column aromatic compound represented by formula (I) and performing a contact reaction;
5) Washing the reacted product with hydrocarbon solvent to obtain the solid catalyst component.
Method 3
1) Dissolving and reacting magnesium halide, titanium halide, a column aromatic compound shown in a formula (I) and other internal electron donors to prepare mother liquor;
2) Blending the superfine carrier and the mother solution to prepare slurry;
3) And carrying out spray drying on the slurry to obtain the solid catalyst component.
Any of the organoaluminum compounds can be used as the activator component of the solid catalyst component, and the titanium atom in the solid catalyst component is reduced to a state that can effectively polymerize an olefin such as ethylene, to give a prereduced solid catalyst component.
Method 4
1) Reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound and an organic alcohol in the presence of an inert solvent;
2) The reaction solution obtained in the step 1) is contacted with a titanium compound and an organosilicon compound for reaction, and is treated at high temperature;
3) Removing unreacted materials and solvent, washing the precipitate, then adding a hydrocarbon solution containing a column aromatic compound represented by formula (I) and performing a contact reaction;
4) Washing the reacted product with hydrocarbon solvent to obtain the solid catalyst component.
Method 5
1) Reacting magnesium halide with an organic epoxy compound and an organic phosphorus compound in the presence of an inert solvent, and then adding an organic anhydride compound (precipitation aid) for continuous reaction to obtain a solution;
2) The solution is contacted and reacted with titanium compound;
3) Adding other internal electron donors into the reaction system to react;
4) Removing unreacted materials and solvent, washing the precipitate, then adding a hydrocarbon solution containing a column aromatic compound represented by formula (I) and performing a contact reaction;
5) Washing the reacted product with hydrocarbon solvent to obtain the solid catalyst component.
Method 6
1) Dispersing magnesium halide alcohol compound in an inert solvent to obtain suspension;
2) Contacting the suspension with an organoaluminum compound and a column aromatic compound represented by formula (I), then removing unreacted materials, and washing with an inert solvent;
3) Contacting the precipitate obtained in step 2) with the titanium compound in the presence of an inert solvent, removing unreacted materials and the solvent, and washing the precipitate to obtain the solid catalyst component.
In step 2), the organoaluminum compound may be specifically selected from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、Al(n-C 6 H 13 ) 3 、AlH(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、AlCl 1.5 (CH 2 CH 3 ) 1.5 、AlCl(CH 2 CH 3 ) 2 、AlCl 2 (CH 2 CH 3 ) And alkyl aluminum compounds. In addition, the organoaluminum compound is preferably Al (CH) 2 CH 3 ) 3 、Al(n-C 6 H 13 ) 3 And Al (i-Bu) 3 One or more of these are more preferably Al (CH) 2 CH 3 ) 3 。
Method 7
1) Dispersing an alkyl magnesium/alkoxy magnesium halide compound in an inert solvent to obtain a solution or suspension;
2) Contacting the solution or suspension with a titanium compound and other internal electron donors, then removing unreacted materials, and washing with an inert solvent;
3) Contacting the precipitate obtained in step 2) with the titanium compound in the presence of an inert solvent, then removing unreacted materials and the solvent, washing the precipitate, then adding a hydrocarbon solution containing a column aromatic compound represented by formula (I) and carrying out a contact reaction;
4) Washing the reacted product with hydrocarbon solvent to obtain the solid catalyst component.
The compounds used in the above preparation methods are all selected conventionally in the art, for example, organic epoxy compounds, organic phosphorus compounds, alcohol compounds, organic silicon compounds, etc. can be selected with reference to the prior art, and are not particularly limited herein. The inert solvents selected for each process may be the same or different and may be selected with reference to the prior art, for example toluene and/or hexane.
In addition, the above preparation methods are described in more detail as examples of the solid catalyst component of the present invention, but the present invention is not limited to these preparation methods.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
a catalyst system for the polymerization of olefins comprising the following components:
1) The solid catalyst component described above;
2) A cocatalyst component selected from organoaluminum compounds.
In some preferred embodiments of the present invention, the organoaluminum compound has the formula AlR 1 d X 1 3-d Wherein R is 1 Is hydrogen or C l ～C 20 Hydrocarbyl, X 1 Is halogen atom, d is more than 0 and less than or equal to 3; preferably, the organoaluminum compound is selected from Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、Al(n-C 6 H 13 ) 3 、AlH(CH 2 CH 3 ) 2 、AlCl(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl 1.5 (CH 2 CH 3 ) 1.5 、AlCl(CH 2 CH 3 ) 2 And AlCl 2 (CH 2 CH 3 ) One or more of these are more preferably Al (CH) 2 CH 3 ) 3 And/or Al (i-Bu) 3 More preferably, the organoaluminum compoundThe molar ratio of the aluminum element to the titanium element in the solid catalyst component is (5 to 500): 1, preferably (20 to 200): 1.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
the use of the solid catalyst component or catalyst system described above in the field of olefin polymerization, in particular in the field of ethylene polymerization.
According to the present invention, the olefin polymerization reaction includes homo-polymerization and copolymerization of olefins.
According to the present invention, the above-mentioned ethylene polymerization includes homo-polymerization of ethylene and copolymerization of ethylene with butene, pentene, hexene, octene or 4-methyl-1-pentene.
In order to achieve the fifth purpose, the technical scheme adopted by the invention is as follows:
a process for the polymerization of olefins comprising: the olefin is polymerized in the presence of the catalyst system described above.
In some preferred embodiments of the invention, the polymerization conditions include: the temperature is 0-150 ℃, preferably 60-100 ℃; the pressure is 0.1MPa to 10MPa, preferably 0.1MPa to 5MPa.
According to the invention, the above-mentioned catalyst systems are suitable for polymerization under various conditions, for example, the olefin polymerization may be carried out in the liquid phase or in the gas phase, or else in combination with a liquid phase and a gas phase polymerization stage. The medium used for the liquid phase polymerization may be selected from inert solvents such as saturated aliphatic or aromatic hydrocarbons, e.g., isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., preferably toluene, n-hexane or cyclohexane.
In addition, in order to adjust the molecular weight of the final polymer, hydrogen may be used as a molecular weight regulator.
The catalyst system comprising the solid catalyst component provided by the invention can be used for participating in polymerization reaction, and the molecular weight of the prepared polymerization product can be obviously improved.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
In the following examples and comparative examples:
in the present invention, the compound represented by the formula (I) can be prepared by referring to the existing literature, for example, the compound J1 is prepared by referring to Org. Lett.2019,21, 3976-3980.
In the following examples and comparative examples,
1. composition of the catalyst component: the measurement was performed by liquid nuclear magnetic resonance 1H-NMR.
2. Determination of Polymer bulk Density: the measurements were made using the test methods of (ASTM D1895) plastic apparent density, bulk factor and pourability.
3. Polymer molecular weight test: the measurement was performed according to ASTM D4020-18.
Preparation example 1
3mmol of 1, 4-di-n-propoxybenzene was added with anhydrous chloroform (50 mL), stirred well, 9mmol of paraformaldehyde, 0.45mmol of ferric chloride were added to the mixture, reacted at 30℃for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate=30:1) to give a mixture C containing compound C1, compound C2 and compound C3. From the nuclear magnetic analysis, c1:c2:c3 (molar ratio) =1: 0.75:0.05.
preparation example 2
3mmol of 1-methoxy-4-bromopropoxybenzene was added with anhydrous chloroform (40 mL), stirred well, 9mmol of paraformaldehyde, 0.50mmol of ferric chloride were added to the mixture, reacted at 30℃for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate=20:1) to give a mixture P comprising compound P1, compound P2 and compound P3. From the nuclear magnetic analysis, it can be seen that p1:p2:p3 (molar ratio) =1: 0.52:0.02.
preparation example 3
3mmol of 1, 4-diisopropyloxybenzene was added with anhydrous chloroform (50 mL), stirred well, 9mmol of paraformaldehyde and 0.45mmol of ferric chloride were added to the mixture, reacted at 30℃for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate=30:1) to give a mixture D containing the compound D1, the compound D2 and the compound D3. From the nuclear magnetic analysis, d1:d2:d3 (molar ratio) =1 in the mixture: 0.43:0.02.
preparation example 4
3mmol of 1, 4-di-n-butoxybenzene was added with anhydrous chloroform (50 mL), stirred well, 9mmol of paraformaldehyde, 0.45mmol of ferric chloride were added to the mixture, reacted at 30℃for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, concentrated, and column chromatography (petroleum ether/ethyl acetate=30:1) was carried out to obtain a mixture E comprising the compound E1, the compound E2 and the compound E3. From the nuclear magnetic analysis, it can be seen that E1:e2:e3 (molar ratio) =1: 0.72:0.05.
preparation example 5
3mmol of 1-methoxy-4-propoxybenzene was added with anhydrous chloroform (40 mL), stirred well, 9mmol of paraformaldehyde, 0.50mmol of ferric chloride were added to the mixture, reacted at 30℃for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate=20:1) to give a mixture G comprising compound G1, compound G2 and compound G3. From the nuclear magnetic analysis, it can be seen that g1:g2:g3 (molar ratio) =1: 0.67:0.04.
example 1
(1) Preparation of solid catalyst component a
6.0g of spherical carrier MgCl is added in sequence into a reactor fully replaced by high-purity nitrogen 2 ·2.6C 2 H 5 OH,120mL toluene, cool to-10℃with stirring, add dropwise 50mL of triethylaluminum in hexane (triethylaluminum: 1.2M) and 0.3g of mixture C, then warm to 60℃and maintain the reaction for 3 hours. Stirring was stopped, the suspension was allowed to separate rapidly, the supernatant was removed, and the precipitate was washed several times with toluene and hexane. 120mL of toluene was added and the system was cooledBut to 0 ℃, 8mL of titanium tetrachloride is slowly added dropwise, and then the temperature is raised to 60 ℃ for reaction for 2 hours. The stirring was stopped, the suspension was allowed to stand still, the supernatant was removed by suction, the precipitate was washed twice with hexane, and then transferred to a chromatography funnel through hexane, and dried with high-purity nitrogen gas to give a solid spherical catalyst component a having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction
After the stainless steel reactor with the volume of 2L was fully replaced by high-purity nitrogen, 1L of hexane and 1.0ml of triethylaluminum with the concentration of 1M were added, then the solid catalyst component (containing 0.6 mg of titanium) prepared by the above method was added, the temperature was raised to 70 ℃, ethylene was introduced so that the total pressure in the reactor became 1.0MPa (gauge pressure), and polymerization was carried out at 70℃for 2 hours, with the polymerization results shown in Table 1.
Comparative example 1
(1) Preparation of solid catalyst component D1
6.0g of spherical carrier MgCl is added in sequence into a reactor fully replaced by high-purity nitrogen 2 ·2.6C 2 H 5 OH,120mL toluene, cool to-10℃with stirring, add 50mL of triethylaluminum in hexane (triethylaluminum: 1.2M) dropwise, then warm to 60℃and maintain the reaction for 3 hours. Stirring was stopped, the suspension was allowed to separate rapidly, the supernatant was removed, and the precipitate was washed several times with toluene and hexane. 120mL of toluene was added, the system was cooled to 0℃and 8mL of titanium tetrachloride was slowly added dropwise, followed by heating to 60℃and reacting for 2 hours. The stirring was stopped, left stand, the suspension was rapidly layered, the supernatant was removed by suction, and after washing the precipitate twice with hexane, it was transferred to a chromatography funnel by hexane and blow-dried with high purity nitrogen gas to give a solid spherical catalyst component D1 having a good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 2
(1) Preparation of solid catalyst component b
4.0 g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate and 4.4mL of ethanol were added to the reaction vessel, and the reaction was carried out at a constant temperature of 70℃for 2 hours. The system was cooled to-10℃and 70mL of titanium tetrachloride was slowly added dropwise, followed by 5mL of tetraethoxysilane, gradually warmed to 85℃and kept at constant temperature for 1 hour. The stirring was stopped, the mixture was allowed to stand, the suspension was rapidly separated, the supernatant was removed, and the mixture was washed twice with toluene. 0.4g of mixture C and 100ml of toluene are added and the temperature is kept at 85℃for 1 hour. The stirring was stopped, and the suspension was allowed to stand, and the supernatant was removed by suction, washed with toluene and washed with hexane several times, and dried to give a solid catalyst component b having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 2
(1) Preparation of solid catalyst component D2
4.0 g of magnesium chloride, 50mL of toluene, 3.0mL of epichlorohydrin, 9mL of tri-n-butyl phosphate and 4.4mL of ethanol were added to the reaction vessel, and the reaction was carried out at a constant temperature of 70℃for 2 hours. The system was cooled to-10℃and 70mL of titanium tetrachloride was slowly added dropwise, followed by 5mL of tetraethoxysilane, gradually warmed to 85℃and kept at constant temperature for 1 hour. The stirring was stopped, and the suspension was allowed to stand, and the supernatant was removed by suction, washed with toluene and washed with hexane several times, and dried to give a solid catalyst component D2 having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 3
(1) Preparation of solid catalyst component c
4.0 g of magnesium chloride, 90mL of toluene, 5.0mL of epichlorohydrin and 13.0mL of tri-n-butyl phosphate are added into a reaction kettle, and the mixture is reacted for 2 hours under the conditions of the stirring rotation speed of 450rpm and the temperature of 60 ℃, 2g of phthalic anhydride is added, the constant temperature is continued for 1 hour, the temperature is reduced to minus 40 ℃, 70mL of titanium tetrachloride is added dropwise, and the temperature is gradually increased to 95 ℃ and is kept constant for 1 hour. 1mL of 2, 2-dimethyl-1, 3-diethoxy-propane was added and the temperature was kept constant for 1 hour. The mother liquor was filtered off and washed twice with toluene. 0.5g of mixture B and 100ml of toluene are added and the temperature is kept at 85℃for 1 hour. The stirring was stopped, and the suspension was allowed to stand, and the supernatant was removed by suction, washed with toluene and washed with hexane several times, and dried to give a solid catalyst component c having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 3
(1) Preparation of solid catalyst component D3
4.0 g of magnesium chloride, 90mL of toluene, 5.0mL of epichlorohydrin and 13.0mL of tri-n-butyl phosphate are added into a reaction kettle, and the mixture is reacted for 2 hours under the conditions of the stirring rotation speed of 450rpm and the temperature of 60 ℃, 2g of phthalic anhydride is added, the constant temperature is continued for 1 hour, the temperature is reduced to minus 40 ℃, 70mL of titanium tetrachloride is added dropwise, and the temperature is gradually increased to 95 ℃ and is kept constant for 1 hour. 1mL of 2, 2-dimethyl-1, 3-diethoxy-propane was added and the temperature was kept constant for 1 hour. The mother liquor was filtered off, washed with toluene and hexane several times and dried to give a solid catalyst component D3 having good flowability, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 4
(1) Preparation of solid catalyst component d
Into a 250mL three-necked flask purged with nitrogen, 1.5g TiCl was successively introduced 4 4.4g anhydrous MgCl 2 0.4g of mixture F and 100mL of tetrahydrofuran are heated to 65 ℃ under stirring, reacted at constant temperature for 3 hours at the temperature, and then cooled to 35 ℃ to obtain mother liquor.
6g of silica gel (Cabot Corporation TS-610 with the particle size of 0.02-0.1 micron) is added into another 250mL three-necked flask which is blown off by nitrogen, the cooled mother solution is added, the temperature is kept at 35 ℃, after stirring for 1h, the mother solution obtained by mixing the silica gel is spray dried by a spray dryer, and the spray conditions are as follows: the inlet temperature is 180 ℃ and the outlet temperature is 110 ℃, so that the solid catalyst component g is obtained, and the composition is shown in Table 1.
(2) Pre-reduction treatment
100mL of hexane, 5g of solid catalyst component and 4mL of tri-n-hexylaluminum (1M) were successively added to a 250mL three-necked flask purged with nitrogen, and the temperature was raised to 50℃with stirring, and the temperature was kept constant for 1 hour; 9mL of diethylaluminum chloride (1M) was added thereto, and the temperature was kept constant for 1 hour. Filtering mother liquor, washing with hexane for multiple times, and drying to obtain the pre-reduced solid catalyst component with good fluidity.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 4
(1) Preparation of solid catalyst component D4
Into a 250mL three-necked flask purged with nitrogen, 1.5g TiCl4 and 4.4g anhydrous MgCl were successively introduced 2 And 100mL of tetrahydrofuran, heating to 65 ℃ under stirring, reacting for 3 hours at constant temperature under the condition of the temperature, and then cooling to 35 ℃ to obtain mother liquor.
6g of silica gel (Cabot Corporation TS-610 with the particle size of 0.02-0.1 micron) is added into another 250mL three-necked flask which is blown off by nitrogen, the cooled mother solution is added, the temperature is kept at 35 ℃, after stirring for 1h, the mother solution obtained by mixing the silica gel is spray dried by a spray dryer, and the spray conditions are as follows: the inlet temperature was 195℃and the outlet temperature was 110℃to obtain a solid catalyst component D4, the composition of which is shown in Table 1.
(2) Pre-reduction treatment
Same as in example 4.
(3) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 5
(1) Preparation of the solid catalyst component e
4.8 g of magnesium chloride, 30mL of decane and 20mL of isooctanol are added into a reaction kettle, the reaction is carried out for 3 hours under the conditions of stirring speed of 300rpm and temperature of 130 ℃, the temperature of the system is reduced to 50 ℃, 3.5mL of tetraethoxysilicon is added, and stirring is continued for 2 hours. The system is cooled to room temperature, slowly dripped into 200mL of titanium tetrachloride at 0 ℃ and kept at a constant temperature for 1h after the dripping is completed. The system was gradually warmed to 110℃and kept at constant temperature for 2 hours. The stirring was stopped, the mixture was allowed to stand, the suspension was rapidly separated, the supernatant was removed, and the mixture was washed twice with toluene. 0.5g of mixture C and 100ml of toluene are added and the temperature is kept at 85℃for 1 hour. The stirring was stopped, and the suspension was allowed to stand, and the supernatant was removed by suction, washed with toluene and washed with hexane several times, and dried to give a solid catalyst component e having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 5
(1) Preparation of solid catalyst component D5
4.8 g of magnesium chloride, 30mL of decane and 20mL of isooctanol are added into a reaction kettle, the reaction is carried out for 3 hours under the conditions of stirring speed of 300rpm and temperature of 130 ℃, the temperature of the system is reduced to 50 ℃, 3.5mL of tetraethoxysilicon is added, and stirring is continued for 2 hours. The system is cooled to room temperature, slowly dripped into 200mL of titanium tetrachloride at 0 ℃ and kept at a constant temperature for 1h after the dripping is completed. The system was gradually warmed to 110℃and kept at constant temperature for 2 hours. The stirring was stopped, and the suspension was allowed to stand, and the supernatant was removed by suction, washed with toluene and hexane several times and dried to give a solid catalyst component D5 having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 6
(1) Preparation of solid catalyst component f
10g of Mg (OEt) 2 and 55mL of toluene were charged into the reaction vessel, and a suspension was formed at a stirring rate of 300 rpm. The system is cooled to 0 ℃, 30mL of titanium tetrachloride is slowly added, the temperature is slowly increased to 90 ℃ after the dripping is completed, and the temperature is kept for 1.5 hours. Stopping stirring, standing, quickly layering the suspension, and pumping out supernatant. 60mL of toluene and 30mL of titanium tetrachloride were added, and the temperature was raised to 90℃and kept constant for 2 hours. Stopping stirring, standing, and removing supernatant. After washing twice with toluene. 0.5G of mixture G and 100ml of toluene are added and the temperature is kept at 85℃for 1 hour. The stirring was stopped, and the suspension was allowed to stand, and the supernatant was removed by suction, washed with toluene and washed with hexane several times, and dried to give a solid catalyst component f having good fluidity, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 6
(1) Preparation of solid catalyst component D6
10g of Mg (OEt) 2 and 55mL of toluene were charged into the reaction vessel, and a suspension was formed at a stirring rate of 300 rpm. The system is cooled to 0 ℃, 30mL of titanium tetrachloride is slowly added, the temperature is slowly increased to 90 ℃ after the dripping is completed, and the temperature is kept for 1.5 hours. The stirring was stopped, the suspension was allowed to stand, and the supernatant was removed by suction. 60mL of toluene and 30mL of titanium tetrachloride were added, and the temperature was raised to 90℃and kept constant for 2 hours. Stopping stirring, standing, and removing supernatant. After washing with toluene and hexane several times, drying was carried out to obtain a solid catalyst component D6 having good flowability, the composition of which is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 7
(1) Preparation of solid catalyst component D7
As in example 6, but Ethyl Acetate (EA) was added as an internal electron donor instead of mixture G.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 7
(1) Preparation of solid catalyst component g
As in example 1, but Ethyl Acetate (EA) and mixture C were added as internal electron donors. The composition of the resulting solid catalyst component g is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 8
(1) Preparation of the solid catalyst component h
The amount of mixture C added was adjusted so that the mass content of mixture C in solid catalyst component h was 10% by weight, as in example 1. The composition of the resulting solid catalyst component g is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 9
The difference from example 1 is only that compound J1 is used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (calculated as titanium element) to the external electron donor and the polymerization result are shown in Table 1.
Example 10
The only difference from example 1 is that mixture K was used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (calculated as titanium element) to the external electron donor and the polymerization result are shown in Table 1.
Example 11
The only difference from example 1 is that mixture L was used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (calculated as titanium element) to the external electron donor and the polymerization result are shown in Table 1.
Example 12
The difference from example 1 is only that mixture P is used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (calculated as titanium element) to the external electron donor and the polymerization result are shown in Table 1.
TABLE 1
Note that: in table 1, "-" means that the component is not contained or the content of the component is 0.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (26)
1. The use of a column aromatic compound of formula (I) as an electron donor in a catalyst system for the polymerization of olefins,
In the formula (I), the middle bracket part represents a base unit, wherein M 1 、M 2 、M 3 、M 4 Identical or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R 3 CHO、-C(O)OH、- R 3 C(O)OH、-C(O)OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C, with or without substituents, halogen atoms 1 -C 10 Alkyl, wherein R is 3 Is C with or without substituents 1 -C 6 Alkylene group, R 4 Is C with or without substituents 1 -C 6 Alkyl groups, said substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen atoms, C 1 -C 6 Alkyl, C 1 -C 6 An alkoxy group; r is R 1 And R is 2 Identical or different, each independently selected from hydrogen, hydroxy, halogen, C with or without substituents 1 -C 10 Alkyl and C with or without substituents 1 -C 10 An alkoxy group;
n represents the number of basic units and is an integer of 4-20;
when the adjacent groups in the base units OR between adjacent base units are-C (O) OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C with or without substituents 1 -C 10 In the case of alkyl groups, two adjacent groups are optionally linked to each other to form a cyclic structure.
2. Use according to claim 1, characterized in that the aromatic column compound of formula (I) is used as internal electron donor in the solid catalyst component for the polymerization of olefins.
3. A solid catalyst component for the polymerization of olefins comprising: magnesium element, titanium element, halogen element, and an internal electron donor comprising a compound selected from the group consisting of aromatic hydrocarbon compounds represented by formula (I),
In the formula (I), the middle bracket part represents a base unit, wherein M 1 、M 2 、M 3 、M 4 Identical or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R 3 CHO、-C(O)OH、- R 3 C(O)OH、-C(O)OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C, with or without substituents, halogen atoms 1 -C 10 Alkyl, wherein R is 3 Is C with or without substituents 1 -C 6 Alkylene group, R 4 Is C with or without substituents 1 -C 6 Alkyl groups, said substituents being selected from the group consisting of hydroxy, amino, -CHO, -C (O) OH, halogen atoms, C 1 -C 6 Alkyl, C 1 -C 6 An alkoxy group; r is R 1 And R is 2 Identical or different, each independently selected from hydrogen, hydroxy, halogen, C with or without substituents 1 -C 10 Alkyl and C with or without substituents 1 -C 10 An alkoxy group;
n represents the number of basic units and is an integer of 4-20;
when the adjacent groups in the base units OR between adjacent base units are-C (O) OR 4 、-R 3 C(O)OR 4 、-OR 4 、-R 3 OR 4 C with or without substituents 1 -C 10 In the case of alkyl groups, two adjacent groups are optionally linked to each other to form a cyclic structure.
4. The solid catalyst component according to claim 3, wherein in formula (I), M 1 、M 2 、M 3 And M 4 The same or different are each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo,Iodine, C 1 -C 10 C substituted by alkyl or halogen atoms 1 -C 10 Alkyl, C 1 -C 10 Alkoxy and halogen atom substituted C 1 -C 10 An alkoxy group; r is R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 10 Alkyl and C with or without substituents 1 -C 10 An alkoxy group; n is an integer of 4 to 10.
5. The solid catalyst component according to claim 4, wherein in formula (I), M 1 、M 2 、M 3 And M 4 The same or different are each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C 1 -C 6 Alkoxy and halogen atom substituted C 1 -C 6 An alkoxy group; r is R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 6 Alkyl and C with or without substituents 1 -C 6 An alkoxy group; n is an integer of 5 to 7.
6. The solid catalyst component according to claim 5, wherein in formula (I), M 1 And M 2 Identical or different, each independently selected from C 1 -C 6 An alkoxy group.
7. The solid catalyst component according to any one of claims 3 to 6, characterized in that the column aromatic compound represented by formula (I) is selected from one or more of the following compounds:
compound A1: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound A2: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound A3: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound B1: m is M 1 =M 2 =OCH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound B2: m is M 1 =M 2 =OCH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound B3: m is M 1 =M 2 =OCH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound C1: m is M 1 =M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound C2: m is M 1 =M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound C3: m is M 1 =M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound D1: m is M 1 =M 2 =OCH(CH 3 ) 2 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound D2: m is M 1 =M 2 =OCH(CH 3 ) 2 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound D3: m is M 1 =M 2 =OCH(CH 3 ) 2 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound E1: m is M 1 =M 2 =OCH 2 CH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound E2: m is M 1 =M 2 =OCH 2 CH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound E3: m is M 1 =M 2 =OCH 2 CH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound F1: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound F2: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound F3: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound G1: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound G2: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound G3: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound H1: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound H2: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound H3: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound I1: m is M 1 =M 2 =OH，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound I2: m is M 1 =M 2 =OH，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound I3: m is M 1 =M 2 =OH，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound J1: m is M 1 =OCH 3 ，M 2 =OH，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound J2: m is M 1 =OCH 3 ，M 2 =OH，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound J3: m is M 1 =OCH 3 ，M 2 =OH，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound K1: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =NH 2 ，R 1 =R 2 =H，n=5；
Compound K2: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =NH 2 ，R 1 =R 2 =H，n=6；
Compound K3: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =NH 2 ，R 1 =R 2 =H，n=7；
Compound L1: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =Cl，R 1 =R 2 =H，n=5；
Compound L2: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =Cl，R 1 =R 2 =H，n=6；
Compound L3: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =Cl，R 1 =R 2 =H，n=7；
Compound M1: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =Br，R 1 =R 2 =CH 3 ，n=5；
Compound M2: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =Br，R 1 =R 2 =CH 3 ，n=6；
Compound M3: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =Br，R 1 =R 2 =CH 3 ，n=7；
Compound N1: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =I，R 1 =R 2 =H，n=5；
Compound N2: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =I，R 1 =R 2 =H，n=6；
Compound N3: m is M 1 =M 2 =OCH 3 ，M 3 =M 4 =I，R 1 =R 2 =H，n=7；
Compound O1: m is M 1 =OCH 3 ，M 2 =CHO，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound O2: m is M 1 =OCH 3 ，M 2 =CHO，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound O3: m is M 1 =OCH 3 ，M 2 =CHO，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound P1: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 2 Br，M 3 =M 4 =H，R 1 =R 2 =H，n=5；
Compound P2: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 2 Br，M 3 =M 4 =H，R 1 =R 2 =H，n=6；
Compound P3: m is M 1 =OCH 3 ；M 2 =OCH 2 CH 2 CH 2 Br，M 3 =M 4 =H，R 1 =R 2 =H，n=7；
Compound Q1: m is M 1 =M 3 =OCH 3 ，M 2 =M 4 =OCH 3 ，R 1 =R 2 =H，n=5；
Compound Q2: m is M 1 =M 3 =OCH 3 ，M 2 =M 4 =OCH 3 ，R 1 =R 2 =H，n=6；
Compound Q3: m is M 1 =M 3 =OCH 3 ，M 2 =M 4 =OCH 3 ，R 1 =R 2 =H，n=7；
Compound R1: m is M 1 =OCH 2 CH 3 ；M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =OCH 3 ，n=5；
Compound R2: m is M 1 =OCH 2 CH 3 ；M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =OCH 3 ，n=6；
Compound R3: m is M 1 =OCH 2 CH 3 ；M 2 =OCH 2 CH 2 CH 3 ，M 3 =M 4 =H，R 1 =R 2 =OCH 3 ，n=7。
8. The solid catalyst component according to any one of claims 3 to 6, wherein the mass content of the column aromatic hydrocarbon compound represented by the formula (I) in the solid catalyst component is 0.1wt% to 20wt%.
9. The solid catalyst component according to claim 8, wherein the mass content of the column aromatic hydrocarbon compound represented by the formula (I) in the solid catalyst component is 1wt% to 15wt%.
10. The solid catalyst component according to claim 9, wherein the mass content of the column aromatic hydrocarbon compound represented by the formula (I) in the solid catalyst component is 2wt% to 10wt%.
11. The solid catalyst component according to any one of claims 3 to 6, wherein the internal electron donor further comprises other internal electron donors selected from one or more of organic alcohol compounds, organic acid ester compounds, organic acid halide compounds, organic acid anhydride compounds, ether compounds, ketone compounds, amine compounds, phosphate compounds, amide compounds, carbonate compounds, phenol compounds, pyridine compounds and polymer compounds having a polar group.
12. The solid catalyst component according to claim 11, wherein the other internal electron donor is one or more of an organic alcohol compound, an ether compound and a phosphate compound.
13. The solid catalyst component according to claim 11, wherein the molar ratio of the other internal electron donor to the magnesium element is (0.01 to 5): 1.
14. The solid catalyst component according to claim 13, wherein the molar ratio of the other internal electron donor to the magnesium element is (0.05-1): 1.
15. The solid catalyst component according to claim 14, wherein the molar ratio of the other internal electron donor to the magnesium element is (0.1 to 1): 1.
16. A catalyst system for the polymerization of olefins comprising the following components:
1) A solid catalyst component according to any one of claims 3 to 15;
2) A cocatalyst component selected from organoaluminum compounds.
17. The catalyst system of claim 16 wherein said organoaluminum compound has the formula AlR 1 d X 1 3-d Wherein R is 1 Is hydrogen or C l ~C 20 Hydrocarbyl, X 1 Is halogen atom, d is more than 0 and less than or equal to 3.
18. The catalyst system of claim 17, wherein the organoaluminum compound is selected from the group consisting of Al (CH 3 ) 3 、Al(CH 2 CH 3 ) 3 、Al(i-Bu) 3 、Al(n-C 6 H 13 ) 3 、AlH(CH 2 CH 3 ) 2 、AlCl(CH 2 CH 3 ) 2 、AlH(i-Bu) 2 、AlCl 1.5 (CH 2 CH 3 ) 1.5 、AlCl(CH 2 CH 3 ) 2 And AlCl 2 (CH 2 CH 3 ) One or more of the following.
19. The catalyst system of claim 18, wherein the organoaluminum compound is Al (CH 2 CH 3 ) 3 And/or Al (i-Bu) 3 。
20. The catalyst system of claim 16, wherein the molar ratio of elemental aluminum in the organoaluminum compound to elemental titanium in the solid catalyst component is (5-500): 1.
21. The catalyst system of claim 20, wherein the molar ratio of elemental aluminum in the organoaluminum compound to elemental titanium in the solid catalyst component is (20-200): 1.
22. Use of the solid catalyst of any one of claims 3-15 or the catalyst system of any one of claims 16-21 in the field of olefin polymerization.
23. Use of the solid catalyst of any one of claims 3-15 or the catalyst system of any one of claims 16-21 in the field of ethylene polymerization.
24. A process for the polymerization of olefins comprising: polymerizing olefins in the presence of the catalyst system of any of claims 16-21.
25. The olefin polymerization process of claim 24 wherein the polymerization conditions comprise: the temperature is 0-150 ℃; the pressure is 0.1-10 MPa.
26. The olefin polymerization process of claim 25 wherein the polymerization conditions comprise: the temperature is 60-100 ℃; the pressure is 0.1-5 MPa.
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