CN107344976B - Catalyst component for olefin polymerization, catalyst system and application thereof - Google Patents
Catalyst component for olefin polymerization, catalyst system and application thereof Download PDFInfo
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- CN107344976B CN107344976B CN201610292550.4A CN201610292550A CN107344976B CN 107344976 B CN107344976 B CN 107344976B CN 201610292550 A CN201610292550 A CN 201610292550A CN 107344976 B CN107344976 B CN 107344976B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a catalyst component for olefin polymerization, a catalyst system and application thereof. The catalyst component provided by the invention comprises titanium, magnesium, halogen and an internal electron donor, wherein the internal electron donor comprises a 2,2 '-dialkyl-1, 3-dicarbonate compound shown in a formula (I) and a 2,2' -dialkyl-1, 3-diether compound shown in a formula (II). The catalyst component and the catalyst system containing the catalyst component are suitable for developing polyolefin, especially polypropylene resin.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst system and application thereof.
Background
The solid titanium catalyst component, known as Ziegler-Natta catalyst, based on magnesium, titanium, halogen and electron donor, can be used for CH2(CHR) olefin polymerization, especially in alpha-olefin polymerization having 3 or more carbon atomsTo obtain a polymer with higher yield and higher stereoregularity. It is well known that electron donor compounds are one of the essential components in Ziegler-Natta catalyst components. It is the development of internal electron donors that has led to the continuous evolution of polyolefin catalysts, from the early disclosures of monocarboxylic acid ester compounds, such as ethyl benzoate, to the currently widely used dibasic aromatic carboxylic acid ester compounds, such as di-n-butyl phthalate or diisobutyl phthalate, to the more recently disclosed 1, 3-diether (CN1020448C), succinate (CN1313869) and 1, 3-diol (CN1213080C) compounds.
CN1213080C discloses a polyol ester compound, which is suitable for the preparation of catalysts for olefin polymerization. The CN1436796A and CN1453298A both describe the polyolefin catalyst active component obtained by taking the special polybasic ester compound as an internal electron donor, and the catalyst has higher activity and better stereospecificity. However, it is difficult to obtain a catalyst component having good hydrogen response using such an alcohol ester compound, and the cost is high.
CN1020448C discloses a 1, 3-diether internal electron donor compound, and the obtained catalyst component has high activity and good hydrogen regulation sensitivity when used for olefin polymerization. However, the preparation cost of the compounds is high, and the molecular weight distribution of the prepared olefin polymer is narrow.
Disclosure of Invention
In view of the above-mentioned prior art, the present inventors have conducted extensive and intensive studies in the field of catalysts for olefin polymerization, and have unexpectedly found that a catalyst prepared by compounding a 2,2 '-dialkyl-1, 3-dicarbonate compound with a 2,2' -dialkyl-1, 3-diether compound as an internal electron donor is particularly suitable for use in CH2(ii) CHR olefin polymerization, wherein R is hydrogen or C1-C6Especially propylene.
Therefore, the invention aims to provide a catalyst active component which uses two compounds with specific structures to be compounded as an electron donor, and a catalyst system containing the component. The catalyst system has high activity, good stereospecificity and hydrogen regulation performance when used for olefin polymerization.
The invention provides a catalyst component for olefin polymerization, which comprises titanium, magnesium, halogen and an internal electron donor, wherein the internal electron donor comprises a 2,2 '-dialkyl-1, 3-dicarbonate compound shown in a general formula (I) and a 2,2' -dialkyl-1, 3-diether compound shown in a formula (II),
in the formula (I), R1And R2Identical or different, independently selected from hydrogen and C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl and C of7-C20Aralkyl of (2), said C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20And/or C7-C20Optionally substituted by a halogen atom, a heteroatom selected from O, S, N, P and Si, C1-C6Linear or linear alkyl or alkoxy, optionally substituted on the carbon atoms of the main chain by at least one heteroatom selected from O, S, N, P and Si; or R1And R2Connected into a ring in any mode; r3And R4Identical or different, independently selected from C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl and C of7-C20Aralkyl of (2), said C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20And/or C7-C20Optionally substituted by a halogen atom, a heteroatom selected from O, S, N, P and Si, C1-C6Linear or linear alkyl or alkoxy, optionally substituted on the carbon atoms of the main chain by at least one heteroatom selected from O, S, N, P and Si;
in the formula (II), R5And R6Identical or different, independently selected from hydrogen and C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20Alkylaryl and C of7-C20Aralkyl of (2), said C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl of C3-C20Cycloalkyl of, C6-C20Aryl of (C)7-C20And/or C7-C20Optionally substituted by a halogen atom, a heteroatom selected from O, S, N, P and Si, C1-C6Linear or linear alkyl or alkoxy, the carbon atoms of the main chain being optionally substituted by at least one heteroatom selected from O, S, N, P and Si; or R5And R6Bonded in any manner to form a ring; r7And R8Identical or different, independently selected from C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10Aralkyl of (2), said C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10And/or C7-C10Optionally substituted by a halogen atom, a heteroatom selected from O, S, N, P and Si, C1-C6By straight-chain or straight-chain alkyl or alkoxy radicals, carbon of the main chainThe atoms are optionally substituted with at least one heteroatom selected from O, S, N, P and Si.
According to a preferred embodiment of the catalyst component of the present invention, R1And R2Independently selected from hydrogen, C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
According to a preferred embodiment of the catalyst component of the present invention, R1And R2Are each independently C1-C6Straight chain alkyl or C3-C6Preferably, R is1And R2Independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 1 ' -dimethylbutyl, 2' -dimethylbutyl, and 3,3 ' -dimethylbutyl.
According to a preferred embodiment of the catalyst component of the present invention, R3And R4Is independently selected from C1-C10Straight chain alkane of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C20Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
According to a preferred embodiment of the catalyst component of the present invention, R3And R4Independently selected from C1-C6Linear alkane of (2) or C3-C6Preferably, R is3And R4Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 1 ' -dimethylbutyl, 2' -dimethylbutyl and 3,3 ' -dimethylbutyl.
According to a preferred embodiment of the catalyst component of the present invention, R1And R2Linked in any way to form a ring and containing, in the skeleton of the ring formed, a double bond or a heteroatom selected from O, S, N, P and Si.
In certain embodiments, R1And R2Methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 1 ' -dimethylbutyl, 2' -dimethylbutyl or 3,3 ' -dimethylbutyl, 1 ', 2-trimethylbutyl, 1 ', 3-trimethylbutyl, 1,3,3 ' -trimethylbutyl, 2', 3-trimethylbutyl, 2-methylpropyl, 2,3,3 ' -trimethylbutyl, 1 ', 2,2' -tetramethylpropyl, dodecyl, tetradecyl, hexadecyl or octadecyl, and the like.
In certain embodiments, R3And R4Is independently selected from C1-C6Linear alkane of (1) and C3-C6Preferably, R is3And R4Independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 1 ' -dimethylbutyl, and 2,2' -dimethylbutyl or 3,3 ' -dimethylbutyl.
The halogen atom in the present invention means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The 2,2' -dialkyl-1, 3-dicarbonate compounds suitable as the internal electron donor in the catalyst component of the present invention may be 2-isopropyl-2-isoamyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-isoamyl-1, 3-diethyldicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisobutylddicarbonate, 2-isopropyl-2-isoamyl, 3-diiso, 2-isopentyl, 2-isopropyl-2-isoamyl-1, 3-di-n-pentyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-isoamyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-isohexyl dicarbonate; 2-methyl-2-n-propyl-1, 3-dimethyldicarbonate, 2-methyl-2-n-propyl-1, 3-diethyldicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-propyldicarbonate, 2-methyl-2-n-propyl-1, 3-diisopropyldicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-butyldicarbonate, 2-methyl-2-n-propyl-1, 3-diisobutyldicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-n-propyl-1, 3-diisoamyl dicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-n-propyl-1, 3-diisohexyl dicarbonate, 2-methyl-2-n-butyl-dimethyl dicarbonate, 2-methyl-2-n-butyl-diethyl dicarbonate, 2-methyl-2-n-butyl-di-n-propyl dicarbonate, 2-methyl-2-n-butyl-diisopropyl dicarbonate, 2-methyl-2-n-butyl-di-n-butyl dicarbonate, 2-methyl-2-n-butyl-diisobutyl dicarbonate, 2-methyl-2-n-butyl-di-n-pentyl dicarbonate, 2-methyl-2-n-butyl-diisoamyl dicarbonate, 2-methyl-2-n-butyl-di-n-hexyl dicarbonate, 2-methyl-2-n-butyl-diisohexyl dicarbonate; 2-methyl-2-isobutyl-1, 3-dimethyldicarbonate, 2-methyl-2-isobutyl-1, 3-diethyldicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-propyldicarbonate, 2-methyl-2-isobutyl-1, 3-diisopropyldicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-butyldicarbonate, 2-methyl-2-isobutyl-1, 3-diisobutyldicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-isobutyl-1, 3-diisoamyl dicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-isobutyl-1, 3-diisohexyl dicarbonate; 2-methyl-2-n-pentyl-1, 3-dimethyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diethyldicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-propyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diisopropyldicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-butyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diisobutyldicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diisoamyl dicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-n-pentyl-1, 3-diisohexyl dicarbonate, 2-methyl-2-isoamyl-1, 3-dimethyl dicarbonate, 2-methyl-2-isoamyl-1, 3-diethyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-propyl dicarbonate, 2-methyl-2-isoamyl-1, 3-diisopropyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-butyl dicarbonate, 2-methyl-2-isoamyl-1, 3-diisobutyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-pentyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-isoamyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-isohexyl dicarbonate; 2-isopropyl-2-n-propyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diethyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisobutyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-pentyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisoamyl dicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisohexyl dicarbonate; 2-isopropyl-2-n-butyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diethyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisobutyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-pentyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisoamyl dicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisohexyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-dimethyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diethyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-propyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diisopropyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-butyl dicarbonate, 3-diisobutyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-pentyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diisopentyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diisohexyl dicarbonate; 2-isopropyl-2-n-pentyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diethyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisobutyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-pentyl-dicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisoamyl dicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisohexyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-dimethyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diethyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-propyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisopropyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-butyl dicarbonate, 3-diisobutyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-pentyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisopentyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-hexyl dicarbonate and 2-isopropyl-2-isoamyl-1, 3-diisohexyl dicarbonate.
According to an embodiment of the catalyst component of the present invention, R5And R6Independently selected from hydrogen, C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Alkylaryl and C of7-C10An aralkyl group of (2).
According to certain embodiments, R5And R6Independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, and phenyl.
According to an embodiment of the catalyst component of the present invention, R7And R8Is C1-C4Straight chain alkyl or C3-C4Branched alkyl groups of (a). According to certain embodiments, R7And R8Independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
According to a preferred embodiment of the present invention, the 2,2 '-dialkyl-1, 3-diether compound represented by the formula (II) is selected from the group consisting of 2,2' -dimethyl-1, 3-dimethyl ether, 2 '-diethyl-1, 3-dimethyl ether, 2' -di-n-propyl-1, 3-dimethyl ether, 2 '-diisopropyl-1, 3-dimethyl ether, 2' -di-n-butyl-1, 3-dimethyl ether, 2 '-diisobutyl-1, 3-dimethyl ether, 2' -ditert-butyl-1, 3-dimethyl ether, 2 '-di-n-pentyl-1, 3-dimethyl ether, 2' -diisopentyl-1, 3-dimethyl ether, dimethyl ether, 2,2' -di (1-methyl) butyl-1, 3-dimethyl ether, 2,2' -di (2-methyl) butyl-1, 3-dimethyl ether, 2,2' -di (1-ethyl) propyl-1, 3-dimethyl ether, 2,2' -di-tert-pentyl-1, 3-dimethyl ether, 2,2' -di-n-hexyl-1, 3-dimethyl ether, 2,2' -di-isohexyl-1, 3-diether, 2,2' -di (1-methyl) pentyl-1, 3-dimethyl ether, 2,2' -di (2-methyl) pentyl-1, 3-dimethyl ether, 2,2' -di (3-methyl) pentyl-1, 3-dimethyl ether, dimethyl, 2,2' -di (1-ethyl) butyl-1, 3-dimethyl ether, 2' -di (2-ethyl) butyl-1, 3-dimethyl ether, 2' -di-tert-hexyl-1, 3-dimethyl ether, 2-methyl-2-ethyl-1, 3-dimethyl ether, 2-methyl-2-n-propyl-1, 3-dimethyl ether, 2-methyl-2-isopropyl-1, 3-dimethyl ether, 2-methyl-2-n-butyl-1, 3-dimethyl ether, 2-methyl-2-isobutyl-1, 3-dimethyl ether, 2-methyl-2-n-pentyl-1, 3-dimethyl ether, dimethyl, 2-methyl-2-isoamyl-1, 3-dimethyl ether, 2-methyl-2-n-hexyl-1, 3-dimethyl ether, 2-methyl-2-isohexyl-1, 3-dimethyl ether, 2-ethyl-2-n-propyl-1, 3-dimethyl ether, 2-ethyl-2-isopropyl-1, 3-dimethyl ether, 2-ethyl-2-n-butyl-1, 3-dimethyl ether, 2-ethyl-2-isobutyl-1, 3-dimethyl ether, 2-ethyl-2-n-pentyl-1, 3-dimethyl ether, 2-ethyl-2-isoamyl-1, 3-dimethyl ether, dimethyl, 2-ethyl-2-n-hexyl-1, 3-dimethyl ether, 2-ethyl-2-isohexyl-1, 3-dimethyl ether, 2-n-propyl-2-isopropyl-1, 3-dimethyl ether, 2-n-propyl-2-n-butyl-1, 3-dimethyl ether, 2-n-propyl-2-isobutyl-1, 3-dimethyl ether, 2-n-propyl-2-n-pentyl-1, 3-dimethyl ether, 2-n-propyl-2-isopentyl-1, 3-dimethyl ether, 2-n-propyl-2-n-hexyl-1, 3-dimethyl ether, 2-n-propyl-2-isohexyl-1, 3-dimethyl ether, 2-isopropyl-2-n-butyl-1, 3-dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethyl ether, 2-isopropyl-2-n-pentyl-1, 3-dimethyl ether, 2-isopropyl-2-isopentyl-1, 3-dimethyl ether, 2-isopropyl-2-n-hexyl-1, 3-dimethyl ether, 2-isopropyl-2-isohexyl-1, 3-dimethyl ether, 2-n-butyl-2-isobutyl-1, 3-dimethyl ether, 2-n-butyl-2-n-pentyl-1, 3-dimethyl ether, 2-n-butyl-2-isopentyl-1, 3-dimethyl ether, 2-n-butyl-2-n-hexyl-1, 3-dimethyl ether, 2-n-butyl-2-isohexyl-1, 3-dimethyl ether, 2-isobutyl-2-n-pentyl-1, 3-dimethyl ether, 2-isobutyl-2-isopentyl-1, 3-dimethyl ether, 2-isobutyl-2-n-hexyl-1, 3-dimethyl ether, 2-isobutyl-2-isohexyl-1, 3-dimethyl ether, 2-n-pentyl-2-isopentyl-1, 3-dimethyl ether, 2-n-pentyl-2-n-hexyl-1, 3-dimethyl ether, 2-n-pentyl-2-isohexyl-1, at least one of 3-dimethyl ether, 2-isoamyl-2-n-hexyl-1, 3-dimethyl ether, 2-isoamyl-2-isohexyl-1, 3-dimethyl ether and 2-n-hexyl-2-isohexyl-1, 3-dimethyl ether;
preferably selected from: 2,2' -dimethyl-1, 3-dimethyl ether, 2' -diethyl-1, 3-dimethyl ether, 2' -di-n-propyl-1, 3-dimethyl ether, 2' -diisopropyl-1, 3-dimethyl ether, 2' -di-n-butyl-1, 3-dimethyl ether, 2' -diisobutyl-1, 3-dimethyl ether, 2' -di-tert-butyl-1, 3-dimethyl ether, 2' -di-n-pentyl-1, 3-dimethyl ether, 2' -di-isoamyl-1, 3-dimethyl ether, 2' -di (1-ethyl) propyl-1, 3-dimethyl ether, 2' -di-tert-pentyl-1, 3-dimethyl ether, 2,2 '-di-n-hexyl-1, 3-dimethyl ether, 2,2' -di-isohexyl-1, 3-diether, 2,2 '-di (2-ethyl) butyl-1, 3-dimethyl ether, 2,2' -di-tert-hexyl-1, 3-dimethyl ether, 2-methyl-2-ethyl-1, 3-dimethyl ether, 2-methyl-2-n-propyl-1, 3-dimethyl ether, 2-methyl-2-isopropyl-1, 3-dimethyl ether, 2-methyl-2-n-butyl-1, 3-dimethyl ether, 2-methyl-2-isobutyl-1, 3-dimethyl ether, 2-methyl-2-n-pentyl-1, 3-dimethyl ether, 2-methyl-2-isoamyl-1, 3-dimethyl ether, 2-methyl-2-isohexyl-1, 3-dimethyl ether, 2-ethyl-2-n-propyl-1, 3-dimethyl ether, 2-ethyl-2-isopropyl-1, 3-dimethyl ether, 2-ethyl-2-n-butyl-1, 3-dimethyl ether, 2-ethyl-2-isobutyl-1, 3-dimethyl ether, 2-ethyl-2-n-pentyl-1, 3-dimethyl ether, 2-ethyl-2-isoamyl-1, 3-dimethyl ether, 2-ethyl-2-isohexyl-1, 3-dimethyl ether, 2-n-propyl-2-isopropyl-1, 3-dimethyl ether, 2-n-propyl-2-n-butyl-1, 3-dimethyl ether, 2-n-propyl-2-isobutyl-1, 3-dimethyl ether, 2-n-propyl-2-n-pentyl-1, 3-dimethyl ether, 2-n-propyl-2-isopentyl-1, 3-dimethyl ether, 2-n-propyl-2-isohexyl-1, 3-dimethyl ether, 2-isopropyl-2-n-butyl-1, 3-dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethyl ether, 2-isopropyl-2-n-pentyl-1, 3-dimethyl ether, 2-isopropyl-2-isoamyl-1, 3-dimethyl ether, 2-isopropyl-2-isohexyl-1, 3-dimethyl ether, 2-n-butyl-2-isobutyl-1, 3-dimethyl ether, 2-n-butyl-2-n-pentyl-1, 3-dimethyl ether, 2-n-butyl-2-isopentyl-1, 3-dimethyl ether, 2-n-butyl-2-isohexyl-1, 3-dimethyl ether, 2-isobutyl-2-n-pentyl-1, 3-dimethyl ether, 2-isobutyl-2-isopentyl-1, 3-dimethyl ether, 2-isobutyl-2-isohexyl-1, at least one of 3-dimethyl ether, 2-n-pentyl-2-isopentyl-1, 3-dimethyl ether, 2-n-pentyl-2-isohexyl-1, 3-dimethyl ether, 2-isopentyl-2-n-hexyl-1, 3-dimethyl ether, 2-isopentyl-2-isohexyl-1, 3-dimethyl ether, and 2-n-hexyl-2-isohexyl-1, 3-dimethyl ether;
more preferably selected from: 2,2 '-dimethyl-1, 3-dimethyl ether, 2' -diethyl-1, 3-dimethyl ether, 2 '-di-n-propyl-1, 3-dimethyl ether, 2' -diisopropyl-1, 3-dimethyl ether, 2 '-di-n-butyl-1, 3-dimethyl ether, 2' -diisobutyl-1, 3-dimethyl ether, 2 '-di-n-pentyl-1, 3-dimethyl ether, 2' -diisopentyl-1, 3-dimethyl ether, 2 '-di-n-hexyl-1, 3-dimethyl ether, 2' -diisohexyl-1, 3-diether, 2-methyl-2-ethyl-1, 3-dimethyl ether, 2-methyl-2-isopropyl-1, 3-dimethyl ether, 2-methyl-2-isobutyl-1, 3-dimethyl ether, 2-methyl-2-isopentyl-1, 3-dimethyl ether, 2-ethyl-2-isopropyl-1, 3-dimethyl ether, 2-ethyl-2-isobutyl-1, 3-dimethyl ether, 2-ethyl-2-isopentyl-1, 3-dimethyl ether, 2-ethyl-2-isohexyl-1, 3-dimethyl ether, 2-n-propyl-2-isopropyl-1, 3-dimethyl ether, 2-n-propyl-2-isobutyl-1, 3-dimethyl ether, 2-n-propyl-2-isoamyl-1, 3-dimethyl ether, 2-n-propyl-2-isohexyl-1, 3-dimethyl ether, 2-isopropyl-2-n-butyl-1, 3-dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethyl ether, 2-isopropyl-2-n-pentyl-1, 3-dimethyl ether, 2-isopropyl-2-isoamyl-1, 3-dimethyl ether, 2-isopropyl-2-isohexyl-1, 3-dimethyl ether, 2-n-butyl-2-isobutyl-1, 3-dimethyl ether, 2-n-butyl-2-isoamyl-1, 3-dimethyl ether, 2-n-butyl-2-isohexyl-1, 3-dimethyl ether, 2-isobutyl-2-n-pentyl-1, 3-dimethyl ether, 2-isobutyl-2-isopentyl-1, 3-dimethyl ether, 2-isobutyl-2-isohexyl-1, 3-dimethyl ether, and 2-n-pentyl-2-isopentyl-1, 3-dimethyl ether.
The catalyst component according to the present invention may further comprise other compounds which may act as internal electron donors.
The catalyst component according to the invention has a titanium content of 1.0 to 8.0 wt.%, preferably 1.6 to 6.0 wt.%, based on the total mass of the catalyst component; the content of magnesium is preferably 10 to 70 wt%, preferably 15 to 40 wt%; the halogen content is 20-90 wt%, preferably 30-85%; the content of the internal electron donor is 2-30 wt%, preferably 3-20 wt%.
According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of the 2,2 '-dialkyl-1, 3-dicarbonate compound represented by formula (I) to the 2,2' -dialkyl-1, 3-diether compound represented by formula (II) in the total internal electron donors is 0.1:1 to 1:0.1, preferably 0.2:1 to 1:0.2, and more preferably 0.3:1 to 1: 0.3.
The preparation method of the catalyst component can be that a magnesium compound, a titanium compound and an electron donor compound are contacted and reacted under certain conditions. The amounts of the titanium compound, the magnesium compound and the internal electron donor used for preparing the olefin polymerization catalyst component are not particularly limited and may be those conventionally used in the art, respectively.
In a preferred case, the magnesium compound may be at least one of a magnesium compound represented by formula (III), a hydrate of the magnesium compound represented by formula (III), and an alcohol adduct of the magnesium compound represented by formula (III),
MgR9R10 (III)
in the formula (III), R9And R10Each of which is one of a halogen, a linear or branched alkoxy group having 1 to 5 carbon atoms, and a linear or branched alkyl group having 1 to 5 carbon atoms.
In the catalyst component of the present invention, the hydrate of the magnesium compound represented by the formula (III) is MgR9R10·qH2O, wherein q is in the range of 0.1 to 6, preferably 2 to 3.5. In the present invention, the alcohol adduct means MgR9R10·pR0OH, wherein R0Is a hydrocarbon group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group and an isopropyl group; p is in the range of 0.1 to 6, preferably 2 to 3.5. Preferably, in the formula (III), R9And R10Each halogen, for example, may be one of chlorine, bromine and iodine.
In a preferred case, the magnesium compound may be at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutyoxymagnesium, dipentyoxymagnesium, dihexomagnesium, bis (2-methyl) hexyloxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymasium bromide, propoxymasium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dichloride, an alcohol adduct of magnesium dibromide, and an alcohol adduct of magnesium diiodide. Most preferably, the magnesium compound is diethoxymagnesium or magnesium dichloride.
The catalyst component according to the invention in which the titanium compound is a compound of formula (IV),
TiXm(OR11)4-m (IV)
in the formula (IV), X is halogen, R11Is a hydrocarbon group having 1 to 20 carbon atoms, and m is an integer of 1 to 4. m may be 0, 1,2, 3 or 4. The halogen may be chlorine, bromine or iodine.
In the formula (IV), X is preferably halogen, R11Alkyl groups having 1 to 5 carbon atoms, for example: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium. Most preferably, the titanium compound is titanium tetrachloride.
In the present invention, the method for preparing the catalyst component of the present invention by reacting the titanium compound, the magnesium compound and the internal electron donor may be performed by a method for preparing an olefin catalyst component, which is conventional in the art. The olefin polymerization catalyst component of the present invention can be prepared, for example, by the following method.
Method one, the catalyst component was prepared according to the following procedure with reference to the CN102453150B method. (1) Contacting and reacting alkoxy magnesium or alkoxy magnesium halide compound with a titanium compound and an internal electron donor shown in a formula (I) in the presence of an inert diluent; (2) washing the solid obtained by the step (1) with an inert solvent to obtain the catalyst component.
Specific examples of the above-mentioned alkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutyoxymagnesium, dipentyoxymagnesium, dihexomagnesium, di (2-methyl) hexyloxymagnesium, and the like, or a mixture thereof, and diethoxymagnesium or a mixture of diethoxymagnesium and other alkoxymagnesium is preferable. The preparation method of the alkoxy magnesium compound can be prepared by a method known in the art, such as the preparation of metal magnesium and fatty alcohol in the presence of a small amount of iodine.
Specific examples of the alkoxymagnesium halide include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, etc., and ethoxymagnesium chloride is preferable. The alkoxy magnesium halide compound can be prepared by a method known in the art, such as a method of mixing a Grignard reagent of butyl magnesium chloride with tetraethoxy titanium and tetraethoxy silicon to prepare ethoxy magnesium chloride.
In step (1), the inert diluent is selected from C6-C10At least one of an alkane or an arene. As specific examples of the inert diluent, hexane, heptane, ethyl acetate, ethyl,One or a mixture of octane, decane, benzene, toluene and xylene; toluene is preferred in the present invention. The order of contacting is not particularly limited, and for example, the components may be contacted in the presence of an inert diluent, or the components may be previously diluted with an inert solvent and contacted. The number of times of contact is not particularly limited, and may be once or more.
The catalyst component obtained by the above contact reaction may be washed with an inert solvent such as: a hydrocarbon compound. Specific examples of the inert solvent may be selected from one of hexane, heptane, octane, decane, benzene, toluene, xylene, or a mixture thereof. Hexane is preferred in the present invention.
In the present invention, the washing method is not particularly limited, and a method such as decantation or filtration is preferable. The amount of the inert solvent to be used, the washing time and the number of washing times are not particularly limited, and the amount of the inert solvent to be used is usually 1 to 1000 mol, preferably 10 to 500 mol, based on 1 mol of the magnesium compound, and the washing time is usually 1 to 24 hours, preferably 10 to 6 hours. In addition, from the viewpoint of washing uniformity and washing efficiency, it is preferable to carry out stirring during the washing operation. It is to be noted that the obtained catalyst component may be stored in a dry state or in an inert solvent.
The amount of each component used in the first process is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the electron-donor compound is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.
The contact temperature of the components is generally-40-200 ℃, preferably-20-150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.
Secondly, referring to the method of patent CN85100997, the magnesium dihalide is dissolved in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, and then the uniform solution is mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation assistant; then the solid is contacted with an internal electron donor shown as a formula (I) in the invention, and the internal electron donor is supported on the solid to obtain the catalyst component.
The secondary precipitant used in the second method may be at least one of an organic acid anhydride, an organic acid, an ether and a ketone. Specific examples of the organic acid anhydride may be at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, and the like, specific examples of the organic acid may be at least one of acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, and the like, specific examples of the ether may be at least one of methyl ether, ethyl ether, propyl ether, butyl ether, and pentyl ether, and the ketone may be at least one of acetone, methyl ethyl ketone, and benzophenone.
The organic epoxy compound used in the second process may be at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and the like, and epichlorohydrin is preferable.
The organophosphorus compound used in the second process may be a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid or phosphorous acid, and specific examples of the organophosphorus compound include: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, or the like, with tributyl orthophosphate being preferred.
The inert diluent used in the second method may employ at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
The amount of each component used in the second method may be 0.2 to 10 moles, preferably 0.5 to 4 moles, of the organic epoxy compound per mole of the magnesium halide; the organic phosphorus compound may be present in an amount of 0.1 to 3 moles, preferably 0.3 to 1.5 moles; the titanium compound may be in the range of 0.5 to 20 moles, preferably 5 to 15 moles; the precipitation-assisting component may be 0.01 to 0.3 mol, preferably 0.02 to 0.08 mol; the total internal electron donor may be 0 to 10 moles, preferably 0.02 to 0.3 moles.
Method three, the catalyst component was prepared according to the preparation method of CN 1091748. The magnesium chloride alcoholate melt is stirred and dispersed at high speed in a dispersion system of white oil and silicone oil to form emulsion, and the emulsion is discharged into cooling liquid to be cooled and shaped at a short speed to form the magnesium chloride alcoholate microspheres. The cooling liquid is inert hydrocarbon solvent with low boiling point, such as petroleum ether, pentane, hexane, heptane, etc. The obtained magnesium chloride alcoholate microspheres are washed and dried to form spherical carriers, and the molar ratio of alcohol to magnesium chloride is 2-3, preferably 2-2.5. The carrier particle size is 10-300 microns, preferably 30-150 microns.
Treating the spherical carrier with excessive titanium tetrachloride at low temperature, gradually heating, adding electron donor during the treatment, washing with inert solvent for several times, and drying to obtain solid powdered spherical catalyst. The molar ratio of titanium tetrachloride to magnesium chloride is 20-200, preferably 30-60; the initial treatment temperature is-30-0 deg.C, preferably-25 deg.C to-20 deg.C; the final treatment temperature is 80-136 deg.C, preferably 100-130 deg.C
The spherical catalyst obtained has the following characteristics: 1.5-3.5 wt% of titanium, 6.0-20.0 wt% of ester, 52-60 wt% of chlorine, 10-20 wt% of magnesium and 1-6 wt% of inert solvent.
The method four comprises the following steps: the catalyst component was prepared with reference to the method disclosed in CN 1506384. Firstly, mixing a magnesium compound and an organic alcohol compound with an inert solvent according to a molar ratio of 2-5, heating to 120-150 ℃ to form a uniform solution, and selectively adding phthalic anhydride used as a precipitation aid, a silicon-containing compound or other assistants beneficial to obtaining good particles; then, according to the molar ratio of titanium/magnesium of 20-50, an alcohol compound and a titanium compound are contacted and reacted for 2-10h, the reaction temperature is-15 to-40 ℃, and the temperature is raised to 90-110 ℃ in the presence of a precipitation aid; adding the electron donor compound according to the magnesium/ester molar ratio of 2-10, reacting at the temperature of 100 ℃ and 130 ℃ for 1-3 hours, and filtering to separate solid particles; then (optionally repeating for 2-3 times) contacting and reacting the solid particles with a titanium compound at 100-130 ℃ for 1.5-3 hours according to the titanium/magnesium molar ratio of 20-50, and filtering to separate out the solid particles; finally, washing the solid particles by using an inert solvent with the temperature of 50-80 ℃, and drying to obtain the catalyst component.
In any of the above four methods for preparing the catalyst component of the present invention, the electron donor may be used alone, or two or more of them may be used in combination.
In any of the above four methods for preparing the catalyst component of the present invention, the internal electron donor can also be added before or during the contacting of the magnesium compound and the titanium compound, for example, in the first method, the internal electron donor is added into the suspension of the alkoxy magnesium or alkoxy magnesium halide in the inert diluent, and then mixed with the titanium compound to prepare the olefin polymerization catalyst; in the second method, the internal electron donor is added into the magnesium halide solution before the magnesium halide solution contacts with the titanide.
In the preparation of the above catalyst component, the molar ratio of the total amount of internal electron donors represented by formula (I) and formula (II) to magnesium atoms may be generally in the range of from 0.01 to 3, preferably in the range of from 0.02 to 0.3.
The catalyst component provided by the invention preferably contains 1-3.5 wt% of titanium, 10-20 wt% of magnesium, 50-70 wt% of chlorine and 6-20 wt% of internal electron donor based on the total weight of the catalyst component, and more preferably contains 1.8-3.2 wt% of titanium, 15-20 wt% of magnesium, 52-60 wt% of chlorine and 7-11 wt% of internal electron donor based on the total weight of the catalyst component.
According to the invention, the olefin polymerization catalyst system used is of the general formula CH2Polymerization of olefins represented by ═ CHR, where R is hydrogen or C1-C6Alkyl group of (1).
In a second aspect the present invention provides a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of: 1) the catalyst component provided by the invention; 2) an alkyl aluminum compound; and 3) optionally an external electron donor compound.
According to the invention, the alkyl aluminium compound may be used in amounts conventional in the art. Preferably, the alkyl aluminium compound is calculated as aluminium, the catalyst component is calculated as titanium, and the molar ratio of the alkyl aluminium compound to the catalyst component is (5-5000): 1; preferably, the molar ratio of the alkylaluminum compound to the catalyst component is (20-1000): 1. more preferably, the molar ratio of the alkylaluminum compound to the catalyst component is (50-500): 1.
in the present invention, the aluminum alkyl compound may be any of various aluminum alkyl compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst of a Ziegler-Natta type catalyst. Preferably, the alkyl aluminum compound may be a compound represented by formula (V),
AlR'n'X'3-n' (V)，
in the formula (V), R' is hydrogen or C1-C20Alkyl or C6-C20X 'is halogen and n' is an integer of 1 to 3. Preferably, specific examples of the alkyl aluminum compound may be, for example, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride.
In the catalyst system for polyolefin according to the present invention, the kind and content of the external electron donor compound are not particularly limited. Preferably, the molar ratio of the alkylaluminum compound to the external electron donor compound, calculated as aluminum, is (0.1-500):1, preferably (1-300):1, more preferably (3-100): 1.
According to the present invention, the external electron donor compound may be various external electron donor compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst of a ziegler-natta type catalyst. Preferably, the external electron donor compound may be an organosilicon compound represented by formula (IV),
R1” m”R2” n”Si(OR3”)4-m”-n” (VI)，
in the formula (VI), R1”And R2”Can be the same or different and are independently selected from halogen, hydrogen atom, C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20One of the haloalkyl groups of (a); r3”Is C1-C20Alkyl of (C)3-C20Cycloalkyl of, C6-C20Aryl and C1-C20Halogenated alkyl group ofOne of (1); m 'and n' are each an integer of 0 to 3, and m "+ n"<4. Specific examples of the external electron donor compound include trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutylbutyldimethoxysilane, t-butylisobutyldimethoxysilane, t-butyl (sec-butyl) dimethoxysilane, t-butylpentyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldimethoxysilane, di-t-butylphenoxysilane, di-t-butylphenoxydimethoxysilane, di-t-butyl, T-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butyldecyldimethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylt-butyldimethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentylpt-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenylditrimethoxysilaneAt least one of methoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane. More preferably, the external electron donor compound may be at least one of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-t-butyldimethoxysilane, and tetramethoxysilane.
A third aspect of the present invention provides an olefin polymerisation process comprising: contacting one or more olefins, at least one of which is represented by the general formula CH, with the catalyst system provided by the present invention under olefin polymerization conditions2Olefins represented by ═ CHR, where R is hydrogen or C1-C12Is preferably C1-C6Alkyl group of (1).
The olefin polymerization method provided by the invention can be used for homopolymerization of olefins and copolymerization of a plurality of olefins. Specific examples of the olefin may include: at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene. Preferably, the olefin may be at least one of ethylene, propylene, 1-n-butene, 4-methyl-1-pentene, and 1-n-hexene. More preferably, the olefin is propylene.
According to the present invention, the catalyst component is applied in the preparation of polyolefin, and the components of the catalyst system for preparing polyolefin, i.e. the catalyst component provided by the present invention, the organoaluminum compound as a cocatalyst and the compound as an external electron donor, can be contacted prior to contacting olefin monomers, which is referred to in the industry as "precontacting" or "preconplexing"; it is also possible to add the three components separately to the olefin monomer and then carry out the polymerization, i.e.without "precontacting". In accordance with the olefin polymerization process provided by the present invention, it is preferred that the components of the olefin polymerization catalyst system be "precontacted". The "precontacting" time is 0.1 to 30min, preferably 1 to 10 min; the temperature of the "precontacting" is from-20 ℃ to 80 ℃, preferably from 10 to 50 ℃.
And polymerizing the catalyst system to a certain extent in the presence of a small amount of olefin monomer to obtain a prepolymerized catalyst, and further contacting the prepolymerized catalyst with the olefin monomer to react to obtain the olefin polymer. This technique, known in the industry as a "prepolymerization" process, contributes to, among other things, increasing the polymerization activity of the catalyst and increasing the bulk density of the polymer. According to the olefin polymerization method provided by the invention, a prepolymerization process can be adopted, a prepolymerization process can also be not adopted, and a prepolymerization process is preferably adopted. The rate of "prepolymerization" is 5 to 1000g PP/g Cat when the olefin monomer is propylene, preferably 10 to 500g PP/g Cat; the temperature of the "prepolymerization" is from-20 ℃ to 80 ℃ and preferably from 10 to 50 ℃.
According to the polymerization method for preparing polyolefin of the present invention, the polymerization conditions may be conventional in the art. The amount of catalyst used may be any of the various catalysts known in the art.
The catalyst system provided by the invention has high activity, good stereospecificity and hydrogen regulation performance when used for olefin polymerization.
Detailed Description
The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the invention.
The test method comprises the following steps:
1. the yield (%) of the catalyst component was (mass of the obtained catalyst/mass of magnesium chloride used) × 100%;
2. titanium content in catalyst component: measuring with 721 spectrophotometer;
3. particle size distribution of the solids of the catalyst component: measuring by a Malvern 2000 laser particle size analyzer according to a normal hexane dispersing agent laser diffraction method;
4. the purity of the internal electron donor is determined by Gas Chromatography (GC);
5. polymer Melt Index (MI): measured according to GB/T3682-2000;
6. propylene polymer Isotacticity Index (II): determination by heptane extraction: 2g of dried polymer sample is put in an extractor and extracted by boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer to 2(g) of the residue is dried to constant weight, namely the isotacticity;
7. polymer molecular weight distribution MWD (MWD ═ Mw/Mn): measured at 150 ℃ using PL-GPC220 and trichlorobenzene as a solvent (standard: polystyrene, flow rate: 1.0mL/min, column: 3X Plgel10um MlxED-B300X 7.5 nm).
8. And (3) activity calculation: catalyst activity (mass of polyolefin prepared)/(mass of solid catalyst component) g/g
9. And (3) measuring the bulk density: the polymer powder obtained in the preparation was allowed to freely fall from a height of 10cm in a funnel into a 100mL container, and the weight of the polymer powder in the container was weighed to M g, whereby the bulk density of the polymer was M/100g/cm3。
Example (b):
firstly, synthesizing an electron donor compound:
a compound A: 2-methyl-2-n-propyl-1, 3-diisopropyl dicarbonate
482.4g of isopropyl chloride was added to a mixed solvent of 300mL of tetrahydrofuran and 400mL of chloroform, and placed in a 2000mL round bottom flask, as solution one. 217.1g of 2-methyl-2-propyl-1, 3-propanediol and 8.0g of 4, 4-dimethylaminopyridine are added to 298.4g of anhydrous pyridine and 200mL of tetrahydrofuran, and the mixture is dropped into the first solution, and the temperature is kept stable at about 5-10 ℃ during the dropping process. After the dropwise addition, the temperature was raised to 40 ℃ and stirred for 4 hours. The reaction was continued at reflux for 8 hours. After the reaction, the solid precipitate and the solvent were removed, 400mL of water was added to the remaining mixture, the pH was adjusted to about 2 with 10% hydrochloric acid, the mixture was separated, the organic phase was washed with a saturated ammonium chloride solution to pH 5 to 6, the organic phase was separated, the solvent was removed by rotation after drying to obtain a crude product. The final product 371.5g was obtained by rectification under reduced pressure, yield 74.3%, purity 98.1% (GC).
Compound B: 2-methyl-2-n-propyl-1, 3-diisobutyl dicarbonate
Using a synthesis analogous to that for Compound A, the conversion of isopropyl chloroformate to isobutyl chloroformate gave 346.1g of 2-methyl-2-n-propyl-1, 3-diisobutyldiocarbonate in 71.6% yield and 98.0% purity (GC).
Compound C: 2-methyl-2-n-propyl-1, 3-di-n-pentyl dicarbonate
Using a synthesis analogous to that of compound a, the conversion of isopropyl chloroformate to n-pentyl chloroformate gave 421.0g of 2-methyl-2-n-propyl-1, 3-di-n-pentyl dicarbonate in 73.8% yield and 98.6% purity (GC).
Preparation of solid catalyst component
Process for preparing solid catalyst component
(1) Preparation of dialkoxy magnesium support
After a 16L pressure-resistant reactor equipped with a stirrer was sufficiently replaced with nitrogen, 10000mL of ethanol, 300mL of 2-ethylhexanol, and 200mL of isopropanol were added to the reactor, and 12g of iodine and 8g of magnesium chloride were added to dissolve them. And after stirring, heating until the reflux temperature of the reaction system is reached. Then 640g of magnesium powder was added in succession. The reaction was allowed to proceed to completion, i.e., no more hydrogen was vented. Then washing, separating and drying are carried out. The dialkoxy magnesium carrier is obtained.
(2) Preparation of the catalyst component
Firstly, the internal electron donor compounds shown in the general formulas (I) and (II) are prepared into a mixture with 3.0g of each part according to different dosage, and the total amount is 9 parts (the specific types and dosage proportions are shown in the table 1), which is marked as 'compound internal electron donor 1-9', and one part is used in each example.
Table 1. kinds and dosage ratios of compound internal electron donors:
aLYEM is 2-isopropyl-2-isoamyl-1, 3-dimethyl ether
Example 1:
10g of the dialkoxy magnesium carrier, 50mL of toluene and 0.8g of compound internal electron donor 1 are respectively taken to prepare suspension. Adding 40mL of toluene and 60mL of titanium tetrachloride into a 300mL reaction kettle repeatedly replaced by high-purity nitrogen, heating to 65 ℃, then slowly adding the prepared suspension into the kettle, keeping the temperature of 65 ℃ for 1 hour, slowly heating to 110 ℃, adding 2.2g of compound internal electron donor 1 when the temperature is raised to 80 ℃, keeping the temperature of 110 ℃ for 1 hour, and performing filter pressing to obtain a solid. The resulting solid was washed twice with 150mL of toluene and the liquid removed by pressure filtration. A mixture of 90mL of toluene and 60mL of titanium tetrachloride was added and the mixture was stirred at 110 ℃ for 1 hour, and the mixture was treated 2 times. And (3) performing filter pressing, washing the obtained solid once by using toluene, washing 4 times by using hexane, filtering by pressing and drying 150mL each time to obtain the catalyst solid component.
Examples 2 to 9:
the internal electron donors are respectively replaced by compound internal electron donors 2-9, and other steps are the same as the step 1 to prepare the catalyst solid component.
Comparative example 1:
3.0g of 2-isopropyl-2-isoamyl-1, 3-dimethyl ether (LYEM) was used as an internal electron donor, and the other steps were the same as in example 1 to prepare a solid catalyst component.
Polymerization of propylene
In a 5L autoclave, after sufficient replacement with vapor phase propylene, 5mL of a hexane solution of triethylaluminum (concentration of triethylaluminum: 0.5mmol/mL), lmL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration of CHMMS: 0.10mmol/mL), 10mL of anhydrous hexane, and 10mg of the solid catalyst component were added at room temperature. The autoclave was closed and 4.5 normal liters of hydrogen and 2 liters of liquid propylene were introduced; the temperature was raised to 70 ℃ over 10 minutes with stirring. After polymerization at 70 ℃ for 1 hour, the stirring was stopped, the unpolymerized propylene monomer was removed, and the polymer was collected.
TABLE 2 Performance of the catalyst
As can be seen from the data in Table 2, the catalyst obtained by compounding the 2,2' -dialkyl-1, 3-dicarbonate compound and 2-isopropyl-2-isoamyl-1, 3-dimethyl ether as an internal electron donor maintains higher bulk density and stereotacticity, the molecular weight distribution of the obtained polymer is improved compared with that of the catalyst obtained by singly using 2-isopropyl-2-isoamyl-1, 3-dimethyl ether, and the polymerization activity of the catalyst can be improved by compounding the two electron donors in most proportion, so the catalyst is more suitable for the development of polypropylene resin.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (21)
1. A catalyst component for olefin polymerization comprises titanium, magnesium, halogen and an internal electron donor, wherein the internal electron donor comprises a 2,2 '-dialkyl-1, 3-dicarbonate compound shown in a formula (I) and a 2,2' -dialkyl-1, 3-diether compound shown in a formula (II),
wherein, in the formula (I), R1And R2Identical or different, independently selected from hydrogen and C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl and C6-C20Aryl of (a); r3And R4Identical or different, independently selected from C1-C20Straight chain alkyl of (2) and C3-C20A branched alkyl group of (a);
in the formula (II), R5And R6Identical or different, independently selected from hydrogen and C1-C20Straight chain alkyl of (2) and C3-C20A branched alkyl group of (a); r7And R8Identical or different, independently selected from C1-C10Straight chain alkyl of (2) and C3-C10A branched alkyl group of (a);
the mol ratio of the 2,2 '-dialkyl-1, 3-dicarbonate compound shown in the formula (I) to the 2,2' -dialkyl-1, 3-diether compound shown in the formula (II) is 0.1:1-1: 0.1.
2. The catalyst component according to claim 1, wherein R is1And R2Independently selected from hydrogen, C1-C10Straight chain alkyl group of (1), C3-C10Branched alkyl and C6-C10Aryl group of (1).
3. The catalyst component according to claim 2 in which R is1And R2Are each independently C1-C6Straight chain alkyl or C3-C6Branched alkyl groups of (a).
4. The catalyst component according to claim 2 in which R is1And R2Independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 1 ' -dimethylbutyl, 2' -dimethylbutyl, and 3,3 ' -dimethylbutyl.
5. The catalyst component according to claim 1, wherein R is3And R4Is independently selected from C1-C10Linear alkane of (1) and C3-C10Branched alkyl groups of (a).
6. The catalyst component according to claim 1, wherein R is3And R4Is independently selected from C1-C6Linear alkane of (1) and C3-C6Branched alkyl groups of (a).
7. The catalyst component according to claim 1, wherein R is3And R4Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl1-methylpropyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1, 4-dimethylbutyl, 1 ' -dimethylbutyl, 2' -dimethylbutyl and 3,3 ' -dimethylbutyl.
8. The catalyst component according to claim 1, wherein R is5And R6Independently selected from hydrogen, C1-C10Straight chain alkyl of (2) and C3-C10Branched alkyl groups of (a).
9. The catalyst component according to claim 1, wherein R is5And R6Is independently selected from C1-C10Straight chain alkyl or C3-C10Branched alkyl groups of (a).
10. The catalyst component according to claim 1, wherein R is5And R6Independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, and tert-pentyl.
11. The catalyst component according to claim 1, wherein R is7And R8Is independently selected from C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a).
12. The catalyst component according to claim 1, wherein R is7And R8Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
13. The catalyst component according to claim 1, wherein the 2,2' -dialkyl-1, 3-dicarbonate compound of formula (I) is selected from one or more of the following compounds: 2-isopropyl-2-isoamyl-1, 3-dimethyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diethyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-propyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisopropyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-butyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisobutyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-pentyl dicarbonate, 3-diisoamyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisohexyl dicarbonate; 2-methyl-2-n-propyl-1, 3-dimethyldicarbonate, 2-methyl-2-n-propyl-1, 3-diethyldicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-propyldicarbonate, 2-methyl-2-n-propyl-1, 3-diisopropyldicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-butyldicarbonate, 2-methyl-2-n-propyl-1, 3-diisobutyldicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-n-propyl-1, 3-diisoamyl dicarbonate, 2-methyl-2-n-propyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-n-propyl-1, 3-diisohexyl dicarbonate, 2-methyl-2-n-butyl-1, 3-dimethyl dicarbonate, 2-methyl-2-n-butyl-1, 3-diethyl dicarbonate, 2-methyl-2-n-butyl-1, 3-di-n-propyl dicarbonate, 2-methyl-2-n-butyl-1, 3-diisopropyl dicarbonate, 2-methyl-2-n-butyl-1, 3-di-n-butyl dicarbonate, 2-methyl-2-n-butyl-1, 3-diisobutyldiocarbonate, 2-methyl-2-n-butyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-n-butyl-1, 3-diisopentyldicarbonate, 2-methyl-2-n-butyl-1, 3-di-n-hexyldicarbonate, 2-methyl-2-n-butyl-1, 3-diisohexyldicarbonate; 2-methyl-2-isobutyl-1, 3-dimethyldicarbonate, 2-methyl-2-isobutyl-1, 3-diethyldicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-propyldicarbonate, 2-methyl-2-isobutyl-1, 3-diisopropyldicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-butyldicarbonate, 2-methyl-2-isobutyl-1, 3-diisobutyldicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-isobutyl-1, 3-diisoamyl dicarbonate, 2-methyl-2-isobutyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-isobutyl-1, 3-diisohexyl dicarbonate; 2-methyl-2-n-pentyl-1, 3-dimethyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diethyldicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-propyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diisopropyldicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-butyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diisobutyldicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-pentyldicarbonate, 2-methyl-2-n-pentyl-1, 3-diisoamyl dicarbonate, 2-methyl-2-n-pentyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-n-pentyl-1, 3-diisohexyl dicarbonate, 2-methyl-2-isoamyl-1, 3-dimethyl dicarbonate, 2-methyl-2-isoamyl-1, 3-diethyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-propyl dicarbonate, 2-methyl-2-isoamyl-1, 3-diisopropyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-butyl dicarbonate, 2-methyl-2-isoamyl-1, 3-diisobutyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-pentyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-isoamyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-n-hexyl dicarbonate, 2-methyl-2-isoamyl-1, 3-di-isohexyl dicarbonate; 2-isopropyl-2-n-propyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diethyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisobutyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-pentyldicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisoamyl dicarbonate, 2-isopropyl-2-n-propyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-n-propyl-1, 3-diisohexyl dicarbonate; 2-isopropyl-2-n-butyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diethyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisobutyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-pentyldicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisoamyl dicarbonate, 2-isopropyl-2-n-butyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-n-butyl-1, 3-diisohexyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-dimethyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diethyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-propyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diisopropyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-butyl dicarbonate, 3-diisobutyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-pentyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diisopentyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-isobutyl-1, 3-diisohexyl dicarbonate; 2-isopropyl-2-n-pentyl-1, 3-dimethyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diethyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-propyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisopropyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-butyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisobutyldicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-pentyl-dicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisoamyl dicarbonate, 2-isopropyl-2-n-pentyl-1, 3-di-n-hexyl dicarbonate, 2-isopropyl-2-n-pentyl-1, 3-diisohexyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-dimethyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diethyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-propyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisopropyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-butyl dicarbonate, 3-diisobutyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-pentyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-diisopentyl dicarbonate, 2-isopropyl-2-isoamyl-1, 3-di-n-hexyl dicarbonate and 2-isopropyl-2-isoamyl-1, 3-diisohexyl dicarbonate.
14. The catalyst component according to claim 1, wherein the 2,2 '-dialkyl-1, 3-diether compound represented by the formula (II) is selected from the group consisting of 2,2' -dimethyl-1, 3-dimethyl ether, 2 '-diethyl-1, 3-dimethyl ether, 2' -di-n-propyl-1, 3-dimethyl ether, 2 '-diisopropyl-1, 3-dimethyl ether, 2' -di-n-butyl-1, 3-dimethyl ether, 2 '-diisobutyl-1, 3-dimethyl ether, 2' -ditert-butyl-1, 3-dimethyl ether, 2 '-di-n-pentyl-1, 3-dimethyl ether, 2' -diisopentyl-1, 3-dimethyl ether, 2,2' -di (1-methyl) butyl-1, 3-dimethyl ether, 2,2' -di (2-methyl) butyl-1, 3-dimethyl ether, 2,2' -di (1-ethyl) propyl-1, 3-dimethyl ether, 2,2' -di-tert-pentyl-1, 3-dimethyl ether, 2,2' -di-n-hexyl-1, 3-dimethyl ether, 2,2' -di-isohexyl-1, 3-diether, 2,2' -di (1-methyl) pentyl-1, 3-dimethyl ether, 2,2' -di (2-methyl) pentyl-1, 3-dimethyl ether, 2,2' -di (3-methyl) pentyl-1, 3-dimethyl ether, 2' -di (1-ethyl) butyl-1, 3-dimethyl ether, 2' -di (2-ethyl) butyl-1, 3-dimethyl ether, 2' -di-tert-hexyl-1, 3-dimethyl ether, 2-methyl-2-ethyl-1, 3-dimethyl ether, 2-methyl-2-n-propyl-1, 3-dimethyl ether, 2-methyl-2-isopropyl-1, 3-dimethyl ether, 2-methyl-2-n-butyl-1, 3-dimethyl ether, 2-methyl-2-isobutyl-1, 3-dimethyl ether, 2-methyl-2-n-pentyl-1, 3-dimethyl ether, 2-methyl-2-isoamyl-1, 3-dimethyl ether, 2-methyl-2-n-hexyl-1, 3-dimethyl ether, 2-methyl-2-isohexyl-1, 3-dimethyl ether, 2-ethyl-2-n-propyl-1, 3-dimethyl ether, 2-ethyl-2-isopropyl-1, 3-dimethyl ether, 2-ethyl-2-n-butyl-1, 3-dimethyl ether, 2-ethyl-2-isobutyl-1, 3-dimethyl ether, 2-ethyl-2-n-pentyl-1, 3-dimethyl ether, 2-ethyl-2-isoamyl-1, 3-dimethyl ether, 2-ethyl-2-n-hexyl-1, 3-dimethyl ether, 2-ethyl-2-isohexyl-1, 3-dimethyl ether, 2-n-propyl-2-isopropyl-1, 3-dimethyl ether, 2-n-propyl-2-n-butyl-1, 3-dimethyl ether, 2-n-propyl-2-isobutyl-1, 3-dimethyl ether, 2-n-propyl-2-n-pentyl-1, 3-dimethyl ether, 2-n-propyl-2-isopentyl-1, 3-dimethyl ether, 2-n-propyl-2-n-hexyl-1, 3-dimethyl ether, 2-n-propyl-2-isohexyl-1, 3-dimethyl ether, 2-isopropyl-2-n-butyl-1, 3-dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethyl ether, 2-isopropyl-2-n-pentyl-1, 3-dimethyl ether, 2-isopropyl-2-isopentyl-1, 3-dimethyl ether, 2-isopropyl-2-n-hexyl-1, 3-dimethyl ether, 2-isopropyl-2-isohexyl-1, 3-dimethyl ether, 2-n-butyl-2-isobutyl-1, 3-dimethyl ether, 2-n-butyl-2-n-pentyl-1, 3-dimethyl ether, 2-n-butyl-2-isopentyl-1, 3-dimethyl ether, 2-n-butyl-2-n-hexyl-1, 3-dimethyl ether, 2-n-butyl-2-isohexyl-1, 3-dimethyl ether, 2-isobutyl-2-n-pentyl-1, 3-dimethyl ether, 2-isobutyl-2-isopentyl-1, 3-dimethyl ether, 2-isobutyl-2-n-hexyl-1, 3-dimethyl ether, 2-isobutyl-2-isohexyl-1, 3-dimethyl ether, 2-n-pentyl-2-isopentyl-1, 3-dimethyl ether, 2-n-pentyl-2-n-hexyl-1, 3-dimethyl ether, 2-n-pentyl-2-isohexyl-1, at least one of 3-dimethyl ether, 2-isoamyl-2-n-hexyl-1, 3-dimethyl ether, 2-isoamyl-2-isohexyl-1, 3-dimethyl ether and 2-n-hexyl-2-isohexyl-1, 3-dimethyl ether.
15. The catalyst component according to claim 1, characterized in that the content of titanium is 1.0-8.0 wt. -%, based on the total mass of the catalyst component; the content of magnesium is 10-70 wt%; the content of halogen is 20-90 wt%; the content of the internal electron donor is 2-30 wt%.
16. The catalyst component according to claim 1, characterized in that the content of titanium is 1.6-6.0 wt. -%, based on the total mass of the catalyst component; the content of magnesium is 15-40 wt%; the content of halogen is 30-85 wt%; the content of the internal electron donor is 3-20 wt%.
17. The catalyst component according to claim 1, wherein the molar ratio of the 2,2 '-dialkyl-1, 3-dicarbonate compound of formula (I) to the 2,2' -dialkyl-1, 3-diether compound of formula (II) is from 0.2:1 to 1: 0.2.
18. The catalyst component according to claim 1, wherein the molar ratio of the 2,2 '-dialkyl-1, 3-dicarbonate compound of formula (I) to the 2,2' -dialkyl-1, 3-diether compound of formula (II) is from 0.3:1 to 1: 0.3.
19. A catalyst system for olefin polymerization comprising the reaction product of:
1) the catalyst component of any one of claims 1-18;
2) an alkyl aluminum compound; and
optionally, 3) an external electron donor compound.
20. An olefin polymerization process, comprising: contacting one or more olefins, at least one of which is of the formula CH, with the catalyst system of claim 19 under olefin polymerization conditions2Olefins represented by ═ CHR, where R is hydrogen or C1-C12A hydrocarbon group of (1).
21. The method of claim 20, wherein R is C1-C6Alkyl group of (1).
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| CN102712704A (en) * | 2009-12-02 | 2012-10-03 | 陶氏环球技术有限责任公司 | Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture |
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| CN102712704A (en) * | 2009-12-02 | 2012-10-03 | 陶氏环球技术有限责任公司 | Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture |
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