CN113929797B - Solid catalyst component and catalyst system for producing polymers - Google Patents
Solid catalyst component and catalyst system for producing polymers Download PDFInfo
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- CN113929797B CN113929797B CN202010609766.5A CN202010609766A CN113929797B CN 113929797 B CN113929797 B CN 113929797B CN 202010609766 A CN202010609766 A CN 202010609766A CN 113929797 B CN113929797 B CN 113929797B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A solid catalyst component for producing a polymer comprising magnesium, titanium, halogen and an internal electron donor compound, the internal electron donor comprising a first internal electron donor compound of formula (I) and a second internal electron donor compound of formula (II). The invention also provides a catalyst system comprising the solid catalyst component. When the catalyst component provided by the invention is used for propylene polymerization, the polymerization activity is high, the stereospecificity is good, the hydrogen regulation sensitivity is good, and the molecular weight distribution of the obtained polymer is moderate.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and in particular relates to a solid catalyst component for producing a polymer, a catalyst system containing the solid catalyst component, and a preparation method and application thereof.
Background
It is known that solid titanium catalyst components based on magnesium, titanium, halogen and electron donor can be used for CH 2 The CHR olefin polymerization reaction, particularly in the polymerization of α -olefins having 3 carbon atoms or more, can give a polymer of higher yield and higher stereoregularity. Among them, the electron donor compound is one of indispensable ingredients in the catalyst component, and the polyolefin catalyst is continuously updated as the internal electron donor compound is developed. Currently, the internal electron donors used industrially are mainly phthalates, which have a high activity and a high stereoregularity, but which are of great interest due to their associated environmental and medical problems. Accordingly, researchers in the field have been working to develop alternative phthalate ester-substituted internal polyolefin catalysts as electron donor compounds.
A wide variety of non-phthalate electron donor compounds have been disclosed, such as mono-or poly-fatty acid esters, anhydrides, ketones, ethers, glycol esters, amines, and the like, and derivatives thereof, as described in patent CN1042547A, CN1143651A, CN1054139A, WO/56830, WO98/56834, WO01/57099, WO01/63231, WO00/55215, and the like.
Most of the electron donors reported so far are oxygen-, nitrogen-, phosphorus-, and sulfur-containing compounds. In these catalyst polymerization systems, the electron donor has varying degrees of influence on activity, stereospecificity, molecular weight distribution and polymer properties.
Patent CN200710055884.0 reports that when a phosphate compound is used for propylene polymerization, a polymer having a broad molecular weight distribution can be obtained, but the polymerization activity and stereoregularity are relatively low.
Patent CN201610565348.4 reports that when a phosphate compound and a diether compound are compounded for propylene polymerization, the catalyst has better hydrogen regulation sensitivity, but lower stereoregularity and narrower molecular weight distribution.
Patent CN201811074788.5 reports that when a phosphine oxide compound and a diether compound are compounded for propylene polymerization, the polymerization activity is high, but the hydrogen regulation sensitivity is still not good enough.
Disclosure of Invention
The inventor finds that the catalyst with excellent comprehensive performance can be obtained by using the compound of the diaryl acyloxy phosphate and the diether compound as the electron donor in the olefin polymerization catalyst through a large number of experiments, and the catalyst has high activity, good stereoregularity and hydrogen regulation sensitivity when being used for propylene polymerization, and the obtained polymer has moderate molecular weight distribution and excellent comprehensive performance.
To this end, a first aspect of the present invention provides a solid catalyst component for the production of polymers 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),
in the general formula (I), R 1 Is C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl, C 3 -C 12 Branched alkyl, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 Aromatic hydrocarbon group of (C) 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl, C 3 -C 12 Branched alkyl, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 2 is hydrogen, halogen or C 1 -C 10 Straight-chain alkyl or C 3 -C 12 Branched alkyl of (C), and said C 1 -C 10 Straight-chain alkyl or C 3 -C 12 The hydrogen on the branched alkyl carbon may be optionally substituted with a substituent;
in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 15 Branched hydrocarbon radical, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 An aromatic hydrocarbon group, and C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 15 Branched hydrocarbon radical, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 The hydrogen on the carbon of the aromatic hydrocarbon radical being optionally substituted by substituents R 3 And R is 4 Optionally may be bonded to form a ring or not.
According to a preferred embodiment of the solid catalyst component of the invention, said substituents are selected from the group consisting of hydroxyl, amino, C1-C6 alkyl-substituted amino (for example-NHCH 3 or-N (CH 3) 2), -CHO, -COOH, halogen (for example fluorine, chlorine, bromine or iodine), C1-C6 alkyl (for example methyl, ethyl or isopropyl) and C1-C6 alkoxy (for example methoxy, ethoxy, N-propoxy or isopropoxy).
The term "branched hydrocarbon group" in the present invention is branched alkyl, branched alkenyl or branched alkynyl group, "cyclic hydrocarbon group" is cycloalkyl, cycloalkenyl or cycloalkynyl group, "hydrocarbon aryl group" is alkylaryl, alkenylaryl or alkynylaryl group, and "aromatic hydrocarbon group" is aralkyl, aralkenyl or aralkynyl group.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 1 Is C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 12 Is a cycloalkane of (C)Radical, C 6 -C 18 Aryl, C of (2) 7 -C 18 Alkylaryl, C 7 -C 18 Aralkyl or C of (C) 7 -C 18 And C is as described 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 12 Cycloalkyl, C 6 -C 18 Aryl, C of (2) 7 -C 18 Alkylaryl, C 7 -C 18 Aralkyl or C of (C) 7 -C 18 Hydrogen on the aralkenyl carbon of (c) may optionally be substituted with one or more substituents.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 1 Is C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 9 Straight chain alkyl, C 2 -C 3 Straight chain alkenyl, C 4 -C 6 Straight chain alkenyl, C 7 -C 9 Straight chain alkenyl, C 3 -C 6 Branched alkyl, C 7 -C 9 Branched alkyl, C 6 -C 10 Aryl, C of (2) 11 -C 15 Aryl, C of (2) 7 -C 10 Alkylaryl, C 11 -C 15 Alkylaryl, C 7 -C 10 Aralkyl of (C) 11 -C 15 Aralkyl of (C) 7 -C 10 Aralkenyl or C of (C) 11 -C 15 According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (I), R 1 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, isobutylphenyl, benzyl, phenethyl, phenylpropyl, styryl or phenylpropenyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 2 Is hydrogen, halogen or C 1 -C 8 Straight-chain alkyl or C 3 -C 10 Branched chain of (2)Alkyl, and C as described 1 -C 8 Straight-chain alkyl or C 3 -C 10 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 2 Is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl or C 9 -C 10 Branched alkyl groups of (a).
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 2 Is hydrogen, a group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl and C of (C) 7 -C 15 And C is said 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl and C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with a substituent, R 3 And R is 4 Optionally may be bonded to form a ring or not.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 And R is 4 The same applies.
According to the inventionPreferred embodiments of the solid catalyst component, in the general formula (II), R 3 And R is 4 Are not identical.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 Selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 9 -C 10 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl and C of (2) 12 -C 15 For example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 4 Selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 9 -C 10 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl and C of (2) 12 -C 15 For example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl.
According to a preferred embodiment of the solid catalyst component of the present invention, the solid catalyst component comprises a magnesium compound, a titanium compound and a reaction product of an internal electron donor compound represented by the general formula (I) and the general formula (II).
According to a preferred embodiment of the solid catalyst component of the invention, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1 (0.5-150): 0.02-0.4.
According to a preferred embodiment of the solid catalyst component of the present invention, 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.
According to a preferred embodiment of the solid catalyst component of the invention, the magnesium compound comprises one or more selected from the group consisting of magnesium dihalide, magnesium alkoxides, alkyl magnesium, hydrates or alkoxides of magnesium dihalides and derivatives of magnesium dihalides in which one halogen atom is replaced by an alkoxy or haloalkoxy group, preferably magnesium dihalide and/or alkoxides of magnesium dihalide, preferably magnesium dihalide or alkoxides of magnesium dihalide, for example magnesium dichloride, magnesium dibromide, magnesium diiodide and alkoxides thereof.
According to a preferred embodiment of the solid catalyst component of the invention, the titanium compound comprises TiX m (OR 1 ) 4-m One or more of the compounds wherein R 1 Is C 1 -C 20 X is halogen, m is more than or equal to 1 and less than or equal to 4.
According to some embodiments of the invention, R 1 Is C 1 -C 20 Alkyl of (C) is preferred 1 -C 10 Alkyl, more preferably C 1 -C 6 An 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 solid catalyst component of the present invention, the titanium compound preferably comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide, more preferably titanium tetrachloride.
In a second aspect the present invention provides a catalyst system for the polymerization of olefins comprising the reaction product of:
component a, the solid catalyst component according to the first aspect of the present invention;
component b, an alkylaluminum compound; and
optionally component c, an external electron donor compound.
According to a preferred embodiment of the present invention, the external electron donor compound includes a compound represented by the general formula (III):
R 2 k Si(OR 3 ) 4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r is R 2 Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or a hydrogen atom; r is R 3 Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
According to a preferred embodiment of the invention, R 2 Is C 1 -C 10 Alkyl, C of (2) 3 -C 10 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 1 -C 10 A haloalkyl group, an amino group, a halogen or a hydrogen atom.
According to a preferred embodiment of the invention, R 3 Is C 1 -C 10 Alkyl, C of (2) 3 -C 10 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 1 -C 10 Haloalkyl or amino.
According to a preferred embodiment of the invention, the molar ratio of component a, component b and component c is 1 (5-1000) in terms of titanium: aluminum: silicon (0-500); preferably 1 (25-100): 25-100.
In a third aspect, the present invention provides a prepolymerization catalyst for olefin polymerization comprising a solid catalyst component according to the first aspect of the present invention and/or a prepolymer obtained by prepolymerizing a catalyst system according to the second aspect of the present invention with an olefin, wherein the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of catalyst component; the general formula of the olefin is CH 2 =chr, wherein R is hydrogen or C 1 -C 6 Alkyl of (a); 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 in the presence of a solid catalyst component according to the first aspect of the invention and/or a catalyst according to the second aspect of the invention and/or a prepolymerized catalyst according to the third aspect of the invention 2 =chr, wherein R is hydrogen or C 1 -C 6 Alkyl of (a); the olefins are preferably ethylene, propylene and/or 1-butene。
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
As mentioned above, the existing olefin polymerization catalysts are improved in all aspects, and the environment protection and safety are not facilitated due to the fact that highly corrosive and unstable compounds are used in the synthesis process. At present, research and development of a catalyst component for olefin polymerization, which has high activity, good stereospecificity, good hydrogen regulation sensitivity, wide molecular weight distribution of the obtained polymer and other comprehensive properties, are needed.
In a first aspect the present invention provides a solid catalyst component for the production of polymers 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),
in the general formula (I), R 1 Is C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl, C 3 -C 12 Branched alkyl, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 Aromatic hydrocarbon group of (C) 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl, C 3 -C 12 Branched alkyl, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 Aromatic hydrocarbon group of (2)Hydrogen on carbon may be optionally substituted with substituents;
R 2 is hydrogen, halogen or C 1 -C 10 Straight-chain alkyl or C 3 -C 12 Branched alkyl of (C), and said C 1 -C 10 Straight-chain alkyl or C 3 -C 12 The hydrogen on the branched alkyl carbon may be optionally substituted with a substituent;
in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 15 Branched hydrocarbon radical, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 An aromatic hydrocarbon group, and C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 15 Branched hydrocarbon radical, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 The hydrogen on the carbon of the aromatic hydrocarbon radical being optionally substituted by substituents R 3 And R is 4 Optionally may be bonded to form a ring or not.
According to a preferred embodiment of the solid catalyst component of the invention, said substituents are selected from the group consisting of hydroxyl, amino, C1-C6 alkyl-substituted amino (for example-NHCH 3 or-N (CH 3) 2), -CHO, -COOH, halogen (for example fluorine, chlorine, bromine or iodine), C1-C6 alkyl (for example methyl, ethyl or isopropyl) and C1-C6 alkoxy (for example methoxy, ethoxy, N-propoxy or isopropoxy).
The term "branched hydrocarbon group" in the present invention is branched alkyl, branched alkenyl or branched alkynyl group, "cyclic hydrocarbon group" is cycloalkyl, cycloalkenyl or cycloalkynyl group, "hydrocarbon aryl group" is alkylaryl, alkenylaryl or alkynylaryl group, and "aromatic hydrocarbon group" is aralkyl, aralkenyl or aralkynyl group.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 1 Is C 1 -C 10 Straight chain alkanes of (2)Radical, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 12 Cycloalkyl, C 6 -C 18 Aryl, C of (2) 7 -C 18 Alkylaryl, C 7 -C 18 Aralkyl or C of (C) 7 -C 18 And C is as described 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 12 Cycloalkyl, C 6 -C 18 Aryl, C of (2) 7 -C 18 Alkylaryl, C 7 -C 18 Aralkyl or C of (C) 7 -C 18 Hydrogen on the aralkenyl carbon of (c) may optionally be substituted with one or more substituents.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 1 Is C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 9 Straight chain alkyl, C 2 -C 3 Straight chain alkenyl, C 4 -C 6 Straight chain alkenyl, C 7 -C 9 Straight chain alkenyl, C 3 -C 6 Branched alkyl, C 7 -C 9 Branched alkyl, C 6 -C 10 Aryl, C of (2) 11 -C 15 Aryl, C of (2) 7 -C 10 Alkylaryl, C 11 -C 15 Alkylaryl, C 7 -C 10 Aralkyl of (C) 11 -C 15 Aralkyl of (C) 7 -C 10 Aralkenyl, C 11 -C 15 Is a compound of formula (I).
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 1 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, isobutylphenyl, benzyl, phenethyl, phenylpropyl, styryl or phenylpropenyl.
According to the inventionPreferred embodiments of the solid catalyst component, in the general formula (I), R 2 Is hydrogen, halogen or C 1 -C 8 Straight-chain alkyl or C 3 -C 10 Branched alkyl of (C), and said C 1 -C 8 Straight-chain alkyl or C 3 -C 10 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 2 Is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl or C 9 -C 10 Branched alkyl groups of (a).
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (I), R 2 Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
According to the solid catalyst component of the present invention, the compound in the general formula (I) is selected from, but not limited to, the following compounds:
acetyloxy diphenyl phosphate, n-propionyloxy diphenyl phosphate, isopropyl acyloxydiphenyl phosphate, n-butyryloxy diphenyl phosphate, isobutyryloxy diphenyl phosphate, n-pentanoyloxy diphenyl phosphate, isovaleryloxy diphenyl phosphate, n-hexanoyloxy diphenyl phosphate, n-heptanyloxy diphenyl phosphate, n-octanoyloxy diphenyl phosphate, n-nonanyloxy diphenyl phosphate, benzoyloxy diphenyl phosphate, p-methylbenzoyloxy diphenyl phosphate, p-ethylbenzoyloxy diphenyl phosphate, p-n-propylbenzoyloxy diphenyl phosphate, p-isopropylbenzoyloxy diphenyl phosphate, p-n-butylbenzoyloxy diphenyl phosphate, p-isobutylbenzoyloxy diphenyl phosphate, p-tert-butylbenzoyloxy diphenyl phosphate, acetyloxy bis (2-tolyl) phosphate, n-propionyloxy bis (2-tolyl) phosphate, isopropoxy bis (2-tolyl) phosphate, n-butyryloxy bis (2-tolyl) phosphate, isobutyryloxy bis (2-tolyl) phosphate, n-pentanoyloxy bis (2-tolyl) phosphate, isopentanoyloxy bis (2-tolyl) phosphate, n-hexanoyloxy bis (2-tolyl) phosphate, n-heptanyloxy bis (2-tolyl) phosphate, n-octanoyloxy bis (2-tolyl) phosphate, n-nonanyloxy bis (2-tolyl) phosphate, benzoyloxy bis (2-tolyl) phosphate, p-methylbenzyloxy bis (2-tolyl) phosphate, di (2-methylbenzoate) p-ethylbenzoyloxy phosphate, di (2-methylbenzoate) p-n-propylbenzoyloxy phosphate, di (2-methylbenzoate) p-isopropylbenzoyloxy phosphate, di (2-methylbenzoate) p-n-butylbenzoyloxy phosphate, di (2-methylbenzoate) p-t-butylbenzoyloxy phosphate, di (2-methylbenzoate) acetoxy phosphate, di (4-methylbenzoate), n-propionyloxy phosphate, di (4-methylbenzoate) isopropyl acyloxyphosphate, di (4-methylbenzoate) n-butyryloxy phosphate, di (4-methylbenzoate) isobutyryloxy phosphate, di (4-methylbenzoate) n-pentanoyloxy phosphate, di (4-methylbenzoate) n-heptanoyloxy phosphate, di (4-methylbenzoate) n-octanoyloxy phosphate, di (4-methylbenzoate) n-nonyloxy phosphate, di (4-methylbenzoate) benzoyl oxy phosphate, di (4-methylbenzoyl phosphate), p-benzoyl oxy phosphate, p-xylyl phosphate, bis (4-methylbenzoate) p-n-butylbenzoyloxy phosphate, bis (4-methylbenzoate) p-isobutylbenzoyloxy phosphate, bis (4-methylbenzoate) p-tert-butylbenzoyloxy phosphate, bis (4-cumyl) acetoxyphosphate, bis (4-cumyl) n-propionyloxy phosphate, bis (4-cumyl) isopropoxyphosphate, bis (4-cumyl) n-butyryloxy phosphate, bis (4-cumyl) isobutyryloxy phosphate, bis (4-cumyl) n-valeryloxy phosphate, bis (4-cumyl) cumyl oxy phosphate, bis (4-cumyl) n-hexanoyloxy phosphate, bis (4-cumyl) n-heptanyloxy phosphate, bis (4-cumyl) n-octanoyloxy phosphate, bis (4-cumyl) n-nonanyloxy phosphate, bis (4-cumyl) benzoyl oxy phosphate, bis (4-cumyl) p-methylbenzoyl phosphate, bis (4-ethylphenyl) p-isopropylphenyl phosphate, bis (4-cumyl) p-benzoyl phosphate, one or more of di (4-isopropylphenyl) p-tert-butylbenzoyloxy phosphate and diphenyl cinnamoyloxy phosphate.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl and C of (C) 7 -C 15 And C is said 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl and C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with a substituent, R 3 And R is 4 Optionally may be bonded to form a ring or not.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 And R is 4 The same applies.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 And R is 4 Are not identical.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 3 Selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 9 -C 10 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl and C of (2) 12 -C 15 For example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 4 Selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 9 -C 10 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl and C of (2) 12 -C 15 For example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl.
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, 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-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-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-isopentyl-1, 3-dimethoxypropane, 2-n-pentyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopentyl-1, 3-dimethoxypropane, 2-pentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-pentyl-1, 3-dimethoxypropane, 2-isopropyl-2-1, 3-pentyl-1, 3-dimethoxypropane, 3-dimethoxy-isopropyl-1 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) -2-benzyl-1, 3-dimethoxypropane, 2-ethylbutyl-2-benzyl-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-dimethyl-1, 3-dimethoxypropane, 2-dimethylbutyl-1, 3-dimethoxypropane, 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 solid catalyst component of the present invention, the solid catalyst component comprises a magnesium compound, a titanium compound and a reaction product of an internal electron donor compound represented by the general formula (I) and the general formula (II).
According to a preferred embodiment of the solid catalyst component of the invention, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1 (0.5-150): 0.02-0.4.
According to a preferred embodiment of the solid catalyst component of the present invention, the reaction product is prepared by a method 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 then mixing with a titanium compound.
The solid catalyst component for olefin polymerization according to the present invention is preferably prepared by reacting a magnesium compound, a titanium compound and an internal electron donor compound represented by the above general formulae (I) and (II). It is particularly pointed out that the preparation by reaction comprises dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent, forming a homogeneous solution, mixing with a titanium compound, and then precipitating a solid in the presence of a precipitation aid; finally, the solid is treated with an internal electron donor compound selected from the group consisting of compounds represented by 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 titanium tetrahalide and an inert diluent. See in particular patent CN85100997.
In some embodiments of the present invention, the organic epoxy compound includes at least one of an aliphatic olefin, a diene or a halogenated aliphatic olefin or an oxide of a diene, a glycidyl ether, and a internal ether having 2 to 8 carbon atoms; specific compounds are, for example, ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether or tetrahydrofuran.
In some embodiments of the invention, the organophosphorus compound includes 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 triphenyl phosphite.
According to a preferred embodiment of the solid catalyst component of the present invention, the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100): 100-1, preferably (1-50): 50-1, further preferably (1-20): 20-1.
According to a preferred embodiment of the solid catalyst component of the present invention, the magnesium compound comprises one or more of magnesium dihalide, magnesium alkoxide, magnesium alkyl, hydrate or alkoxide of magnesium dihalide, and derivative in which one halogen atom in the formula of magnesium dihalide is replaced with an alkoxy group or haloalkoxy group; preferably, the magnesium compound is magnesium dihalide and/or an alkoxide of magnesium dihalide; more preferably, the magnesium compound is an alkoxide of magnesium dihalide, such as magnesium dichloride, magnesium dibromide, magnesium diiodide, and an alkoxide thereof.
According to a preferred embodiment of the solid catalyst component of the invention, the titanium compound comprises a catalyst selected from the group consisting of the general formula TiX m (OR 1 ) 4-m One or more of the compounds shown, R 1 Is C 1 -C 20 Is a hydrocarbon group of (2); x is halogen; m is more than or equal to 1 and less than or equal to 4.
In some embodiments of the invention, the titanium compound comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium chlorotriethoxy, titanium dichlorodiethoxy and titanium trichloromonoethoxy; preferably, the titanium compound is titanium tetrachloride.
In a second aspect the present invention provides a catalyst system for the polymerization of olefins comprising the reaction product of:
component a, the solid catalyst component according to the first aspect of the present invention;
component b, an alkylaluminum compound; and
optionally component c, an external electron donor compound.
According to a preferred embodiment of the present invention, the external electron donor compound includes a compound represented by the general formula (III):
R 2 k Si(OR 3 ) 4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r is R 2 Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or a hydrogen atom; r is R 3 Is alkyl, cycloalkyl, aryl, haloalkyl or amino.
According to some embodiments of the invention, R 2 Is C 1 -C 10 Alkyl, C of (2) 3 -C 10 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 1 -C 10 A haloalkyl group, an amino group, a halogen or a hydrogen atom.
According to some embodiments of the invention, R 3 Is C 1 -C 10 Alkyl, C of (2) 3 -C 10 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 1 -C 10 Haloalkyl or amino.
In the catalyst system of the invention, the alkyl aluminum compound is represented by the general formula AlR 4 n X 3-n Wherein R is 4 Is hydrogen or hydrocarbon group with 1-20 carbon atoms, X is halogen, n is a number of 1 < n.ltoreq.3. Specifically, the catalyst can be one or more selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride. Preferably, the alkyl aluminum compound is triethylaluminum and/or triisobutylaluminum.
For applications where highly stereoregular olefin polymers are desired, it is desirable to add external electron donor compounds, e.g. of the formula R 2 k Si(OR 3 ) 4-k Wherein k is 0.ltoreq.3, R 2 And R is 3 Is the same or different alkyl, cycloalkyl, aryl, haloalkyl, R 2 Or may be a halogen or a hydrogen atom. For example: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisobutyldiethoxysilane, dibutyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane.
According to a preferred embodiment of the invention, the molar ratio of component a, component b and component c is 1 (5-1000) in terms of titanium: aluminum: silicon (0-500); preferably 1 (25-100): 25-100.
In a third aspect, the present invention provides a prepolymerization catalyst for olefin polymerization comprising a solid catalyst component according to the first aspect of the present invention and/or a prepolymer obtained by prepolymerizing a catalyst system according to the second aspect of the present invention with an olefin, wherein the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of catalyst component; the general formula of the olefin is CH 2 =chr, wherein R is hydrogen or C 1 -C 6 Alkyl of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
The term "prepolymerized catalyst" as used herein refers to a catalyst which has undergone a polymerization step at a relatively low degree of conversion. According to the present invention, the same alpha-olefin as the olefin used for the polymerization can be used for the prepolymerization, wherein the olefin to be subjected to the prepolymerization is preferably 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 g polymer per g solid catalyst component.
The term "prepolymerized olefin" as used herein refers to an alpha-olefin, preferably ethylene and/or propylene, which is used for the 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 in liquid or gas phase at a temperature of from-20℃to 80℃and preferably from 0 to 50 ℃. The prepolymerization step can be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers having a catalyst component content of from 0.5 to 20g/g, the batch prepolymerization of the catalyst according to the invention with ethylene is particularly preferred. The polymerization pressure is 0.01-10MPa.
In a fourth aspect the present invention provides a process for the polymerisation of olefins having the general formula CH in the presence of a solid catalyst component according to the first aspect of the invention and/or a catalyst system according to the second aspect of the invention and/or a prepolymerized catalyst according to the third aspect of the invention 2 =chr, wherein R is hydrogen or C 1 -C 6 Alkyl of (a); 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 directly added to the reactor for use in the polymerization process. Alternatively, the catalyst may be pre-polymerized prior to being fed to the first polymerization reactor.
The olefin polymerization of the present invention can be carried out according to a known polymerization method, in a liquid phase or a gas phase, or in a combination of liquid phase and gas phase polymerization stages. Conventional techniques such as slurry processes, gas-phase fluidised beds and the like are employed wherein the olefin is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, in particular the homo-polymerization of propylene or the co-polymerization 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 solid catalyst component for producing the polymer provided by the invention has the following advantages:
(1) The catalyst prepared by using the compound of the acyloxy diaryl phosphate with a special structure and the 1, 3-diether compound as an internal electron donor has high activity and good hydrogen regulation sensitivity;
(2) When the catalyst is used for propylene polymerization, the obtained polypropylene resin has good stereoregularity, moderate polymer molecular weight distribution and excellent comprehensive performance.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The test method of the invention is as follows:
(1) Polymer isotactic index II: measurement by heptane extraction (heptane boiling extraction for 6 hours): 2g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, and the residue was dried to constant weight to give a polymer weight (g) to 2 ratio, i.e.isotactic index.
(2) Melt index MI: the melt flow rate was measured using a melt flow meter 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): the gel permeation chromatography was carried out using PL-GPC220 with trichlorobenzene as solvent at 150℃as a standard sample (polystyrene, flow rate: 1.0mL/min, column: 3xPlgel 10um M1xED-B300X 7.5 nm).
Example 1
Preparation of the solid catalyst component: in a reactor fully replaced by high purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are added in sequence, the temperature is raised to 50 ℃ under stirring and maintained for 2.5h, the solid is completely dissolved, 1.4g of phthalic anhydride is added, and the maintenance is continued for 1h. The solution was cooled to below-25℃and 56mL TiCl was added dropwise over 1h 4 Slowly heating to 80deg.C, gradually precipitating solid during heating, adding 4.2mmol of cinnamoyl diphenyl phosphate and 0.8mmol of 9, 9-bis (methoxymethyl) fluorene compound, maintaining the temperature for 1 hr, filtering, and washing with 70mL toluene for 2 times to obtain solid precipitateA starch. 60mL of toluene and 40mL of TiCl were then added 4 Heating to 110 ℃, maintaining for 2 hours, repeating the same operation once, washing with 70mL of toluene at 110 ℃ for 3 times for 10min each, adding 60mL of hexane, and washing for 2 times to obtain the solid catalyst component.
Propylene polymerization experiment: and respectively carrying out propylene polymerization on the obtained solid catalyst components. The propylene polymerization procedure was: a stainless steel reactor having a volume of 5L was fully replaced with gaseous propylene and charged with 2.5mmol of AlEt 3 And 0.l mmol of external electron donor compound dicyclopentyl dimethoxy silane, 8-10mg of solid catalyst component and 1.2NL of hydrogen are added, 2.3L of liquid propylene is introduced, the temperature is raised to 70 ℃, and the temperature is maintained for 1 hour; cooling and decompressing to obtain PP powder. The catalyst activity was 58.0kg PP/(g.cat), the isotactic index was 98.1%, the melt index was 12.9g/10min, and the molecular weight distribution was 7.6.
Example 2
The procedure is as in example 1 except that the internal electron donor compound is a built-up internal electron donor compound of 0.5mmol of diphenyl acetoxyphosphate and 4.5mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane. The catalyst activity was 67.3kg PP/(g.cat), the isotactic index was 98.5%, the melt index was 13.0g/10min, and the molecular weight distribution was 7.4.
Example 3
The procedure is as in example 1 except that the internal donor compound is a built-up internal donor compound of 2.5mmol of bis (2-methylphenyl) p-isobutylbenzoyloxy phosphate and 2.5mmol of 2, 2-diisobutyl-1, 3-dimethoxypropane. The catalyst activity was 60.5kg PP/(g.cat), the isotactic index was 98.3%, the melt index was 13.5g/10min, and the molecular weight distribution was 7.5.
Comparative example 1
The procedure is as in example 1 except that the internal electron donor compound is 5mmol of bis (2-methylphenyl) p-isobutylbenzoyloxy phosphate. The catalyst activity was 32.2kg PP/(g.cat), the isotactic index was 96.6%, the melt index was 8.4g/10min, and the molecular weight distribution was 7.8.
Comparative example 2
The process is as in example 1, except that the internal electron donor compound is 5mmol of 2, 2-diisobutyl-1, 3-dimethoxypropane. The catalyst activity was 59.9kg PP/(g.cat), the isotactic index was 98.3%, the melt index was 7.7g/10min, and the molecular weight distribution was 4.6.
Comparative example 3
The procedure is as in example 1 except that the internal electron donor compound is a built-up internal electron donor compound of 2.5mmol of cinnamoyloxy diphenylphosphine oxide and 2.5mmol of 2, 2-diisobutyl-1, 3-dimethoxypropane. The catalyst activity was 53.1kg PP/(g.cat), the isotactic index was 97.9%, the melt index was 7.4g/10min, and the molecular weight distribution was 9.0.
The structural formula of the cinnamoyl oxy diphenyl phosphine oxide is as follows:
comparative example 4
The procedure is as in example 1, except that the internal donor compound is a built-up internal donor compound of 2.5mmol of tributyl phosphate and 2.5mmol of 2, 2-diisobutyl-1, 3-dimethoxypropane. The catalyst activity was 43.8kg PP/(g.cat), the isotactic index was 97.4%, the melt index was 7.6g/10min, and the molecular weight distribution was 5.3.
The tributyl phosphate has the following structural formula:
TABLE 1 propylene polymerization results
Wherein:
a: cinnamoyloxy diphenyl phosphate 9, 9-bis (methoxymethyl) fluorene (molar ratio) =5.25:1
B: acetyloxy diphenyl phosphate 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane (molar ratio) =1:9
C: bis (2-methylphenyl) p-isobutylbenzoyloxy phosphate 2, 2-diisobutyl-1, 3-dimethoxypropane=1:1
D: cinnamoyloxy diphenyl phosphine oxide 2, 2-diisobutyl-1, 3-dimethoxy propane (molar ratio) =1:1
E: tributyl phosphate 2, 2-diisobutyl-1, 3-dimethoxypropane (molar ratio) =1:1
As can be seen from Table 1, the catalyst system provided by the invention has very high polymerization activity and very good hydrogen regulation sensitivity, and the obtained polymer has high isotactic index, moderate molecular weight distribution and excellent comprehensive performance, and is beneficial to developing resins with different brands.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (20)
1. A solid catalyst component for producing a polymer 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),
in the general formula (I) of the present invention,
R 1 is C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl, C 3 -C 12 Branched alkyl, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 Aromatic hydrocarbon group of (C) 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl, C 3 -C 12 Branched alkyl, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 2 is hydrogen, halogen or C 1 -C 10 Straight-chain alkyl or C 3 -C 12 Branched alkyl of (C), and said C 1 -C 10 Straight-chain alkyl or C 3 -C 12 The hydrogen on the branched alkyl carbon may be optionally substituted with a substituent;
the substituents are selected from hydroxy, amino, C 1 -C 6 Alkyl-substituted amino, -CHO, -COOH, halogen atom, C 1 -C 6 Alkyl and C of (C) 1 -C 6 Alkoxy groups of (a);
in the general formula (II) of the present invention,
R 3 and R is 4 Identical or different, independently selected from C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 15 Branched hydrocarbon radical, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 An aromatic hydrocarbon group, and C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 15 Branched hydrocarbon radical, C 3 -C 15 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl or C of (2) 7 -C 20 The hydrogen on the carbon of the aromatic hydrocarbon radical being optionally substituted by substituents R 3 And R is 4 Optionally may be bonded to form a ring or not;
the solid catalyst component comprises a reaction product of a magnesium compound, a titanium compound and an internal electron donor compound, wherein the molar ratio of the magnesium compound to the titanium compound to the internal electron donor compound is 1 (0.5-150): 0.02-0.4); the molar ratio of the first internal electron donor to the second internal electron donor compound is (1-100): 100-1.
2. The solid catalyst component according to claim 1, wherein in the general formula (I), R 1 Is C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 12 Cycloalkyl, C 6 -C 18 Aryl, C of (2) 7 -C 18 Alkylaryl, C 7 -C 18 Aralkyl or C of (C) 7 -C 18 And C is as described 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 12 Cycloalkyl, C 6 -C 18 Aryl, C of (2) 7 -C 18 Alkylaryl, C 7 -C 18 Aralkyl or C of (C) 7 -C 18 Hydrogen on the aralkenyl carbon of (c) may optionally be substituted with one or more substituents;
R 2 is hydrogen, halogen or C 1 -C 8 Straight-chain alkyl or C 3 -C 10 Branched alkyl of (C), and said C 1 -C 8 Straight-chain alkyl or C 3 -C 10 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents.
3. The solid catalyst component according to claim 2, wherein in the general formula (I), R 1 Is C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 9 Straight chain alkyl, C 2 -C 3 Straight chain alkenyl, C 4 -C 6 Straight chain alkenyl, C 7 -C 9 Straight chain alkenyl, C 3 -C 6 Branched alkyl, C 7 -C 9 Branched alkyl, C 6 -C 10 Aryl, C of (2) 11 -C 15 Aryl, C of (2) 7 -C 10 Alkylaryl, C 11 -C 15 Alkylaryl, C 7 -C 10 Aralkyl of (C) 11 -C 15 Aralkyl of (C) 7 -C 10 Aralkenyl or C of (C) 11 -C 15 Is a aralkenyl group of (a);
R 2 is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl or C 9 -C 10 Branched alkyl groups of (a).
4. The solid catalyst component according to claim 1, wherein in the general formula (I), R 1 Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, isobutylphenyl, benzyl, phenethyl, phenylpropyl, styryl or phenylpropenyl;
and/or R 2 Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
5. The solid catalyst component according to claim 1, wherein the compound of formula (I) is selected from the group consisting of diphenyl acetoxy phosphate, diphenyl n-propionyloxy phosphate, diphenyl n-butyryloxy phosphate, diphenyl isobutyryloxy phosphate, diphenyl n-pentanoyloxy phosphate, diphenyl isovaleryloxy phosphate, diphenyl n-hexanoyloxy phosphate, diphenyl n-heptanyloxy phosphate, diphenyl n-octanoyloxy phosphate, diphenyl n-nonanyloxy phosphate, diphenyl benzoyloxy phosphate, diphenyl p-methylbenzyloxy phosphate, diphenyl p-ethylbenzoyloxy phosphate, diphenyl p-n-propylbenzoyloxy phosphate, diphenyl p-isopropylbenzoyloxy phosphate, p-n-butylbenzoyloxy diphenyl phosphate, p-isobutylbenzoyloxy diphenyl phosphate, p-tert-butylbenzoyloxy diphenyl phosphate, acetyloxy di (2-tolyl) phosphate, n-propionyloxy di (2-tolyl) phosphate, n-butyryloxy di (2-tolyl) phosphate, isobutyryloxy di (2-tolyl) phosphate, n-pentanoyloxy di (2-tolyl) phosphate, isopentanoyloxy di (2-tolyl) phosphate, n-hexanoyloxy di (2-tolyl) phosphate, n-heptanyloxy di (2-tolyl) phosphate, n-octanoyloxy di (2-tolyl) phosphate, n-nonanyloxy di (2-tolyl) phosphate, benzoyloxy di (2-tolyl) phosphate, p-methylbenzoyloxy phosphate bis (2-methylbenzoate), p-ethylbenzoyloxy phosphate bis (2-methylbenzoate), p-n-propylbenzoyloxy phosphate bis (2-methylbenzoate), p-isopropylbenzoyloxy phosphate bis (2-methylbenzoate), p-n-butylbenzoyloxy phosphate bis (2-methylbenzoate), p-tert-butylbenzoyloxy phosphate bis (2-methylbenzoate), acetoxy phosphate bis (4-methylbenzoate), n-propionyloxy phosphate bis (4-methylbenzoate), n-butyryloxy phosphate bis (4-methylbenzoate), isobutyryloxy phosphate bis (4-methylbenzoate), n-pentanoyloxy phosphate bis (4-methylbenzoate), isovaleryloxy phosphate bis (4-methylbenzoate), n-hexanoyloxy phosphate bis (4-methylbenzoate), n-heptanyloxy phosphate bis (4-methylbenzoate), n-octanoyloxy phosphate bis (4-methylbenzoate), n-nonyloxy phosphate bis (4-methylbenzoate), p-n-butyryloxy phosphate, p-xylyl phosphate, bis (4-methylbenzoate) p-n-butylbenzoyloxy phosphate, bis (4-methylbenzoate) p-isobutylbenzoyloxy phosphate, bis (4-methylbenzoate) p-tert-butylbenzoyloxy phosphate, bis (4-cumyl) acetoxyphosphate, bis (4-cumyl) n-butyryloxy phosphate, bis (4-cumyl) isobutyryloxy phosphate, bis (4-cumyl) n-pentanoyloxy phosphate, bis (4-cumyl) n-hexanoyloxy phosphate, bis (4-cumyl) n-heptanyloxy phosphate, bis (4-cumyl) n-octanoyloxy phosphate, bis (4-cumyl) n-nonanyloxy phosphate, bis (4-cumyl) benzoyloxy phosphate, bis (4-methylbenzoyl phosphate), bis (4-cumyl) p-ethylbenzoyloxy phosphate, bis (4-cumyl) p-propylbenzoyl phosphate, bis (4-cumyl) p-benzoyl phosphate, bis (4-cumyl) n-benzoyl phosphate, one or more of di (4-isopropylphenyl) p-tert-butylbenzoyloxy phosphate and diphenyl cinnamoyloxy phosphate.
6. The solid catalyst component according to claim 1, wherein in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl and C of (C) 7 -C 15 And C is said 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 10 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl and C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with a substituent, R 3 And R is 4 Optionally may be bonded to form a ring or not.
7. According to claim 6A solid catalyst component characterized in that in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 8 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 9 -C 10 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl and C of (2) 12 -C 15 Is one of the aryl groups of (a).
8. The solid catalyst component according to claim 7, wherein in the general formula (II), R 3 And R is 4 The same or different and independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or phenyl.
9. The solid catalyst component according to claim 1, characterized in that, the compound of the general formula (II) is selected from 2, 2-dimethyl-1, 3-dimethoxy propane, 2-diethyl-1, 3-dimethoxy propane, 2-di-n-propyl-1, 3-dimethoxy propane, 2-diisopropyl-1, 3-dimethoxy propane 2, 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-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-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, 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-benzyl-1, 3-dimethoxypropane, 2- (2-methylbutyl) -2-benzyl-1, 3-dimethoxypropane, 2- (2-ethylhexyl) -2-benzyl-1, 3-dimethoxypropane, 2-ethylhexyl-2-benzyl-2-dimethoxypropane, 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-dimethyl-1, 3-dimethoxypropane, 2-dimethylbutyl-1, 3-dimethoxypropane, one or more of 2, 2-bis (2-ethylhexyl) -1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene.
10. The solid catalyst component according to claim 1, characterized in that the reaction product is prepared by a method comprising dissolving a magnesium compound in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a homogeneous mixed solution and mixing with a titanium compound.
11. The solid catalyst component according to claim 1, wherein the molar ratio of the first internal electron donor and the second internal electron donor compound is (1-50): 50-1;
and/or the magnesium compound comprises one or more selected from magnesium dihalide, magnesium alkoxide, magnesium alkyl, hydrate or alkoxide of magnesium dihalide, and derivatives in which one halogen atom in the formula of magnesium dihalide is replaced with an alkoxy group or a haloalkoxy group;
and/or the titanium compound comprises a compound selected from TiX m (OR 1 ) 4-m One or more of the compounds wherein R 1 Is C 1 -C 20 X is halogen, m is more than or equal to 1 and less than or equal to 4.
12. The solid catalyst component according to claim 1, wherein the molar ratio of the first internal electron donor and the second internal electron donor compound is (1-20): 20-1;
and/or the magnesium compound is magnesium dihalide and/or an alkoxide of magnesium dihalide;
And/or the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide.
13. The solid catalyst component according to claim 12, characterized in that the titanium compound is titanium tetrachloride.
14. A catalyst system for the polymerization of olefins comprising the reaction product of:
component a, a solid catalyst component according to any one of claims 1 to 13;
component b, an alkylaluminum compound; and
optionally component c, an external electron donor compound.
15. The catalyst system of claim 14, wherein the external electron donor compound comprises a compound of formula (III):
R 2 k Si(OR 3 ) 4-k (III)
in the general formula (III), k is more than or equal to 0 and less than or equal to 3; r is R 2 Is C 1 -C 10 Alkyl, C of (2) 3 -C 10 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 1 -C 10 A haloalkyl, amino, halogen or hydrogen atom; r is R 3 Is C 1 -C 10 Alkyl, C of (2) 3 -C 10 Cycloalkyl, C 6 -C 20 Aryl, C of (2) 1 -C 10 Haloalkyl or amino;
and/or the molar ratio of the component a, the component b and the component c is 1 (5-1000) in terms of titanium to aluminum to silicon (0-500).
16. The catalyst system of claim 15 wherein the molar ratio of component a, component b and component c is 1 (25-100) to (25-100) in terms of titanium to aluminum to silicon.
17. A prepolymerization catalyst for olefin polymerization comprising a solid catalyst component according to any one of claims 1 to 13 and/or a prepolymer obtained by prepolymerizing a catalyst system according to any one of claims 14 to 16 with an olefin, wherein the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of catalyst component; the general formula of the olefin is CH 2 =chr, wherein R is hydrogen or C 1 -C 6 Is a hydrocarbon group.
18. The prepolymerized catalyst according to claim 17, characterized in that the olefin is ethylene, propylene and/or 1-butene.
19. A process for the polymerization of olefins having the general formula CH in the presence of a solid catalyst component according to any of claims 1 to 13 and/or a catalyst system according to any of claims 14 to 16 and/or a prepolymerized catalyst according to claim 17 or 18 2 =chr, wherein R is hydrogen or C 1 -C 6 Is a hydrocarbon group.
20. The process according to claim 19, wherein the olefin is ethylene, propylene and/or 1-butene.
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