CN115960282A - Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin - Google Patents

Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin Download PDF

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CN115960282A
CN115960282A CN202111189965.6A CN202111189965A CN115960282A CN 115960282 A CN115960282 A CN 115960282A CN 202111189965 A CN202111189965 A CN 202111189965A CN 115960282 A CN115960282 A CN 115960282A
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phosphite
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俸艳芸
黄庭
孙竹芳
苟清强
李颖
贺国强
杨红旭
王毅
马冬
曹昌文
梁云
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical field of olefin polymerization catalysts, and discloses a catalyst component and a catalyst for olefin polymerization, and a method for preparing ultrahigh molecular weight polyolefin and application thereof. The preparation method of the catalyst component comprises the following steps: dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound; reacting the solution with an organic acid anhydride compound and an acetate compound, then contacting with a titanium compound, and then heating; adding an electron donor a into the system, and keeping the temperature constant; removing unreacted substances and solvent, washing for 1-2 times, addingAdding a solvent to form a mixture; reacting the mixture with a titanium compound and an electron donor b, and keeping the temperature constant; removing unreacted substances and a solvent, and washing to obtain a catalyst component; the electron donor a is at least one selected from compounds shown in a general formula (I) and a general formula (II), and the electron donor b is at least one selected from compounds shown in a general formula (III) and a general formula (IV).

Description

Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for preparing ultrahigh molecular weight polyolefin and application.
Background
Ultra-high molecular weight polyethylene (UHMWPE) is a thermoplastic engineering plastic with a linear structure, and the relative molecular mass is between 100 and 1600 ten thousand. At present, most commercial UHMWPE is prepared by a Ziegler-Natta catalyst (Z-N catalyst for short), and has the performances of super impact resistance, abrasion resistance, chemical corrosion resistance, low temperature resistance, stress cracking resistance, adhesion resistance, excellent insulation, safety, sanitation, self lubrication (low friction coefficient) and the like.
Patent document CN201110253287.5 produces an ultrahigh molecular weight polyethylene resin by treating a supported titanium catalyst with ultrasonic waves. The prepared ultra-high molecular weight polyethylene resin has higher viscosity average molecular weight and adjustable molecular weight, and effectively reduces the content of fine powder in resin particles, but the catalyst can not prepare ultra-high molecular weight polyethylene powder with the viscosity average molecular weight higher than 600 ten thousand. Patent document CN201710723985.4 is to prepare an ultra-high molecular weight polyethylene catalyst with narrow molecular weight distribution, uniform particle size distribution and good fluidity by adjusting the type and proportion of the electron-donating of the catalyst, and the catalyst has polymerization activity temperature and is convenient for controlling process parameters. The internal electron donor comprises methyl benzoate, ethyl benzoate and the like, but the catalyst can not prepare polyethylene powder with viscosity average molecular weight higher than 400 ten thousand.
Two key requirements for high-end UHMWPE products are: 1. has a sufficiently high molecular weight; 2. good particle shape, narrow particle size distribution and less ash content. In particular, when UHMWPE products are used in the field of fibers or artificial joints, their molecular weight must reach over 600 ten thousand in order to guarantee sufficient mechanical strength; when the UHMWPE product is applied to the fields of lithium battery separators or artificial joints, etc., it must have a low ash content to improve the puncture resistance of the product or reduce the impact on the human body. At present, most of high-end UHMWPE products widely applied come from abroad, particularly medical ultrahigh polyethylene materials, and domestic UHMWPE powder manufacturers have a gap in ash content and partial mechanical properties compared with imported high-end products. The global market for UHMWPE, which has been produced in excess of 180kt per year, is growing at a growth rate of 5% with a wide future development space.
Disclosure of Invention
In view of the above situation, the inventors of the present invention have found through research that at least one of the ring-three veratrum hydrocarbon and its derivatives or the ring-four veratrum hydrocarbon and its derivatives is used as a compound internal electron donor, and at the same time, during the preparation of the catalyst component, the ring-three veratrum hydrocarbon and its derivatives or the ring-four veratrum hydrocarbon and its derivatives and the titanium compound are used to perform a secondary treatment on the intermediate product (magnesium/titanium-containing solid particles) of the catalyst component, so that the polymerization activity and the polymer molecular weight of the catalyst can be significantly improved. Based on the above, the invention aims to provide a catalyst component for olefin polymerization, a catalyst, a method for preparing ultrahigh molecular weight polyolefin and application.
In a first aspect the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component being prepared by a process comprising the steps of:
s1, dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution;
s2, reacting the uniform solution with an organic acid anhydride compound and an acetate compound, then contacting with a titanium compound, and then heating to separate out magnesium/titanium-containing solid particles;
s3, adding an electron donor a into the system obtained in the step S2, and carrying out constant temperature treatment to obtain a mixture;
s4, removing unreacted substances and the solvent from the mixture obtained in the step S3, washing for 1-2 times by using an inert hydrocarbon solvent, and adding the inert hydrocarbon solvent to form a mixture;
s5, reacting the mixture obtained in the step S4 with a titanium compound and an electron donor b, and carrying out constant-temperature treatment to obtain a mixture;
s6, removing unreacted substances and a solvent from the mixture obtained in the step S5, and washing to obtain the catalyst component;
the electron donor a is selected from at least one of compounds shown in a general formula (I) and a general formula (II), and the electron donor b is selected from at least one of compounds shown in a general formula (III) and a general formula (IV):
Figure BDA0003300436370000031
in the formula (I), R 1 And R 2 Independently of one another, methyl or ethyl, R 3 And R 4 Independently hydrogen or methyl;
in the formula (II), R 5 And R 6 Independently is methyl or ethyl, R 7 、R 8 、R 9 And R 10 Same or different, independently hydrogen, halogen, C 1 -C 10 Straight chain alkyl group of (1), C 1 -C 10 Branched alkyl or C 1 -C 10 Alkoxy group of (a);
in the formula (III), M 1 、M 2 、M 3 、M 4 、M 5 And M 6 The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R 1 OR-OR 2 Wherein R is 1 And R 2 Each being substituted or unsubstituted C 1 -C 10 A hydrocarbyl group, the substituent being selected from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group or a heteroatom; when two radicals M are adjacent on the benzene ring 1 And M 2 Or M 3 And M 4 Or M 5 And M 6 Are each selected from the group consisting of-R 1 OR-OR 2 When the two adjacent groups are optionally cyclic with each other;
in the formula (IV), N 1 、N 2 、N 3 、N 4 、N 5 、N 6 、N 7 And N 8 The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R 3 ' OR-OR 4 ', wherein R 3 ' and R 4 ' each is substituted or unsubstituted C 1 -C 10 The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom.
A second aspect of the present invention provides a catalyst for the polymerisation of olefins, the catalyst comprising the following components:
a) The method comprises the following steps The above-mentioned catalyst component;
b) The method comprises the following steps The general formula is AlR' d X’ 3-d Wherein R' is hydrogen or C 1 -C 20 A hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 < d.ltoreq.3.
A third aspect of the present invention provides a process for preparing an ultrahigh molecular weight polyolefin, the process comprising: reacting one or more olefins of the general formula CH in the presence of the above-described catalyst 2 = CHR where R is hydrogen or C 1 -C 6 Alkyl group of (1).
In a fourth aspect the present invention provides the use of a catalyst component as described above or a catalyst as described above or a process as described above for the preparation of an ultra high molecular weight polyolefin.
According to the preparation method, the organic acid anhydride compound, the acetate compound, the electron donor a and the electron donor b are introduced into an N-type polyolefin catalyst preparation system to serve as compound electron donors, and meanwhile, the electron donor b and the titanium compound are used for carrying out secondary treatment on an intermediate product (magnesium/titanium-containing solid particles) of the catalyst component by adopting a specific preparation method, so that the active center of the catalyst component can be optimized, and the catalyst component is endowed with more excellent performance. When the catalyst containing the catalyst component is used for slurry polymerization/copolymerization of ethylene, ultrahigh molecular weight polyethylene powder with the viscosity average molecular weight of more than 750 ten thousand can be obtained; the catalyst activity was greater than 9000gPE/gcat.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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 preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a catalyst component for the polymerisation of olefins, the catalyst component being prepared by a process comprising the steps of:
s1, dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution;
s2, reacting the uniform solution with an organic acid anhydride compound and an acetate compound, then contacting with a titanium compound, and heating to separate out magnesium/titanium-containing solid particles;
s3, adding an electron donor a into the system obtained in the step S2, and carrying out constant temperature treatment to obtain a mixture;
s4, removing unreacted substances and the solvent from the mixture obtained in the step S3, washing 1=2 times by using an inert hydrocarbon solvent, and adding the inert hydrocarbon solvent to form a mixture;
s5, reacting the mixture obtained in the step S4 with a titanium compound and an electron donor b, and carrying out constant-temperature treatment to obtain a mixture;
s6, removing unreacted substances and a solvent from the mixture obtained in the step S5, and washing to obtain the catalyst component;
the electron donor a is selected from at least one of compounds shown in a general formula (I) and a general formula (II), and the electron donor b is selected from at least one of compounds shown in a general formula (III) and a general formula (IV):
Figure BDA0003300436370000051
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Figure BDA0003300436370000061
in the formula (I), R 1 And R 2 Independently is methyl or ethyl, R 3 And R 4 Independently hydrogen or methyl;
in the formula (II), R 5 And R 6 Independently is methyl or ethyl, R 7 、R 8 、R 9 And R 10 Same or different, independently hydrogen, halogen, C 1 -C 10 Straight chain alkyl group of (1), C 1 -C 10 Branched alkyl or C 1 -C 10 Alkoxy group of (a);
in the formula (III), M 1 、M 2 、M 3 、M 4 、M 5 And M 6 The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R 1 OR-OR 2 Wherein R is 1 And R 2 Each being substituted or unsubstituted C 1 -C 10 A hydrocarbon group, isThe substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom; when two radicals M are adjacent on the benzene ring 1 And M 2 Or M 3 And M 4 Or M 5 And M 6 Each is selected from-R 1 OR-OR 2 When the two adjacent groups are optionally cyclic with each other;
in the formula (IV), N 1 、N 2 、N 3 、N 4 、N 5 、N 6 、N 7 And N 8 The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R 3 ' OR-OR 4 ', wherein R 3 ' and R 4 ' each is substituted or unsubstituted C 1 -C 10 The substituent is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or hetero atom.
Preferably, the compound of formula (I) is selected from at least one of 2,2-dimethyl-1,3-diethoxy-propane, 2,2-dimethyl-1,3-dimethoxy-propane and 2,2-dimethyl-1-ethoxy-3-methoxy-propane.
Preferably, in formula (II), R 5 And R 6 Independently is methyl or ethyl, R 7 、R 8 、R 9 And R 10 The same or different, independently hydrogen, fluorine, chlorine, bromine, iodine, C 1 -C 6 Straight chain alkyl group of (1), C 1 -C 6 Branched alkyl or C 1 -C 6 Alkoxy group of (2). More preferably, the compound represented by formula (II) is at least one selected from the group consisting of o-dimethylether, o-diethylether and 1-ethoxy-2-methoxybenzene.
In the present invention, the compound represented by formula (III) may be at least one selected from the group consisting of cyclotri veratrole and derivatives thereof, and is preferably at least one selected from the group consisting of:
a compound A: m is a group of 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 3 ；
Compound B: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 2 CH 3 ；
Compound C: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 2 CH 2 CH 3 ；
Compound D: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH(CH 3 ) 2 ；
Compound E: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 2 CH 2 CH 2 CH 3 ；
Compound F: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 3 ；
Compound G: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 CH 3 ；
Compound H: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 CH 2 CH 3 ；
A compound I: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝Cl；
Compound J: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝Br；
Compound K: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝I；
Compound M: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OH；
Compound N: m 1 ＝M 3 ＝M s ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 Br。
According to the invention, the compound represented by formula (IV) may be selected from at least one of cyclotetraveratrole and its derivatives, preferably at least one of the following compounds:
compound O: n is a radical of 1 ＝N 2 ＝N 3 ＝N 4 ＝N 5 ＝N 6 ＝N 7 ＝N 8 ＝OCH 3 ；
Compound P: n is a radical of 1 ＝N 2 ＝N 3 ＝N 4 ＝N 5 ＝N 6 ＝N 7 ＝N 8 ＝OCH 2 CH 3 ；
Compound Q: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OCH 2 CH 3 ；
A compound R: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OCH 2 CH 2 CH 3 ；
A compound S: n is a radical of hydrogen 1 ＝N 2 ＝N 3 ＝N 4 ＝N 5 ＝N 6 ＝N 7 ＝N 8 ＝OH；
A compound T: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OH；
Compound U: n is a radical of hydrogen 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝NH 2 ；
Compound V: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝Cl；
A compound W: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝Br；
Compound X: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝I；
Compound Y: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝CHO；
Compound Z: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OCH 2 CH 2 Br。
In the present invention, the magnesium halide is selected from magnesium dihalide or a complex of magnesium dihalide with water, alcohol or an electron donor. The magnesium dihalide may be magnesium dichloride, magnesium dibromide, magnesium difluoride or magnesium diiodide, preferably magnesium dichloride. The complex of magnesium dihalide with water, alcohol or electron donor may be selected from the group consisting of complexes of magnesium dihalide with water, methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia, hydroxyamine, ethers, esters. The magnesium halides can be used individually or in admixture.
According to the invention, the organic epoxy compound may be C 2 -C 18 At least one of an oxide, glycidyl ether and internal ether of an aliphatic olefin, diolefin or halogenated aliphatic olefin or diolefin. Preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether.
In the present invention, the organophosphorus compound is a hydrocarbyl ester or a halogenated hydrocarbyl ester of orthophosphoric acid or phosphorous acid. Specific examples of the organophosphorus compound include, but are not limited to: trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-t-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-t-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, di-n-butyl phosphite, and the like. The organic phosphorus compound is preferably at least one of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.
In order to make the dissolution more sufficient, the solvent system of step S1 optionally contains an inert diluent. The inert diluent is an aromatic compound or an alkane compound, and the aromatic compound can be selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene and derivatives thereof; the alkane compound is at least one selected from linear alkanes, branched alkanes and cyclic alkanes having 3 to 20 carbon atoms, and is preferably at least one selected from butane, pentane, hexane, cyclohexane and heptane, as long as it can contribute to the dissolution of the magnesium halide.
In the present invention, the organic epoxy compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 1.5 moles, per mole of the magnesium halide; the amount of the organic phosphorus compound is 0.1 to 10 moles, preferably 0.5 to 1.5 moles; the inert diluent is preferably used in an amount of 0 to 5L.
According to the invention, the structure of the organic acid anhydride compound is shown as the formula (V):
Figure BDA0003300436370000091
in the formula (V), R 1 And R 2 Independently is hydrogen or C 1 -C 10 Alkyl, aryl, heteroaryl, and heteroaryl,C 2 -C 10 Alkenyl radical, C 2 -C 10 Alkynyl, C 3 -C 8 Cycloalkyl or C 6 -C 10 Aromatic hydrocarbon radical, R 1 And R 2 Can be arbitrarily cyclized.
Preferably, the organic acid anhydride-based compound is at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, crotonic anhydride and maleic anhydride.
In the invention, the general formula of the acetate compound is CH 3 COOR 3 In the formula, R 3 Is C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 3 -C 8 Cycloalkyl radical, C 2 -C 10 Alkynyl or C 6 -C 10 Aromatic hydrocarbon radical, R 3 Preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-octyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl or xylyl.
Preferably, the acetate-based compound is at least one selected from the group consisting of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, and n-octyl acetate.
In the present invention, the titanium compound has the general formula of Ti (OR) 4 ) a X b In the formula, R 4 Is C 1 -C 10 Aliphatic hydrocarbon radical of (C) 6 -C 14 X is halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2,b is an integer from 1 to 4, and a + b =3 or 4.
According to the present invention, the term "aliphatic hydrocarbon group" means a straight-chain or branched-chain hydrocarbon group composed of only carbon atoms and hydrogen atoms, and specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, vinyl, 1-propenyl, allyl, ethynyl, 1-propynyl, 2-propynyl, butynyl and the like. "aromatic hydrocarbon group" means a hydrocarbon group having a benzene ring, and includes an aryl group, an aryl-substituted hydrocarbon group or a hydrocarbon-substituted aryl group, such as a phenyl group, a benzyl group, an anthryl group, a naphthyl group and the like.
In the present invention, R 4 Can be selected from C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 3 -C 8 Cycloalkyl or C 6 -C 1o An aromatic hydrocarbon group of (1). Preferably, R 4 Selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclopropyl, methylcyclopropyl, n-pentyl, methylcyclopentyl, cyclohexyl, phenyl, benzyl or xylyl.
Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, chlorotriethoxytitanium, titanium trichloride, dichlorodiethoxytitanium, and trichloromonoethoxytitanium.
In the invention, the organic acid anhydride compound is used in an amount of 0.03-1.0 mol, preferably 0.1-0.5 mol, per mol of magnesium halide; the dosage of the acetate compound is 0.01-1 mol, preferably 0.03-0.2 mol; the amount of the titanium compound used in the step S2 is 0.5 to 120 mol, preferably 5 to 20 mol; the amount of the titanium compound used in the step S5 is 0.1 to 20 mol, preferably 0.3 to 5 mol; the dosage of the electron donor a is 0.01-1.0 mol, preferably 0.1-0.3 mol; the amount of the electron donor b is 0.0005 to 1.0 mol, preferably 0.001 to 0.3 mol.
Preferably, in the step S1, the dissolving temperature is 50-70 ℃ and the time is 1-3 hours; more preferably, the dissolution temperature is 60 ℃ and the time is 2h.
In step S2 of the present invention, the solution after the reaction is cooled to-60 ℃ to-10 ℃, preferably to-60 ℃ to-20 ℃, and then contacted with the titanium compound, wherein the temperature rise is preferably gradual, and the temperature rise is 60 ℃ to 100 ℃, preferably 75 ℃ to 100 ℃, and more preferably 80 ℃ to 95 ℃.
Preferably, in step S3, the constant temperature is the same as the temperature rise temperature in step S2, and the treatment time is 0.5 to 3 hours, more preferably 1 to 2 hours.
The inert hydrocarbon solvent for washing in step S4 and step S6 may be isobutane, hexane, heptane, cyclohexane, benzene, toluene, xylene, etc., preferably toluene and/or hexane, and the washing temperature may be 20 to 50 ℃.
Preferably, in step S5, the mixture is cooled to-60 ℃ to-10 ℃, preferably-60 ℃ to-20 ℃, then contacted with the titanium compound, and then heated to 60 ℃ to 100 ℃, preferably 75 ℃ to 100 ℃, more preferably 80 ℃ to 95 ℃, and kept at the constant temperature for 0.5 to 3 hours, and finally the electron donor b is added, and kept at the constant temperature for 0.5 to 3 hours, preferably 1 to 2 hours.
Other parameters, which are not defined in the preparation of the catalyst component of the present invention, can be selected with reference to the prior art.
According to a second aspect of the present invention, there is provided a catalyst for the polymerisation of olefins, the catalyst comprising the following components:
a) The method comprises the following steps The above-mentioned catalyst component;
b) The method comprises the following steps The general formula is AlR' d X’ 3-d Wherein R' may be hydrogen or C 1 -C 20 A hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, 0 < d.ltoreq.3.
In the present invention, R' is preferably C 1 -C 20 Alkyl of (C) 1 -C 20 Aralkyl or C 1 -C 20 Aryl group of (1). The organoaluminum compound may be Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、AlH(CH 2 CH 3 ) 2 、Al(i-Bu) 3 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 、AlCl(CH 2 CH 3 ) 2 Or AlCl 2 (CH 2 CH 3 ) Preferably Al (CH) 2 CH 3 ) 3 Or Al (i-Bu) 3 。
According to the invention, the molar ratio of aluminium in component B) to titanium in component A) is preferably from 5: 1 to 500: 1, more preferably from 20: 1 to 200: 1, most preferably from 50: 1 to 100: 1.
According to a third aspect of the present invention, there is provided a process for producing an ultrahigh molecular weight polyolefin, the process comprising: reacting one or more olefins in the presence of the above-described catalyst.
According to the invention, the olefin has the general formula CH 2 = CHR where R is hydrogen or C 1 -C 6 Preferably ethylene, propylene and/or butylene.
The catalyst of the present invention may be used in homopolymerization of ethylene and copolymerization of ethylene and alpha-olefin, and the comonomer may be propylene, butene, pentene, hexene, octene or 4-methyl-1-pentene.
In the present invention, the pressure of the reaction is 0.1 to 3MPa, preferably 0.5 to 1.5MPa, and more preferably 1.0MPa. The temperature of the reaction is 30 to 100 ℃, preferably 70 to 85 ℃, more preferably 70 ℃. The reaction time is 1.5 to 10 hours, preferably 1.5 to 2.5 hours, more preferably 2 hours.
The olefin reaction may be carried out by slurry polymerization or gas phase polymerization. The catalyst has an activity in the slurry homopolymerization of ethylene of more than 9000gPE/gcat.
The slurry polymerization medium comprises: and inert solvents such as saturated aliphatic hydrocarbons and aromatic hydrocarbons, such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.
According to a fourth aspect of the present invention there is provided the use of a catalyst component as described above or a catalyst as described above or a process as described above for the preparation of ultra high molecular weight polyolefins.
Preferably, the ultrahigh molecular weight polyolefin is ultrahigh molecular weight polyethylene, the powder particles of the ultrahigh molecular weight polyethylene are spherical or ellipsoidal, the viscosity average molecular weight is more than 750 ten thousand, and the catalyst activity is more than 9000gPE/gcat.
The present invention will be further described with reference to the following examples. But is not limited by these examples.
In the following examples and comparative examples:
1. determination of the bulk Density of the Polymer: the measurements were carried out using (ASTM D1895) test methods for apparent density, bulk factor and pourability of plastics.
2. Polymer molecular weight (viscosity average molecular weight) test: measured according to ASTM D4020-18.
3. Determination of the Span value of the Polymer: and (4) measuring by using a Microtrac laser particle size particle shape analyzer.
4. Determination of the ash value of the Polymer: the assay was performed according to GB T9345.1-2008.
Example 1
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the condition of stirring rotation speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature constant for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 1mL of 2, 2-dimethyl-1,3-diethoxy-propane, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing stirring and settling, filtering mother liquor, washing twice by using an inert diluent toluene, then adding 90mL of toluene, keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 5mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 0.2g of compound A, and continuously keeping the temperature for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component with good fluidity.
(2) Polymerisation reaction
A stainless steel reaction vessel having a capacity of 2L was sufficiently purged with high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethylaluminum were added, the catalyst component (containing 0.6 mg of titanium) prepared by the above method was added, the temperature was raised to 80 ℃ and ethylene was introduced so that the total pressure in the vessel became 1.0MPa (gauge pressure), and polymerization was carried out at 80 ℃ for 2 hours, the polymerization results being shown in Table 1.
Example 2
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the condition of stirring rotation speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature constant for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 1mL of 2, 2-dimethyl-1-ethoxy-3-methoxy-propane, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing, stirring and settling, filtering out mother liquor, washing twice by using an inert diluent toluene, then adding 90mL of toluene, keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 5mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 0.2g of compound B, and continuously keeping the temperature for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component with good fluidity.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 3
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epichlorohydrin and 15.0mL of tributyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 1mL of phthalic ether, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing stirring and settling, filtering mother liquor, washing twice by using an inert diluent, adding 90mL of toluene, keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 5mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 0.1g of compound P, and continuously keeping the temperature for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component with good fluidity.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 4
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epichlorohydrin and 15.0mL of tributyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 1mL of phthalic ether, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing stirring and settling, filtering mother liquor, washing twice by using an inert diluent, adding 90mL of toluene, keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 5mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 0.1g of compound A, and continuously keeping the temperature for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component with good fluidity.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 5
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the condition of stirring rotation speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature constant for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 1mL of phthalic ether, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing stirring and settling, filtering mother liquor, washing twice by using inert diluent hexane, adding 90mL of hexane, keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 8mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 0.1g of compound M and 0.1g of compound P, and continuously keeping the temperature for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component with good fluidity.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Example 6
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the condition of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature constant for 1 hour, cooling to-40 ℃, dropwise adding 70mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 1mL of 1, 3-diethoxy-propane, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing stirring and settling, filtering out mother liquor, washing twice by using an inert diluent toluene, adding 90mL of toluene, keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 8mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature for 1 hour, adding 0.1g of compound B and 0.2g of compound R, and continuously keeping the temperature for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component with good fluidity.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 1
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 75mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. 1mL of 2, 2-dimethyl-1,3-diethoxy-propane and 0.2g of Compound A were added and the incubation was continued for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 2
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 75mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. Add 1ml of 2,2-dimethyl =1= ethoxy =3= methoxy = propane and 0.2g of compound B, and continue to thermostatting for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 3
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 75mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. 1mL of o-dimethyl ether and 0.1g of Compound P were added, and the temperature was kept constant for 1 hour. Filtering to remove mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying to obtain the catalyst component.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 4
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 75mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. 1mL of o-dimethyl ether and 0.1g of Compound A were added, and the temperature was kept constant for 1 hour. Filtering to remove mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying to obtain the catalyst component.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
Comparative example 5
(1) Preparation of the catalyst component
Adding 4.8 g of magnesium chloride, 90mL of toluene, 5.0mL of epoxy chloropropane and 15.0mL of tri-n-butyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 1.2g of phthalic anhydride and 0.8mL of ethyl acetate, continuously keeping the temperature for 1 hour, cooling to-40 ℃, dropwise adding 75mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. 1mL of o-dimethyl ether and 0.1g of Compound M and 0.1g of Compound P were added, and the incubation was continued for 1 hour. Filtering mother liquor, washing the mother liquor for many times by using an inert diluent toluene and an organic solvent hexane, and drying the washed mother liquor to obtain the catalyst component.
(2) Polymerization reaction: the polymerization results are shown in Table 1, as in example 1.
TABLE 1
Figure BDA0003300436370000181
As can be seen from the data in Table 1, the catalyst of the present invention has a polymerization activity of greater than 9000gPE/gcat, a powder bulk density of greater than 0.45g/mL, and a polymer viscosity average molecular weight of greater than 780X 10 4 g/mol, powder Span value below 0.70, and low ash content of the polymer. The catalyst component of the invention can effectively improve the polymerization activity of the catalyst and the molecular weight of the polymerization powder. In addition, the polymer powder prepared by the embodiment of the invention is observed by a scanning electron microscope, and is spherical or ellipsoidal.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. A catalyst component for the polymerization of olefins, characterized in that it is prepared by a process comprising the steps of:
s1, dissolving magnesium halide in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution;
s2, reacting the uniform solution with an organic acid anhydride compound and an acetate compound, then contacting with a titanium compound, and then heating to separate out magnesium/titanium-containing solid particles;
s3, adding an electron donor a into the system obtained in the step S2, and carrying out constant temperature treatment to obtain a mixture;
s4, removing unreacted substances and the solvent from the mixture obtained in the step S3, washing for 1-2 times by using an inert hydrocarbon solvent, and adding the inert hydrocarbon solvent to form a mixture;
s5, reacting the mixture obtained in the step S4 with a titanium compound and an electron donor b, and carrying out constant-temperature treatment to obtain a mixture;
s6, removing unreacted substances and a solvent from the mixture obtained in the step S5, and washing to obtain the catalyst component;
the electron donor a is selected from at least one of compounds shown in a general formula (I) and a general formula (II), and the electron donor b is selected from at least one of compounds shown in a general formula (III) and a general formula (IV):
Figure FDA0003300436360000011
Figure FDA0003300436360000021
in the formula (I), R 1 And R 2 Independently is methyl or ethyl, R 3 And R 4 Independently hydrogen or methyl;
in the formula (II), R 5 And R 6 Independently is methyl or ethyl, R 7 、R 8 、R 9 And R 10 Same or different, independently hydrogen, halogen, C 1 -C 10 Straight chain alkyl of (1), C 1 -C 10 Branched alkyl or C 1 -C 10 Alkoxy group of (a);
in the formula (III), M 1 、M 2 、M 3 、M 4 、M 5 And M 6 The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R 1 OR-OR 2 Wherein R is 1 And R 2 Each being substituted or unsubstituted C 1 -C 10 A hydrocarbyl group, the substituent being selected from a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, an acyl group, a halogen atom, an alkoxy group or a heteroatom; when two groups M are adjacent on the benzene ring 1 And M 2 Or M 3 And M 4 Or M 5 And M 6 Are each selected from the group consisting of-R 1 OR-OR 2 When the two adjacent groups are optionally cyclic with each other;
in the formula (IV), N 1 、N 2 、N 3 、N 4 、N 5 、N 6 、N 7 And N 8 The same or different, each being selected from hydrogen, hydroxyl, amino, aldehyde, carboxyl, acyl, halogen atom, -R 3 ' OR-OR 4 ', wherein R 3 ' and R 4 ' each is substituted or unsubstituted C 1 -C 10 The substituent of the hydrocarbyl group is selected from hydroxyl, amino, aldehyde group, carboxyl, acyl, halogen atom, alkoxy or heteroatom.
2. The catalyst component for the polymerization of olefins according to claim 1 in which the compound of formula (I) is selected from at least one of 2,2-dimethyl-1,3-diethoxy-propane, 2,2-dimethyl-1,3-dimethoxy-propane and 2,2-dimethyl-1-ethoxy-3-methoxy-propane;
in the formula (II), R 5 And R 6 Independently is methyl or ethyl, R 7 、R 8 、R 9 And R 10 The same or different, independently are hydrogen, fluorine, chlorine, bromine, iodine, C 1 -C 6 Straight chain alkyl group of (1), C 1 -C 6 Branched alkyl or C 1 -C 6 Alkoxy group of (a); preferably, the compound represented by formula (II) is at least one selected from the group consisting of o-dimethylether, o-diethylether and 1-ethoxy-2-methoxybenzene.
3. The catalyst component for the polymerization of olefins according to claim 1 in which the compound of formula (III) is chosen from at least one of the following compounds:
a compound A: m is a group of 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 3 ；
Compound B: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 2 CH 3 ；
Compound C: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 2 CH 2 CH 3 ；
Compound D: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH(CH 3 ) 2 ；
Compound E: m 1 ＝M 2 ＝M 3 ＝M 4 ＝M 5 ＝M 6 ＝OCH 2 CH 2 CH 2 CH 3 ；
Compound F: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 3 ；
Compound G: m 1 ＝M 3 ＝M s ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 CH 3 ；
Compound H: m is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 CH 2 CH 3 ；
A compound I: m is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝Cl；
Compound J: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝Br；
Compound K: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝I；
Compound M: m is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OH；
Compound N: m 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 Br；
The compound represented by the formula (IV) is selected from at least one of the following compounds:
compound O: n is a radical of 1 ＝N 2 ＝N 3 ＝N 4 ＝N 5 ＝N 6 ＝N 7 ＝N 8 ＝OCH 3 ；
Compound P: n is a radical of 1 ＝N 2 ＝N 3 ＝N 4 ＝N 5 ＝N 6 ＝N 7 ＝N 8 ＝OCH 2 CH 3 ；
Compound Q: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OCH 2 CH 3 ；
A compound R: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OCH 2 CH 2 CH 3 ；
A compound S: n is a radical of 1 ＝N 2 ＝N 3 ＝N 4 ＝N 5 ＝N 6 ＝N 7 ＝N 8 ＝OH；
A compound T: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OH；
A compound U: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝NH 2 ；
Compound V: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝C1；
A compound W: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝Br；
Compound X: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝I；
Compound Y: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝CHO；
Compound Z: n is a radical of 1 ＝N 3 ＝N 5 ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝OCH 2 CH 2 Br。
4. The catalyst component for the polymerization of olefins according to claim 1 in which the magnesium halide is selected from magnesium dihalides or from complexes of magnesium dihalides with water, alcohols or electron donors; the magnesium dihalide is magnesium dichloride, magnesium dibromide, magnesium difluoride or magnesium diiodide, preferably magnesium dichloride; the complex of magnesium dihalide and water, alcohol or electron donor is selected from the complex of magnesium dihalide and water, methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia, hydroxyamine, ether and ester;
the organic epoxy compound is C 2 -C 18 At least one of an oxide, glycidyl ether and internal ether of an aliphatic olefin, diolefin or halogenated aliphatic olefin or diolefin of (a); preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether and butyl glycidyl ether;
the organophosphorus compound is a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid or phosphorous acid; preferably at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-t-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-t-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite and di-n-butyl phosphite, more preferably at least one selected from the group consisting of triethyl phosphate, tri-n-propyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite;
optionally, the solvent system in step S1 contains an inert diluent, wherein the inert diluent is an aromatic compound or an alkane compound, and the aromatic compound is selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene and derivatives thereof; the alkane compound is selected from at least one of straight-chain alkane, branched-chain alkane or cycloalkane with the carbon number of 3-20, preferably at least one of butane, pentane, hexane, cyclohexane and heptane;
the organic epoxy compound is preferably used in an amount of 0.2 to 10 moles, more preferably 0.5 to 1.5 moles, per mole of the magnesium halide; the organic phosphorus compound is preferably used in an amount of 0.1 to 10 moles, more preferably 0.5 to 1.5 moles; the inert diluent is preferably used in an amount of 0 to 5L.
5. The catalyst component for olefin polymerization according to claim 1, wherein the organic acid anhydride compound has a structure represented by formula (V):
Figure FDA0003300436360000051
in the formula (V), R 1 And R 2 Independently is hydrogen or C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 10 Alkynyl, C 3 -C 8 Cycloalkyl or C 6 -C 10 Aromatic hydrocarbon radical, R 1 And R 2 Can renForming a ring;
preferably, the organic acid anhydride compound is selected from at least one of acetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, phthalic anhydride, crotonic anhydride and maleic anhydride;
the general formula of the acetate compound is CH 3 COOR 3 In the formula, R 3 Is C 1 -C 10 Alkyl radical, C 2 -C 10 Alkenyl radical, C 3 -C 8 Cycloalkyl radical, C 2 -C 10 Alkynyl or C 6 -C 10 An aromatic hydrocarbon group;
preferably, the acetate compound is selected from at least one of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, and n-octyl acetate.
6. The catalyst component for the polymerization of olefins according to claim 1 in which the titanium compound has the general formula Ti (OR) 4 ) a X b In the formula, R 4 Is C 1 -C 10 Aliphatic hydrocarbon radical of (C) 6 -C 14 X is halogen, preferably fluorine, chlorine or bromine, a is 0, 1 or 2,b is an integer from 1 to 4, and a + b =3 or 4;
preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, chlorotriethoxytitanium, titanium trichloride, dichlorodiethoxytitanium, and trichloromonoethoxytitanium.
7. The catalyst component for olefin polymerization according to claim 1, wherein the organic acid anhydride-based compound is used in an amount of 0.03 to 1.0 mole, preferably 0.1 to 0.5 mole, per mole of magnesium halide; the dosage of the acetate compound is 0.01-1 mol, preferably 0.03-0.2 mol; the amount of the titanium compound used in the step S2 is 0.5 to 120 mol, preferably 5 to 20 mol; the amount of the titanium compound used in the step S5 is 0.1 to 20 mol, preferably 0.3 to 5 mol; the dosage of the electron donor a is 0.01-1.0 mol, preferably 0.1-0.3 mol; the dosage of the electron donor b is 0.0005-1.0 mol, preferably 0.001-0.3 mol;
preferably, in the step S1, the dissolving temperature is 50-70 ℃ and the time is 1-3 hours;
preferably, in step S2, the solution after the reaction is cooled to-60 ℃ to-10 ℃, and then contacted with a titanium compound; the temperature of the temperature rise is 60-100 ℃;
preferably, in step S5, the mixture is cooled to-60 ℃ to-10 ℃, then contacted with the titanium compound, then heated to 60 ℃ to 100 ℃, kept at the constant temperature for 0.5 to 3 hours, and finally added with the electron donor b, and kept at the constant temperature for 0.5 to 3 hours.
8. A catalyst for the polymerization of olefins, characterized in that it comprises the following components:
a) The method comprises the following steps The catalyst component of any one of claims 1 to 7;
b) The method comprises the following steps The general formula is AIR' d X’ 3-d Wherein R' is hydrogen or C 1 -C 20 A hydrocarbon group, X' is a halogen atom, preferably fluorine, chlorine or bromine, and d is more than 0 and less than or equal to 3;
the organoaluminum compound is preferably Al (CH) 3 ) 3 、Al(CH 2 CH 3 ) 3 、AlH(CH 2 CH 3 ) 2 、Al(i-Bu) 3 、AlH(i-Bu) 2 、AlCl(CH 2 CH 3 ) 2 、Al 2 Cl 3 (CH 2 CH 3 ) 3 、AlCl(CH 2 CH 3 ) 2 Or AlCl 2 (CH 2 CH 3 ) More preferably Al (CH) 2 CH 3 ) 3 Or Al (i-Bu) 3 ；
The molar ratio of aluminium in component B) to titanium in component A) is preferably from 5: 1 to 500: 1, more preferably from 20: 1 to 200: 1, most preferably from 50: 1 to 100: 1.
9. A process for preparing an ultrahigh molecular weight polyolefin, the process comprising: reacting one or more olefins of the formula CH in the presence of the catalyst of claim 8 2 = CHR where R is hydrogen or C 1 -C 6 Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or butene;
the pressure of the reaction is 0.1-3Mpa, preferably 0.5-1.5Mpa; the reaction temperature is 30-100 ℃, and preferably 70-85 ℃; the reaction time is 1.5-10h, preferably 1.5-2.5h.
10. Use of the catalyst component of any one of claims 1 to 7 or the catalyst of claim 8 or the process of claim 9 for the preparation of ultra high molecular weight polyolefins;
preferably, the ultrahigh molecular weight polyolefin is ultrahigh molecular weight polyethylene, powder particles of the ultrahigh molecular weight polyethylene are spherical or ellipsoidal, the viscosity average molecular weight is more than 750 ten thousand, and the catalyst activity is more than 9000gPE/gcat.
CN202111189965.6A 2021-10-12 2021-10-12 Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin Pending CN115960282A (en)

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CN105440185A (en) * 2015-11-20 2016-03-30 万华化学集团股份有限公司 Supported catalyst, preparation method thereof, and method for applying supported catalyst to propylene polymerization
CN109280109A (en) * 2017-07-19 2019-01-29 中国石油化工股份有限公司 A kind of catalyst system and its application for olefinic polymerization
CN109280101A (en) * 2017-07-19 2019-01-29 中国石油化工股份有限公司 Ingredient of solid catalyst and catalyst system and olefine polymerizing process for olefinic polymerization
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CN101153062A (en) * 2006-09-29 2008-04-02 中国石油化工股份有限公司 Olefins polymerizing solid catalyst component, producing method and application of the same
CN105440185A (en) * 2015-11-20 2016-03-30 万华化学集团股份有限公司 Supported catalyst, preparation method thereof, and method for applying supported catalyst to propylene polymerization
CN109280109A (en) * 2017-07-19 2019-01-29 中国石油化工股份有限公司 A kind of catalyst system and its application for olefinic polymerization
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