CN113754799A - Solid catalyst component and solid catalyst system containing same - Google Patents
Solid catalyst component and solid catalyst system containing same Download PDFInfo
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- CN113754799A CN113754799A CN202010508037.0A CN202010508037A CN113754799A CN 113754799 A CN113754799 A CN 113754799A CN 202010508037 A CN202010508037 A CN 202010508037A CN 113754799 A CN113754799 A CN 113754799A
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- 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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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The present invention provides a solid catalyst component for olefin polymerization comprising: magnesium element, titanium element, halogen and an internal electron donor, wherein the internal electron donor comprises a columnar aromatic hydrocarbon compound shown in a formula (I). The inventor of the application finds that the molecular weight of a polymerization product can be improved after the columnar aromatic hydrocarbon and the derivatives thereof are taken as internal electron donors and are introduced into the 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 (UHMWPE) is a special polyethylene variety with molecular weight greater than 150 ten thousand. At present, most commercial UHMWPE is prepared by a 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, small density and the like which are incomparable with common polyethylene and other engineering plastics.
One key indicator for UHMWPE products is the high and low molecular weight, with higher molecular weight UHMWPE products having better mechanical properties and higher added value. Therefore, it is desirable to introduce 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, an object of the present invention is to provide a use of a pillar arene and a derivative thereof as an internal electron donor in a solid catalyst component for olefin polymerization. The inventor of the application finds that the molecular weight of a polymerization product can be improved after the columnar aromatic hydrocarbon and the derivatives thereof are taken as internal electron donors and are introduced into the Z-N catalyst.
The second purpose of the present invention is to provide a solid catalyst component for olefin polymerization, which uses a pillar arene and a derivative thereof 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 the second object.
The fourth object of the present invention is 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 purposes, the technical scheme adopted by the invention is as follows:
an application of a column aromatic hydrocarbon compound shown in a formula (I) as an electron donor in a catalyst system for olefin polymerization, in particular as an internal electron donor in a solid catalyst component for olefin polymerization,
in the formula (I), the part in parentheses represents a basic unit, wherein M1、M2、M3、M4、R1And R2The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R3CHO、-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 4-20;
when adjacent groups within OR between adjacent base units are-C (O) OR4、-R3C(O)OR4、-OR4、-R3OR4C with or without substituents1-C10Hydrocarbyl and C with or without substituents1-C10In the case of hydrocarbyloxy groups, two adjacent groups are optionally linked to each other to form a cyclic structure.
The inventor of the application finds that the molecular weight of a polymerization product can be improved after the columnar aromatic hydrocarbon and the derivatives thereof are taken as internal electron donors and are introduced into the Z-N catalyst.
According to the invention, the values of n can be listed 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 units1、M2、M3、M4、R1And R2May be the same or different.
In the context of the present specification, C1～C10The hydrocarbyl group may be selected from C1～C10Alkyl radical, C3～C10Cycloalkyl radical, C2～C10Alkenyl radical, C2～C10Alkynyl, C6～C10Aryl and C7～C10An aralkyl group.
C1～C10Alkyl is C1～C10Straight chain alkyl or C3～C10Non-limiting examples of branched alkyl groups of (a) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
C3～C10Examples of cycloalkyl groups may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6～C10Examples of aryl groups may include, but are not limited to: phenyl, 4-methylphenyl and 4-ethylphenyl.
C2～C10Examples of alkenyl groups may include, but are not limited to: vinyl and allyl.
C2～C10Examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.
C7～C10Examples 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 the present specification, "substituted C1～C10The "hydrocarbon group" of (A) means "C1～C10A hydrogen atom (preferably one hydrogen atom) on the hydrocarbon group of) Or carbon atoms are substituted with said substituents. Wherein the substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or heteroatom. The hetero atom means an atom generally contained in the molecular structure of other pillar aromatic hydrocarbons and derivatives thereof, such as O, N, S, P, Si and B, etc., except for halogen atoms, carbon atoms and hydrogen atoms.
According to the invention, the 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＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound E2: m1＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound E3: m1＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound F1: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound F2: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound F3: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound G1: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound G2: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound G3: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound H1: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound H2: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound H3: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound I1: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound I2: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound I3: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound J1: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound J2: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound J3: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound K1: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝5；
Compound K2: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝6；
Compound K3: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝7；
Compound L1: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝5；
Compound L2: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝6；
Compound L3: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝7；
Compound M1: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝5；
Compound M2: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝6；
Compound M3: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝7；
Compound N1: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝5；
Compound N2: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝6；
Compound N3: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝7；
Compound O1: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound O2: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound O3: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound P1: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound P2: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound P3: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound Q1: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝5；
Compound Q2: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝6；
Compound Q3: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝7；
Compound R1: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝5；
Compound R2: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝6；
Compound R3: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝7。
In order to achieve the second purpose, the invention adopts the following technical scheme:
a solid catalyst component for the polymerization of olefins comprising: magnesium element, titanium element, halogen and an internal electron donor, wherein the internal electron donor comprises a columnar aromatic hydrocarbon compound shown as a formula (I),
in the formula (I), the part in parentheses represents a basic unit, wherein M1、M2、M3、M4、R1And R2The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R3CHO、-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 4-20;
when adjacent groups within OR between adjacent base units are-C (O) OR4、-R3C(O)OR4、-OR4、-R3OR4C with or without substituents1-C10Hydrocarbyl and C with or without substituents1-C10In the case of hydrocarbyloxy groups, two adjacent groups are optionally linked to each other to form a cyclic structure.
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; 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.
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; r1And R2Are the same or different and are each independently selected from hydrogen,With or without substituents C1-C6Alkyl and C with or without substituents1-C6An alkoxy group; n is an integer of 5 to 7.
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 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＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound E2: m1＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound E3: m1＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound F1: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound F2: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound F3: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound G1: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound G2: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound G3: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound H1: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound H2: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound H3: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound I1: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound I2: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound I3: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound J1: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound J2: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound J3: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound K1: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝5；
Compound K2: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝6；
Compound K3: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝7；
Compound L1: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝5；
Compound L2: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝6；
Compound L3: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝7；
Compound M1: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝5；
Compound M2: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝6；
Compound M3: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝7；
Compound N1: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝5；
Compound N2: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝6；
Compound N3: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝7；
Compound O1: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound O2: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound O3: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound P1: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound P2: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound P3: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound Q1: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝5；
Compound Q2: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝6；
Compound Q3: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝7；
Compound R1: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝5；
Compound R2: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝6；
Compound R3: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝7。
In some preferred embodiments of the present invention, the mass content of the column aromatic compound represented by the formula (I) in the solid catalyst component is 0.1 wt% to 20 wt%, preferably 1 wt% to 15 wt%, and more preferably 2 wt% to 10 wt%.
In some preferred embodiments of the present invention, the internal electron donor further comprises another internal electron donor, wherein the other internal electron donor is selected from one or more of organic alcohol compounds, organic acid ester compounds, organic acyl 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 with polar groups, preferably one or more of organic alcohol compounds, ether compounds and phosphate compounds, more preferably, the molar ratio of the other internal electron donor to the magnesium element is (0.01-5): 1, preferably (0.05-1): 1, and further preferably (0.1-1): 1.
According to the invention, the other internal electron donor is selected from 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, dimethyl ether, diethyl phthalate, methanol, ethanol, propanol, isopropanol, butanol, isooctanol, octylamine, triethylamine, acetone, butanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, phenol, hydroquinone, ethylene oxide, propylene oxide, epichlorohydrin, trimethyl phosphate, methyl acetate, n-octyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, 2-dimethyl-1, 3-diethoxypropane, 2-dimethyl-1, 3-dimethoxypropane, dimethyl phthalate, 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, methyl propionate, ethyl acetate, methyl propionate, ethyl propionate, and ethyl propionate, and ethyl propionate, one or more of triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, trihexyl phosphate, polymethyl methacrylate, polystyrene, polyepichlorohydrin, 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 a magnesium halide.
In some preferred embodiments of the present invention, the magnesium element is derived from a magnesium-containing compound, preferably from a magnesium halide, more preferably from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, further preferably magnesium dichloride; preferably, in the solid catalyst component, the molar ratio of the column aromatic compound represented by the formula (I) to the magnesium element is (0.001-0.1): 1, preferably (0.001-0.05): 1, and more preferably (0.002-0.05): 1.
In some preferred embodiments of the present invention, in the solid catalyst component, the titanium element originates from TiCl3、TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4And Ti (OC)4H9)4More preferably TiCl, more preferably TiCl3、TiCl4、TiBr4、Ti(OC2H5)Cl3、Ti(OC2H5)2Cl2And Ti (OC)2H5)3One or more of Cl, more preferably TiCl4And/or TiCl3。
In some preferred embodiments of the present invention, the molar ratio of the magnesium element to the 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 superfine carrier is 0.01-10 μm, and the superfine carrier can be one or more selected from alumina, activated carbon, clay, silica, titanium dioxide, polystyrene and calcium carbonate.
According to the present invention, the solid catalyst component can be prepared according to any one of the methods of the prior art.
According to the invention, the solid catalyst component can be prepared by the following method:
method 1
1) Mixing and grinding magnesium halide and optional titanium compound under the condition that magnesium halide is activated;
2) treating the mixed and ground product one or more times by adopting excessive titanium compound;
3) washing the treated product with a hydrocarbon solvent, and then adding a hydrocarbon solution containing the column aromatic compound shown in the formula (I) and carrying out contact reaction;
4) washing the product after reaction with a 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 for contact reaction;
3) carrying out contact reaction on the system in the step 2) and a titanium compound;
4) removing unreacted substances and solvent, washing precipitate, adding a hydrocarbon solution containing the column aromatic hydrocarbon compound shown in the formula (I) and carrying out contact reaction;
5) washing the product after reaction with a hydrocarbon solvent to obtain the solid catalyst component.
Method 3
1) Dissolving magnesium halide, titanium halide, a columnar aromatic hydrocarbon compound shown in a formula (I) and other internal electron donors, and reacting to prepare a mother solution;
2) mixing a superfine carrier with the mother liquor to prepare slurry liquid;
3) and carrying out spray drying on the slurry liquid to obtain the solid catalyst component.
Any of the organoaluminum compounds mentioned above can be used as an activator component of the solid catalyst component to reduce the titanium atom in the solid catalyst component to a state in which an olefin such as ethylene can be efficiently polymerized to obtain a prereduced solid catalyst component.
Method 4
1) Reacting a magnesium halide with an organic epoxy compound, an organic phosphorus compound and an organic alcohol in the presence of an inert solvent;
2) contacting the reaction solution obtained in the step 1) with a titanium compound and an organic silicon compound for reaction, and carrying out high-temperature treatment;
3) removing unreacted substances and solvent, washing precipitate, adding a hydrocarbon solution containing the column aromatic hydrocarbon compound shown in the formula (I) and carrying out contact reaction;
4) washing the product after reaction with a hydrocarbon solvent to obtain the solid catalyst component.
Method 5
1) In the presence of an inert solvent, reacting magnesium halide with an organic epoxy compound and an organic phosphorus compound, and then adding an organic anhydride compound (a precipitation aid) to continue reacting to obtain a solution;
2) contacting the solution with a titanium compound for reaction;
3) adding other internal electron donors into a reaction system to carry out reaction;
4) removing unreacted substances and solvent, washing precipitate, adding a hydrocarbon solution containing the column aromatic hydrocarbon compound shown in the formula (I) and carrying out contact reaction;
5) washing the product after reaction with a hydrocarbon solvent to obtain the solid catalyst component.
Method 6
1) Dispersing a magnesium halide alcoholate in an inert solvent to obtain a suspension;
2) contacting the suspension with an organic aluminum compound and a column aromatic hydrocarbon compound shown as a formula (I) for reaction, removing unreacted substances, and washing with an inert solvent;
3) contacting the precipitate obtained in the step 2) with the titanium compound in the presence of an inert solvent for reaction, then removing unreacted substances 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(CH2CH3)3、Al(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、AlCl1.5(CH2CH3)1.5、AlCl(CH2CH3)2、AlCl2(CH2CH3) And the like alkyl aluminum compounds. In addition, the organoaluminum compound is preferably Al (CH)2CH3)3、Al(n-C6H13)3And Al (i-Bu)3More preferably Al (CH)2CH3)3。
Method 7
1) Dispersing an alkyl magnesium/alkoxy magnesium halide compound in an inert solvent to obtain a solution or a suspension;
2) contacting the solution or the suspension with a titanium compound and other internal electron donors for reaction, then removing unreacted substances, and washing with an inert solvent;
3) contacting the precipitate obtained in the step 2) with the titanium compound in the presence of an inert solvent for reaction, removing unreacted substances and the solvent, washing the precipitate, and then adding a hydrocarbon solution containing the column aromatic hydrocarbon compound shown in the formula (I) for contact reaction;
4) washing the product after reaction with a hydrocarbon solvent to obtain the solid catalyst component.
The compounds used in the above preparation methods are all conventionally selected in the art, and for example, the organic epoxy compound, the organic phosphorus compound, the alcohol compound, and the silicone compound can be selected according to the prior art, and are not particularly limited herein. The inert solvent used in 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 more detailed 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 above solid catalyst component;
2) a co-catalyst component selected from organoaluminum compounds.
In some preferred embodiments of the present invention, the organoaluminum compound has the formula AlR1 dX1 3-dIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1Is halogen atom, d is more than 0 and less than or equal to 3; preferably, the organoaluminium compound is selected from Al (CH)3)3、Al(CH2CH3)3、Al(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlCl(CH2CH3)2、AlH(i-Bu)2、AlCl1.5(CH2CH3)1.5、AlCl(CH2CH3)2And AlCl2(CH2CH3) More preferably Al (CH)2CH3)3And/or Al (i-Bu)3More preferably, the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (5-500): 1, preferably (20-200): 1.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
the solid catalyst component or catalyst system described above is used in the field of olefin polymerization, especially in the field of ethylene polymerization.
According to the present invention, the olefin polymerization includes homopolymerization and copolymerization of olefins.
According to the present invention, the above ethylene polymerization includes homopolymerization of ethylene and copolymerization of ethylene with butene, pentene, hexene, octene or 4-methyl-1-pentene.
In order to realize the fifth 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 catalyst system described above.
In some preferred embodiments of the present invention, the polymerization conditions include: the temperature is 0-150 ℃, and preferably 60-100 ℃; the pressure is 0.1MPa to 10MPa, preferably 0.1MPa to 5 MPa.
According to the invention, the above-described catalyst system is suitable for polymerization under various conditions, for example, the olefin polymerization can be carried out in liquid or gas phase, or else in an operation combining liquid and gas phase polymerization stages. The medium used for the liquid phase polymerization may be selected from inert solvents such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., and toluene, n-hexane, or cyclohexane is preferable.
In addition, hydrogen gas may be used as a molecular weight modifier in order to adjust the molecular weight of the final polymer.
The invention has the beneficial effects that at least, the molecular weight of the prepared polymerization product can be obviously improved by the polymerization reaction participated by the catalyst system containing the solid catalyst component provided by the invention.
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 following examples and comparative examples:
in the present invention, the compounds of formula (I) can be prepared by reference to the existing literature, for example, compound J1 by reference to org.Lett.2019,21, 3976-.
In the following examples and comparative examples,
1. composition of the catalyst component: the measurement was carried out by liquid nuclear magnetic 1H-NMR.
2. Determination of the bulk Density of the Polymer: the measurements were carried out using (ASTM D1895) test methods for apparent density, bulk factor and pourability of plastics.
3. Polymer molecular weight test: measured according to ASTM D4020-18.
Preparation example 1
Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-di-n-propoxybenzene, and the mixture was 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 C containing a compound C1, a compound C2, and a compound C3. Nuclear magnetic analysis revealed that the molar ratio of C1: C2: C3 in the mixture was 1: 0.75: 0.05.
preparation example 2
Anhydrous chloroform (40mL) was added to 3mmol of 1-methoxy-4-bromopropoxybenzene, and the mixture was stirred uniformly, 9mmol of paraformaldehyde and 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 dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate ═ 20: 1) to obtain a mixture P containing a compound P1, a compound P2, and a compound P3. Nuclear magnetic analysis revealed that the molar ratio of P1: P2: P3 in the mixture was 1: 0.52: 0.02.
preparation example 3
Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-diisopropoxybenzene, and the mixture was 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 D containing a compound D1, a compound D2, and a compound D3. Nuclear magnetic analysis revealed that the molar ratio of D1: D2: D3 in the mixture was 1: 0.43: 0.02.
preparation example 4
Anhydrous chloroform (50mL) was added to 3mmol of 1, 4-di-n-butoxybenzene, and the mixture was stirred uniformly, 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 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 E containing a compound E1, a compound E2, and a compound E3. Nuclear magnetic analysis revealed that the molar ratio of E1: E2: E3 in the mixture was 1: 0.72: 0.05.
preparation example 5
Anhydrous chloroform (40mL) was added to 3mmol of 1-methoxy-4-propoxybenzene, and the mixture was stirred uniformly, 9mmol of paraformaldehyde and 0.50mmol 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 ═ 20: 1) to obtain a mixture G containing a compound G1, a compound G2, and a compound G3. Nuclear magnetic analysis revealed that the molar ratio of G1: G2: G3 in the mixture was 1: 0.67: 0.04.
example 1
(1) Preparation of solid catalyst component a
6.0g of MgCl on a spherical support are added in sequence to a reactor which is fully replaced by high-purity nitrogen2·2.6C2H5OH, 120mL of toluene, was cooled to-10 ℃ with stirring, 50mL of a hexane solution of triethylaluminum (triethylaluminum: 1.2M) and 0.3g of mixture C were added dropwise, then the temperature was raised to 60 ℃ and the reaction was maintained for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession. 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. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing the precipitate twice with hexane, transferring the precipitate into a chromatography funnel through hexane, and drying the precipitate with high-purity nitrogen to obtain a solid spherical catalyst component a with good fluidity, wherein the composition of the solid spherical catalyst component a is shown in table 1.
(2) Polymerisation reaction
A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, 1L of hexane and 1.0ml of 1M triethylaluminum were added, the solid catalyst component (containing 0.6 mg of titanium) prepared by the above method was added, the temperature was raised to 70 ℃ and ethylene was introduced so that the total pressure in the vessel became 1.0MPa (gauge pressure), and polymerization was carried out at 70 ℃ for 2 hours, the polymerization results being shown in Table 1.
Comparative example 1
(1) Preparation of solid catalyst component D1
6.0g of MgCl on a spherical support are added in sequence to a reactor which is fully replaced by high-purity nitrogen2·2.6C2H5OH, 120mL of toluene, was cooled to-10 ℃ with stirring, 50mL of a hexane solution of triethylaluminum (triethylaluminum: 1.2M) was added dropwise, and the temperature was raised to60 ℃ and the reaction was maintained for 3 hours. Stirring was stopped, the suspension was allowed to settle, the supernatant was removed quickly, and the precipitate was washed several times with toluene and hexane in succession. 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. Stirring was stopped, the suspension was allowed to stand still, the supernatant was quickly separated, the precipitate was washed twice with hexane, transferred to a chromatography funnel with hexane, and blown dry with high purity nitrogen to obtain a solid spherical catalyst component D1 having good fluidity and having a composition 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 a reaction kettle, and a reaction was carried out at a constant temperature of 70 ℃ for 2 hours. The system is cooled to-10 ℃, 70mL of titanium tetrachloride is slowly dropped, 5mL of tetraethoxysilane is added, the temperature is gradually raised to 85 ℃, and the constant temperature is kept for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, and washing twice with toluene. 0.4g of mixture C and 100ml of toluene were added and the temperature was maintained at 85 ℃ for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component b with good fluidity, wherein the composition of the solid catalyst component b 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 a reaction kettle, and a reaction was carried out at a constant temperature of 70 ℃ for 2 hours. The system is cooled to-10 ℃, 70mL of titanium tetrachloride is slowly dropped, 5mL of tetraethoxysilane is added, the temperature is gradually raised to 85 ℃, and the constant temperature is kept for 1 hour. The stirring was stopped, the suspension was allowed to stand, the supernatant liquid was quickly separated, and the supernatant liquid was taken out, washed with toluene and hexane for a plurality of times, and then dried to obtain 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
Adding 4.0 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 13.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 2g of phthalic anhydride, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 95 ℃, and keeping the temperature 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 were added and the temperature was maintained at 85 ℃ for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component c with good fluidity, wherein the composition of the solid catalyst component c 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
Adding 4.0 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 13.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 2g of phthalic anhydride, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 95 ℃, and keeping the temperature 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 obtain 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
Passing nitrogen gas onceA250 mL three-necked flask was charged with 1.5g TiCl followed by another44.4g of anhydrous MgCl20.4g of the mixture F and 100mL of tetrahydrofuran are heated to 65 ℃ under stirring, and react for 3 hours at the constant temperature, and then the temperature is reduced to 35 ℃ to obtain mother liquor.
Adding 6g of silica gel (Cabot Corporation TS-610, particle size of 0.02-0.1 micron) into another 250mL three-necked bottle which is blown off by nitrogen, adding the mother liquor after cooling, keeping the temperature at 35 ℃, stirring for 1h, and then carrying out spray drying on the mother liquor after mixing the silica gel by using a spray dryer, wherein the spray conditions are as follows: the inlet temperature was 180 ℃ and the outlet temperature was 110 ℃ to obtain the solid catalyst component g, the composition of which is shown in Table 1.
(2) Pre-reduction treatment
Adding 100mL of hexane, 5g of the solid catalyst component and 4mL of tri-n-hexylaluminum (1M) into a 250mL three-necked flask which is blown off by nitrogen, heating to 50 ℃ under stirring, and keeping the temperature constant for 1 h; 9mL of diethyl aluminum monochloride (1M) were added, and the temperature was kept constant for 1 hour. The mother liquor is filtered, washed by hexane for a plurality of times and then dried 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 were charged 1.5g of TiCl4 followed by 4.4g of anhydrous MgCl2And 100mL of tetrahydrofuran, heating to 65 ℃ under stirring, reacting for 3 hours at the constant temperature, and then cooling to 35 ℃ to obtain mother liquor.
Adding 6g of silica gel (Cabot Corporation TS-610, particle size of 0.02-0.1 micron) into another 250mL three-necked bottle which is blown off by nitrogen, adding the mother liquor after cooling, keeping the temperature at 35 ℃, stirring for 1h, and then carrying out spray drying on the mother liquor after mixing the silica gel by using a spray dryer, wherein the spray conditions are as follows: the inlet temperature was 195 ℃ and the outlet temperature was 110 ℃ to give a solid catalyst component D4, the composition of which is shown in Table 1.
(2) Pre-reduction treatment
The 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 solid catalyst component e
Adding 4.8 g of magnesium chloride, 30mL of decane and 20mL of isooctanol into a reaction kettle, reacting for 3 hours under the conditions of stirring speed of 300rpm and temperature of 130 ℃, cooling the system to 50 ℃, adding 3.5mL of tetraethoxysilane, and continuing stirring for 2 hours. The system is cooled to room temperature, slowly dropped into 200mL titanium tetrachloride at 0 ℃, and kept at the constant temperature for 1h after the dropping is finished. The system was gradually warmed to 110 ℃ and held at that temperature for 2 hours. Stopping stirring, standing, quickly layering the suspension, removing supernatant, and washing twice with toluene. 0.5g of mixture C and 100ml of toluene were added and the temperature was maintained at 85 ℃ for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component e with good fluidity, wherein the composition of the solid catalyst component e 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
Adding 4.8 g of magnesium chloride, 30mL of decane and 20mL of isooctanol into a reaction kettle, reacting for 3 hours under the conditions of stirring speed of 300rpm and temperature of 130 ℃, cooling the system to 50 ℃, adding 3.5mL of tetraethoxysilane, and continuing stirring for 2 hours. The system is cooled to room temperature, slowly dropped into 200mL titanium tetrachloride at 0 ℃, and kept at the constant temperature for 1h after the dropping is finished. The system was gradually warmed to 110 ℃ and held at that temperature for 2 hours. The stirring was stopped, the suspension was allowed to stand, the supernatant liquid was quickly separated, and the supernatant liquid was removed, washed with toluene and hexane several times and dried to obtain 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, 55mL of toluene were added to the reaction vessel and a suspension was formed at a stirring rate of 300 rpm. The temperature of the system is reduced to 0 ℃, 30mL of titanium tetrachloride is slowly added, the temperature is slowly increased to 90 ℃ after the dropwise addition, and the constant temperature is kept for 1.5 hours. Stopping stirring and standing, quickly demixing the suspension, and pumping out the supernatant. Then, 60mL of toluene and 30mL of titanium tetrachloride were added, and the temperature was raised to 90 ℃ and maintained at the same temperature for 2 hours. Stopping stirring, standing, and removing supernatant. After two washes with toluene. 0.5G of mixture G and 100ml of toluene were added and the temperature was maintained at 85 ℃ for 1 hour. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene and hexane for multiple times, and drying to obtain a solid catalyst component f with good fluidity, wherein the composition of the solid catalyst component f 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, 55mL of toluene were added to the reaction vessel and a suspension was formed at a stirring rate of 300 rpm. The temperature of the system is reduced to 0 ℃, 30mL of titanium tetrachloride is slowly added, the temperature is slowly increased to 90 ℃ after the dropwise addition, and the constant temperature is kept for 1.5 hours. Stopping stirring, standing, quickly demixing the suspension, and removing the supernatant. Then, 60mL of toluene and 30mL of titanium tetrachloride were added, and the temperature was raised to 90 ℃ and maintained at the same temperature for 2 hours. Stopping stirring, standing, and removing supernatant. After washing with toluene and hexane for a plurality of times, and drying, a solid catalyst component D6 having good flowability was obtained, 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
The same as example 6, but with the addition of Ethyl Acetate (EA) instead of mixture G as internal electron donor.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 7
(1) Preparation of solid catalyst component g
The same as example 1, but with the addition of ethyl acetate (EA for short) and of the mixture C as internal electron donor. The composition of the solid catalyst component g obtained 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 solid catalyst component h
The same procedure as in example 1 was repeated, except that the amount of mixture C added was adjusted so that the mass content of mixture C in the solid catalyst component h was 10% by weight. The composition of the solid catalyst component g obtained is shown in Table 1.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 9
The only difference from example 1 is that compound J1 is used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (in terms of titanium) to the external electron donor and the polymerization results are shown in Table 1.
Example 10
The only difference from example 1 is the use of mixture K instead of mixture C as external electron donor.
The molar ratio of the solid catalyst component (in terms of titanium) to the external electron donor and the polymerization results are shown in Table 1.
Example 11
The only difference from example 1 is that mixture L is used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (in terms of titanium) to the external electron donor and the polymerization results are shown in Table 1.
Example 12
The only difference from example 1 is that mixture P is used as external electron donor instead of mixture C.
The molar ratio of the solid catalyst component (in terms of titanium) to the external electron donor and the polymerization results are shown in Table 1.
TABLE 1
Note: in table 1, "-" indicates that the component is not contained or that the content of the component is 0.
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. An application of a column aromatic hydrocarbon compound shown in a formula (I) as an electron donor in a catalyst system for olefin polymerization, in particular as an internal electron donor in a solid catalyst component for olefin polymerization,
in the formula (I), the part in parentheses represents a basic unit, wherein M1、M2、M3、M4、R1And R2The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R3CHO、-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 4-20;
when adjacent groups within OR between adjacent base units are-C (O) OR4、-R3C(O)OR4、-OR4、-R3OR4C with or without substituents1-C10Hydrocarbyl and C with or without substituents1-C10In the case of hydrocarbyloxy groups, two adjacent groups are optionally linked to each other to form a cyclic structure.
2. A solid catalyst component for the polymerization of olefins comprising: magnesium element, titanium element, halogen and an internal electron donor, wherein the internal electron donor comprises a columnar aromatic hydrocarbon compound shown as a formula (I),
in the formula (I), the part in parentheses represents a basic unit, wherein M1、M2、M3、M4、R1And R2The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, -R3CHO、-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 4-20;
when in the base unitThe vicinal radicals OR vicinal radicals between adjacent basic units being-C (O) OR4、-R3C(O)OR4、-OR4、-R3OR4C with or without substituents1-C10Hydrocarbyl and C with or without substituents1-C10In the case of hydrocarbyloxy groups, two adjacent groups are optionally linked to each other to form a cyclic structure.
3. The solid catalyst component according to claim 2, characterized in that in formula (I), M is1、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 5 to 7;
more preferably, in formula (I), M1And M2Are the same or different and are each independently selected from C1-C6An alkoxy group.
4. The solid catalyst component according to claim 2 or 3, 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＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound E2: m1＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound E3: m1＝M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound F1: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound F2: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound F3: m1＝OCH3；M2＝OCH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound G1: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound G2: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound G3: m1＝OCH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound H1: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound H2: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound H3: m1＝OCH3；M2＝OCH2CH2CH2CH3，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound I1: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound I2: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound I3: m1＝M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound J1: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound J2: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound J3: m1＝OCH3，M2＝OH，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound K1: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝5；
Compound K2: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝6；
Compound K3: m1＝M2＝OCH3，M3＝M4＝NH2，R1＝R2＝H，n＝7；
Compound L1: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝5；
Compound L2: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝6；
Compound L3: m1＝M2＝OCH3，M3＝M4＝Cl，R1＝R2＝H，n＝7；
Compound M1: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝5；
Compound M2: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝6；
Compound M3: m1＝M2＝OCH3，M3＝M4＝Br，R1＝R2＝CH3，n＝7；
Compound N1: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝5；
Compound N2: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝6；
Compound N3: m1＝M2＝OCH3，M3＝M4＝I，R1＝R2＝H，n＝7；
Compound O1: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound O2: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound O3: m1＝OCH3，M2＝CHO，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound P1: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝5；
Compound P2: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝6；
Compound P3: m1＝OCH3；M2＝OCH2CH2CH2Br，M3＝M4＝H，R1＝R2＝H，n＝7；
Compound Q1: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝5；
Compound Q2: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝6；
Compound Q3: m1＝M3＝OCH3，M2＝M4＝OCH3，R1＝R2＝H，n＝7；
Compound R1: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝5；
Compound R2: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝6；
Compound R3: m1＝OCH2CH3；M2＝OCH2CH2CH3，M3＝M4＝H，R1＝R2＝OCH3，n＝7。
5. The solid catalyst component according to any of claims 2 to 4, wherein the mass content of the column aromatic compound of formula (I) in the solid catalyst component is 0.1 to 20 wt. -%, preferably 1 to 15 wt. -%, more preferably 2 to 10 wt. -%.
6. The solid catalyst component according to any one of claims 2 to 5, wherein the internal electron donor further comprises other internal electron donors, wherein the other internal electron donors are selected from one or more of organic alcohol compounds, organic acid ester compounds, organic acyl halide compounds, organic acid anhydride compounds, ether compounds, ketone compounds, amine compounds, phosphate compounds, amide compounds, carbonate compounds, phenol compounds, pyridine compounds and high molecular compounds with polar groups, preferably from one or more of organic alcohol compounds, ether compounds and phosphate compounds, more preferably the molar ratio of the other internal electron donors to the magnesium element is (0.01-5): 1, preferably (0.05-1): 1, more preferably (0.1 to 1): 1.
7. A catalyst system for the polymerization of olefins comprising the following components:
1) the solid catalyst component of any one of claims 2 to 6;
2) a co-catalyst component selected from organoaluminum compounds.
8. The catalyst system of claim 7, wherein the organoaluminum compound has the formula AlR1 dX1 3-dIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1Is halogen atom, d is more than 0 and less than or equal to 3; preferably, the organoaluminium compound is selected from Al (CH)3)3、Al(CH2CH3)3、Al(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlCl(CH2CH3)2、AlH(i-Bu)2、AlCl1.5(CH2CH3)1.5、AlCl(CH2CH3)2And AlCl2(CH2CH3) More preferably Al (CH)2CH3)3And/or Al (i-Bu)3More preferably, the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (5-500): 1, preferably (20-200): 1.
9. Use of a solid catalyst according to any one of claims 2 to 6 or of a catalyst system according to claim 7 or 8 in the field of olefin polymerization, in particular ethylene polymerization.
10. An olefin polymerization process comprising: subjecting an olefin to a polymerization reaction in the presence of the catalyst system of claim 7 or 8, preferably under conditions comprising: the temperature is 0-150 ℃, and preferably 60-100 ℃; the pressure is 0.1MPa to 10MPa, preferably 0.1MPa to 5 MPa.
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