CN114085301B - Solid catalyst component for preparing olefin polymer and application thereof - Google Patents

Solid catalyst component for preparing olefin polymer and application thereof Download PDF

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CN114085301B
CN114085301B CN202010609744.9A CN202010609744A CN114085301B CN 114085301 B CN114085301 B CN 114085301B CN 202010609744 A CN202010609744 A CN 202010609744A CN 114085301 B CN114085301 B CN 114085301B
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straight chain
phosphate
aryl
bis
alkyl
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CN114085301A (en
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李昌秀
许景琦
刘文蕊
何世雄
胡建军
马吉星
马晶
蔡晓霞
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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
    • 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 the preparation of olefin polymers is disclosed 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) or (III). The invention also discloses a catalyst system for olefin polymerization. When the solid catalyst component provided by the invention is used for propylene polymerization, the polymerization activity is high, the stereoregularity is high, the hydrogen regulation sensitivity is good, and the molecular weight distribution of the obtained polypropylene resin is moderate.

Description

Solid catalyst component for preparing olefin polymer and application thereof
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a solid catalyst component for preparing an olefin polymer 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.
Both patent CN1436766a and CN1552740a disclose an internal electron donor of carboxylic acid glycol ester and a process for preparing the same. Although the prepared catalyst is used for propylene polymerization and has the characteristics of higher polymerization activity and wide polymer molecular weight distribution, when the spherical catalyst containing carboxylic glycol ester internal electron donor is used for propylene polymerization, the stereotacticity is poor and the isotacticity of the obtained polypropylene is low. Patent CN201811076102.6 reports that when a phosphine oxide compound and a glycol ester compound are compounded for propylene polymerization, a polymer having a relatively wide molecular weight distribution can be obtained, but the polymerization activity is not sufficiently high.
Disclosure of Invention
The inventor finds that a catalyst with excellent comprehensive performance can be obtained by using a compound of an acyloxy diaryl phosphate compound and a diol ester compound as electron donors in an 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 molecular weight distribution of the obtained polymer is moderate, so that the catalyst is beneficial to the development of polymer brands.
To this end, a first aspect of the present invention provides a solid catalyst component for the preparation of an olefin 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) or (III),
Figure BDA0002560578390000021
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;
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 10 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 Aromatic hydrocarbons of (2)Radical, and C as described 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 5 、R 6 、R 7 and R is 8 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Hydrogen on the aryl carbon of (2) may optionally be substituted with a substituent, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring;
in the general formula (III) of the present invention,
R 9 and R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 Aromatic hydrocarbon radical, R 9 And R is 10 Optionally bonded to form a ring;
R 11 and R is 12 Identical or different, independently selected from halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 13 and R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl and C 3 -C 12 Branched alkyl of (C), and said C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl and C 3 -C 12 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with a substituent.
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 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 or C of (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 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 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 7 Branched alkyl or C 8 -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 or hexyl.
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 8 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 8 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 (c) may be optionally substituted with a substituent.
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 of the invention, in the presence ofIn the formula (II), R 3 Selected from C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 And C is said 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 The hydrogen on the aralkyl carbon of (c) may be optionally substituted with one or more substituents such as phenyl, benzyl, phenethyl and phenylpropyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 4 Selected from C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 And C is said 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 The hydrogen on the aralkyl carbon of (c) may be optionally substituted with one or more substituents such as phenyl, benzyl, phenethyl and phenylpropyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 5 、R 6 、R 7 And R is 8 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with one or more substituents, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 5 、R 6 、R 7 And R is 8 Is the same or different and is independently selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 And C is said 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with one or more substituents, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 5 Is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl or C 6 -C 8 For example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 6 Is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl or C 6 -C 8 For example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 7 Is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl or C 6 -C 8 For example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 8 Is hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl or C 6 -C 8 Branched alkyl groups of (2), e.g. hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butylIsobutyl, sec-butyl, tert-butyl or pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 And R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or arylalkyl radicals R 9 And R is 10 Optionally can be bonded to form a ring.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 And R is 10 The same applies.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 And R is 10 Are not identical.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 Selected from hydrogen, halogen atoms, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 Branched alkyl groups of (a), such as hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 10 Selected from hydrogen, halogen atoms, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 Branched alkyl groups of (a), such as hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
According toPreferred embodiments of the solid catalyst component of the invention, in the general formula (III), R 11 And R is 12 Independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (c) may be optionally substituted with one or more substituents;
according to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 11 And R is 12 The same applies.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 11 And R is 12 Are not identical.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 11 Selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 The hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
The solid catalyst component according to the invention In the general formula (III), R is 12 Selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 The hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 13 And R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl and C 3 -C 10 Branched alkyl of (C), and said C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl and 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 (III), R 13 And R is 14 The same applies.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 13 And R is 14 Are not identical.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 13 Selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl and C of (2) 9 -C 10 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl and C of (2) 9 -C 10 The hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 14 Selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl and C of (2) 9 -C 10 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl and C of (2) 9 -C 10 The hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.
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 the general formula (I) with an internal electron donor compound represented by the general formula (II) or (III).
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 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 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 (IV):
R 2 k Si(OR 3 ) 4-k (IV)
in the general formula (IV), 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 olefins are preferably ethylene, propylene and/or1-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 olefin is 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 preparation of an olefin 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) or (III),
Figure BDA0002560578390000101
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Figure BDA0002560578390000111
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;
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 10 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 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 5 、R 6 、R 7 and R is 8 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Hydrogen on the aryl carbon of (2) may optionally be substituted with a substituent, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring;
in the general formula (III) of the present invention,
R 9 and R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 Aromatic hydrocarbon radical, R 9 And R is 10 Optionally bonded to form a ring;
R 11 and R is 12 Identical or different, independently selected from halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 Cyclic hydrocarbon radicals, C 6 -C 20 Aryl, C of (2) 7 -C 20 Hydrocarbon aryl and C of (C) 7 -C 20 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 13 and R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl and C 3 -C 12 Branched alkyl of (C), and said C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl and C 3 -C 12 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with a substituent.
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 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 or C of (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 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 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 7 Branched alkyl or C 8 -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 or hexyl.
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 8 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 alkanes of (2)Radical, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 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 (c) may be optionally substituted with a substituent.
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 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 And C is said 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 Hydrogen on the aralkyl 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 (II), R 3 And R is 4 The same or different is independently selected from phenyl, benzyl, phenethyl and phenylpropyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 5 、R 6 、R 7 And R is 8 Identical or different and independently selected from hydrogen, halogen, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an oxygen atom and a nitrogen atom, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 5 、R 6 、R 7 And R is 8 Is the same or different and is independently selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 And C is said 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl and C of (C) 13 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with one or more substituents, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may beBonded into a ring.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (II), R 5 、R 6 、R 7 And R is 8 The same or different is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
According to the solid catalyst component of the present invention, the compound in the general formula (II) is selected from, but not limited to, the following compounds:
1, 2-phenylene dibenzoate, 1, 2-phenylene bis (2, 4, 6-trimethylbenzoate), 4-methyl-1, 2-phenylene dibenzoate, 4-methyl-1, 2-phenylene bis (2-methylbenzoate), 4-methyl-1, 2-phenylene bis (2, 4, 6-trimethylbenzoate), 4-tert-butyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene bis (2-methylbenzoate), 4-tert-butyl-1, 2-phenylene bis (2, 4, 6-trimethylbenzoate), 3, 6-dimethyl-1, 2-phenylene dibenzoate, 3, 6-dichloro-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3-tert-butyl-5-methyl-1, 2-phenylene dibenzoate, 3, 5-di-tert-butyl-1, 2-phenylene dibenzoate, 3-methyl-1, 2-phenylene dibenzoate, 3-dimethyl-1, 2-diphenyl benzoate, 3-dimethyl-1, 2-phenylene dibenzoate, 3-dimethyl-1, 5-dimethyl-ethoxy-2-phenylene dibenzoate, 3-dichloro-1, 2-phenylene dibenzoate, 3-dimethyl-5-p-dimethyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-fluorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-chlorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (2, 4, 6-trimethylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (1-naphthoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (2-naphthoate), 1, 2-naphthalenedibenzoate and 2, 3-naphthalenedibenzoate.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 And R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or arylalkyl radicals R 9 And R is 10 Optionally can be bonded to form a ring;
according to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 And R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 Branched alkyl of R 9 And R is 10 Optionally bonded to form a ring.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 9 And R is 10 The same or different is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 11 And R is 12 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl 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 (III), R 11 And R is 12 Identical or different, independently selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl and C of (2) 6 -C 8 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 (III), R 11 And R is 12 The same or different is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
According to a preferred embodiment of the solid catalyst component according to the invention, in the general formula (III), R 13 And R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl and C 3 -C 10 Branched alkyl of (C), and said C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl and 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 (III), R 13 And R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl and C of (2) 9 -C 10 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl and C of (2) 9 -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 (III), R 13 And R is 14 The same or different is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.
According to the solid catalyst component of the present invention, the compound in the general formula (III) is selected from, but not limited to, the following compounds:
2, 4-pentanediol dibenzoate, 2, 4-pentanediol bis (4-methylbenzoate), 2, 4-pentanediol bis (3-methylbenzoate), 2, 4-pentanediol bis (2-methylbenzoate), 2, 4-pentanediol bis (4-ethylbenzoate), 2, 4-pentanediol bis (4-n-propylbenzoate), 2, 4-pentanediol bis (4-isopropylbenzoate), 2, 4-pentanediol bis (4-n-butylbenzoate), 2, 4-pentanediol bis (4-isobutylbenzoate), 2, 4-pentanediol bis (4-tert-butylbenzoate), 2, 4-pentanediol dicannamate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol bis (4-methylbenzoate), 3-ethyl-2, 4-pentanediol bis (4-ethylbenzoate), 3-ethyl-2, 4-pentanediol bis (4-ethyl benzoate), 3-ethyl-2, 4-pentanediol bis (4-n-propyl benzoate), 3-ethyl-2, 4-pentanediol dibenzoate), 3-ethyl-2-n-butyl benzoate, 3-ethyl-2, 4-pentanediol bis (4-isobutyl benzoate), 3-ethyl-2, 4-pentanediol bis (4-tert-butyl benzoate), 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 3-chloro-2, 4-pentanediol dibenzoate, 3-bromo-2, 4-pentanediol dibenzoate, 3, 5-heptanediol bis (4-methylbenzoate), 3, 5-heptanediol bis (4-ethylbenzoate), 3, 5-heptanediol bis (4-n-propyl benzoate), 3, 5-heptanediol bis (4-isopropylbenzoate), 3, 5-heptanediol bis (4-n-butyl benzoate), 3, 5-heptanediol bis (4-isobutyl benzoate), 3, 5-heptanediol bis (4-tert-butyl benzoate), 3, 5-heptanediol dicannamate, 4-methyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4-ethyl-4-heptanediol benzoate, 4-ethyl-heptanediol dibenzoate, 4-ethyl-4-heptanediol benzoate, 4-ethyl-3, 5-heptanediol bis (4-n-propyl benzoate), 4-ethyl-3, 5-heptanediol bis (4-isopropyl benzoate), 4-ethyl-3, 5-heptanediol bis (4-n-butyl benzoate), 4-ethyl-3, 5-heptanediol bis (4-isobutyl benzoate), 4-ethyl-3, 5-heptanediol bis (4-t-butyl benzoate), 4-propyl-2, 4-pentanediol dibenzoate, 4-butyl-2, 4-pentanediol dibenzoate, 4-chloro-2, 4-pentanediol dibenzoate, 4-bromo-2, 4-pentanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 4-chloro-3, 5-heptanediol dibenzoate, and 4-bromo-3, 5-heptanediol dibenzoate, and the like.
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 the general formula (I) with an internal electron donor compound represented by the general formula (II) or (III).
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.
In some embodiments of the invention, the magnesium compound comprises one or more of magnesium dihalide, magnesium alkoxide, magnesium alkyl, hydrate or alkoxide of magnesium dihalide, and derivatives of magnesium dihalide in which one halogen atom is replaced with an alkoxy 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.
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 the present invention, the solid catalyst component can be obtained by dissolving a magnesium compound in a solvent system containing a hydrocarbon compound and an alcohol compound, then mixing a titanium compound with the above solution at-40 to 40 ℃, adding an electron donor compound at-40 to 150 ℃, and washing with an inert diluent.
The hydrocarbon compound comprises a straight or branched C 6 -C 12 Alkanes and C 6 -C 15 Such as hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, etc.
The alcohol compound comprises fatty alcohol, alicyclic alcohol and aromatic alcohol, wherein the fatty alcohol is straight chain or branched C 1 -C 10 Aliphatic alcohol, alicyclic alcohol is C 3 -C 10 The cycloaliphatic fatty alcohol and the aromatic alcohol are C 6 -C 20 Aryl or alkylaryl alcohols of (a); such as ethanol, propanol, butanol, pentanol, hexanol, octanol, isooctanol, and the like, or mixtures thereof.
The inert diluent is selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene and xylene.
The solid catalyst component described in the present invention can be prepared by the following method: the solid catalyst component was prepared according to the method disclosed in patent CN 1040379. Firstly, mixing a magnesium compound and an organic alcohol compound according to a molar ratio of 2-5 and an inert solvent, heating to 120-150 ℃, and reacting for 1-5 hours according to a molar ratio of 5-10 of magnesium/anhydride. Then adding the alcohol compound cooled to room temperature into titanium compound solution precooled to-15 to 40 ℃ according to the molar ratio of titanium to magnesium of 20-50, heating to 90-110 ℃, adding an internal electron donor compound selected from the general formulas (I) and (II) according to the molar ratio of magnesium to electron donor of 2-10, reacting for 1-3 hours at 100-130 ℃, and filtering to separate solid particles. Adding the solid particles into the titanium compound solution according to the molar ratio of titanium to magnesium of 20-50, stirring and reacting for 1.5-3 hours at 100-130 ℃, and filtering to separate the solid particles. Finally, washing the solid particles by using an inert solvent at 50-80 ℃ and drying to obtain the solid catalyst component.
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.
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 (IV):
R 2 k Si(OR 3 ) 4-k (IV)
in the general formula (IV), 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 in 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 preparing the olefin polymer provided by the invention has the following advantages:
(1) The catalyst prepared by using the compound of the acyloxy diaryl phosphate and the diol ester with special structures as the 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 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 solid catalyst component a: under the protection of nitrogen, adding 4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent into a 500ml reactor with a stirrer, heating to 130 ℃, reacting for 1.5 hours until the magnesium chloride is completely dissolved, adding 1.1g of phthalic anhydride, and continuously maintaining the temperature of 130 ℃ for reacting for 1 hour to obtain an alkoxide; the alcohol was cooled to room temperature. Under the protection of nitrogen, the alcohol compound is dropwise added into 120ml of titanium tetrachloride solution precooled to the temperature of minus 22 ℃, the temperature is slowly raised to 100 ℃, 4mmol of 4-n-butylbenzoyloxy di (4-methyl phenyl phosphate) and 1mmol of 3-ethyl-2, 4-pentanediol di-p-butyl benzoate compound as an internal electron donor compound are added, the temperature is raised to 110 ℃ for 2 hours, and the mixture is filtered while the mixture is hot. Then 120ml of titanium tetrachloride is added, the temperature is raised to 110 ℃ for reaction for 1 hour, filtration is carried out, the solid particles are washed by anhydrous hexane for 4 times, and the solid catalyst component is obtained after drying.
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, 8-10 mg of solid catalyst component a 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 58.2kg PP/(g.cat), the isotactic index was 98.2%, the melt index was 6.9g/10min, and the molecular weight distribution was 7.5.
Example 2
The procedure is as in example 1 except that the internal donor compound is a built-up internal donor compound of 0.5mmol of bis (4-isopropylphenyl) isovaleryloxy phosphate and 4.5mmol of 2, 4-hexanediol dibenzoate. The catalyst activity was 59.9kg PP/(g.cat), the isotactic index was 98.5%, the melt index was 8.4g/10min, and the molecular weight distribution was 7.2.
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 diphenyl acetoxy phosphate and 2.5mmol of 4-ethyl 3, 5-heptanediol di-p-tert-butyl benzoate. The catalyst activity was 58.7kg PP/(g.cat), the isotactic index was 98.2%, the melt index was 7.9g/10min, and the molecular weight distribution was 7.8.
Comparative example 1
The process is the same as in example 1 except that the internal electron donor compound is 5mmol of diphenyl acetoxy phosphate. The catalyst activity was 33.0kg PP/(g.cat), the isotactic index was 96.2%, the melt index was 8.3g/10min, and the molecular weight distribution was 7.7.
Comparative example 2
The process is as in example 1 except that the internal electron donor compound is 5mmol of 4-ethyl 3, 5-heptanediol di-p-tert-butyl benzoate. The catalyst activity was 56.5kg PP/(g.cat), the isotactic index was 98.1%, the melt index was 2.9g/10min, and the molecular weight distribution was 7.0.
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 4-ethyl 3, 5-heptanediol di-p-tert-butyl benzoate. The catalyst activity was 51.9kg PP/(g.cat), the isotactic index was 98.0%, the melt index was 7.4g/10min, and the molecular weight distribution was 9.2.
The structural formula of the cinnamoyl oxy diphenyl phosphine oxide is as follows:
Figure BDA0002560578390000241
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 4-ethyl 3, 5-heptanediol di-p-tert-butyl benzoate. 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 6.8.
Example 4
The procedure is as in example 1 except that the internal donor compound is a built-up internal donor compound of 4.2mmol of bis (4-methylphenyl) p-butylbenzoyloxy phosphate and 0.8mmol of 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-methylbenzoate). The catalyst activity was 44.0kg PP/(g.cat), the isotactic index was 98.0%, the melt index was 7.8g/10min, and the molecular weight distribution was 7.8.
Example 5
The procedure is as in example 1 except that the internal donor compound is a built-up internal donor compound of 1mmol of bis (4-isopropylphenyl) isovaleryloxy phosphate and 4mmol of 1, 2-naphthalene dibenzoate. The catalyst activity was 35.1kg PP/(g.cat), the isotactic index was 98.2%, the melt index was 7.9g/10min, and the molecular weight distribution was 7.7.
Example 6
The procedure is as in example 1 except that the internal donor compound is a built-up internal donor compound of 2.5mmol of diphenyl acetoxyphosphate and 2.5mmol of 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-chlorobenzoate). The catalyst activity was 42.5kg PP/(g.cat), the isotactic index was 98.1%, the melt index was 8.0g/10min, and the molecular weight distribution was 7.5.
Comparative example 5
The process is as in example 1 except that the internal electron donor compound is 5mmol of 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-chlorobenzoate). The catalyst activity was 42.4kg PP/(g.cat), the isotactic index was 98.2%, the melt index was 1.5g/10min, and the molecular weight distribution was 6.3.
TABLE 1 propylene polymerization results
Figure BDA0002560578390000251
Wherein:
a: bis (4-methylphenyl) 4-n-butylbenzoyloxy phosphate 3-ethyl-2, 4-pentanediol di-n-butylbenzoate (molar ratio) =4:1
B: bis (4-isopropylphenyl) isovaleryloxy phosphate 2, 4-hexanediol dibenzoate (molar ratio) =1:9
C: acetyloxy diphenyl phosphate 4-ethyl-3, 5-heptanediol di-p-tert-butyl benzoate (molar ratio) =1:1
D: cinnamoyloxy diphenylphosphine oxide 4-ethyl-3, 5-heptanediol di-p-tert-butylbenzoate (molar ratio) =1:1
E: tributyl phosphate 4-ethyl 3, 5-heptanediol di-p-tert-butyl benzoate (molar ratio) =1:1
F: bis (4-methylphenyl) p-butylbenzoyloxy phosphate 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-methylbenzoate) (molar ratio) =5.25:1
G: bis (4-isopropylphenyl) isovaleryloxy phosphate 1, 2-naphthalene dibenzoate (molar ratio) =1:4
H: acetyloxy diphenyl phosphate 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-chlorobenzoate) (molar ratio) =1:1
In conclusion, the catalyst system provided by the invention can greatly improve the hydrogen regulation sensitivity while maintaining the high polymerization activity and isotactic index of the catalyst and the moderate wide molecular weight distribution of the obtained polymer, and the obtained polymer has excellent comprehensive performance, thus being very beneficial to the development of resins of 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 (25)

1. A solid catalyst component for the preparation of an olefin 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) or (III),
Figure FDA0004087586820000011
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;
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 10 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 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Hydrogen on the aryl carbon of (c) may be optionally substituted with a substituent;
R 5 、R 6 、R 7 and R is 8 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Aromatic hydrocarbon group of (C) 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 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 Hydrogen on the aryl carbon of (2) may optionally be substituted with a substituent, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring;
in the general formula (III) of the present invention,
R 9 and R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 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 radical, R 9 And R is 10 Optionally bonded to form a ring;
R 11 and R is 12 Identical or different, independently selected from halogen atoms, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 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 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl, C 3 -C 10 Branched hydrocarbon radical, C 3 -C 10 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 13 and R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl or C 3 -C 12 Branched alkyl of (C), and said C 1 -C 12 Straight chain alkyl, C 2 -C 12 Straight chain alkenyl or C 3 -C 12 Hydrogen on the branched alkyl carbon of (2) may optionally be substituted with a substituent;
in the solid catalyst component, 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 compound to the second internal electron donor compound is (1-100): 100-1;
The substituents are selected from hydroxy, amino, C 1 -C 6 Alkyl-substituted amino, -CHO, -COOH, halogen atom, C 1 -C 6 Alkyl or C of (2) 1 -C 6 Alkoxy groups of (a).
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;
and/or 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);
and/or 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 7 Branched alkyl or C 8 -C 10 Branched alkyl groups of (a).
4. The solid catalyst component according to claim 2, wherein 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;
and/or R 2 Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl.
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-t-butylbenzoyloxy phosphate, bis (4-methylbenzoate) acetoxy phosphate, bis (4-isopropylphenyl) n-propionyloxy phosphate, bis (4-isopropylphenyl) n-butyryloxy phosphate, bis (4-isopropylphenyl) isobutyryloxy phosphate, bis (4-isopropylphenyl) n-pentanoyloxy phosphate, bis (4-isopropylphenyl) pivaloyloxy phosphate, bis (4-isopropylphenyl) n-hexanoyloxy phosphate, bis (4-isopropylphenyl) n-heptanyloxy phosphate, bis (4-isopropylphenyl) n-octanoyloxy phosphate, bis (4-nonyloxy phosphate), bis (4-isopropylphenyl) benzoyloxy phosphate, bis (4-isopropylphenyl) p-methylbenzyloxy phosphate, bis (4-isopropylphenyl) p-ethylbenzoyloxy phosphate, bis (4-isopropylphenyl) p-n-propionyloxy phosphate, bis (4-isopropylphenyl) p-butyloxy phosphate, one or more of di (4-isopropylphenyl) p-tert-butylbenzoyloxy phosphate and diphenyl cinnamoyloxy phosphate.
6. The solid catalyst component according to any one of claims 1 to 5, characterized in that 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 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (c) may be optionally substituted with a substituent;
and/or R 5 、R 6 、R 7 And R is 8 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with one or more substituents, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring.
7. The solid catalyst component according to claim 6, wherein in the general formula (II), R 3 And R is 4 Identical or different, independently selected from C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl or C of (C) 13 -C 15 And C is said 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl or C of (C) 13 -C 15 Hydrogen on the aralkyl carbon of (c) may be optionally substituted with one or more substituents;
and/or R 5 、R 6 、R 7 And R is 8 Is the same or different and is independently selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl or C of (C) 13 -C 15 And C is said 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 3 -C 5 Branched alkyl, C 6 -C 8 Branched alkyl, C 6 -C 8 Aryl, C of (2) 9 -C 11 Aryl, C of (2) 12 -C 15 Aryl, C of (2) 7 -C 9 Alkylaryl, C 10 -C 12 Alkylaryl, C 13 -C 15 Alkylaryl, C 7 -C 9 Aralkyl of (C) 10 -C 12 Aralkyl or C of (C) 13 -C 15 Hydrogen on the aralkyl carbon of (2) may be optionally substituted with one or more substituents, R 5 、R 6 、R 7 And R is 8 Any two adjacent groups may be bonded to form a ring.
8. The solid catalyst component according to claim 1, characterized in that the compound of formula (II) is selected from: 1, 2-phenylene dibenzoate, 1, 2-phenylene bis (2, 4, 6-trimethylbenzoate), 4-methyl-1, 2-phenylene dibenzoate, 4-methyl-1, 2-phenylene bis (2-methylbenzoate), 4-methyl-1, 2-phenylene bis (2, 4, 6-trimethylbenzoate), 4-tert-butyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene bis (2-methylbenzoate), 4-tert-butyl-1, 2-phenylene bis (2, 4, 6-trimethylbenzoate), 3, 6-dimethyl-1, 2-phenylene dibenzoate, 3, 6-dichloro-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3-tert-butyl-5-methyl-1, 2-phenylene dibenzoate, 3, 5-di-tert-butyl-1, 2-phenylene dibenzoate, 3-methyl-1, 2-phenylene dibenzoate, 3-dimethyl-1, 2-diphenyl benzoate, 3-dimethyl-1, 2-phenylene dibenzoate, 3-dimethyl-1, 5-dimethyl-ethoxy-2-phenylene dibenzoate, 3-dichloro-1, 2-phenylene dibenzoate, 3-dimethyl-5-p-dimethyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-fluorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (4-chlorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (2, 4, 6-trimethylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (1-naphthoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (2-naphthoate), 1, 2-naphthalenedibenzoate and 2, 3-naphthalenedibenzoate.
9. The solid catalyst component according to any one of claims 1 to 5, characterized in that in the general formula (III), R 9 And R is 10 Identical or different, independently selected from hydrogen, halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Aralkyl of R 9 And R is 10 Optionally can be bonded to form a ring;
and/or R 11 And R is 12 Identical or different, independently selected from halogen atoms, C 1 -C 8 Straight chain alkyl, C 2 -C 8 Straight chain alkenyl, C 3 -C 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or 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 8 Branched alkyl, C 3 -C 8 Cycloalkyl, C 6 -C 15 Aryl, C of (2) 7 -C 15 Alkylaryl or C of (C) 7 -C 15 Hydrogen on the aralkyl carbon of (c) may be optionally substituted with one or more substituents;
and/or R 13 And R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl or C 3 -C 10 Branched alkyl of (C), and said C 1 -C 10 Straight chain alkyl, C 2 -C 10 Straight chain alkenyl or C 3 -C 10 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents.
10. The solid catalyst component according to claim 9, wherein in the general formula (III), R 9 And R is 10 The same or different are independently selected from hydrogen, halogen atoms, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl or C 6 -C 8 Branched alkyl of R 9 And R is 10 Optionally can be bonded to form a ring;
and/or R 11 And R is 12 Identical or different, independently selected from C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl or C 6 -C 8 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 6 Straight chain alkenyl, C 3 -C 5 Branched alkyl or C 6 -C 8 Hydrogen on the branched alkyl carbon of (2) may optionally be substituted with one or more substituents;
and/or R 13 And R is 14 Is the same or different and is independently selected from hydrogen, C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl or C 9 -C 10 Branched alkyl of (C), and said C 1 -C 3 Straight chain alkyl, C 4 -C 6 Straight chain alkyl, C 7 -C 10 Straight chain alkyl, C 2 -C 4 Straight chain alkenyl, C 5 -C 7 Straight chain alkenyl, C 8 -C 10 Straight chain alkenyl, C 3 -C 5 Branched alkyl, C 6 -C 9 Branched alkyl or C 9 -C 10 Hydrogen on the branched alkyl carbon of (c) may optionally be substituted with one or more substituents.
11. The solid catalyst component according to claim 10, wherein in the general formula (III), R 9 And R is 10 The same or different and independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl;
and/or R 11 And R is 12 The same or different and independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or amyl.
12. The solid catalyst component according to claim 1, wherein the compound of formula (III) is selected from the group consisting of 2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (4-methylbenzoate), 2, 4-pentanediol di (3-methylbenzoate), 2, 4-pentanediol di (2-methylbenzoate), 2, 4-pentanediol di (4-ethylbenzoate), 2, 4-pentanediol di (4-n-propyl benzoate), 2, 4-pentanediol di (4-isopropylbenzoate), 2, 4-pentanediol di (4-n-butylbenzoate), 2, 4-pentanediol di (4-isobutyl benzoate), 2, 4-pentanediol di (4-tert-butylbenzoate), 2, 4-pentanediol dicannamate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol di (4-methyl benzoate), 3-ethyl-2, 4-pentanediol di (4-ethylbenzoate), 3-ethyl-2, 4-pentanediol di (4-n-butylbenzoate), 3-ethyl-2, 4-ethylbenzoate, 4-ethyl-pentanediol di (4-n-propyl benzoate), 3-ethyl-2, 4-pentanediol bis (4-n-butyl benzoate), 3-ethyl-2, 4-pentanediol bis (4-isobutyl benzoate), 3-ethyl-2, 4-pentanediol bis (4-t-butyl benzoate), 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 3-chloro-2, 4-pentanediol dibenzoate, 3-bromo-2, 4-pentanediol dibenzoate, 3, 5-heptanediol bis (4-methyl benzoate), 3, 5-heptanediol bis (4-ethyl benzoate), 3, 5-heptanediol bis (4-n-propyl benzoate), 3, 5-heptanediol bis (4-isopropyl benzoate), 3, 5-heptanediol bis (4-n-butyl benzoate), 3, 5-heptanediol bis (4-t-butyl benzoate), 3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 4-dimethyl-heptanediol dibenzoate, 4-ethyl benzoate, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, one or more of 4-ethyl-3, 5-heptanediol bis (4-ethylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-n-propylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-isopropylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-n-butylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-isobutylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-tert-butylbenzoate), 4-propyl-2, 4-pentanediol dibenzoate, 4-butyl-2, 4-pentanediol dibenzoate, 4-chloro-2, 4-pentanediol dibenzoate, 4-bromo-2, 4-pentanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 4-chloro-3, 5-heptanediol dibenzoate, and 4-bromo-3, 5-heptanediol dibenzoate.
13. The solid catalyst component according to any one of claims 1 to 5, 7 to 8, 10 to 12, characterized in that it comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound;
and/or the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-50): 50-1.
14. The solid catalyst component according to claim 13 in which the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-20): 20-1.
15. The solid catalyst component according to any one of claims 1 to 5, 7 to 8, 10 to 12, wherein the magnesium compound comprises one or more selected from the group consisting of magnesium dihalide, magnesium alkoxide, magnesium alkyl, hydrates or alkoxides of magnesium dihalide and derivatives of magnesium dihalide in which one halogen atom is replaced by 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.
16. The solid catalyst component according to claim 13, characterized in that the magnesium compound comprises 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.
17. The solid catalyst component according to claim 16, wherein the titanium compound is titanium tetrachloride.
18. 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 17;
component b, an alkylaluminum compound; and
optionally component c, an external electron donor compound.
19. The catalyst system of claim 18, wherein the external electron donor compound comprises a compound of formula (IV):
R 2 k Si(OR 3 ) 4-k (IV)
in the general formula (IV), 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.
20. The catalyst system of any of claims 18-19, wherein 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.
21. The catalyst system of any of claims 18-19, 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.
22. A prepolymerized catalyst for olefin polymerization comprising the catalyst according toA prepolymer obtained by prepolymerizing the solid catalyst component according to any one of claims 1 to 17 and/or the catalyst system according to any one of claims 18 to 21 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.
23. The prepolymerized catalyst according to claim 22, characterized in that the olefin is ethylene, propylene and/or 1-butene.
24. 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 17 and/or a catalyst system according to any of claims 18 to 21 and/or a prepolymerized catalyst according to claim 22 or 23 2 =chr, wherein R is hydrogen or C 1 -C 6 Is a hydrocarbon group.
25. The process of claim 24, wherein the olefin is ethylene, propylene, and/or 1-butene.
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