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CN113773424A - Catalyst component for olefin polymerization and application - Google Patents

Catalyst component for olefin polymerization and application Download PDF

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Publication number
CN113773424A
CN113773424A CN202010517954.5A CN202010517954A CN113773424A CN 113773424 A CN113773424 A CN 113773424A CN 202010517954 A CN202010517954 A CN 202010517954A CN 113773424 A CN113773424 A CN 113773424A
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Prior art keywords
phosphate
dimethoxypropane
methyl
tolyl
butyl
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Inventor
李昌秀
宋建会
冯华升
高明智
周俊领
刘海涛
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention discloses a catalyst component for olefin polymerization reaction, which comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor comprises a first internal electron donor compound with a general formula (I) and a second internal electron donor compound with a general formula (II). The invention also discloses a catalyst for olefin polymerization. The catalyst provided by the invention can obtain polymers with high isotactic index and wide molecular weight distribution while keeping high polymerization activity and hydrogen regulation sensitivity of the catalyst, and the polymers have excellent comprehensive performance, which is very beneficial to the development of different grades of resins.

Description

Catalyst component for olefin polymerization and application
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a catalyst component for olefin polymerization reaction, a catalyst system containing the catalyst component and application.
Background
Polyolefins are a class of polymers derived from simple olefins. Known processes for preparing polyolefins involve the use of Ziegler-Natta polymerization catalysts. The catalyst can be used for CH as solid titanium catalyst component containing magnesium, titanium, halogen and electron donor as essential components2The CHR olefin polymerization reaction has higher polymerization activity and stereospecificity particularly in propylene polymerization. Wherein, the electron donor compound is one of the essential components in the catalyst component, and plays a decisive role in important indexes such as polymerization activity, isotactic index molecular weight of polymer, molecular weight distribution and the like. With the development of internal electron donor compounds, polyolefin catalysts are continuously updated.
At present, a large number of non-phthalate electron donor compounds have been disclosed, such as mono-or poly-carboxylic acid esters, anhydrides, ketones, ethers, glycol esters, amines, etc. and derivatives thereof, see patents CN1042547A, CN1143651A, CN1054139A, WO98/56830, WO98/56834, WO01/57099, WO01/63231, and WO00/55215, etc.
Patent CN1041752A discloses a class of 1, 3-diether internal electron donor compounds for preparing Ziegler-Natta catalysts, and the obtained catalyst component has high catalytic activity and good hydrogen response 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. Patent CN201610565348.4 reports that when a phosphate compound and a diether compound are compounded for propylene polymerization, the catalyst has good hydrogen regulation sensitivity, but has relatively low stereoregularity and relatively narrow molecular weight distribution.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst component for olefin polymerization reaction aiming at the defects of the prior art, and the catalyst with excellent comprehensive performance can be obtained by using the diaryl alkoxy phosphate compound shown in the formula (I) and the 1, 3-diether compound to be compounded as an internal electron donor. When the catalyst is used for propylene polymerization reaction, the catalyst has high activity, good hydrogen regulation sensitivity and stereospecificity, and wide polymer molecular weight distribution, and is beneficial to the development of polymer grades.
To this end, a first aspect of the present invention provides a catalyst component for olefin polymerization comprising magnesium, titanium, halogen and an internal electron donor compound comprising a first internal electron donor compound of formula (I) and a second internal electron donor compound of formula (II),
Figure BDA0002530832520000021
in the general formula (I), R1Is C1-C15Straight chain alkyl group of (1), C3-C15Branched alkyl of C3-C15Cycloalkyl or C7-C20And said C is aralkyl, and1-C15straight chain alkyl group of (1), C3-C15Branched alkyl of C3-C15Cycloalkyl and C7-C20The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent;
R2selected from hydrogen, halogen atoms, C1-C10Straight chain alkyl of (2) and C3-C10And said C is a branched alkyl group of1-C10Straight chain alkyl of (2) and C3-C10The hydrogen on the branched alkyl carbon of (a) is optionally substituted with a substituent;
in the general formula (II), R3And R4Identical or different, independently selected from C1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C3-C15A branched hydrocarbon group of3-C15A cycloalkyl group of6-C20Aryl of (C)7-C20And C is a hydrocarbon aryl group7-C20And said C is an aromatic hydrocarbon group1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C3-C15A branched hydrocarbon group of3-C15A cycloalkyl group of6-C20Aryl of (C)7-C20And C is a hydrocarbon aryl group7-C20The hydrogen on the arylcarbon of (a) is optionally substituted with one or more substituents, R3And R4Optionally, they may be bonded to form a ring or not.
According to a preferred embodiment of the catalyst component according to the present invention, the substituents are selected from hydroxyl, amino, C1-C6Alkyl-substituted amino (e.g. -NHCH)3or-N (CH)3)2) CHO, -COOH, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), C1-C6Alkyl (e.g. methyl, ethyl or isopropyl) and C1-C6Alkoxy (e.g., methoxy, ethoxy, n-propoxy, or isopropoxy).
In the present invention, the term "branched alkyl group" is a branched alkyl group, a branched alkenyl group or a branched alkynyl group, "cyclic alkyl group" is a cycloalkyl group, a cycloalkenyl group or a cyclic alkynyl group, "hydrocarbon aryl group" is an alkylaryl group, an alkenylaryl group or an alkynylaryl group, and "aromatic alkyl group" is an arylalkyl group, an arylalkenyl group or an arylalkynyl group.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R1Is C1-C12Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C12Cycloalkyl or C7-C15And said C is an aralkyl group1-C12Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C12Cycloalkyl and C7-C15The hydrogen on the aralkyl carbon of (a) may be optionally substituted by one or more substituentsAnd (4) generation.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R1Is C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C9Straight chain alkyl group of (1), C10-C12Straight chain alkyl group of (1), C3-C4Branched alkyl of C5-C7Branched alkyl of C8-C10Branched alkyl of C7-C9Aralkyl of (2), C10-C12Aralkyl or C13-C15An aralkyl group of (2).
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenethyl or phenylpropyl.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R2Is hydrogen, halogen atom, C1-C8Straight chain alkyl or C3-C10And said C is a branched alkyl group of1-C8Straight chain alkyl of (2) and C3-C10The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R2Is hydrogen, C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C8Straight chain alkyl group of (1), C3-C5Branched alkyl of C6-C8Branched alkyl or C9-C10Branched alkyl groups of (a).
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R2Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
According to a preferred embodiment of the catalyst component of the invention, of the general formulaIn (II), R3And R4Identical or different, independently selected from C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl and C of7-C15Aralkyl, and said C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl and C of7-C15The hydrogens on the arylalkyl carbon may be optionally substituted with one or more substituents, R3And R4Optionally, they may be bonded to form a ring or not.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3And R4The same is true.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3And R4Are not identical.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3Is selected from C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C8Straight chain alkyl group of (1), C3-C5Branched alkyl of C6-C8Branched alkyl of C9-C10Branched alkyl of C6-C8Aryl of (C)9-C11Aryl and C12-C15Aryl groups of (2) such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and phenyl.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R4Is selected from C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C8Straight chain alkyl group of (1), C3-C5Branched alkyl group of、C6-C8Branched alkyl of C9-C10Branched alkyl of C6-C8Aryl of (C)9-C11Aryl and C12-C15Aryl groups of (2) such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and phenyl.
According to a preferred embodiment of the catalyst component of the present invention, the solid catalyst component comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound.
According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1 (0.5-150) to (0.02-0.4).
According to a preferred embodiment of the catalyst component of the present invention, the reaction product is prepared by a process comprising dissolving a magnesium compound in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform mixed solution and mixing with a titanium compound.
According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of the first internal electron donor compound and the second internal electron donor compound is (1-100): 100-1, preferably (1-50): 50-1, and more preferably (1-20): 20-1.
According to a preferred embodiment of the catalyst component of the present invention, the magnesium compound comprises one or more selected from the group consisting of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides in which one of the halogen atoms of the molecular formula has been replaced by an alkoxy group or a haloalkoxy group, preferably magnesium dihalides and/or alcoholates, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
According to a preferred embodiment of the catalyst component according to the invention, the titanium compound comprises a compound chosen from TiXm(OR1)4-mOne or more of the compounds, R1Is C1-C20X is halogen, and m is more than or equal to 1 and less than or equal to 4.
According to the inventionIn some embodiments, R1Is C1-C20Alkyl of (3), preferably C1-C10Alkyl, more preferably C1-C6An alkyl group.
According to some embodiments of the invention, X is selected from fluorine, chlorine, bromine and iodine.
According to a preferred embodiment of the catalyst component of the present invention, the titanium compound preferably comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium, more preferably titanium tetrachloride.
In a second aspect the present invention provides a catalyst system for the polymerisation of olefins comprising the reaction product of:
component a, the catalyst component according to the first aspect of the present invention;
component b, an alkyl aluminum compound; and
optionally component c, an external electron donor compound.
According to a preferred embodiment of the present invention, the external electron donor compound comprises a compound represented by the general formula (III):
R2 kSi(OR3)4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r2Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r3Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
According to a preferred embodiment of the invention, R2Is C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C20Aryl of (C)1-C10A haloalkyl group, an amino group, a halogen atom or a hydrogen atom.
According to a preferred embodiment of the invention, R3Is C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C20Aryl of (C)1-C10A haloalkyl or amino group.
According to a preferred embodiment of the present invention, the molar ratio of component a, component b and component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).
In a third aspect, the present invention provides a prepolymerized catalyst for olefin polymerization, comprising a prepolymer obtained by prepolymerizing an olefin with the catalyst component according to the first aspect of the present invention and/or the catalyst system according to the second aspect of the present invention, wherein the prepolymer has a prepolymerization ratio of 0.1 to 1000g of an olefin polymer per g of the catalyst component. The olefin may be of the formula CH2Wherein R is hydrogen or C1-C6Alkyl group of (1). The olefin is preferably ethylene, propylene and/or 1-butene.
In a fourth aspect, the present invention provides a process for the polymerisation of olefins having the general formula CH and polymerized in the presence of a catalyst component according to the first aspect of the present invention and/or a catalyst system according to the second aspect of the present invention and/or a prepolymerised catalyst according to the third aspect of the present invention2Wherein R is hydrogen or C1-C6Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
The catalyst component for olefin polymerization provided by the invention has the following advantages:
(1) by using an alkoxy diaryl phosphate compound with a special structure and a 1, 3-diether compound to be compounded as an internal electron donor, the prepared catalyst has high activity and good hydrogen regulation sensitivity;
(2) when the catalyst is used for propylene polymerization, the obtained polypropylene resin has good stereoregularity, especially the polymer has wider molecular weight distribution, and the comprehensive performance of the catalyst is excellent.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
As mentioned above, the existing olefin polymerization catalysts are to be improved in all aspects, and because compounds with extremely strong corrosiveness and instability are used in the synthesis process, the catalysts are not beneficial to environmental protection and safety. At present, the catalyst component for olefin polymerization with high activity, good stereospecificity, good hydrogen regulation sensitivity, wide molecular weight distribution of the obtained polymer and other excellent comprehensive properties needs to be researched and developed.
The first aspect of the present invention provides a catalyst component for olefin polymerization comprising magnesium, titanium, halogen and an internal electron donor compound, the internal electron donor compound comprising a first internal electron donor compound of formula (I) and a second internal electron donor compound of formula (II):
Figure BDA0002530832520000061
in the general formula (I), R1Is C1-C15Straight chain alkyl group of (1), C3-C15Branched alkyl of C3-C15Cycloalkyl or C7-C20And said C is aralkyl, and1-C15straight chain alkyl group of (1), C3-C15Branched alkyl of C3-C15Cycloalkyl and C7-C20The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent;
R2selected from hydrogen, halogen atoms, C1-C10Straight chain alkyl of (2) and C3-C10And said C is a branched alkyl group of1-C10Straight chain alkyl of (2) and C3-C10The hydrogen on the branched alkyl carbon of (a) is optionally substituted with a substituent;
in the general formula (II), R3And R4Identical or different, independently selected from C1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C3-C15A branched hydrocarbon group of3-C15A cycloalkyl group of6-C20Aryl of (C)7-C20And C is a hydrocarbon aryl group7-C20An aromatic hydrocarbon group of, andc of (A)1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C3-C15A branched hydrocarbon group of3-C15A cycloalkyl group of6-C20Aryl of (C)7-C20And C is a hydrocarbon aryl group7-C20The hydrogen on the arylcarbon of (a) is optionally substituted with one or more substituents, R3And R4Optionally, they may be bonded to form a ring or not.
According to a preferred embodiment of the catalyst component according to the present invention, the substituents are selected from hydroxyl, amino, C1-C6Alkyl-substituted amino (e.g. -NHCH)3or-N (CH)3)2) CHO, -COOH, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), C1-C6Alkyl (e.g. methyl, ethyl or isopropyl) and C1-C6Alkoxy (e.g., methoxy, ethoxy, n-propoxy, or isopropoxy).
In the present invention, the term "branched alkyl group" is a branched alkyl group, a branched alkenyl group or a branched alkynyl group, "cyclic alkyl group" is a cycloalkyl group, a cycloalkenyl group or a cyclic alkynyl group, "hydrocarbon aryl group" is an alkylaryl group, an alkenylaryl group or an alkynylaryl group, and "aromatic alkyl group" is an arylalkyl group, an arylalkenyl group or an arylalkynyl group.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R1Is C1-C12Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C12Cycloalkyl or C7-C15And said C is an aralkyl group1-C12Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C12Cycloalkyl and C7-C15The hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R1Is C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C9Straight chain alkyl group of (1), C10-C12Straight chain alkyl group of (1), C3-C4Branched alkyl of C5-C7Branched alkyl of C8-C10Branched alkyl of C7-C9Aralkyl of (2), C10-C12Aralkyl or C13-C15An aralkyl group of (2).
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenethyl or phenylpropyl.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R2Is hydrogen, halogen atom, C1-C8Straight chain alkyl or C3-C10And said C is a branched alkyl group of1-C8Straight chain alkyl of (2) and C3-C10The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R2Is hydrogen, C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C8Straight chain alkyl group of (1), C3-C5Branched alkyl of C6-C8Branched alkyl or C9-C10Branched alkyl groups of (a).
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (I), R2Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
According to the catalyst component of the present invention, the compound of formula (I) is selected from, but not limited to, the following compounds:
diphenylmethyl phosphate, diphenylethyl phosphate, diphenyl-n-propyl phosphate, diphenylisopropyl phosphate, diphenyl-n-butyl phosphate, diphenylisobutyl phosphate, diphenyl-t-butyl phosphate, diphenyl-n-pentyl phosphate, diphenylisoamyl phosphate, diphenylhexyl phosphate, diphenylheptyl phosphate, diphenyloctyl phosphate, diphenylnonyl phosphate, diphenylbenzyl phosphate, di-2-tolyl-methyl phosphate, di-2-tolyl-ethyl phosphate, di-2-tolyl-n-propyl phosphate, di-2-tolyl-isopropyl phosphate, di-2-tolyl-n-butyl phosphate, di-2-tolyl-isobutyl phosphate, di-2-tolyl-t-butyl phosphate, di-2-tolyl-n-pentyl phosphate, di-tert-butyl phosphate, di-2-tolyl phosphate, di-n-pentyl phosphate, di-octyl phosphate, di-hexyl phosphate, di-tert-hexyl phosphate, di-benzyl phosphate, di-butyl phosphate, di-2-tolyl-n-butyl phosphate, di-pentyl phosphate, di-butyl phosphate, di-2-butyl phosphate, di-2-pentyl phosphate, di-butyl phosphate, di-2-butyl phosphate, di-2-benzyl phosphate, di-butyl phosphate, di-2-butyl phosphate, di-butyl phosphate, di (2-tolyl) isoamyl phosphate, di (2-tolyl) hexyl phosphate, di (2-tolyl) heptyl phosphate, di (2-tolyl) octyl phosphate, di (2-tolyl) nonyl phosphate, di (2-tolyl) benzyl phosphate, di (4-tolyl) methyl phosphate, di (4-tolyl) ethyl phosphate, di (4-tolyl) n-propyl phosphate, di (4-tolyl) isopropyl phosphate, di (4-tolyl) n-butyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) t-butyl phosphate, di (4-tolyl) n-pentyl phosphate, di (4-tolyl) isoamyl phosphate, di (4-tolyl) hexyl phosphate, Di (4-tolyl) heptyl phosphate, di (4-tolyl) octyl phosphate, di (4-tolyl) nonyl phosphate, di (4-tolyl) benzyl phosphate, di (4-cumyl) methyl phosphate, di (4-cumyl) ethyl phosphate, di (4-cumyl) n-propyl phosphate, di (4-cumyl) isopropyl phosphate, di (4-cumyl) n-butyl phosphate, di (4-cumyl) isobutyl phosphate, di (4-cumyl) tert-butyl phosphate, di (4-cumyl) n-pentyl phosphate, di (4-cumyl) isopentyl phosphate, di (4-cumyl) hexyl phosphate, di (4-cumyl) heptyl phosphate, di (4-cumyl) octyl phosphate, di (4-tolyl) n-propyl phosphate, di (4-cumyl) isopropyl phosphate, di (4-cumyl) hexyl phosphate, di (4-cumyl) heptyl phosphate, di (4-isopropyl) butyl phosphate, di (4-isopropyl) heptyl phosphate, di (4-isopropyl) butyl phosphate, n-propyl phosphate, n-butyl phosphate, One or more of di (4-cumyl) octyl phosphate, di (4-cumyl) nonyl phosphate, and di (4-cumyl) benzyl phosphate.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3And R4Identical or different, independently selected from C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C3-C10Branched alkyl group of、C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl and C of7-C15Aralkyl, and said C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl and C of7-C15The hydrogens on the arylalkyl carbon may be optionally substituted with one or more substituents, R3And R4Optionally, they may be bonded to form a ring or not.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3And R4Identical or different, independently selected from C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C8Straight chain alkyl group of (1), C3-C5Branched alkyl of C6-C8Branched alkyl of C9-C10Branched alkyl of C6-C8Aryl of (C)9-C11Aryl and C12-C15Aryl of (A), R3And R4Optionally, they may be bonded to form a ring or not.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3And R4The same is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl, R3And R4Optionally, they may be bonded to form a ring or not.
According to a preferred embodiment of the catalyst component of the present invention, in the general formula (II), R3And R4Is not identical, independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and phenyl, R3And R4Optionally, they may be bonded to form a ring or not.
In some embodiments of the present invention, the second internal electron donor compound may be selected from, but is not limited to:
2, 2-dimethyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-di-n-propyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-di-n-butyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-di-n-pentyl-1, 3-dimethoxypropane, 2-diisopentyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-n-propyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-n-butyl-1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2-n-pentyl-1, 3-dimethoxypropane, 2-methyl-2-isopentyl-1, 3-dimethoxypropane, 2-ethyl-2-n-propyl-1, 3-dimethoxypropane, 2-ethyl-2-isopropyl-1, 3-dimethoxypropane, 2-ethyl-2-n-butyl-1, 3-dimethoxypropane, 2-dimethyl-2-isopropyl-1, 3-dimethoxypropane, 2-dimethyl-2-n-butyl-1, 3-dimethoxypropane, methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-2-n-butyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-2-pentyl-1, 3-dimethoxypropane, 2-methyl-2-pentyl-2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-dimethyl-2-dimethyl-methyl-2-methyl-2-dimethyl-propyl-2-dimethyl-methyl-ethyl-2-ethyl-methyl-ethyl-methyl-2-propyl-methyl-2-methyl-2-methyl-2-ethyl-methyl-2-methyl-2-methyl-propyl-1, 3-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-1, 2-methyl-2-methyl-2-methyl, 2-ethyl-2-isobutyl-1, 3-dimethoxypropane, 2-ethyl-2-n-pentyl-1, 3-dimethoxypropane, 2-ethyl-2-isopentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopropyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-butyl-1, 3-dimethoxypropane, 2-n-propyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopentyl-1, 3-dimethoxypropane, 2-ethyl-2-isobutyl-1, 3-dimethoxypropane, 2-pentyl-2-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-propyl-dimethoxypropane, 2-pentyl-dimethoxypropane, 2-propyl-2-isopentyl-dimethoxypropane, 2-propyl-2-pentyl-2, 3-dimethoxypropane, 2-propyl-methyl-2, 2-propyl, 2, or a-pentyl-propyl, or a, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-n-pentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-n-butyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-butyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-butyl-2-isopentyl-1, 3-dimethoxypropane, 2-isobutyl-2-n-pentyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane, and mixtures thereof, 2-isobutyl-2-phenyl-1, 3-dimethoxypropane, 2-isopentyl-2-phenyl-1, 3-dimethoxypropane, 2- (2-methyl-n-butyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2-phenyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-ethyl-2-phenyl-1, 3-dimethoxypropane, 2-isobutyl-2-benzyl-1, 3-dimethoxypropane, 2-isopentyl-2-benzyl-1, 3-dimethoxypropane, 2- (2-methylbutyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-benzyl-1, 3-dimethoxypropane, 2-n-propyl-2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 2-isobutyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, a salt thereof, a base thereof, a stabilizer, a 3-3, a stabilizer, a 3, a stabilizer, a 3-2-, 2-isopentyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2- (2-methylbutyl) -2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-methyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-ethyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-isobutyl-2- (2-methylbutyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-methylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2- (2-methylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2- (2-methylbutyl) -1, 3-dimethoxypropane, 2-isobutyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-bis (2-methylbutyl) -1, 3-dimethoxypropane, 2-dimethylolpropane, 2-ethylbutyl-dimethylolpropane, 2-ethylbutyl-2-dimethylolpropane, 3-dimethylolpropane, 2-dimethylolpropane, 2-1, 3-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethoxypropane, 2-1, 2-dimethoxypropane, 2-dimethylolpropane, 2-1, 2-dimethoxypropane, 2, One or more of 2, 2-bis (2-ethylhexyl) -1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene.
According to a preferred embodiment of the catalyst component of the present invention, the solid catalyst component comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound.
According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1 (0.5-150) to (0.02-0.4).
According to a preferred embodiment of the catalyst component of the present invention, the reaction product is prepared by a process comprising dissolving a magnesium compound in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform mixed solution and mixing with a titanium compound.
The catalyst component for olefin polymerization reaction of the present invention is preferably prepared by reacting a magnesium compound, a titanium compound, and internal electron donor compounds represented by the above general formulas (I) and (II). In particular, the reaction preparation comprises dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, mixing the uniform solution with a titanium compound, and then precipitating a solid in the presence of a precipitation assistant; finally, the solid is treated by an internal electron donor compound selected from the group consisting of compounds represented by the general formulae (I) and (II). The internal electron donor compounds represented by the general formulae (I) and (II) can be supported on the solid by treatment, and if necessary, the solid is treated with a titanium tetrahalide and an inert diluent. See in particular patent CN 85100997.
In some embodiments of the invention, the organic epoxy compound comprises at least one of an oxide, a glycidyl ether, and an internal ether of an aliphatic olefin, a diolefin or a halogenated aliphatic olefin or diolefin having 2 to 8 carbon atoms; specific compounds are, for example, ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether or tetrahydrofuran.
In some embodiments of the invention, the organophosphorus compound comprises at least one of a hydrocarbyl ester of orthophosphoric acid, a hydrocarbyl ester of phosphorous acid, and a halogenated hydrocarbyl ester; specific compounds are as follows: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, or trityl phosphite.
According to a preferred embodiment of the catalyst component of the present invention, the molar ratio of the first internal electron donor compound and the second internal electron donor compound is (1-100): 100-1, preferably (1-50): 50-1, and more preferably (1-20): 20-1.
According to a preferred embodiment of the catalyst component of the present invention, the magnesium compound comprises one or more selected from the group consisting of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides in which one of the halogen atoms of the molecular formula has been replaced by an alkoxy group or a haloalkoxy group, preferably magnesium dihalides and/or alcoholates, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
According to a preferred embodiment of the catalyst component according to the present invention, the titanium compound comprises a compound selected from the general formula TiXm(OR1)4-mOne or more of the compounds shown, R1Is C1-C20A hydrocarbon group of (a); x is halogen; m is more than or equal to 1 and less than or equal to 4.
According to a preferred embodiment of the catalyst component of the present invention, the titanium compound preferably comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium, more preferably titanium tetrachloride.
In a second aspect the present invention provides a catalyst system for the polymerisation of olefins comprising the reaction product of:
component a, the catalyst component according to the first aspect of the present invention;
component b, an alkyl aluminum compound; and
optionally component c, an external electron donor compound.
According to a preferred embodiment of the present invention, the external electron donor compound comprises a compound represented by the general formula (III):
R2 kSi(OR3)4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r2Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r3Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
According to a preferred embodiment of the invention, R2Is C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C20Aryl of (C)1-C10A haloalkyl group, an amino group, a halogen atom or a hydrogen atom.
According to a preferred embodiment of the invention, R3Is C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C20Aryl of (C)1-C10With haloalkyl or with ammoniaAnd (4) a base.
In the catalyst system of the invention, the alkyl aluminum compound has a general formula of AlR3 nX3-nA compound of (1), wherein R3Is hydrogen or alkyl with 1-20 carbon atoms, X is halogen, and n is a number which is more than 1 and less than or equal to 3. Specifically, the aluminum chloride can be selected from one or more of triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, diethyl aluminum monohydrogen, diisobutyl aluminum monohydrogen, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride. Preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.
For the application of olefin polymers with high stereoregularity, an external electron donor compound is added, for example, the general formula R2 kSi(OR3)4-kIn the formula, k is more than or equal to 0 and less than or equal to 3, R2And R3Is the same or different alkyl, cycloalkyl, aryl, haloalkyl, R2And may be a halogen or hydrogen atom. Preferably, R2And R3Each independently is C1-C10Alkyl radical, C3-C10Cycloalkyl radical, C6-C12Aryl radical, C1-C10A haloalkyl group. Examples of the organosilicon compound include: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisobutyldiethoxysilane, dibutyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane.
According to a preferred embodiment of the present invention, the molar ratio of component a, component b and component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).
In a third aspect, the present invention provides a prepolymerized catalyst for olefin polymerization comprising the first catalyst of the present inventionThe catalyst component according to the aspect and/or the catalyst system according to the second aspect of the present invention may be a prepolymer obtained by prepolymerizing an olefin, wherein the prepolymerization ratio of the prepolymer is from 0.1 to 1000g of the olefin polymer per g of the catalyst component. The olefin may be of the formula CH2Wherein R is hydrogen or C1-C6Alkyl group of (1). The olefin is preferably ethylene, propylene and/or 1-butene.
The expression "prepolymerized catalyst" as used in the present invention refers to a catalyst which has undergone a polymerization step with a relatively low degree of conversion. According to the invention, the prepolymerization can be carried out using the same alpha-olefin as the olefin used for the polymerization, the olefin to be subjected to the prepolymerization preferably being ethylene, propylene or 1-butene. In particular, it is particularly preferred to carry out the prepolymerization with ethylene or a mixture of one or more alpha-olefins in a remaining amount of up to 20 mol%. Preferably, the degree of conversion of the prepolymerized catalyst component is from about 0.2 to 500 grams of polymer per gram of solid catalyst component.
The expression "prepolymerized olefin" as used herein means an alpha-olefin, preferably ethylene and/or propylene, which is used in a prepolymerization reaction with the solid catalyst component or catalyst system as described herein to obtain a prepolymerized catalyst.
The prepolymerization step can be carried out at a temperature of-20 ℃ to 80 ℃, preferably 0-50 ℃, in liquid or gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers in amounts of from 0.5 to 20g/g of catalyst component, batch prepolymerization of the catalyst of the invention with ethylene is particularly preferred. The polymerization pressure is 0.01-0 MPa.
In a fourth aspect the present invention provides a process for the polymerisation of olefins carried out in the presence of a catalyst component according to the first aspect of the present invention and/or a catalyst system according to the second aspect of the present invention and/or a prepolymerised catalyst according to the third aspect of the present invention. The olefin has the general formula CH2Wherein R is hydrogen or C1-C6Alkyl group of (1). The olefin is preferably ethylene, propylene and/or 1-butene.
The catalysts of the invention are also suitable for the production of polyethylene and copolymers of ethylene with alpha-olefins, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene.
The catalyst of the present invention may be added directly to the reactor for use in the polymerization process. Alternatively, the catalyst may be prepolymerized before being fed into the first polymerization reactor.
The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. Conventional techniques such as slurry processes, gas phase fluidized beds and the like are employed wherein the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, particularly the homopolymerization of propylene or the copolymerization of propylene with other olefins. The following reaction conditions are preferably employed: the polymerization temperature is 0-150 ℃. Preferably, the polymerization temperature is 60 to 90 ℃.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
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 of the invention is as follows:
(1) polymer isotactic index II: a2 g dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer to 2, which is obtained by drying the residue to constant weight, is the isotactic index, determined by adopting a heptane extraction method (boiling extraction for 6 hours).
(2) Melt index MI: measured using a melt index apparatus at 230 ℃ under a pressure of 2.16kg according to ASTM D1238-99 Standard test method for measuring thermoplastic melt flow Rate with an extrusion plastometer.
(3) Polymer molecular weight distribution MWD (MWD ═ Mw/Mn): measured at 150 ℃ by gel permeation chromatography using PL-GPC220 with trichlorobenzene as a solvent (standard: polystyrene, flow rate: 1.0mL/min, column: 3xPlgel 10um M1 xED-B300 x7.5nm).
Examples 1 to 4 and comparative examples 1 to 4
(1) Preparation of solid catalyst component a
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 50 ℃ under stirring, the mixture is maintained for 2.5 hours, the solid is completely dissolved, 1.4g of phthalic anhydride is added, and the mixture is maintained for 1 hour. The solution was cooled to below-25 ℃ and 56mL of TiCl were added dropwise over 1h4Slowly heating to 80 ℃, gradually precipitating solids in the heating process, adding 5mmol of the compound internal electron donor compound shown in the table 1, maintaining the temperature for 1h, filtering, and washing with 70mL of toluene for 2 times respectively to obtain solid precipitates. Then 60mL of toluene, 40mL of TiCl were added4The temperature is raised to 110 ℃ and maintained for 2h, the same operation is repeated once, 70mL of toluene is used for washing at 110 ℃ for 3 times, the time is 10min each, 60mL of hexane is added, and the washing is carried out for 2 times, so as to obtain the solid catalyst component a.
(2) Experiment on propylene polymerization
The solid catalyst components obtained above were separately subjected to propylene polymerization. The propylene polymerization procedure was: a stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and 2.5mmol of AlEt is added3And 0.l mmol of dicyclopentyldimethoxysilane as an external electron donor compound, adding 8-10mg of solid catalyst component and 1.2NL of hydrogen, introducing 2.3L of liquid propylene, heating to 70 ℃, and maintaining the temperature for 1 hour; and (3) cooling and depressurizing to obtain PP powder of examples 1-4 and comparative examples 1-4. The data are shown in Table 1.
TABLE 1 propylene polymerization results
Figure BDA0002530832520000151
Wherein:
a: diphenylphenyl methyl phosphate 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (molar ratio) ═ 1:4
B: bis (4-cumyl) n-nonyl phosphate 9, 9-bis (methoxymethyl) fluorene (molar ratio) 4:1
C: diphenyl n-butyl phosphate 9, 9-bis (methoxymethyl) fluorene (molar ratio) 8:1
D: bis (4-tolyl) benzyl phosphate 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (molar ratio) 1:10
E: tributyl phosphate 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane (molar ratio) 1:10
F: triphenyl phosphate 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane (molar ratio) 1:10
As can be seen from Table 1, the catalyst system provided by the invention can maintain high polymerization activity, good hydrogen regulation sensitivity and high stereospecificity of the catalyst, and simultaneously, the molecular weight distribution of the obtained polymer is widened, and the comprehensive performance of the polymer is excellent, which is very beneficial to the development of different grades of resins.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A catalyst component for olefin polymerization reaction comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises a first internal electron donor compound with a general formula (I) and a second internal electron donor compound with a general formula (II),
Figure FDA0002530832510000011
in the general formula (I),
R1is C1-C15OfChain alkyl radical, C3-C15Branched alkyl of C3-C15Cycloalkyl or C7-C20And said C is aralkyl, and1-C15straight chain alkyl group of (1), C3-C15Branched alkyl of C3-C15Cycloalkyl and C7-C20The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent;
R2selected from hydrogen, halogen atoms, C1-C10Straight chain alkyl of (2) and C3-C10And said C is a branched alkyl group of1-C10Straight chain alkyl of (2) and C3-C10The hydrogen on the branched alkyl carbon of (a) is optionally substituted with a substituent;
in the general formula (II), the compound represented by the formula (II),
R3and R4Identical or different, independently selected from C1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C3-C15A branched hydrocarbon group of3-C15A cycloalkyl group of6-C20Aryl of (C)7-C20And C is a hydrocarbon aryl group7-C20And said C is an aromatic hydrocarbon group1-C10Straight chain alkyl group of (1), C2-C10Linear alkenyl of (A), C3-C15A branched hydrocarbon group of3-C15A cycloalkyl group of6-C20Aryl of (C)7-C20And C is a hydrocarbon aryl group7-C20The hydrogen on the arylcarbon of (a) is optionally substituted with one or more substituents, R3And R4Optionally may be bonded to form a ring or not,
preferably, the substituents are selected from hydroxy, amino, C1-C6Alkyl-substituted amino, -CHO, -COOH, halogen atom, C1-C6Alkyl and C1-C6Alkoxy group of (2).
2. The catalyst component according to claim 1 in which in the formula (I), R is1Is C1-C12Linear chain of (2)Alkyl radical, C3-C10Branched alkyl of C3-C12Cycloalkyl or C7-C15And said C is an aralkyl group1-C12Straight chain alkyl group of (1), C3-C10Branched alkyl of C3-C12Cycloalkyl and C7-C15The hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents;
R2is hydrogen, halogen atom, C1-C8Straight chain alkyl or C3-C10And said C is a branched alkyl group of1-C8Straight chain alkyl of (2) and C3-C10The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.
3. The catalyst component according to claim 1 or 2, characterized in that in the general formula (I), R is1Is C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C9Straight chain alkyl group of (1), C10-C12Straight chain alkyl group of (1), C3-C4Branched alkyl of C5-C7Branched alkyl of C8-C10Branched alkyl of C7-C9Aralkyl of (2), C10-C12Aralkyl or C13-C15Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenethyl or phenylpropyl,
more preferably, said compound of formula (I) is selected from the group consisting of diphenylmethyl phosphate, diphenylethyl phosphate, diphenyl-n-propyl phosphate, diphenylisopropyl phosphate, diphenyl-n-butyl phosphate, diphenylisobutyl phosphate, diphenyl-t-butyl phosphate, diphenyl-n-pentyl phosphate, diphenylisopentyl phosphate, diphenylhexyl phosphate, diphenylheptyl phosphate, diphenyloctyl phosphate, diphenylnonyl phosphate, diphenylbenzyl phosphate, di-2-tolyl methyl phosphate, di-2-tolyl ethyl phosphate, di-2-tolyl-n-propyl phosphate, di-2-tolyl isopropyl phosphate, di-2-tolyl-n-butyl phosphate, di-2-tolyl isobutyl phosphate, di-2-tolyl-t-butyl phosphate, di-2-tolyl-n-butyl phosphate, diphenyl-n-propyl phosphate, diphenylisopropyl phosphate, diphenylethyl phosphate, diphenylisopropyl phosphate, diphenylmethyl phosphate, diphenylisopropyl phosphate, tert-2-butyl phosphate, and mixtures thereof, Di (2-tolyl) n-pentyl phosphate, di (2-tolyl) isoamyl phosphate, di (2-tolyl) hexyl phosphate, di (2-tolyl) heptyl phosphate, di (2-tolyl) octyl phosphate, di (2-tolyl) nonyl phosphate, di (2-tolyl) benzyl phosphate, di (4-tolyl) methyl phosphate, di (4-tolyl) ethyl phosphate, di (4-tolyl) n-propyl phosphate, di (4-tolyl) isopropyl phosphate, di (4-tolyl) n-butyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) t-butyl phosphate, di (4-tolyl) n-pentyl phosphate, di (4-tolyl) isoamyl phosphate, di (2-tolyl) hexyl phosphate, di (2-tolyl) heptyl phosphate, di (4-tolyl) octyl phosphate, di (4-tolyl) isopropyl phosphate, di (4-tolyl) n-butyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) t-butyl phosphate, di (4-tolyl) n-pentyl phosphate, di (4-tolyl) isoamyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) butyl phosphate, di (4-butyl) butyl phosphate, di (4-tolyl) butyl phosphate, di (4-butyl) butyl phosphate, di (4-butyl phosphate, di-butyl) butyl phosphate, di-butyl phosphate, di (4-butyl phosphate, di-butyl phosphate, n-butyl phosphate, di-butyl phosphate, and the like, Di (4-tolyl) hexyl phosphate, di (4-tolyl) heptyl phosphate, di (4-tolyl) octyl phosphate, di (4-tolyl) nonyl phosphate, di (4-tolyl) benzyl phosphate, di (4-cumyl) methyl phosphate, di (4-cumyl) ethyl phosphate, di (4-cumyl) n-propyl phosphate, di (4-cumyl) isopropyl phosphate, di (4-cumyl) n-butyl phosphate, di (4-cumyl) isobutyl phosphate, di (4-cumyl) tert-butyl phosphate, di (4-cumyl) n-pentyl phosphate, di (4-cumyl) isoamyl phosphate, di (4-cumyl) hexyl phosphate, One or more of di (4-cumyl) heptyl phosphate, di (4-cumyl) octyl phosphate, di (4-cumyl) nonyl phosphate and di (4-cumyl) benzyl phosphate.
4. The catalyst component according to any of claims 1 to 3 in which in the general formula (II) R is3And R4Identical or different, independently selected from C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl and C of7-C15Aralkyl, and said C1-C8Straight chain alkyl group of (1), C2-C8Linear alkenyl of (A), C3-C10Branched alkyl of C3-C10Cycloalkyl of, C6-C15Aryl of (C)7-C15Alkylaryl or C of7-C15The hydrogens on the arylalkyl carbon may be optionally substituted with one or more substituents, R3And R4Optionally may be bonded to form a ring or not,
preferably, in formula (II), R3And R4Identical or different, independently selected from C1-C3Straight chain alkyl group of (1), C4-C6Straight chain alkyl group of (1), C7-C8Straight chain alkyl group of (1), C3-C5Branched alkyl of C6-C8Branched alkyl of C9-C10Branched alkyl of C6-C8Aryl of (C)9-C11Aryl and C12-C15Aryl of (2), for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl, R3And R4Optionally may be bonded to form a ring or not,
more preferably, the compound of formula (II) is selected from the group consisting of 2, 2-dimethyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-di-n-propyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-di-n-butyl-1, 3-dimethoxypropane, 2-di-isobutyl-1, 3-dimethoxypropane, 2-di-n-pentyl-1, 3-dimethoxypropane, 2-di-isoamyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-n-propyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-n-butyl-1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2-n-pentyl-1, 3-dimethoxypropane, 2-methyl-2-isopentyl-1, 3-dimethoxypropane, 2-ethyl-2-n-propyl-1, 3-dimethoxypropane, 2-ethyl-2-isopropyl-1, 3-dimethoxypropane, 2-ethyl-2-n-butyl-1, 3-dimethoxypropane, 2-dimethyl-2-isopropyl-1, 3-dimethoxypropane, 2-dimethyl-2-n-butyl-1, 3-dimethoxypropane, methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-2-n-butyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-2-pentyl-1, 3-dimethoxypropane, 2-methyl-2-pentyl-2-dimethyl-1, 3-dimethoxypropane, 2-dimethyl-propyl-dimethyl-2-dimethyl-methyl-2-methyl-2-dimethyl-propyl-2-dimethyl-methyl-ethyl-2-ethyl-methyl-ethyl-methyl-2-propyl-methyl-2-methyl-2-methyl-2-ethyl-methyl-2-methyl-2-methyl-propyl-1, 3-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-2-methyl-1, 2-methyl-2-methyl-2-methyl, 2-ethyl-2-isobutyl-1, 3-dimethoxypropane, 2-ethyl-2-n-pentyl-1, 3-dimethoxypropane, 2-ethyl-2-isopentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopropyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-butyl-1, 3-dimethoxypropane, 2-n-propyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-propyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-propyl-2-isopentyl-1, 3-dimethoxypropane, 2-ethyl-2-isobutyl-1, 3-dimethoxypropane, 2-pentyl-2-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-propyl-dimethoxypropane, 2-pentyl-dimethoxypropane, 2-propyl-2-isopentyl-dimethoxypropane, 2-propyl-2-pentyl-2, 3-dimethoxypropane, 2-propyl-methyl-2, 2-propyl, 2, or a-pentyl-propyl, or a, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-n-pentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-n-butyl-2-isobutyl-1, 3-dimethoxypropane, 2-n-butyl-2-n-pentyl-1, 3-dimethoxypropane, 2-n-butyl-2-isopentyl-1, 3-dimethoxypropane, 2-isobutyl-2-n-pentyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane, and mixtures thereof, 2-isobutyl-2-phenyl-1, 3-dimethoxypropane, 2-isopentyl-2-phenyl-1, 3-dimethoxypropane, 2- (2-methyl-n-butyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2-phenyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-ethyl-2-phenyl-1, 3-dimethoxypropane, 2-isobutyl-2-benzyl-1, 3-dimethoxypropane, 2-isopentyl-2-benzyl-1, 3-dimethoxypropane, 2- (2-methylbutyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-benzyl-1, 3-dimethoxypropane, 2-n-propyl-2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 2-isobutyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, a salt thereof, a base thereof, a stabilizer, a 3-3, a stabilizer, a 3, a stabilizer, a 3-2-, 2-isopentyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2- (2-methylbutyl) -2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-methyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-ethyl-2- (2-ethylbutyl) -1, 3-dimethoxypropane, 2-isobutyl-2- (2-methylbutyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-methylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylbutyl) -2- (2-methylbutyl) -1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2- (2-methylbutyl) -1, 3-dimethoxypropane, 2-isobutyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopentyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-bis (2-methylbutyl) -1, 3-dimethoxypropane, 2-dimethylolpropane, 2-ethylbutyl-dimethylolpropane, 2-ethylbutyl-2-dimethylolpropane, 3-dimethylolpropane, 2-dimethylolpropane, 2-1, 3-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethylolpropane, 2-1, 2-dimethoxypropane, 2-1, 2-dimethoxypropane, 2-dimethylolpropane, 2-1, 2-dimethoxypropane, 2, One or more of 2, 2-bis (2-ethylhexyl) -1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene.
5. The catalyst component according to any of claims 1 to 4, wherein the solid catalyst component comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound, preferably the molar ratio of magnesium compound, titanium compound and internal electron donor compound is 1 (0.5-150) to (0.02-0.4).
6. The catalyst component according to any of claims 1 to 5 in which the reaction product is prepared by a process comprising dissolving a magnesium compound in a solvent system comprising an organic epoxy compound and an organic phosphorus compound to form a homogeneous mixed solution and mixing with a titanium compound.
7. The catalyst component according to any of claims 1 to 6 wherein the molar ratio of the first internal electron donor and the second internal electron donor compound is (1-100): (100-1), preferably (1-50): (50-1), further preferably (1-20): (20-1);
and/or the magnesium compound comprises one or more selected from magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcoholate of magnesium dihalide and derivative of magnesium dihalide with one halogen atom in the molecular formula replaced by alkoxy or haloalkoxy, preferably magnesium dihalide and/or alcoholate of magnesium dihalide;
and/or the titanium compound comprises a compound selected from TiXm(OR1)4-mOne or more of the compounds, R1Is C1-C20X is halogen, m is more than or equal to 1 and less than or equal to 4; the titanium compound preferably includes titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitaniumAnd titanium mono ethoxy trichloride, more preferably titanium tetrachloride.
8. A catalyst system for the polymerization of olefins comprising the reaction product of:
component a, the catalyst component of any one of claims 1 to 7;
component b, an alkyl aluminum compound; and
optionally component c, an external electron donor compound, preferably said external electron donor compound comprises a compound of formula (III):
R2 kSi(OR3)4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r2Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r3Is alkyl, cycloalkyl, aryl, haloalkyl or amino, preferably, R2Is C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C20Aryl of (C)1-C10A haloalkyl group of (a), an amino group, a halogen atom or a hydrogen atom; r3Is C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C20Aryl of (C)1-C10Haloalkyl or amino of (a);
preferably, the molar ratio of the component a to the component b to the component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).
9. A prepolymerized catalyst for olefin polymerization comprising the catalyst component according to any one of claims 1 to 7 and/or a prepolymer obtained by prepolymerizing the catalyst system according to claim 8 with an olefin, wherein the prepolymer has a prepolymerization ratio of 0.1 to 1000g of olefin polymer per g of catalyst component; the olefin has the general formula CH2Wherein R is hydrogen or C1-C6Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
10. A process for the polymerization of olefins having the general formula CH in the presence of a catalyst component according to any of claims 1 to 7 and/or a catalyst system according to claim 8 and/or a prepolymerized catalyst according to claim 92Wherein R is hydrogen or C1-C6Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
CN202010517954.5A 2020-06-09 2020-06-09 Catalyst component for olefin polymerization and application Pending CN113773424A (en)

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Application publication date: 20211210