CN111072813B - Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method - Google Patents

Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method Download PDF

Info

Publication number
CN111072813B
CN111072813B CN201811223690.1A CN201811223690A CN111072813B CN 111072813 B CN111072813 B CN 111072813B CN 201811223690 A CN201811223690 A CN 201811223690A CN 111072813 B CN111072813 B CN 111072813B
Authority
CN
China
Prior art keywords
compound
catalyst component
substituted
electron donor
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811223690.1A
Other languages
Chinese (zh)
Other versions
CN111072813A (en
Inventor
赵瑾
夏先知
刘月祥
凌永泰
谭扬
李威莅
陈龙
任春红
高富堂
刘涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201811223690.1A priority Critical patent/CN111072813B/en
Publication of CN111072813A publication Critical patent/CN111072813A/en
Application granted granted Critical
Publication of CN111072813B publication Critical patent/CN111072813B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

The invention belongs to the field of catalysts, and relates to a catalyst component and a catalyst for olefin polymerization, application thereof and an olefin polymerization method. The catalyst component comprises the reaction product of: (1) a solid component; (2) at least one titanium compound; and (3) an internal electron donor compound; wherein the solid component is at least one sulfur-containing magnesium compound; the internal electron donor compound comprises an internal electron donor compound a and an internal electron donor compound b, wherein the internal electron donor compound a is a glycol ester compound, and the internal electron donor compound b is a diether compound. The catalyst of the present invention shows ultrahigh stereospecificity when used for olefin polymerization, especially propylene polymerization.

Description

Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, application of the catalyst component and the catalyst, and an olefin polymerization method.
Background
It is known that a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor compound as essential components is used in olefin polymerization, and particularly has high polymerization activity and stereospecificity in propylene polymerization. The electron donor compound is one of essential components in the solid titanium catalyst component, plays a decisive role in important indexes such as polymerization activity, isotactic index of polymer, molecular weight distribution and the like, and the continuous updating of the polyolefin catalyst is carried out along with the development of the internal electron donor compound.
In order to improve the overall performance of the catalyst, researchers have been conducting a great deal of research. In some researches, the compound of two (or more) internal electron donors is adopted to make up the deficiency of the performance of a single internal electron donor and improve the comprehensive performance of the catalyst. Such as: in the technology disclosed in the patent US6825309B2, the succinate and the phthalate are compounded, so that the characteristic of wide molecular mass distribution of a polymer of the succinate catalyst is maintained, and the stereospecificity of the catalyst is further improved; the catalyst component and the catalyst disclosed in Chinese patent ZL200410073623.8 are prepared by compounding 1, 3-diol ester and dibutyl phthalate, and are used for propylene polymerization to obtain a polymer with high isotacticity and wide molecular weight distribution. The catalyst component and the catalyst disclosed in the Chinese patent CN1743346 are prepared by compounding three electron donors, specifically 1, 3-diol ester, dibutyl phthalate and ethyl benzoate, so that the activity of the obtained catalyst is improved, and the molecular weight distribution and isotacticity of the obtained polymer are also improved.
In some studies, the catalyst performance is improved by improving the catalyst preparation process, and the microstructures of the solid catalyst components obtained by different preparation processes may be greatly different, which causes the number of active centers and the distribution of various active centers to be different, so that the catalyst performance is greatly different. The improvement of the catalyst preparation process mainly comprises the use of different magnesium chloride carriers, different preparation methods and optimization of preparation conditions. The preparation of the catalyst component is disclosed in patent WO02/48208, which strongly suggests the use of very high solids concentrations, indicating that the activity and isotactic index decrease with decreasing solids concentration. The preparation of the solid catalyst component according to the technique of patent US4226741 achieves significant improvements in both activity and stereoselectivity. CN101472681A provides a method for preparing a catalyst by adding ester step by step, and when the catalyst obtained by the method is used for olefin polymerization, the content of fine powder in the polymer can be obviously reduced.
Due to the morphological characteristics of the spherical polypropylene catalyst and the existence of the phenomenon of 'duplication' from the catalyst to the polymer (namely, only the spherical catalyst can obtain the spherical polymer), the spherical catalyst has great advantages in the polymerization production process and the subsequent processing process of the polymer, and is particularly beneficial to the production of high molecular alloy. Therefore, in the polypropylene catalysts currently used in industry, the proportion of spherical catalysts is very large. The spherical carrier and the internal electron donor are two important components of the spherical polypropylene catalyst. The spherical carrier is mainly from a magnesium chloride alcohol compound carrier, magnesium chloride and alcohol react at high temperature to form the magnesium chloride alcohol compound, the magnesium chloride alcohol compound is melted and dispersed in an inert component, then emulsion is formed through high shearing, and the alcohol compound is solidified and formed after the emulsion is transferred into a low-temperature medium to obtain the carrier. In the production process of the carrier, melting at high temperature and solidification at low temperature are required, and thus, a large amount of energy is consumed. In order to solve the problem, CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an oxirane compound, and specifically discloses adding the oxirane compound after melting and dispersing the magnesium halide alcoholate; or the magnesium halide alcoholate is directly added into a reactor containing the ethylene oxide compound after being melted and dispersed. However, the catalyst carrier prepared by the method has the defects of unstable preparation process, easy carrier adhesion, poor carrier forming effect and wide particle size distribution.
The magnesium chloride alcoholate carrier cannot prepare a spherical carrier having a particle size of less than 20 μm due to its characteristics, and the above method cannot obtain a carrier having the same particle size. In general, small particle size supports not only reduce the fines of polymer from the catalyst produced but are also widely used in various gas phase polymerization processes.
Therefore, there is an urgent need to develop a small-particle-size spherical polyolefin catalyst having high stereospecificity.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, the use of the catalyst component and the catalyst, and a process for olefin polymerization.
The inventor of the present invention has unexpectedly found in the research that sulfur is added in the preparation process of the olefin polymerization catalyst carrier, so that a carrier shown in formula I with a novel composition can be obtained, the carrier has good particle shape, smooth surface and basically no special-shaped particles, and the particle size can be realized to be less than 20 microns, and the particle size distribution is narrow. The sulfur-containing spherical magnesium compound is used as a carrier, and the glycol ester compound and the 1, 3-diether compound in a specific ratio are used as internal electron donors, so that the spherical catalyst with the average particle size of less than 25 micrometers can be prepared, the obtained catalyst shows ultrahigh stereospecificity when used for olefin polymerization, particularly propylene polymerization, and the activity is not remarkably improved along with the increase of the hydrogenation amount in polymerization.
In this regard, a first aspect of the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component comprising the reaction product of:
(1) a solid component;
(2) at least one titanium compound; and
(3) an internal electron donor compound;
wherein the solid component is at least one sulfur-containing magnesium compound represented by formula I;
Figure BDA0001835409330000041
in the formula I, R1Is C1-C8Linear or branched alkyl of, or C3-C8Cycloalkyl groups of (a);
R2and R3Identical or different, each independently of the others, is hydrogen or C1-C5The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be optionally substituted with a halogen atom;
x is halogen, preferably chlorine or bromine;
m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0< q is less than or equal to 0.5;
wherein the internal electron donor compound comprises an internal electron donor compound a and an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.1-30: 1, preferably 0.25 to 10: 1; the internal electron donor compound a is a diol ester compound shown as a formula II, and the internal electron donor compound b is a diether compound shown as a formula III;
Figure BDA0001835409330000042
in the formula II, R4And R5Identical or different, each independently is halogen, C1-C20Straight or branched alkyl of (2), C2-C20Linear or branched alkenyl of (C)3-C20Substituted or unsubstituted cycloalkyl of (1), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is optionally substituted by halogen, C1-C6And C is a straight or branched alkyl group1-C6Substituted with one or more of alkoxy groups of (a);
R6、R7、R8、R9and R1-R2nThe same or different, each independently is hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted alkylaryl of, C7-C20Substituted or unsubstituted aralkyl of (1), C2-C10And C is a linear or branched alkylene group2-C20One of the ester groups of (1), R6、R7、R8、R9And R1-R2nOptionally substituted with heteroatoms, which are one or more of halogen, nitrogen, oxygen, sulfur, silicon and phosphorus; or, R6、R7、R8、R9And R1-R2nTwo or more of them are mutually bonded to form a ring;
n is an integer of 0 to 10;
Figure BDA0001835409330000051
in the formula III, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstitutedAralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is one of substituted or unsubstituted alkaryl groups.
In the present invention, C1-C20Examples of the linear or branched alkyl group of (b) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, n-eicosyl.
In the present invention, C2-C20Examples of the linear or branched alkenyl groups of (a) may include, but are not limited to: vinyl, allyl, isopropenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, phenylvinyl, phenyl-n-butenyl, geranyl, 1-decenyl, 1-tetradecenyl, 1-octadecenyl, 9-octadecenyl, 1-eicosenyl, 1-octadecenyl, 3,7,11, 15-tetramethyl-1-hexadecenyl.
In the present invention, C3-C20Examples of the substituted or unsubstituted cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, cyclododecyl.
In the present invention, C6-C20The substituted or unsubstituted aryl group of (1) includes C6-C20Substituted or unsubstituted phenyl of, also including C10-C20Examples of the substituted or unsubstituted fused ring aryl group of (a) may include, but are not limited to: phenyl, naphthyl, methylnaphthyl, ethylnaphthyl, anthryl, methylanthryl, ethylanthryl, phenanthryl, methylphenanthryl and ethylphenanthryl, pyrenyl, indenyl.
In the present invention, C7-C20The substituted or unsubstituted aralkyl group of (2) means an alkyl group having an aryl substituent and having 7 to 20 carbon atoms. C7-C20Examples of the substituted or unsubstituted aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl-isopropyl, phenyl-n-pentyl.
In the present invention, C7-C20The substituted or unsubstituted alkylaryl group of (2) means an aryl group having an alkyl substituent and having 7 to 20 carbon atoms. C7-C20Examples of substituted or unsubstituted alkaryl groups of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl, isopropylphenyl, n-pentylphenyl.
In the present invention, C1-C6Examples of alkoxy groups of (a) may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, hexoxy.
In the present invention, the above-mentioned groups in other carbon number ranges can be selected correspondingly within the carbon number range defined, and are not described in detail herein.
According to the invention, the internal electron donor compound a is a diol ester compound shown as a formula II,
Figure BDA0001835409330000071
the middle bracket of the formula II]The term "in" denotes that n carbon atoms are bonded in succession and that each carbon atom is further bonded to 2 substituents, i.e. there are n carbon atoms and R in total in the parenthesis1、R2、R3…R2nAnd 2n substituents. Wherein n is an integer of 0 to 10, and when n is 0, the substituent is R in the diol ester compound shown in the formula II6、R7The carbon atom directly bonded to the substituent is R8、R9Is bonded to the carbon atom(s) of (a).
Preferably, the internal electron donor compound a is a diol ester compound shown in formula IV,
Figure BDA0001835409330000072
in the formula IV, R10、R11、R12、R13、R14、R15、R16And R17The same or different, each independently selected from hydrogen, halogen atom, C1-C20Straight or branched alkyl of (C)3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of, C7-C20Substituted or unsubstituted alkylaryl and C7-C20And (c) one of substituted or unsubstituted aralkyl groups.
According to a preferred embodiment of the invention, in formula IV, R10、R11、R12、R13、R14And R15Are the same or different and are each independently hydrogen or C1-C20Straight or branched alkyl of R16And R17Are all phenyl groups.
According to the present invention, examples of the internal electron donor compound a may include, but are not limited to: 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-butyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 2-ethyl-2-butyl-1, 3-propanediol dibenzoate, 2-diethyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-methyl-2-methyl-diol, 3-dibenzoate, 2-methyl-2-methyl-diol, 2-methyl-diol, 3-diol, 2-dibenzoate, 2-diol, 2-diol, 2-and/or a mixture, 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, and 3-pentanediol dibenzoate, 2,2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-dimethyl-1, 5-pentanediol dibenzoate, 1, 6-hexanediol dibenzoate, 6-heptene-2, 4-heptanediol dibenzoate, 2-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-methyl-6-heptene-2, 4-heptanediol dibenzoate, 4-methyl-6-heptene-2, 4-heptanediol dibenzoate, 5-methyl-6-heptene-2, 4-heptanediol dibenzoate, a salt thereof, and a salt thereof, 6-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 4-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 5-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 6-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-propyl-6-heptene-2, 4-heptanediol dibenzoate, 4-propyl-6-heptene-2, 4-heptanediol dibenzoate, 5-propyl-6-heptene-2, 4-heptanediol dibenzoate, a salt thereof, and a salt thereof, 6-propyl-6-heptene-2, 4-heptanediol dibenzoate, 3-butyl-6-heptene-2, 4-heptanediol dibenzoate, 4-butyl-6-heptene-2, 4-heptanediol dibenzoate, 5-butyl-6-heptene-2, 4-heptanediol dibenzoate, 6-butyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 3-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 5-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, and mixtures thereof, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3, 4-dimethyl-3, 5-heptanediol dibenzoate, 3, 5-dimethyl-3, 5-heptanediol dibenzoate, 3, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-propyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 2-methyl-5-propyl-3, 5-heptanediol dibenzoate, 3-methyl-3-propyl-3, 5-heptanediol dibenzoate, 3-methyl-4-propyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 3-methyl-5-propyl-3, 5-heptanediol dibenzoate, 4-methyl-3-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-5-propyl-3, 5-heptanediol dibenzoate.
Further preferably, the internal electron donor compound a is pentanediol ester and/or heptanediol ester, such as 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate.
According to the invention, preferably, the internal electron donor compound b is a1, 3-diether compound shown in formula V,
Figure BDA0001835409330000091
in formula V, R9' and R10' same or different, each independently hydrogen, halogen, C1-C18Straight or branched alkyl of (2), C3-C18Substituted or unsubstituted cycloalkyl of (A), C6-C18Substituted or unsubstituted aryl and C7-C18Or one of substituted or unsubstituted aralkyl, or R9' and R10' bonding to each other to form a ring; r is11' and R12' same or different, each independently C1-C10Linear or branched alkyl.
According to the present invention, examples of the internal electron donor compound b may include, but are not limited to: 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-isopropylphenyl-dimethoxypropane, 2-cyclohexylpropyl-2-dimethoxypropane, 2-isopropylphenyl-1, 3-dimethoxypropane, 2-isopropylphenyl-2-cyclohexylpropyl-1, 3-dimethoxypropane, 2-isopropylphenyl-2, 2-dimethoxypropane, 2-isopropylphenyl-2-1, 3-dimethoxypropane, 2,3, 2, or one, 2,3, 2, or one, 2, or one, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-propyl, 2-methyl-2-methyl-ethyl-2-methyl-ethyl, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene.
Most preferably, the internal electron donor compound b is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
In the present invention, the 1, 3-diether compound can be synthesized by the methods disclosed in CN1020448C, CN100348624C and CN 1141285A. The disclosure of which is incorporated herein by reference in its entirety. This is not described in detail herein.
The inventor of the invention finds that when 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate are used as the internal electron donor compound a and 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene are used as the internal electron donor compound b in the research process, the obtained catalyst has high stereospecificity, can obtain an olefin polymer with high isotactic index, and has high polymerization activity.
According to the present invention, the internal electron donor comprises a glycol ester compound and a diether compound, which are capable of generating a certain synergistic effect, and the total amount of the malonate compound and the glycol ester compound is preferably 70 to 100 wt%, more preferably 80 to 100 wt%, even more preferably 90 to 100 wt%, and most preferably 100 wt%, based on the amount of the internal electron donor.
According to the olefin polymerization catalyst component of the present invention, the content of the internal electron donor component is not particularly limited and may vary within a wide range, and it is preferable that the total amount of the internal electron donor compound a and the internal electron donor compound b is 0.1 to 0.8 mole based on 1 mole of magnesium element.
According to the present invention, preferably, the raw material for synthesizing the spherical carrier of the olefin polymerization catalyst comprises elemental sulfur and has a general formula of MgX1Magnesium halide of Y, formula R1OH compounds, ethylene oxide compounds;
general formula MgX1In Y, X1Is halogen, Y is halogen, C1-C5Alkyl of (C)1-C5Alkoxy group of (1), C6-C10Aryl or C of6-C10An aryloxy group of (a);
general formula R1In OH, R1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a);
the structure of the oxirane compound is shown as a formula X:
Figure BDA0001835409330000111
in the formula X, R25And R26Each independently is hydrogen, C1-C5Alkyl or C1-C5The haloalkyl group of (1).
According to a preferred embodiment of the present invention, the sulfur-containing magnesium compound is prepared by a method comprising the steps of:
(1) elemental sulfur with the general formula of MgX1Magnesium halide of Y, formula R1Mixing and heating an OH compound, an optional inert liquid medium, and an optional surfactant to obtain a liquid mixture;
(2) and (2) carrying out contact reaction on the liquid mixture obtained in the step (1) and an ethylene oxide compound.
According to the present invention, the inert liquid medium may be any of various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products. For example: the inert liquid medium may be a silicone oil type solvent and/or a hydrocarbon type solvent. Specifically, the inert liquid medium may be at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil. The inert liquid medium according to the invention is particularly preferably white oil. The inert liquid medium may be used in an amount according to the formula MgX1The amount of the magnesium halide of Y is determined. Generally, 1mol of MgX is represented by the formula1The inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on the magnesium halide of Y.
According to the present invention, a surfactant such as at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol, polyacrylic acid salt, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkylacrylate copolymer-modified polyethyleneimine, a polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethyleneoxide-propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenylpolyoxyethylene ether, and polyalkylmethacrylate may be used in the reaction, and preferably at least one of polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer, and polyethylene glycol. 1mol of MgX1The amount of the surfactant is preferably 1 to 20g based on the magnesium halide of Y.
According to the inventionIn the step (1), elemental sulfur with a general formula of MgX1Magnesium halide of Y, formula R1The conditions under which the compound of OH, optionally in admixture with an inert liquid medium and/or a surfactant, is heated are not particularly limited, provided that the heating conditions are such as to give a compound of formula MgX1The magnesium halide of Y is melted and fully reacted with sulfur. Generally, the conditions of heating include: the temperature is 80-120 ℃, and the time is 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the time is 0.5-3 hours.
According to the present invention, the conditions for contacting the liquid mixture with the ethylene oxide in step (2) may be any of the existing conditions capable of forming a carrier for an olefin polymerization catalyst, for example, the conditions for contacting include: the temperature is 40-120 ℃, and the time is 15-60 minutes; preferably, the conditions of the contact reaction include: the temperature is 60-100 ℃, and the time is 20-50 minutes.
According to the invention, the method can also comprise the steps of carrying out solid-liquid separation on the product obtained by the contact reaction, washing the solid-phase product obtained by the separation and drying the solid-phase product. The solid-liquid separation may be any of various conventional methods for separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation is a pressure filtration method. In the present invention, the conditions for the pressure filtration are not particularly limited, and it is considered that the separation of the solid phase and the liquid phase is sufficiently achieved as much as possible. The washing may be carried out by washing the obtained solid phase product by a method known to those skilled in the art, and for example, the obtained solid phase product may be washed by an inert hydrocarbon solvent (e.g., pentane, hexane, heptane, petroleum ether and gasoline). In the present invention, the drying conditions are not particularly limited, and examples thereof include: the drying temperature can be 20-70 ℃, and the drying time can be 0.5-10 hours. According to the invention, the drying can be carried out under atmospheric or reduced pressure.
According to the invention, the content of the above-mentioned components in the spherical support of the olefin polymerization catalyst can be selected and varied within wide limits, preferably 1mol of MgX1Elemental sulfur based on magnesium halide of YThe dosage of the compound is 0.0001-0.5mol, and the general formula is R1The dosage of OH compound is 4-30mol, and the dosage of ethylene oxide compound is 1-10 mol; further preferably, MgX is present in an amount of 1mol1Based on magnesium halide of Y, the general formula is R1The dosage of the OH compound is 6-20mol, and the dosage of the ethylene oxide compound is 2-6 mol.
In the present invention, the elemental sulfur may be any subtype of elemental sulfur, including but not limited to: at least one of alpha-sulfur, beta-sulfur, gamma-sulfur, and polymeric sulfur. The elemental sulphur may be anhydrous elemental sulphur or elemental sulphur containing bound water. The above elemental sulphur is commercially available.
According to the invention, of the formula MgX1In Y, X1Preferably chlorine or bromine, Y is preferably chlorine, bromine, C1-C5Alkoxy or C6-C10An aryloxy group of (1). Said C is1-C5The alkyl group of (A) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl, C1-C5The alkoxy group of (C) may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, C6-C10The aryl group of (A) may be, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, an m-ethylphenyl group, a p-ethylphenyl group or a naphthyl group, said C6-C10The aryloxy group of (a) may be, for example, a phenoxy group or a naphthoxy group. A general formula of MgX1The magnesium halide of Y may be one kind of magnesium halide or a mixture of plural kinds of magnesium halides. A general formula of MgX1Specific examples of magnesium halides of Y may be, but are not limited to: at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride. Magnesium chloride is preferred from the viewpoint of availability of raw materials.
According to the invention, of the formula R1In OH, R1Can be C1-C8Alkyl or C3-C8In which C is3-C8All carbon atoms in the cycloalkyl group(s) may participate in the ring formation, or may be present in the ring formationPart of the component participates in the cyclization, C3-C8The cycloalkyl group of (b) may be, for example, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexyl group or a cyclohexylmethyl group. R1Preferably C1-C8Alkyl groups of (a); said C is1-C8The alkyl group of (b) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group or an isooctyl group. Has the general formula R1Specific examples of compounds of OH may be, but are not limited to: at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol, 2-ethylhexanol, and n-octanol.
According to the invention, in the oxirane compound with the structure shown as the formula X, R25And R26Preferably each independently hydrogen, C1-C3Alkyl or C1-C3A haloalkyl group of (a); specific examples of the oxirane compound may be, but are not limited to: at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
The average particle size of the spherical support for the olefin polymerization catalyst of the present invention can be controlled in a wide range and may be, for example, 10 to 100 μm. According to a preferred embodiment of the present invention, the average particle diameter (D50) of the spherical support for olefin polymerization catalyst can be controlled to 30 μm or less, preferably to 20 μm or less, and the particle size distribution ((D90-D10)/D50) is less than 1.2; the particle size distribution is preferably 0.8 or less. In the preferred embodiment, the catalyst prepared from the spherical support of the olefin polymerization catalyst can give an olefin polymer having a higher bulk density. In the present invention, the average particle diameter and the particle size distribution of the spherical support for an olefin polymerization catalyst can be measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).
When the solid component (olefin polymerization catalyst support) is spherical particles, the catalyst component obtained by reacting the support with the titanium compound, the internal electron donor compound a, and the internal electron donor compound b is also spherical particles. Further, since the spherical carrier has a small particle diameter and a narrow particle diameter distribution, the catalyst component obtained is also small in particle diameter and narrow in particle diameter distribution.
When the solid component (olefin polymerization catalyst support) is spherical particles, the catalyst component obtained by reacting the support with the titanium compound, the internal electron donor compound a, and the internal electron donor compound b is also spherical particles.
According to the invention, the spherical support of the olefin polymerization catalyst may contain water originating from traces of water carried by the synthesis raw materials and the reaction medium. According to the present invention, a slight amount of water in each of the above reactants may also participate in the reaction for forming the spherical support of the olefin polymerization catalyst.
In the present invention, in the olefin polymerization catalyst component, the contents of the magnesium, titanium, halogen and internal electron donor are not particularly limited, and the contents of each component may be appropriately selected according to the amounts conventionally used in the art. Preferably, in the catalyst component, the weight ratio of titanium calculated as titanium element, magnesium calculated as magnesium element, halogen calculated as halogen element and internal electron donor is 1: 2-15: 8-30: 2-10; preferably 1: 3-12: 10-25: 3-8; more preferably, the weight ratio of titanium in terms of titanium element, magnesium in terms of magnesium element and internal electron donor is 1: 4-10: 4-7.
In the present invention, the titanium compound may be a titanium compound commonly used in the art. Preferably, the titanium compound is a compound represented by formula XI and/or formula XII:
TiXp(OR27)4-pa compound of the formula XI,
TiXq(OR28)3-qin the formula XII, the reaction mixture is,
in the formulae XI and XII, X is halogen and R27、R28Each independently is C1-C20P is an integer of 1 to 4, and q is an integer of 1 to 3.
Further preferably, the titanium compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride, ethoxytitanium trichloride, and titanium trichloride. Most preferably, the titanium compound is titanium tetrachloride.
The method for preparing the catalyst component for olefin polymerization of the present invention may comprise the steps of: reacting a sulfur-containing magnesium compound shown as a formula I with a titanium compound, and adding an internal electron donor in one or more time periods before, during and after the reaction of the magnesium compound and the titanium compound, wherein the internal electron donor is the internal electron donor compound a and the internal electron donor compound b.
In the present invention, the reaction of the magnesium compound with the titanium compound can be carried out according to the methods disclosed in the prior art, for example, the titanium compound can be cooled to 0 ℃ or less (preferably-5 ℃ to-25 ℃), then the magnesium compound is added and stirred and mixed at that temperature for 10 to 60 minutes, and then warmed to the reaction temperature (preferably 60 to 130 ℃) and maintained at that reaction temperature for 0.5 to 10 hours. Adding an internal electron donor compound a and an internal electron donor compound b in the temperature rising process. Then adding a titanium compound for one or more treatments, and finally, washing with an inert solvent for a plurality of times, thereby obtaining the catalyst component. Examples of the inert solvent may include, but are not limited to: hexane, heptane, octane, decane, toluene.
In the preparation method of the catalyst component for olefin polymerization, the internal electron donor component is added in one or more periods of time before, during and after the reaction of the magnesium compound and the titanium compound. The period of time before the reaction of the magnesium compound with the titanium compound means a period of time after the magnesium compound is added to the reactor and before the temperature is raised to the reaction temperature.
In the present invention, the internal electron donor compound a and the internal electron donor compound b may be added to the mixture of the magnesium compound and the titanium compound in several times or simultaneously when preparing the catalyst component. When the internal electron donor compound a and the internal electron donor compound b are added to the mixture of the magnesium compound and the titanium compound for several times, the internal electron donor compound a and the internal electron donor compound b can be added first; or the internal electron donor compound b can be added firstly, and then the internal electron donor compound a can be added.
According to the present invention, in the preparation of the catalyst component, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor component is not particularly limited and may be varied within a wide range, and preferably, the molar ratio of the magnesium compound as magnesium element, the titanium compound as titanium element and the internal electron donor is 1: 10-200: 0.04 to 0.8, and more preferably, the molar ratio of the magnesium compound in terms of magnesium element, the titanium compound in terms of titanium element, and the internal electron donor is 1: 50-180: 0.05 to 0.5, most preferably, the molar ratio of the magnesium compound calculated as magnesium element, the titanium compound calculated as titanium element and the internal electron donor is 1: 70-150: 0.1-0.4.
A second aspect of the present invention provides the use of a catalyst component as described above in the preparation of a catalyst for the polymerisation of olefins.
A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:
(1) the above catalyst components;
(2) an alkylaluminum compound as a cocatalyst; and
(3) optionally an external electron donor compound.
According to the present invention, in the above-mentioned catalyst for olefin polymerization, the aluminum alkyl compound may be any of various aluminum alkyl compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst for an olefin polymerization catalyst. Preferably, the alkyl aluminum compound is a compound represented by formula XIII,
AlR’n'X’3-n'the compound of the formula XIII is shown in the specification,
in the formula XIII, R' is C1-C8X' is halogen, preferably chlorine, bromineAnd iodine, more preferably chlorine, and n' is an integer of 1 to 3.
More preferably, the aluminum alkyl compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum dichloride, Al (n-C)6H13)3And Al (n-C)8H17)3One or more of (a).
Most preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.
According to the invention, the alkyl aluminium compound may be used in amounts conventional in the art. Preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 1 to 2000: 1. further preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 10 to 500: 1.
the present invention is not particularly limited with respect to the type and content of the external electron donor in the olefin polymerization catalyst. Preferably, the molar ratio of aluminium in the aluminium alkyl compound and the external electron donor compound is 2-200: 1, more preferably 2.5 to 100: 1.
according to the present invention, the use of the external electron donor compound in combination with the internal electron donor compound a and the internal electron donor compound b can further improve the isotactic index of the olefin polymer obtained by the method of the present invention. The external electron donor compound may be any of various external electron donor compounds commonly used in the art to achieve the above-mentioned objects, such as: one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds. Preferably, the external electron donor compound is an organosilicon compound represented by formula XIV,
(R29)m’(R30)p’Si(OR31)q’the compound of the formula XIV is shown in the specification,
in the formula XIV, R29、R30And R31Each independently is C1-C18Optionally containing heteroatoms, said heteroatoms being one or more of F, Cl, Br, N and I; m 'and p' are each independently an integer from 0 to 2, q 'is an integer from 1 to 3, and the sum of m', p ', and q' is 4.
Preferably, R29And R30Each independently is C3-C10Straight-chain or branched alkyl of C3-C10Linear or branched alkenyl of (C)3-C10Substituted or unsubstituted alkylene of (A), C3-C10Substituted or unsubstituted cycloalkyl and C6-C10Optionally containing heteroatoms which are one or more of F, Cl, Br, N and I; r31Is C1-C10More preferably methyl.
According to the present invention, specific examples of the external electron donor compound may include, but are not limited to: one or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, t-hexyltrimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.
More preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane and/or dicyclopentyldimethoxysilane.
According to the present invention, in the preparation process of the catalyst for olefin polymerization, the alkylaluminum and the optional external electron donor compound may be respectively mixed with the catalyst component for olefin polymerization and then reacted, or the alkylaluminum and the optional external electron donor compound may be mixed in advance and then mixed with the catalyst component for olefin polymerization and reacted.
According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor may be added into the polymerization reactor separately, or may be added into the polymerization reactor after mixing, or may be added into the polymerization reactor after olefin prepolymerization by a prepolymerization method known in the art.
A fourth aspect of the invention provides the use of a catalyst as described above in the polymerisation of olefins.
A fifth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions. The improvement of the present invention is that a new catalyst component and catalyst for olefin polymerization are used, so that the specific kind of olefin, the polymerization reaction method and conditions of olefin can be the same as those in the prior art. The olefin is at least one olefin represented by the formula CH2 ═ CHR, where R is hydrogen or C1-C6Linear or branched alkyl. The general formula CH2Specific examples of olefins represented by ═ CHR may include: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, 4-methyl-1-pentene. Preferably, the general formula CH2The olefins represented by ═ CHR are ethylene, propylene, 1-n-butene, 1-n-hexene, 4-methyl-1-pentene. More preferably, the general formula CH2The olefin represented by ═ CHR is propylene.
The olefin polymerization method of the present invention may be homopolymerization of a single olefin or copolymerization of a plurality of olefins.
According to the olefin polymerization process of the present invention, the olefin polymerization conditions may be conventional in the art. In liquid phase monomer or inert solvent containing polymerized monomer, or in gas phase, or by combined polymerization processes in gas and liquid phase. In general, the olefin polymerization conditions may include: the temperature is 0-150 ℃, the time is 0.1-8 hours, and the pressure is 0.01-10 MPa. Preferably, the olefin polymerization conditions comprise: the temperature is 50-100 ℃, the time is 0.5-3 hours, and the pressure is 0.5-5 MPa. The amount of the catalyst for olefin polymerization may be various conventional amounts of olefin polymerization catalysts of the prior art. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen can be used as a polymer molecular weight regulator to be added into the polymerization reactor to regulate the molecular weight and melt index of the polymer. The alkyl aluminum compound and the optional external electron donor compound can be contacted and reacted with the active component singly or as a mixture of two components. The catalyst component, the alkyl aluminum and the external electron donor compound can be respectively added into a polymerization reactor, can be mixed and then added into the polymerization reactor, and can also be added into the polymerization reactor after propylene is prepolymerized by adopting a prepolymerization method known in the industry.
The olefin polymerization catalyst carrier used in the invention is added with sulfur in the preparation process, and the sulfur can reduce the collision probability among unformed particles and reduce the adhesion among carrier particles, so that the obtained carrier particles have small particle size, narrow distribution and good shape. The olefin polymerization catalyst component adopts a sulfur-containing magnesium compound as a carrier, adopts a glycol ester compound and a1, 3-diether compound in a specific ratio as internal electron donors, can prepare a spherical catalyst with the average particle size of less than 30 micrometers, and shows ultrahigh stereospecificity when the catalyst is used for olefin polymerization, particularly propylene polymerization.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
FIG. 1 is an optical micrograph of a spherical support of an olefin polymerization catalyst prepared in preparation example 1;
FIG. 2 is an optical micrograph of an olefin polymerization catalyst support prepared in comparative preparation example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the following examples and comparative examples:
1. the average particle diameter and the particle size distribution of the olefin polymerization catalyst component and the carrier were measured using a Masters Sizer 2000 particle Sizer (manufactured by Malvern Instruments Ltd.);
2. the apparent morphology of the olefin polymerization catalyst support was observed by means of an optical microscope, commercially available from Nikon, under the model Eclipse E200;
3. the polymer isotacticity index was determined by heptane extraction (6 hours of heptane boil extraction): a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours, and the ratio of the weight (g) of the polymer to 2(g) of the residue was dried to a constant weight, which was the isotactic index.
Preparation example 1
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 8.0g (0.08mol) of magnesium chloride, 56mL (0.96mol) of ethanol, 1g (0.03mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as surfactants into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epichlorohydrin, reacting at constant temperature of 90 ℃ for half an hour, performing pressure filtration, washing the pressure-filtered product with hexane for 5 times, and finally drying the product in vacuum to obtain the olefin polymerization catalyst spherical carrier Z1.
The olefin polymerization catalyst spherical carrier Z1 has an average particle diameter (D50) of 15 micrometers and a particle size distribution ((D90-D10)/D50) of 0.6. As shown in FIG. 1, the spherical support Z1 for olefin polymerization catalyst has regular particle morphology, smooth surface, substantially spherical shape, concentrated particle size distribution and substantially no irregular particles.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z1 is as follows:
Figure BDA0001835409330000221
preparation example 2
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.3g (0.009mol) of beta-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature of 100 ℃ for 20 minutes, carrying out pressure filtration, washing a pressure filtration product for 5 times by using hexane, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z2.
The olefin polymerization catalyst spherical carrier Z2 has an average particle diameter (D50) of 18 microns and a particle size distribution ((D90-D10)/D50) of 0.7. The spherical carrier Z2 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z2 is as follows:
Figure BDA0001835409330000222
preparation example 3
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.2g (0.006mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature of 100 ℃ for 20 minutes, carrying out pressure filtration, washing a pressure filtration product for 5 times by using hexane, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z3.
The olefin polymerization catalyst spherical carrier Z3 has an average particle diameter (D50) of 20 micrometers and a particle size distribution ((D90-D10)/D50) of 0.8. The spherical carrier Z3 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z3 is as follows:
Figure BDA0001835409330000231
preparation example 4
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
Adding 8.0g (0.08mol) of magnesium chloride, 59mL (0.48mol) of cyclohexylmethanol, 0.3g (0.009mol) of beta-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 60 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature for 20 minutes at 60 ℃, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z4.
The average particle diameter (D50) of the spherical olefin polymerization catalyst carrier Z4 was 25 micrometers, and the particle size distribution ((D90-D10)/D50) was 0.9. The spherical carrier Z4 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z4 is as follows:
Figure BDA0001835409330000241
preparation example 5
This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.
In a 0.6L reaction kettle, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.3g (0.009mol) of alpha-sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant are added, the temperature is raised to 70 ℃ under stirring, after 1 hour of constant temperature reaction, 11.2mL (0.16mol) of propylene oxide is added, the constant temperature reaction is continued for 20 minutes at 70 ℃, then, the pressure filtration is carried out, the pressure filtration product is washed 5 times by hexane, and finally, the product is dried in vacuum, thus obtaining the olefin polymerization catalyst spherical carrier Z5.
The olefin polymerization catalyst spherical carrier Z5 has an average particle diameter (D50) of 26 microns and a particle size distribution ((D90-D10)/D50) of 0.9. The spherical carrier Z5 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.
According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z5 is as follows:
Figure BDA0001835409330000242
comparative preparation example 1
This comparative preparation is intended to illustrate a reference olefin polymerization catalyst support and a process for its preparation.
Adding 0.08mol of magnesium chloride, 0.96mol of ethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epoxy chloropropane, continuing reacting at constant temperature of 90 ℃ for half an hour, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally drying the product in vacuum to obtain the catalyst carrier DZ1 for olefin polymerization.
The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ1 was 60 μm, and the particle size distribution ((D90-D10)/D50) was 1.3. The particle morphology observed with an optical microscope is shown in fig. 2. As can be seen from fig. 2, the catalyst carrier for olefin polymerization DZ1 had irregular particles and a rough surface.
Comparative preparation example 2
Adding 8.0g (0.08mol) of magnesium chloride, 59mL (0.48mol) of cyclohexylmethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 60 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature for 20 minutes at 60 ℃, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier DZ 2.
The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ2 was 80 μm, and the particle size distribution ((D90-D10)/D50) was 1.5. The particle morphology is observed by an optical microscope, and special-shaped particles exist in DZ2, and the surface is rough.
Comparative preparation example 3
Adding 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 70 ℃ under stirring, reacting at constant temperature for 1 hour, adding 11.2mL (0.16mol) of propylene oxide, continuing to react at constant temperature of 70 ℃ for 20 minutes, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier DZ 3.
The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ3 was 88 μm, and the particle size distribution ((D90-D10)/D50) was 1.7. The particle morphology is observed by an optical microscope, and special-shaped particles exist in DZ3, and the surface is rough.
Example 1
This example illustrates the preparation of the catalyst component and catalyst for olefin polymerization and the propylene polymerization process provided by the present invention.
(1) Preparation of the catalyst component for olefin polymerization:
adding 90ml of titanium tetrachloride and 10ml of hexane into a 300ml glass reaction bottle with stirring, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of spherical carrier Z1, slowly heating while stirring, adding 5mmol of 2, 4-pentanediol dibenzoate and 6mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane during heating, continuously heating to 110 ℃, keeping the temperature for 0.5h after the temperature is reached, removing liquid by suction filtration, washing with titanium tetrachloride, washing with hexane, and drying in vacuum to obtain the spherical catalyst C1.
(2) Propylene polymerization reaction:
the liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. To the reaction vessel were added 1ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 0.2ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1mmol/ml) and 6mg of the above solid catalyst C1 in this order under a nitrogen blanket. The autoclave was closed and hydrogen (standard volume) and 2.3L of liquid propylene were added. The temperature is raised to 70 ℃, after 1 hour of reaction, the temperature is reduced, the pressure is relieved, the material is discharged, the obtained propylene homopolymer is weighed and analyzed after being dried, and the results are shown in table 1.
Example 2
This example is intended to illustrate the catalyst component for olefin polymerization, the olefin polymerization catalyst and the olefin polymerization process of the present invention.
An olefin polymerization catalyst component was prepared according to the method of example 1, except that the spherical carrier Z2 was added in place of the carrier Z1, and 2.5mmol of 2, 4-pentanediol dibenzoate and 7.2mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase.
Polypropylene was prepared according to the method of example 1 and the test results at different hydrogen addition levels are shown in table 1.
Example 3
This example is intended to illustrate the catalyst component for olefin polymerization, the olefin polymerization catalyst and the olefin polymerization process of the present invention.
An olefin polymerization catalyst component was prepared according to the method of example 1, except that 2mmol of 3, 5-heptanediol dibenzoate and 8mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase.
The polypropylene was prepared according to the method of example 1 and the test results are shown in table 1.
Example 4
This example is intended to illustrate the catalyst component for olefin polymerization, the olefin polymerization catalyst and the olefin polymerization process of the present invention.
An olefin polymerization catalyst component was prepared according to the method of example 2, except that 10mmol of 2, 4-pentanediol dibenzoate and 1mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase.
The polypropylene was prepared according to the method of example 1 and the test results are shown in table 1.
Example 5
This example is intended to illustrate the catalyst component for olefin polymerization, the olefin polymerization catalyst and the olefin polymerization process of the present invention.
An olefin polymerization catalyst component was prepared according to the method of example 2, except that 1.8mmol of 2, 4-pentanediol dibenzoate and 9, 9-dimethoxymethylfluorene were added during the temperature rise.
The polypropylene was prepared according to the method of example 1 and the test results are shown in table 1.
Comparative example 1
Preparation of the catalyst component for olefin polymerization:
adding 90ml of titanium tetrachloride and 10ml of hexane into a 300ml glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of spherical magnesium chloride alcoholate carrier (the preparation method is shown in Chinese patent CN1330086A), adding 1.5mmol of 2, 4-pentanediol dibenzoate and 10mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane during the temperature rising process, continuing to heat to 110 ℃, keeping the temperature for 0.5h after the temperature rising, removing liquid by suction filtration, washing with titanium tetrachloride, washing with hexane, and drying in vacuum to obtain the spherical catalyst.
Polypropylene was prepared according to the method of example 1, and the test results at different hydrogen addition amounts are shown in Table 1.
Comparative example 2
An olefin polymerization catalyst component was prepared according to the method of comparative example 1, except that 10mmol of 2, 4-pentanediol dibenzoate and 0.2mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature rise.
The polypropylene was prepared according to the method of example 1 and the test results are shown in table 1.
Comparative example 3
An olefin polymerization catalyst component was prepared according to the method of comparative example 1, except that 9mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was added during the temperature rise.
The polypropylene was prepared according to the method of example 1 and the test results are shown in table 1.
Comparative example 4
An olefin polymerization catalyst component was prepared by following the procedure of comparative example 1 except that 10mmol of 2, 4-pentanediol dibenzoate was added during the temperature elevation.
The polypropylene was prepared according to the method of example 1 and the test results are shown in table 1.
Comparative example 5
Liquid bulk polymerization of propylene was carried out in the same manner as in example 1, except that the catalyst component was replaced with the same weight part of a DQ catalyst component (the internal electron donor was diisobutylphthalate) available from the ohda catalyst division, petrochemical, china, and the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in table 1.
Comparative example 6
An olefin polymerization catalyst component was prepared by following the procedure of example 1 except that the carrier Z1 was replaced with an equal amount of the carrier DZ1 to obtain a catalyst component.
The polypropylene was produced in the same manner as in example 1, except that the above catalyst component was used in place of the olefin polymerization catalyst component A1, and the results are shown in Table 1.
TABLE 1
Figure BDA0001835409330000291
Figure BDA0001835409330000301
As can be seen from the comparison of the data of the examples in Table 1 and the comparative examples, the sulfur-containing magnesium compound carrier and the two electron donor compounds which are compounded are used in the invention, and the molar ratio of the two electron donor compounds is controlled within a certain range, the obtained catalyst has high activity and high stereospecificity, so that the prepared polymer has high isotactic index, and the average diameter of the catalyst particles is far smaller than that of the catalyst taking the spherical magnesium halide alcoholate as the carrier. As can be seen from the comparison of the data of example 2 and comparative example 1 in table 1, the polymerization activity of the catalyst did not increase significantly with the increase in the amount of hydrogen used.
As can be seen from the comparison of example 1 with comparative example 6 in Table 1, the catalyst of the present invention using a sulfur-containing magnesium compound as a carrier has significantly higher activity and stereospecificity than the catalyst using a sulfur-free magnesium compound as a carrier, and the average particle size of the catalyst is greatly reduced.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (30)

1. A catalyst component for the polymerization of olefins, the catalyst component comprising the reaction product of:
(1) a solid component;
(2) at least one titanium compound; and
(3) an internal electron donor compound;
wherein the solid component is at least one sulfur-containing magnesium compound represented by formula I;
Figure FDA0003497431760000011
in the formula I, R1Is C1-C8Linear or branched alkyl of, or C3-C8Cycloalkyl groups of (a);
R2and R3Identical or different, each independently of the others, is hydrogen or C1-C5The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be optionally substituted with a halogen atom;
x is halogen;
m is 0.1-1.9, n is 0.1-1.9, m + n is 2, q is more than 0 and less than or equal to 0.5;
wherein the internal electron donor compound comprises an internal electron donor compound a and an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.1-30: 1; the internal electron donor compound a is a diol ester compound shown as a formula II, and the internal electron donor compound b is a diether compound shown as a formula III;
Figure FDA0003497431760000012
in formula II, R4And R5Identical or different, each independently is halogen, C1-C20Straight or branched alkyl of (2), C2-C20Linear or branched alkylene of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; the hydrogen atom on the aromatic ring of the aryl, aralkyl or alkaryl group being optionally substituted by halogen, C1-C6And C is a straight or branched alkyl group1-C6Substituted with one or more of alkoxy groups of (a);
R6、R7、R8、R9and R1-R2nThe same or different, each independently is hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted alkylaryl of, C7-C20Substituted or unsubstituted aralkyl of (1), C2-C20And C is a linear or branched alkylene group2-C20One of the ester groups of (1), R6、R7、R8、R9And R1-R2nOptionally substituted with heteroatoms, which are one or more of halogen, nitrogen, oxygen, sulfur, silicon and phosphorus; or, R6、R7、R8、R9And R1-R2nTwo or more of them are mutually bonded to form a ring;
n is an integer of 0 to 10;
Figure FDA0003497431760000021
in the formula III, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Or a substituted or unsubstituted alkylaryl group.
2. The catalyst component according to claim 1 in which X is chlorine or bromine.
3. The catalyst component according to claim 1 in which the molar ratio of the internal electron donor compound a to the internal electron donor compound b is between 0.25 and 10: 1.
4. the catalyst component according to claim 1 in which the starting material for the synthesis of the sulphur-containing magnesium compound comprises elemental sulphur, of general formula MgX1Magnesium halide of Y, formula R1OH compounds, ethylene oxide compounds;
general formula MgX1In Y, X1Is halogen, Y is halogen, C1-C5Alkyl of (C)1-C5Alkoxy group of (C)6-C10Aryl or C of6-C10An aryloxy group of (a);
general formula R1In OH, R1Is C1-C8Alkyl or C3-C8Cycloalkyl groups of (a);
the structure of the oxirane compound is shown as a formula X:
Figure FDA0003497431760000031
in the formula X, R25And R26Each independently is hydrogen, C1-C5Alkyl or C1-C5A haloalkyl group of (a).
5. The catalyst component according to claim 4 in which the sulphur-containing magnesium compound is obtained by a process comprising the steps of:
(1) elemental sulfur with the general formula of MgX1Magnesium halide of Y, formula R1Mixing and heating an OH compound, an optional inert liquid medium, and an optional surfactant to obtain a liquid mixture;
(2) and (2) carrying out contact reaction on the liquid mixture obtained in the step (1) and an ethylene oxide compound.
6. The catalyst component according to claim 5 in which the inert liquid medium is a silicone-oil type solvent and/or a hydrocarbon type solvent; 1mol of MgX1The amount of the inert liquid medium is 0.8-10L based on magnesium halide of Y.
7. The catalyst component according to claim 6 in which the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.
8. The catalyst component according to claim 5 in which the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid salts, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkylacrylate copolymer modified polyethyleneimine, polymers of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethyleneoxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkylmethacrylate; 1mol of MgX1The dosage of the surfactant is 1-20g based on magnesium halide of Y.
9. The catalyst component according to claim 5 in which in step (1) the heating is carried out at a temperature of from 80 to 120 ℃ for a time of from 0.5 to 5 hours; in the step (2), the contact reaction conditions include: the temperature is 40-120 ℃, and the time is 15-60 minutes.
10. The catalyst component according to claim 9 in which the heating in step (1) is carried out at a temperature of from 80 to 100 ℃ for a time of from 0.5 to 3 hours.
11. The catalyst component according to claim 9 in which in step (2) the conditions of the contact reaction comprise: the temperature is 60-100 ℃, and the time is 20-50 minutes.
12. The catalyst component according to any of claims 4 to 11 in which 1mol of formula MgX is present1The magnesium halide of Y is taken as a reference, the dosage of the elemental sulfur is 0.0001 to 0.5mol, and the general formula is R1The dosage of the OH compound is 4-30mol, and the dosage of the ethylene oxide compound is 1-10 mol.
13. The catalyst component according to claim 12 in which MgX is present in 1mol1Based on magnesium halide of Y, the general formula is R1The dosage of the OH compound is 6-20mol, and the dosage of the ethylene oxide compound is 2-6 mol.
14. The catalyst component according to any of claims 4-11 in which the elemental sulphur is selected from at least one of alpha sulphur, beta sulphur, gamma sulphur and polymeric sulphur.
15. The catalyst component according to any of claims 4 to 11 in which the general formula MgX1In Y, X1Is chlorine or bromine, Y is chlorine, bromine, C1-C5Alkoxy or C6-C10An aryloxy group of (1).
16. The catalyst component according to claim 15 in whichFormula is MgX1The magnesium halide of Y is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.
17. The catalyst component according to any of claims 4 to 11 in which R is of the general formula1In OH, R1Is C1-C8Alkyl group of (1).
18. The catalyst component according to claim 17 in which the general formula is R1The compound of OH is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, 2-ethylhexanol, and n-octanol.
19. The catalyst component according to any of claims 4-11 in which in the oxirane compound of formula X, R is25And R26Each independently is hydrogen, C1-C3Alkyl or C1-C3The haloalkyl group of (1).
20. The catalyst component according to claim 19 in which the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
21. The catalyst component according to claim 1 in which the sulphur-containing magnesium compound has an average particle diameter of less than or equal to 30 microns and a particle size distribution of less than 1.2.
22. The catalyst component according to claim 21 in which the sulphur-containing magnesium compound has an average particle diameter of 20 microns or less and a particle size distribution of 0.8 or less.
23. The catalyst component according to any of claims 1-11 and 21-22 in which the internal electron donor compound a is a diol ester compound of formula iv,
Figure FDA0003497431760000061
in the formula IV, R10、R11、R12、R13、R14、R15、R16And R17The same or different, each independently selected from hydrogen, halogen atom, C1-C20Straight or branched alkyl of (C)3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of, C7-C20Substituted or unsubstituted alkylaryl and C7-C20And (c) one of substituted or unsubstituted aralkyl groups.
24. The catalyst component according to any of claims 1-11 and 21-22 in which the internal electron donor compound b is a1, 3-diether compound of formula v,
Figure FDA0003497431760000071
in formula V, R9' and R10' same or different, each independently hydrogen, halogen, C1-C18Straight or branched alkyl of (2), C3-C18Substituted or unsubstituted cycloalkyl of (A), C6-C18Substituted or unsubstituted aryl and C7-C18Or one of substituted or unsubstituted aralkyl, or R9' and R10' bonding to each other to form a ring; r11' and R12' same or different, each independently C1-C10Linear or branched alkyl.
25. The catalyst component of any of claims 1-11 and 21-22, wherein the weight ratio of titanium, magnesium, halogen, and internal electron donor, calculated as halogen, in the catalyst component is 1: 2-15: 8-30: 2-10.
26. The catalyst component according to claim 25 in which the weight ratio of titanium, magnesium, halogen and internal electron donor, expressed as halogen, is 1: 3-12: 10-25: 3-8.
27. Use of the catalyst component according to any one of claims 1 to 26 in the preparation of a catalyst for the polymerization of olefins.
28. A catalyst for the polymerization of olefins, the catalyst comprising:
(1) the catalyst component of any one of claims 1 to 26;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
29. Use of the catalyst of claim 28 in olefin polymerization reactions.
30. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of claim 28 under olefin polymerization conditions.
CN201811223690.1A 2018-10-19 2018-10-19 Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method Active CN111072813B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811223690.1A CN111072813B (en) 2018-10-19 2018-10-19 Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811223690.1A CN111072813B (en) 2018-10-19 2018-10-19 Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method

Publications (2)

Publication Number Publication Date
CN111072813A CN111072813A (en) 2020-04-28
CN111072813B true CN111072813B (en) 2022-05-24

Family

ID=70308492

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811223690.1A Active CN111072813B (en) 2018-10-19 2018-10-19 Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method

Country Status (1)

Country Link
CN (1) CN111072813B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4425258A (en) * 1981-06-24 1984-01-10 Denki Kagaku Kogyo Kabushiki Kaisha Catalysts for polymerization of olefins
CN104558282A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application
CN105440177A (en) * 2014-08-15 2016-03-30 中国石油化工股份有限公司 Olefin polymerization catalyst component and preparation method thereof and olefin polymerization catalyst and application thereof
CN107915794A (en) * 2016-10-09 2018-04-17 中国石油化工股份有限公司 Catalyst and its application and olefine polymerizing process for the catalytic component of olefinic polymerization and its application and for olefinic polymerization

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4425258A (en) * 1981-06-24 1984-01-10 Denki Kagaku Kogyo Kabushiki Kaisha Catalysts for polymerization of olefins
CN104558282A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application
CN105440177A (en) * 2014-08-15 2016-03-30 中国石油化工股份有限公司 Olefin polymerization catalyst component and preparation method thereof and olefin polymerization catalyst and application thereof
CN107915794A (en) * 2016-10-09 2018-04-17 中国石油化工股份有限公司 Catalyst and its application and olefine polymerizing process for the catalytic component of olefinic polymerization and its application and for olefinic polymerization

Also Published As

Publication number Publication date
CN111072813A (en) 2020-04-28

Similar Documents

Publication Publication Date Title
CN111072812B (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN101165074B (en) Catalyst component used for olefin polymerization and catalyst thereof
CN111072797B (en) Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application
CN111072810B (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN111072806B (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN111072804B (en) Olefin polymerization catalyst component and application thereof, olefin polymerization catalyst and olefin polymerization method
CN111072811A (en) Olefin polymerization catalyst spherical carrier and preparation method thereof, catalyst component, catalyst and application thereof
CN111072803A (en) Olefin polymerization catalyst carrier, preparation method and application thereof
WO2020078352A1 (en) Catalyst component and catalyst for olefin polymerization, and application thereof
CN111072808B (en) Catalyst component, catalyst, application thereof and olefin polymerization method
CN111072813B (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN107915796B (en) Catalyst component for olefin polymerization and application thereof, catalyst for olefin polymerization and application thereof, and olefin polymerization method
CN107915793B (en) Olefin polymerization catalyst component and olefin polymerization catalyst, application thereof and olefin polymerization method
CN111072809B (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN111072816B (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN107915794B (en) Catalyst component for olefin polymerization and application thereof, catalyst for olefin polymerization and application thereof, and olefin polymerization method
CN111072815A (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
CN107915791B (en) Olefin polymerization catalyst carrier and preparation method thereof, olefin polymerization catalyst component and olefin polymerization catalyst and application thereof
CN111072805A (en) Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method
RU2801219C2 (en) Catalyst component and catalyst for olefin polymerization and its applications
RU2801219C9 (en) Catalyst component and catalyst for olefin polymerization and its applications
CN112661883A (en) Solid catalyst component for preparing polyolefin, catalyst system and application thereof
CN115975075A (en) Catalyst component for olefin polymerization, catalyst and application
TWI832912B (en) Carrier for olefin polymerization catalyst and preparation method and application thereof
CN112759687B (en) Catalyst component for olefin polymerization and preparation method thereof, catalyst and olefin polymerization method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant