CN115960281A - 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

Info

Publication number
CN115960281A
CN115960281A CN202111189962.2A CN202111189962A CN115960281A CN 115960281 A CN115960281 A CN 115960281A CN 202111189962 A CN202111189962 A CN 202111189962A CN 115960281 A CN115960281 A CN 115960281A
Authority
CN
China
Prior art keywords
compound
och
group
phosphate
phosphite
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.)
Pending
Application number
CN202111189962.2A
Other languages
Chinese (zh)
Inventor
俸艳芸
孙竹芳
黄庭
苟清强
李颖
贺国强
杨红旭
王毅
马冬
曹昌文
梁云
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 CN202111189962.2A priority Critical patent/CN115960281A/en
Publication of CN115960281A publication Critical patent/CN115960281A/en
Pending legal-status Critical Current

Links

Classifications

    • 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 technical field of olefin polymerization catalysts, and discloses a catalyst component and a catalyst for olefin polymerization, and a method and application for preparing ultrahigh molecular weight polyolefin. 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 heating; adding an electron donor a into the system, and keeping the temperature constant; removing unreacted material and solvent, washing, adding solvent to formMixing; reacting the mixture with a titanium compound, an electron donor b and an alcohol compound, and keeping the temperature constant; removing unreacted substances and a solvent, and washing to obtain a catalyst component; the electron donor a is selected from at least one of the compounds shown in the general formula (I) and the general formula (II), and the electron donor b is selected from at least one of the compounds shown in the general formula (III) and the 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 million. 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 uses an ultrasonic treatment supported titanium catalyst to produce an ultra-high molecular weight polyethylene resin. 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. In patent document CN201710723985.4, an ultrahigh molecular polyethylene catalyst with narrow molecular weight distribution, uniform particle size distribution and good fluidity is prepared by adjusting the type and the proportion of electrons given by the catalyst, and the catalyst has polymerization activity temperature and is convenient for process parameter control. 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 field 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 compound internal electron donors is cyclotri-veratryl hydrocarbon and its derivatives or cyclotetra-veratryl hydrocarbon and its derivatives, and during the preparation of the catalyst component, the intermediate product (magnesium/titanium-containing solid particles) of the catalyst component is subjected to secondary treatment by using the cyclotri-veratryl hydrocarbon and its derivatives or cyclotetra-veratryl hydrocarbon and its derivatives, the titanium compound and the alcohol compound, so that the polymerization activity of the catalyst can be significantly improved. Based on the above, the invention aims to provide a catalyst component and a catalyst for olefin polymerization, and a method and application for preparing ultrahigh molecular weight polyolefin.
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 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, an electron donor b and an alcohol compound, 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 BDA0003299904750000031
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 of one another, 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, 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 hetero atom; 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 used, two adjacent groups may optionally form a ring 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.
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 radical, X' is a halogen atom, preferably fluorine, chlorine or bromine,0＜d≤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, wherein 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, the titanium compound and the alcohol compound are used for carrying out secondary treatment on the 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 650 ten thousand can be obtained; the catalyst activity was more than 12000gPE/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 present 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 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, an electron donor b and an alcohol compound, 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 BDA0003299904750000051
Figure BDA0003299904750000061
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 of (2);
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 is takenSubstituted 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 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-dimethyl-1, 3-dimethoxy-propane and 2, 2-dimethyl-1-ethoxy-3-methoxy-propane.
Preferably, in formula (II), R 5 And R 6 Independently methyl or ethyl, R7, 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 of (1), C 1 -C 6 Branched alkyl or C 1 -C 6 An 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 selected from at least one of cyclotri veratryl hydrocarbon and its derivatives, preferably 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 is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 3 ；
Compound G: m is a group of 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 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；
A compound M: m 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。
According to the invention, the compound shown in the formula (IV) can be selected from at least one of cyclo-tetraveratrum and derivatives thereof, and is 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 hydrogen 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 hydrogen 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 hydrogen 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 can be selected from the group consisting of magnesium dihalide complexes with water, methanol, ethanol, propanol, butanol, pentanol, hexanol, isooctanol, ammonia, hydroxyamine, ether, ester. 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 at least one selected from benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene and derivatives thereof; the alkane compound is at least one selected from the group consisting of linear alkanes, branched alkanes and cyclic alkanes having 3 to 20 carbon atoms, and may be used as long as it helps the magnesium halide to dissolve, and is preferably at least one selected from the group consisting of butane, pentane, hexane, cyclohexane and heptane.
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 BDA0003299904750000091
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 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 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 hydrocarbyl" refers to a hydrocarbyl group having a benzene ring, including aryl, aryl-substituted hydrocarbyl or hydrocarbyl-substituted aryl, such as phenyl, benzyl, anthracenyl, naphthyl, 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 10 An aromatic hydrocarbon group of (2). 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.
According to the invention, the alcohol compound has the general formula R S OH，R 5 Is C 1 -C 10 Alkyl radical, R 5 And may be methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl or isooctyl.
Preferably, the alcohol compound is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-hexanol, n-octanol, and isooctanol.
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 o.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; the amount of the alcohol compound is 0.01 to 20 mol, preferably 0.1 to 10 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-60 ℃ to-20 ℃, and then contacted with the titanium compound, wherein the temperature rise is preferably gradual temperature rise, 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, then heated to 60 ℃ to 100 ℃, preferably 75 ℃ to 100 ℃, more preferably 80 ℃ to 95 ℃, kept at the constant temperature for 0.5 to 3 hours, then the electron donor b is added, kept at the constant temperature for 0.5 to 3 hours, preferably 1 to 2 hours, and finally the alcohol compound is added, 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 G-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 (2). 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 in the range from 5: 1 to 500: 1, more preferably in the range from 20: 1 to 200: 1, most preferably in the range from 50: 1 to 100: 1.
According to a third aspect of the present invention, there is provided a process for preparing ultra-high molecular weight polyolefins, 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 12000gPE/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 650 ten thousand, and the catalyst activity is more than 12000gPE/gcat.
The present invention is further illustrated by 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, volume 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 carried out 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 epichlorohydrin and 15.0mL of tributyl phosphate into a reaction kettle, reacting for 2 hours under the condition that the stirring speed is 450rpm and the temperature is 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 2, 2-dimethyl-1, 3-diethoxy-propane, continuously keeping the temperature for 1 hour, cooling to 50 ℃, closing the 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 0.2g of a compound A, continuously keeping the temperature for 1 hour, then adding 1mL of ethanol, 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 volume of 2L was fully replaced with high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethylaluminum were added, the solid catalyst component prepared by the above method (containing 0.6 mg of titanium) 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.omL of tributyl 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 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, continuously keeping the temperature for 1 hour, then adding 1mL of ethanol, 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. Mu.l of tributyl phosphate into a reaction kettle, reacting for 2 hours under the condition that the stirring speed is 450rpm and the temperature is 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, continuously keeping the temperature for 1 hour, then adding 2mL of ethanol, 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 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 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, continuously keeping the temperature for 1 hour, then adding 2mL of ethanol, and continuously keeping the temperature for 1 hour. Filtering to remove mother liquor, washing for many times by using an inert diluent toluene and an organic solvent hexane, and drying to obtain the solid 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, continuously keeping the temperature for 1 hour, then adding 3mL of ethanol, and continuously keeping the temperature for 1 hour. Filtering to remove mother liquor, washing for many times by using an inert diluent toluene and an organic solvent hexane, and drying to obtain the solid 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 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, continuously keeping the temperature for 1 hour, then adding 3mL of ethanol, 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 temperature was kept constant for 1 hour, then 1mL of ethanol was added and the temperature was kept constant 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. 1mL of 2, 2-dimethyl-1-ethoxy-3-methoxy-propane and 0.2g of Compound B were added and the temperature was maintained for 1 hour, then 1mL of ethanol was added and the temperature was maintained 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 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 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 an inert diluent toluene, 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 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 70mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. Adding 1mL of o-dimethyl ether, keeping the temperature constant 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 constant for 1 hour, cooling to-40 ℃, dropwise adding 5mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature constant for 1 hour, adding 0.1g of compound A, and keeping the temperature constant 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 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 70mL of titanium tetrachloride, gradually heating to 90 ℃, and keeping the temperature for 1 hour. Adding 1mL of o-dimethyl ether, keeping the temperature constant for 1 hour, cooling to 50 ℃, closing stirring and settling, filtering out mother liquor, washing twice by using an inert diluent hexane, then adding 90mL of hexane, keeping the temperature constant for 1 hour, cooling to-40 ℃, dropwise adding 8mL of titanium tetrachloride, gradually heating to 90 ℃, keeping the temperature constant for 1 hour, adding 0.1g of compound M and 0.1g of compound P, and keeping the temperature constant 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 BDA0003299904750000191
As can be seen from the data in Table 1, the catalyst of the present invention has a polymerization activity of more than 12000gPE/gcat, a powder bulk density of more than 0.44g/mL, and a polymer viscosity average molecular weight of more than 650X 10 4 g/mol, powder Span value below 0.74, and low ash content of the polymer. The catalyst component of the invention can effectively improve the polymerization activity of the catalyst. In addition, the polymer powder prepared by the embodiment of the invention is observed by a scanning electron microscope, and is spherical or ellipsoidal.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. 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 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, an electron donor b and an alcohol compound, 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 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):
Figure FDA0003299904740000011
Figure FDA0003299904740000021
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 of one another, 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 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 Are identical to each otherOr different, each 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.
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-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 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 of (2); preferably, the compound represented by formula (II) is at least one selected from the group consisting of o-dimethyl ether, o-diethyl ether 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 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 is a group of 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 ；
A compound F: m is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 3 ；
Compound G: m is a group of 1 ＝M 3 ＝M 5 ＝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 is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝Br；
Compound K: m is a group of 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 is a group of 1 ＝M 3 ＝M 5 ＝OCH 3 ；M 2 ＝M 4 ＝M 6 ＝OCH 2 CH 2 Br；
The compound shown in 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 hydrogen 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 hydrogen 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；
Compound T: n is a radical of hydrogen 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 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 s ＝N 7 ＝OCH 3 ；N 2 ＝N 4 ＝N 6 ＝N 8 ＝Cl；
A compound W: n is a radical of hydrogen 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 hydrogen 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 hydrogen 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 chosen from magnesium dihalides or complexes of magnesium dihalides with water, alcohols or electron donors; the magnesium dihalide is magnesium dichloride, magnesium dibromide, magnesium difluoride or magnesium diiodide, and is 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 mol, more preferably 0.5 to 1.5 mol; 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 FDA0003299904740000051
in the formula (V), R 1 And R 2 Independently 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 form a ring at will;
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;
the general formula of the alcohol compound is R 5 OH，R 5 Is C 1 -C 10 An alkyl group; preferably, the alcohol compound is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-hexanol, n-octanol, and isooctanol.
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 o.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; the dosage of the alcohol compound is 0.01-20 mol, preferably 0.1-10 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 the step S5, the mixture is cooled to-60 ℃ to-10 ℃, then is contacted with the titanium compound, is heated to 60 ℃ to 100 ℃, is kept at the constant temperature for 0.5 to 3 hours, then is added with the electron donor b, is kept at the constant temperature for 0.5 to 3 hours, and finally is added with the alcohol compound, and is 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 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, 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 in the range from 5: 1 to 500: 1, more preferably in the range from 20: 1 to 200: 1, most preferably in the range from 50: 1 to 100: 1.
9. A process for preparing ultrahigh molecular weight polyolefins comprisingComprises the following steps: 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, the powder particles of the ultrahigh molecular weight polyethylene are spherical or ellipsoidal, the viscosity-average molecular weight is more than 650 ten thousand, and the catalyst activity is more than 12000gPE/gcat.
CN202111189962.2A 2021-10-12 2021-10-12 Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin Pending CN115960281A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111189962.2A CN115960281A (en) 2021-10-12 2021-10-12 Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111189962.2A CN115960281A (en) 2021-10-12 2021-10-12 Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin

Publications (1)

Publication Number Publication Date
CN115960281A true CN115960281A (en) 2023-04-14

Family

ID=87362070

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111189962.2A Pending CN115960281A (en) 2021-10-12 2021-10-12 Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin

Country Status (1)

Country Link
CN (1) CN115960281A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110016093A (en) * 2018-01-10 2019-07-16 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
CN111234067A (en) * 2018-11-29 2020-06-05 中国石油化工股份有限公司 Solid catalyst component and catalyst for olefin polymerization and application thereof
CN111234066A (en) * 2018-11-29 2020-06-05 中国石油化工股份有限公司 Solid catalyst component for olefin polymerization, olefin polymerization catalyst and application thereof
CN111234064A (en) * 2018-11-29 2020-06-05 中国石油化工股份有限公司 Solid catalyst component for olefin polymerization, olefin polymerization catalyst and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110016093A (en) * 2018-01-10 2019-07-16 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
CN111234067A (en) * 2018-11-29 2020-06-05 中国石油化工股份有限公司 Solid catalyst component and catalyst for olefin polymerization and application thereof
CN111234066A (en) * 2018-11-29 2020-06-05 中国石油化工股份有限公司 Solid catalyst component for olefin polymerization, olefin polymerization catalyst and application thereof
CN111234064A (en) * 2018-11-29 2020-06-05 中国石油化工股份有限公司 Solid catalyst component for olefin polymerization, olefin polymerization catalyst and application thereof

Similar Documents

Publication Publication Date Title
KR102172790B1 (en) Method for preparation of a catalyst component used for olefin polymerization
KR101571054B1 (en) A Catalyst Component for Ethylene Polymerization, Preparation thereof and a Catalyst Comprising the Catalyst Component
JP7038797B2 (en) Olefin polymerization catalyst containing cyclotribellatrilen and its derivatives
RU2560179C2 (en) Method of producing polyolefin polymer with improved wax deposition
CN110734510B (en) Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives
CN114181334B (en) Catalyst component and catalyst for olefin polymerization and preparation method thereof
CN114181335B (en) Catalyst component and catalyst for olefin polymerization and preparation method thereof
CN115960281A (en) Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin
CN110016096B (en) Catalyst carrier for olefin polymerization and preparation method thereof, solid catalyst component, catalyst system and olefin polymerization method
CN115960282A (en) Catalyst component and catalyst for olefin polymerization, and method and application for preparing ultrahigh molecular weight polyolefin
CN114478861B (en) Catalyst component for olefin polymerization, preparation method thereof, catalyst, method for preparing ultrahigh molecular weight polyolefin and application of catalyst component
CN114478854A (en) Catalyst component for olefin polymerization, preparation method thereof, catalyst, method for preparing ultrahigh molecular weight polyolefin and application
CN110903418B (en) Solid catalyst component for olefin polymerization, catalyst and application thereof
CN112759681B (en) Catalyst composition, catalyst and preparation method thereof, composite catalyst and olefin polymerization method
CN114426605A (en) Catalyst component for olefin polymerization and preparation method and application thereof
CN106478844B (en) Catalyst carrier, catalyst component and catalyst for olefin polymerization
KR101885812B1 (en) Process of preparation of drag reducing polymers and usage thereof
CN107880170B (en) Catalyst component for olefin polymerization and preparation and application thereof
JPH0822890B2 (en) Method for producing propylene polymer
RU2682163C1 (en) Method for preparation of vanadium magnesium polymerization catalyst of ethylene and copolimerization of ethylene with alpha olefines
CN110903420B (en) Solid catalyst component for olefin polymerization, catalyst and application thereof
CN107880164B (en) Catalyst component for olefin polymerization and preparation and application thereof
CN107880176B (en) Catalyst component for olefin polymerization and preparation and application thereof
CN112724284A (en) Solid catalyst component, preparation method thereof, olefin polymerization catalyst and application
CN108341902B (en) Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization

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