CN110407963B - Catalyst component for olefin polymerization and preparation method thereof - Google Patents
Catalyst component for olefin polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN110407963B CN110407963B CN201810401572.9A CN201810401572A CN110407963B CN 110407963 B CN110407963 B CN 110407963B CN 201810401572 A CN201810401572 A CN 201810401572A CN 110407963 B CN110407963 B CN 110407963B
- Authority
- CN
- China
- Prior art keywords
- heptanediol
- methyl
- compound
- ethyl
- heptene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a catalyst component for olefin polymerization, which comprises the reaction product of the following components: (1) a magnesium compound; (2) a lewis base compound; (3) has the general formula R2An acyl halide compound of COX wherein R2Is hydrogen, substituted or unsubstituted C1-C10 hydrocarbyl or epoxy, X is halogen; (4) a compound containing two hydroxyl groups; (5) a titanium compound. In the present invention, in the preparation process of the catalyst component, the acid halide compound and the compound containing two hydroxyl groups generate diol ester in situ. The obtained catalyst is compounded with an organic silicon compound to obtain the catalyst with excellent comprehensive performance, and when the catalyst is used for olefin polymerization, the activity of the catalyst is higher under the condition that the obtained polymer has high stereospecificity.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization, and relates to a catalyst component for olefin polymerization and a preparation method thereof.
Background
Currently, Ziegler-Natta catalyst systems are the predominant catalysts in the reaction for the preparation of polyolefins. High efficiency supported catalysts have been rapidly developed since US4495388 which proposes active magnesium halides as the support for Ziegler-Natta catalysts. The catalyst takes magnesium, titanium, halogen and an internal electron donor as main components; an organic aluminum compound is used as a cocatalyst component, and in addition, an organic silicon compound serving as an external electron donor component is added during polymerization according to needs. In the catalysts, the development of internal electron donor compounds enables the polypropylene catalysts to be continuously updated. In order to improve the competitiveness of the catalyst, several companies in the world strengthen the research and development work of novel electron donors and further improve the performance of the titanium efficient catalyst. Commonly used electron donor compounds include polycarboxylic acids, monocarboxylic acid esters or polycarboxylic acid esters, anhydrides, ketones, monoethers or polyethers, alcohols, amines, and the like, and derivatives thereof, among which more commonly used are aromatic dibasic carboxylates such as di-n-butyl phthalate or diisobutyl phthalate, for example, U.S. Pat. No. 4,4784983. It has been proved that the phthalate ester compound can bring harm to the reproductive system, immune system and digestive system of human body, such as damaging male reproductive ability, promoting female sexual precocity, etc. Therefore, corresponding laws and regulations limiting the use of benzoate substances in various industries are successively issued by various countries, so that the catalyst which does not contain phthalate compounds as internal electron donors is widely concerned and applied, and a catalyst which does not contain phthalate electron donors, is simple in preparation method and has excellent performance is very required to be found.
In recent years, glycol ester compounds have been researched and developed as internal electron donors, but currently, in the preparation of catalysts using glycol ester compounds as internal electron donors, glycol ester compounds need to be synthesized in advance and then added in the preparation process of the catalysts. The synthesis and purification processes of the diol ester compound are complex, so that the preparation cost of the catalyst is high, and the popularization and application of the catalyst are not facilitated.
Disclosure of Invention
The inventor of the invention has found through intensive research that in the preparation process of the olefin polymerization catalyst, a diol compound can be reacted with an acyl halide compound to generate an internal electron donor of the diol ester compound in situ and directly participate in the synthesis of the catalyst component, an epoxy cosolvent and a phthalic anhydride settling aid are not required to be used, and the generation of the phthalate compound in the catalyst can be avoided. Because the diol ester electron donor is generated in situ, the separate preparation process of the diol ester compound is reduced, so that the catalyst has the excellent performance of the diol ester compound as the electron donor and the preparation process of the catalyst is simplified. The obtained catalyst is compounded with an organic silicon compound to obtain the catalyst with excellent comprehensive performance, and when the catalyst is used for olefin polymerization, the activity of the catalyst is higher under the condition that the obtained polymer has high stereospecificity.
It is a first object of the present invention to provide a catalyst component for the polymerization of olefins comprising or consisting of the reaction product of: (1) a magnesium compound; (2) a lewis base compound; (3) has the general formula R2An acyl halide compound of COX wherein R2Is hydrogen, substituted or unsubstituted C1-C10 hydrocarbyl or epoxy, X is halogen; (4) a compound containing two hydroxyl groups; (5) a titanium compound.
According to a preferred embodiment of the invention, the magnesium compound is of the general formula MgR1 nX2-nWherein X is halogen, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine, bromine or iodine, and R is1Is C1-C20 alkyl, alkoxy or halogenated alkoxy, and n is more than or equal to 0 and less than or equal to 2. Preferably, the magnesium compound is selected from one or more of magnesium dihalides (including magnesium dichloride, magnesium dibromide, magnesium diiodide), alcoholates of magnesium dihalides and magnesium alkoxides.
According to a preferred embodiment of the invention, said lewis base compound is an organophosphorus lewis base compound, preferably a phosphoric acid ester, including phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triesters, more preferably a trialkyl phosphate, preferably a trialkyl phosphate represented by formula (I):
wherein R is7-R9Each independently selected from methyl, ethyl, C3-C10 straight or branched chain alkyl groups (e.g., n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, and isohexyl, etc.). In one embodiment of the present invention, the trialkyl phosphate is tributyl phosphate.
According to a preferred embodiment of the present invention, X in the acid halide compound is preferably chlorine. The hydrocarbon group includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Preferably, R2Is a halogen substituted or unsubstituted phenyl group, a C1-C4 alkyl group or a 5-membered cyclic epoxy group, preferably, the acid halide compound is selected from one or more of acetyl chloride, propionyl chloride, isopropionyl chloride, butyryl chloride, isobutyryl chloride, benzoyl chloride and furoyl chloride, and more preferably, one or more of benzoyl chloride and 2-furoyl chloride.
According to a preferred embodiment of the invention, the compound comprising two hydroxyl groups is represented by formula (II):
wherein R is1-R6The groups are the same or different and are independently selected from H, halogen, C1-C20 hydrocarbyl (including C1-C20 straight chain or branched chain alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkenyl or fused ring aryl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, alkyl substituted phenyl, naphthyl, ethenyl, propenyl, etc.), R1-R6Not hydrogen at the same time; preferably, R1、R2At least one of which is not H, e.g. may be R1Is H, R2Is not H; or R2Is H, R1Is not H; or R1、R2Are not all H.
According to a preferred embodiment of the invention, the compound comprising two hydroxyl groups is a symmetrical compound, i.e. the substituents on C to which the two hydroxyl groups are attached are identical.
Examples of the compound having two hydroxyl groups include, but are not limited to, 1, 3-diphenyl-2-methyl-1, 3-propanediol, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol, 1, 3-di-t-butyl-2-ethyl-1, 3-propanediol, 1, 3-diisopropyl-1, 3-propanediol, 1-phenyl-2-amino-1, 3-propanediol, 1-phenyl-2-methyl-1, 3-butanediol, 1-furan-2-methyl-1, 3-butanediol, 4, 4, 4-trifluoro-1- (2-naphthalene) -1, 3-butanediol, 1, 2-diphenyl-2-methyl-1, 3-propanediol, and mixtures thereof, 2, 4-pentanediol, 3-methyl-2, 4-pentanediol, 3-ethyl-2, 4-pentanediol, 3-propyl-2, 4-pentanediol, 3-butyl-2, 4-pentanediol, 3-dimethyl-2, 4-pentanediol, (2S, 4S) - (+) -2, 4-pentanediol, (2R, 4R) - (+) -2, 4-pentanediol, 1, 3-pentanediol, 2-methyl-1, 3-pentanediol, 2-ethyl-1, 3-pentanediol, 2-butyl-1, 3-pentanediol, 2-dimethyl-1, 3-pentanediol, 2-allyl-1, 3-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 1-trifluoromethyl-3-methyl-2, 4-pentanediol, 3-methyl-3-butyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, 2-propyl-1, 3-hexanediol, 2-butyl-1, 3-hexanediol, 4-ethyl-1, 3-hexanediol, 4-methyl-1, 3-hexanediol, 3-ethyl-1, 3-hexanediol, 2,4, 6, 6-pentamethyl-3, 5-hexanediol, 6-heptene-2, 4-heptanediol, 2-methyl-6-heptene-2, 4-heptanediol, 3-methyl-6-heptene-2, 4-heptanediol, 4-methyl-6-heptene-2, 4-heptanediol, 5-methyl-6-heptene-2, 4-heptanediol, 6-methyl-6-heptene-2, 4-heptanediol, 3-ethyl-6-heptene-2, 4-heptanediol, 4-ethyl-6-heptene-2, 4-heptanediol, 5-ethyl-6-heptene-2, 4-heptanediol, 6-ethyl-6-heptene-2, 4-heptanediol, a mixture thereof, and a mixture thereof, 3-propyl-6-heptene-2, 4-heptanediol, 4-propyl-6-heptene-2, 4-heptanediol, 5-propyl-6-heptene-2, 4-heptanediol, 6-propyl-6-heptene-2, 4-heptanediol, 3-butyl-6-heptene-2, 4-heptanediol, 4-butyl-6-heptene-2, 4-heptanediol, 5-butyl-6-heptene-2, 4-heptanediol, 6-butyl-6-heptene-2, 4-heptanediol, 3, 5-dimethyl-6-heptene-2, 4-heptanediol, 3, 5-diethyl-6-heptene-2, 4-heptanediol, 3, 5-dipropyl-6-heptene-2, 4-heptanediol, 3, 5-dibutyl-6-heptene-2, 4-heptanediol, 3-dimethyl-6-heptene-2, 4-heptanediol, 3-diethyl-6-heptene-2, 4-heptanediol, 3-dipropyl-6-heptene-2, 4-heptanediol, 3-dibutyl-6-heptene-2, 4-heptanediol, 3, 5-heptanediol, 2-methyl-3, 5-heptanediol, 3-methyl-3, 5-heptanediol, heptanediol, 4-methyl-3, 5-heptanediol, 5-methyl-3, 5-heptanediol, 6-methyl-3, 5-heptanediol, 3-ethyl-3, 5-heptanediol, 4-ethyl-3, 5-heptanediol, 5-ethyl-3, 5-heptanediol, 3-propyl-3, 5-heptanediol, 4-propyl-3, 5-heptanediol, 3-butyl-3, 5-heptanediol, 2, 3-dimethyl-3, 5-heptanediol, 2, 4-dimethyl-3, 5-heptanediol, 2, 5-dimethyl-3, 5-heptanediol, 2, 6-dimethyl-3, 5-heptanediol, 2, 6-dimethyl-3, 5-heptanediol, 2, 5-diol, 2, 5-heptanediol, 2, 5-diol, 2, 5-heptanediol, 2, 5, 2, 5, and the like, 3, 3-dimethyl-3, 5-heptanediol, 4-dimethyl-3, 5-heptanediol, 6-dimethyl-3, 5-heptanediol, 3, 4-dimethyl-3, 5-heptanediol, 3, 5-dimethyl-3, 5-heptanediol, 3, 6-dimethyl-3, 5-heptanediol, 4, 5-dimethyl-3, 5-heptanediol, 4, 6-dimethyl-3, 5-heptanediol, 2-methyl-3-ethyl-3, 5-heptanediol, 2-methyl-4-ethyl-3, 5-heptanediol, 2-methyl-5-ethyl-3, 5-heptanediol, a mixture of these, and a mixture of these, 3-methyl-3-ethyl-3, 5-heptanediol, 3-methyl-4-ethyl-3, 5-heptanediol, 3-methyl-5-ethyl-3, 5-heptanediol, 4-methyl-3-ethyl-3, 5-heptanediol, 4-methyl-4-ethyl-3, 5-heptanediol, 4-methyl-5-ethyl-3, 5-heptanediol, 2-methyl-3-propyl-3, 5-heptanediol, 2-methyl-4-propyl-3, 5-heptanediol, 2-methyl-5-propyl-3, 5-heptanediol, 3-methyl-3-propyl-3, 5-heptanediol, 3-methyl-4-propyl-3, 5-heptanediol, 3-methyl-5-propyl-3, 5-heptanediol, 4-methyl-3-propyl-3, 5-heptanediol, 4-methyl-4-propyl-3, 5-heptanediol, 4-methyl-5-propyl-3, 5-heptanediol, 6-methyl-2, 4-heptanediol, 3, 6-dimethyl-2, 4-heptanediol, 2, 6, 6-tetramethyl-3, 5-heptanediol, 4-methyl-3, 5-octanediol, 4-ethyl-3, 5-octanediol, 4-propyl-3, 5-octanediol, 5-propyl-3, 5-octanediol, 4-butyl-3, 5-octanediol, 4-dimethyl-3, 5-octanediol, 4-diethyl-3, 5-octanediol, 4-dipropyl-3, 5-octanediol, 4-methyl-4-ethyl-3, 5-octanediol, 3-phenyl-3, 5-octanediol, 2-methyl-3-ethyl-3, 5-octanediol, 2-methyl-4-ethyl-3, 5-octanediol, 2-methyl-5-ethyl-3, 5-octanediol, 2-methyl-6-ethyl-3, 5-octanediol, 5-methyl-4, 6 nonanediol, 5-ethyl-4, 6 nonanediol, 5-propyl-4, 6 nonanediol, 5-butyl-4, 6 nonanediol, 5-dimethyl-4, 6 nonanediol, 5-diethyl-4, 6 nonanediol, 5-dipropyl-4, 6 nonanediol, 5-dibutyl-4, 6 nonanediol, 5-methyl-4-ethyl-4, 6 nonanediol, 5-phenyl-4, 6 nonanediol, and 4-butyl-3, 5-heptanediol.
According to a preferred embodiment of the invention, the titanium compound is of the general formula TiXp(OR”)4-pThe compound shown in the specification, wherein X is halogen, preferably chlorine, bromine and iodine, R' is C1-C14 hydrocarbon group, preferably C1-C14 alkyl, more preferably C1-C5 alkyl, such as methyl, ethyl, propyl, butyl, pentyl and the like, and p is more than or equal to 0 and less than or equal to 4. According to a preferred embodiment of the present invention, the titanium compound includes one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
According to a preferred embodiment of the present invention, the lewis base compound is added to the catalyst component in an amount of 0.01 to 10 moles, preferably 0.02 to 4 moles, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4 moles and any value therebetween, per mole of the magnesium compound.
According to a preferred embodiment of the invention, the catalyst components are fed in an amount of 0.005 to 5 moles, preferably 0.25 to 1 mole, for example 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1 mole and any value in between, of the compound containing two hydroxyl groups per mole of magnesium compound.
According to a preferred embodiment of the invention, the catalyst components are fed with the titanium compound in an amount of 0.2 to 100 moles, preferably 1.0 to 50 moles, for example 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 moles and any value in between, per mole of magnesium compound.
According to a preferred embodiment of the present invention, the amount of the acid halide compound added to each of the catalyst components is 0.01 to 4.0 moles, preferably 1 to 2 moles, for example, 1.0, 1.05, 1.10, 1.15, 1.20, 1.25, 1.3, 1.35, 1.4, 1.45, 1.50, 1.55, 1.6, 1.7, 1.8, 1.9, 2.0 moles and any value therebetween, per mole of the magnesium compound.
According to a preferred embodiment of the present invention, it is disadvantageous to include an alcohol in the catalyst component, that is to say without the compound having two hydroxyl groups, in a molar ratio of the acid halide compound to the compound having two hydroxyl groups of 2 to 3, which may be, for example, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 and any value therebetween, preferably 2.2 to 2.6.
It is another object of the present invention to provide a process for the preparation of said catalyst component.
The preparation method of the catalyst component comprises the following steps: the catalyst component is prepared by the steps of carrying out contact reaction on a magnesium compound, a Lewis base compound, an acyl halide compound and a compound containing two hydroxyl groups to obtain a magnesium compound solution, and then carrying out contact reaction on the magnesium compound solution and a titanium compound to precipitate a solid.
According to a preferred embodiment of the present invention, the preparation method of the catalyst component comprises the steps of:
(i) firstly, a magnesium compound, a Lewis base compound and a compound containing two hydroxyl groups are in contact reaction to obtain a contact reaction product;
(ii) mixing the contact reaction product with acyl halide compound to obtain mixed solution;
(iii) and (3) carrying out contact reaction on the mixed solution and a titanium compound to separate out a solid, thus obtaining the catalyst component.
In the process for the preparation of the catalyst component, in step (i), a magnesium compound, a Lewis base compound and a compound containing two hydroxyl groups are contact-reacted at 0 to 100 ℃, for example, 0 ℃, 1 ℃,4 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 98 ℃, 100 ℃ and any temperature therebetween, preferably at 40 to 70 ℃, optionally in the presence of an inert diluent. The inert diluent may be exemplified by benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbons. By "inert" is meant that the diluent does not participate in the reaction and does not adversely affect the dissolution of the magnesium compound.
In the step (ii), while the contact reaction product in the step (i) is mixed with the acid halide compound, the acid halide compound is added dropwise to the contact reaction product to sufficiently react the acid halide compound with the compound having two hydroxyl groups.
According to a preferred embodiment of the present invention, in step (iii), the mixed solution is contacted with a titanium compound at-35 ℃ to 60 ℃, for example, -30 ℃, -25 ℃, -20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 58 ℃, 60 ℃ and any temperature therebetween, preferably at-30 ℃ to 50 ℃, either by slowly adding the titanium compound dropwise to the mixed solution or by adding the mixed solution dropwise to the titanium compound. Optionally, during the contacting of the mixture with the titanium compound, other electron donor compounds such as alkoxysilanes may be added. After the completion of the dropwise addition, the temperature is raised to 10 to 150 ℃, preferably 20 to 130 ℃, and the mixed solution is reacted with a titanium compound to precipitate a solid.
In the present invention, in the method for producing the catalyst component, it is preferable to further include a step (iv) of subjecting the solid precipitate (catalyst component) obtained in the step (iii) to a post-treatment.
The post-treatment step comprises aging the solid precipitate with a titanium compound or a titanium compound diluted with an inert diluent at 10 to 150 ℃, preferably 20 to 130 ℃ for 2 to 3 times, and then washing the solid with a hydrocarbon solvent such as toluene or hexane to obtain the catalyst component. The catalyst components may be used in the form of solids or suspensions.
It is a further object of the present invention to provide a catalyst for olefin polymerization.
The present invention provides a catalyst for olefin polymerization, comprising:
(1) the catalyst component as hereinbefore described;
(2) an alkyl aluminum compound;
(3) optionally, an external electron donor component.
According to a preferred embodiment of the invention, the alkylaluminum compound is of the general formula AlR3 qX3-qAn alkylaluminum compound of the formula wherein R3Is hydrogen or C1-C20 alkyl, X is halogen, q is more than 0 and less than or equal to 3;
the expression "optionally, an external electron donor component" means that the addition or non-addition of an external electron donor compound is optional, as desired. For the applications requiring olefin polymers with high stereoregularity, it is necessary to add (3) an external electron donor component, which, according to a preferred embodiment of the present invention, is of the general formula (R)4)kSi(OR5)4-kA compound shown in the formula, wherein k is more than or equal to 0 and less than or equal to 3, R4And R5Identical or different, R5Is C1-C20Alkyl, cycloalkyl, aryl, haloalkyl and amino, R4Selected from halogen, hydrogen atom and C1-C20Alkyl, cycloalkyl, aryl, haloalkyl or amino. Examples of the external electron donor include, but are not limited to, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-n-butyldimethoxysilane, dicyclopentyldimethoxysilane, bis (cyclobutylmethyl) dimethoxysilane, preferably one or more of cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-n-butyldimethoxysilane, dicyclopentyldimethoxysilane and bis (cyclobutylmethyl) dimethoxysilane.And (4) a plurality of.
In the catalyst, the molar ratio of the component (1), the component (2) and the component (3) is 1:5-1000:0-500, wherein the catalyst component is titanium, the alkyl aluminum compound is aluminum, and the outer electron component is silicon; preferably 1:25-100: 25-100.
It is a further object of the present invention to provide said catalyst component or the use of said catalyst in the polymerization of olefins, preferably of the general formula CH2Olefins of CHR, wherein R is hydrogen or C1-C12A hydrocarbyl or aryl group of (a).
The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. Conventional techniques such as slurry processes, gas phase fluidized beds and the like are employed wherein the olefin is preferably selected from one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, particularly the homopolymerization of propylene and or the copolymerization of propylene with other olefins. The polymerization temperature is generally from 0 to 150 ℃ and preferably from 60 to 90 ℃.
The method adopts a magnesium compound as a catalyst carrier, prepares the catalyst component by reacting with a Lewis base compound, a compound containing two hydroxyl groups and an acyl halide compound, utilizes the reaction of a diol compound and the acyl halide compound to generate an internal electron donor of the diol ester compound in situ and directly participate in the synthesis of the catalyst component, does not need to use an epoxy cosolvent and a phthalic anhydride settling aid, and can avoid the generation of the phthalate compound in the catalyst. Because the diol ester electron donor is generated in situ, the separate preparation process of the diol ester compound is reduced, the catalyst has the excellent performance of the diol ester compound as the electron donor, the preparation process of the catalyst is simplified, and the production cost of the catalyst is reduced. The obtained catalyst is compounded with an organic silicon compound to obtain the catalyst with excellent comprehensive performance, and when the catalyst is used for olefin polymerization, the activity of the catalyst is higher under the condition that the obtained polymer has high stereospecificity.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Test method
Polymer isotacticity II: as determined by heptane extraction (6 hours of heptane boil extraction): a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours, and the ratio of the weight (g) of the polymer to 2, which was obtained by drying the residue to a constant weight, was determined as the isotacticity.
Melt index MI: measured using a melt index apparatus at 230 ℃ under a pressure of 2.16kg according to ASTM D1238-99 Standard test method for measuring thermoplastic melt flow Rate with an extrusion plastometer.
Preparation of solid catalyst component
Example 1
4.8g (0.05mol) of magnesium chloride, 95mL of toluene, 0.025mol of 2, 4-pentanediol and 12.5mL (0.46mol) of tributyl phosphate are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 60 ℃ under stirring, 5.8mL (0.05mol) of benzoyl chloride is slowly added dropwise, the solution is maintained for 2.5 hours, then the solution is cooled to below-25 ℃, and 56mL (0.50mol) of TiCl is added dropwise in 1 hour4Slowly raising the temperature to 80 ℃, maintaining the temperature for 1 hour, filtering, and respectively adding 70mL of toluene and washing twice to obtain solid precipitates. Then, 60mL of toluene and TiCl were added to the precipitate440mL, heating to 110 ℃, maintaining for 2 hours, and filtering; the same operation was repeated 1 time. 60mL of toluene was further added and the mixture was washed at 110 ℃ for 5 minutes, 60mL of hexane was added and the mixture was washed at 68 ℃ twice for 5 minutes each, and 60mL of hexane was further added and the mixture was washed at room temperature twice for 5 minutes each to obtain 5.6g of a solid catalyst component.
Example 2
The same as in example 1 except that 3-methyl-2, 4-pentanediol, the compound, was used instead of 2, 4-pentanediol.
Example 3
The same as in example 1 except that 3, 5-heptanediol was used instead of 2, 4-pentanediol.
Example 4
The same as in example 1 except that 2, 4-pentanediol was used in an amount of 0.0125mol and benzoyl chloride was used in an amount of 0.025 mol.
Example 5
The same as in example 1 except that 2, 4-pentanediol was used in an amount of 0.05mol and benzoyl chloride was used in an amount of 0.1 mol.
Example 6
The same as in example 1 except that benzoyl chloride was used in an amount of 0.55 mol.
Example 7
The same as in example 1, except that benzoyl chloride was used in an amount of 0.06 mol.
Example 8
The same as example 1 except that m-chlorobenzoyl chloride was used in place of benzoyl chloride in example 1.
Example 9
The same as in example 1, except that 2-ethyl-2, 4-pentanediol was used instead of 2, 4-pentanediol.
Example 10
The same as in example 1, except that 2-ethyl-1, 3-pentanediol was used instead of 2, 4-pentanediol.
Example 11
The same as in example 1 except that 2, 4-pentanediol was used in an amount of 0.03mol and benzoyl chloride was used in an amount of 0.06 mol.
Example 12
The same as in example 1 except that 2, 4-pentanediol was used in an amount of 0.0125 mol.
Example 13
The same as in example 1 except that benzoyl chloride was used in an amount of 0.065 mol.
Example 14
The same as in example 1, except that benzoyl chloride was used in an amount of 0.075 mol.
Example 15
The same as in example 1 except that benzoyl chloride was used in an amount of 0.10 mol.
Example 16
Same as example 1 except that 46mL of toluene was added and 35mL of TiCl was added dropwise over 1 hour4Mixed with 50mL of toluene.
Example 17
The same as in example 1 except that magnesium diethoxide was used in place of magnesium chloride.
Example 18
The same as in example 1 except that 2, 4-pentanediol was used in an amount of 0.06mol and benzoyl chloride was used in an amount of 0.12 mol.
Example 19
The same as in example 1 except that 4-methyl-4-ethyl-3, 5-heptanediol was used instead of 2, 4-pentanediol.
Example 20
The same as in example 1 except that 4-methyl-4-butyl-3, 5-heptanediol was used in place of 2, 4-pentanediol.
Comparative example 1
The same as in example 1, except that ethanol was used in place of 2, 4-pentanediol.
Comparative example 2
The same as in example 1, except that benzoyl chloride was replaced by phthaloyl chloride.
Comparative example 3
The same as in example 1, except that 1, 4-butanediol was used in place of 2, 4-pentanediol.
Comparative example 4
The same as in example 1, except that 0.025mol of phthaloyl chloride was used instead of 0.05mol of benzoyl chloride.
Experiment on propylene polymerization
The catalyst components obtained in the above examples were each subjected to propylene polymerization. The propylene polymerization procedure was: the stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mmol, 0.1mmol of methylcyclohexyldimethoxysilane (CHMMS), 8 to 10mg of the above solid catalyst component and 1.2L of hydrogen were added, 2.3L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour. And (5) cooling and decompressing to obtain the PP powder. The polymerization results are shown in Table 1.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (24)
1. A catalyst component for the polymerization of olefins comprising or consisting of the reaction product of: (1) a magnesium compound; (2) a lewis base compound; (3) has the general formula R2An acyl halide compound of COX wherein R2Is hydrogen, substituted or unsubstituted C1-C10 hydrocarbyl or epoxy, X is halogen; (4) a compound containing two hydroxyl groups; (5) a titanium compound;
the Lewis base compound is a trialkyl phosphate represented by formula (I):
wherein R is7-R9Each independently selected from methyl, ethyl, C3-C10 straight or branched alkyl groups; and is
The compound containing two hydroxyl groups is represented by the formula (II):
wherein R is1-R6The groups are the same or different and are respectively and independently selected from H, halogen,C1-C20 straight or branched chain alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkenyl or condensed ring aryl, R1-R6Not hydrogen at the same time;
wherein the preparation method of the catalyst component comprises the following steps:
(i) contacting and reacting the magnesium compound, the Lewis base compound and the compound containing two hydroxyl groups to obtain a contact reaction product;
(ii) mixing the contact reaction product with the acyl halide compound to obtain a mixed solution;
(iii) and (3) carrying out contact reaction on the mixed solution and the titanium compound to precipitate a solid to obtain the catalyst component.
2. The catalyst component according to claim 1 in which the magnesium compound is of the general formula MgR1 nX2-nThe compound shown in the specification, or a hydrate or an alcoholate thereof, wherein X is halogen and R is1Is C1-C20 alkyl, alkoxy or halogenated alkoxy, and n is more than or equal to 0 and less than or equal to 2.
3. The catalyst component according to claim 2 in which the magnesium compound is selected from one or more of magnesium dihalides, alcoholates of magnesium dihalides and magnesium alkoxides.
4. The catalyst component according to any of claims 1 to 3 in which R is2Is phenyl, C1-C4 alkyl or furyl, which is substituted or unsubstituted by halogen.
5. The catalyst component according to any of claims 1 to 3 characterized in that the acyl halide compound is selected from one or more of acetyl chloride, propionyl chloride, isopropionyl chloride, butyryl chloride, isobutyryl chloride, benzoyl chloride and furoyl chloride.
6. The catalyst component according to any of claims 1 to 3, characterized in that,R1、R2at least one of which is not H.
7. The catalyst component according to any of claims 1 to 3 wherein the compound containing two hydroxyl groups is selected from 1, 3-diphenyl-2-methyl-1, 3-propanediol, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol, 1, 3-diisopropyl-1, 3-propanediol, 1-phenyl-2-amino-1, 3-propanediol, 1-phenyl-2-methyl-1, 3-butanediol, 1-furan-2-methyl-1, 3-butanediol, 4, 4, 4-trifluoro-1- (2-naphthalene) -1, 3-butanediol, 2, 4-pentanediol, 3-methyl-2, 4-pentanediol, 3-ethyl-2, 4-pentanediol, 3-propyl-2, 4-pentanediol, 3-butyl-2, 4-pentanediol, 3-dimethyl-2, 4-pentanediol, 1, 3-pentanediol, 2-methyl-1, 3-pentanediol, 2-ethyl-1, 3-pentanediol, 2-butyl-1, 3-pentanediol, 2-dimethyl-1, 3-pentanediol, 2-allyl-1, 3-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 1-trifluoromethyl-3-methyl-2, 4-pentanediol, 3-methyl-3-butyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, 2-propyl-1, 3-hexanediol, 2-butyl-1, 3-hexanediol, 4-ethyl-1, 3-hexanediol, 4-methyl-1, 3-hexanediol, 3-ethyl-1, 3-hexanediol, 2,4, 6, 6-pentamethyl-3, 5-hexanediol, 6-heptene-2, 4-heptanediol, 2-methyl-6-heptene-2, 4-heptanediol, 3-methyl-6-heptene-2, 4-heptanediol, 4-methyl-6-heptene-2, 4-heptanediol, 5-methyl-6-heptene-2, 4-heptanediol, 6-methyl-6-heptene-2, 4-heptanediol, 3-ethyl-6-heptene-2, 4-heptanediol, 4-ethyl-6-heptene-2, 4-heptanediol, 5-ethyl-6-heptene-2, 4-heptanediol, 6-ethyl-6-heptene-2, 4-heptanediol, 3-propyl-6-heptene-2, 4-heptanediol, 4-propyl-6-heptene-2, 4-heptanediol, a mixture thereof, and a mixture thereof, 5-propyl-6-heptene-2, 4-heptanediol, 6-propyl-6-heptene-2, 4-heptanediol, 3-butyl-6-heptene-2, 4-heptanediol, 4-butyl-6-heptene-2, 4-heptanediol, 5-butyl-6-heptene-2, 4-heptanediol, 6-butyl-6-heptene-2, 4-heptanediol, 3, 5-dimethyl-6-heptene-2, 4-heptanediol, 3, 5-diethyl-6-heptene-2, 4-heptanediol, 3, 5-dipropyl-6-heptene-2, 4-heptanediol, a mixture of these, and a solvent, 3, 5-dibutyl-6-heptene-2, 4-heptanediol, 3-dimethyl-6-heptene-2, 4-heptanediol, 3-diethyl-6-heptene-2, 4-heptanediol, 3-dipropyl-6-heptene-2, 4-heptanediol, 3-dibutyl-6-heptene-2, 4-heptanediol, 3, 5-heptanediol, 2-methyl-3, 5-heptanediol, 3-methyl-3, 5-heptanediol, 4-methyl-3, 5-heptanediol, 5-methyl-3, 5-heptanediol, 6-methyl-3, 5-heptanediol, a mixture of 3, 4-dimethyl-6-heptene-2, 4-heptanediol and 3, 3-dimethyl-6-heptene-2, 4-heptanediol, 3-ethyl-3, 5-heptanediol, 4-ethyl-3, 5-heptanediol, 5-ethyl-3, 5-heptanediol, 3-propyl-3, 5-heptanediol, 4-propyl-3, 5-heptanediol, 3-butyl-3, 5-heptanediol, 2, 3-dimethyl-3, 5-heptanediol, 2, 4-dimethyl-3, 5-heptanediol, 2, 5-dimethyl-3, 5-heptanediol, 2, 6-dimethyl-3, 5-heptanediol, 3-dimethyl-3, 5-heptanediol, 4-dimethyl-3, 5-heptanediol, 6-dimethyl-3, 5-heptanediol, 3, 4-dimethyl-3, 5-heptanediol, 3, 5-dimethyl-3, 5-heptanediol, 3, 6-dimethyl-3, 5-heptanediol, 4, 5-dimethyl-3, 5-heptanediol, 4, 6-dimethyl-3, 5-heptanediol, 2-methyl-3-ethyl-3, 5-heptanediol, 2-methyl-4-ethyl-3, 5-heptanediol, 2-methyl-5-ethyl-3, 5-heptanediol, 3-methyl-3-ethyl-3, 5-heptanediol, 3-methyl-4-ethyl-3, 5-heptanediol, 3-methyl-3, 5-heptanediol, a mixture of these, 3-methyl-5-ethyl-3, 5-heptanediol, 4-methyl-3-ethyl-3, 5-heptanediol, 4-methyl-4-ethyl-3, 5-heptanediol, 4-methyl-5-ethyl-3, 5-heptanediol, 2-methyl-3-propyl-3, 5-heptanediol, 2-methyl-4-propyl-3, 5-heptanediol, 2-methyl-5-propyl-3, 5-heptanediol, 3-methyl-3-propyl-3, 5-heptanediol, 3-methyl-4-propyl-3, 5-heptanediol, 3-methyl-5-propyl-3, 5-heptanediol, 4-methyl-3-propyl-3, 5-heptanediol, 4-methyl-4-propyl-3, 5-heptanediol, 4-methyl-5-propyl-3, 5-heptanediol, 6-methyl-2, 4-heptanediol, 3, 6-dimethyl-2, 4-heptanediol, 2, 6, 6-tetramethyl-3, 5-heptanediol, 4-methyl-3, 5-octanediol, 4-ethyl-3, 5-octanediol, 4-propyl-3, 5-octanediol, 5-propyl-3, 5-octanediol, 4-butyl-3, 5-octanediol, 4-dimethyl-3, 5-octanediol, 4-diethyl-3, 5-octanediol, 4-dipropyl-3, 5-octanediol, 4-methyl-4-ethyl-3, 5-octanediol, 3-phenyl-3, 5-octanediol, 2-methyl-3-ethyl-3, 5-octanediol, 2-methyl-4-ethyl-3, 5-octanediol, 2-methyl-5-ethyl-3, 5-octanediol, 2-methyl-6-ethyl-3, 5-octanediol, 5-methyl-4, 6-nonanediol, 5-ethyl-4, 6-nonanediol, 5-propyl-4, 6-nonanediol, a mixture of these, and a mixture of these, One or more of 5-butyl-4, 6-nonanediol, 5-dimethyl-4, 6-nonanediol, 5-diethyl-4, 6-nonanediol, 5-dipropyl-4, 6-nonanediol, 5-dibutyl-4, 6-nonanediol, 5-methyl-4-ethyl-4, 6-nonanediol, 5-phenyl-4, 6-nonanediol, and 4-butyl-3, 5-heptanediol.
8. The catalyst component according to any of claims 1 to 3 in which the titanium compound is of the general formula TiXp(OR”)4-pThe compound is shown in the specification, wherein X is halogen, R' is C1-C14 alkyl, and p is more than or equal to 0 and less than or equal to 4.
9. The catalyst component according to claim 8 in which R "is a C1-C4 alkyl group.
10. The catalyst component according to any of claims 1-3 characterized in that the titanium compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium chlorotriethoxyxide, titanium dichlorodiethoxide and titanium trichloromonoethoxyxide.
11. The catalyst component according to any of claims 1 to 3 wherein the catalyst component is fed with the Lewis base compound in an amount of 0.01 to 10 moles per mole of the magnesium compound; and/or 0.005-5 mol of compound containing two hydroxyl groups; and/or, the titanium compound is 0.2 to 100 moles; and/or the acid halide compound is 0.1 to 10 mol.
12. The catalyst component according to any of claims 1 to 3 wherein the catalyst component is fed with the Lewis base compound in an amount of 0.02 to 4 moles per mole of the magnesium compound; and/or 0.25 to 1 mole of a compound containing two hydroxyl groups; and/or, the titanium compound is 1.0 to 50 mol; and/or 1-2 mol of acyl halide compound.
13. The catalyst component according to any of claims 1 to 3 wherein the molar ratio of acid halide compound to compound containing two hydroxyl groups in the catalyst component is from 2 to 3.
14. The catalyst component according to any of claims 1 to 3 wherein the molar ratio of acid halide compound to compound containing two hydroxyl groups in the catalyst component is from 2.2 to 2.6.
15. The catalyst component according to claim 7 in which the 2, 4-pentanediol is (2S, 4S) - (+) -2, 4-pentanediol and/or (2R, 4R) - (+) -2, 4-pentanediol.
16. A process for preparing the catalyst component of any one of claims 1 to 15, comprising: the catalyst component is obtained by the contact reaction of a magnesium compound, a Lewis base compound, an acyl halide compound, a compound containing two hydroxyl groups and a titanium compound.
17. The process for the preparation of the catalyst component according to claim 16, characterized by comprising the steps of:
(i) contacting and reacting a magnesium compound, a Lewis base compound and a compound containing two hydroxyl groups to obtain a contact reaction product;
(ii) mixing the contact reaction product with acyl halide compound to obtain mixed solution;
(iii) and (3) contacting the mixed solution with a titanium compound to react and separate out a solid to obtain the catalyst component.
18. The process of claim 17, wherein the step (i) contact reaction is carried out at 0-100 ℃; and/or, the step (iii) contacts the mixed solution with a titanium compound at-35-60 ℃, and then heats to 10-150 ℃ to react the mixed solution with the titanium compound to separate out a solid.
19. The process of claim 17, wherein step (i) the contacting reacts the magnesium compound, the lewis base compound, and the compound having two hydroxyl groups in the presence of an inert diluent.
20. A catalyst for the polymerization of olefins comprising:
(1) a catalyst component as claimed in any one of claims 1 to 15, or a catalyst component obtainable by a process as claimed in any one of claims 16 to 19;
(2) an alkyl aluminum compound;
(3) optionally, an external electron donor component.
21. The catalyst according to claim 20, characterized in that the alkylaluminum compound is chosen from AlR of general formula3 qX3-qAn alkylaluminum compound of the formula wherein R3Is hydrogen or C1-C20 alkyl, X is halogen, and q is more than 0 and less than or equal to 3.
22. The catalyst of claim 20, wherein the external electron donor component is selected from the group consisting of those of the general formula (R)4)kSi(OR5)4-kA compound shown in the formula, wherein k is more than or equal to 0 and less than or equal to 3, R4And R5Identical or different, R5Is C1-C20Alkyl, cycloalkyl, aryl, haloalkyl and amino, R4Selected from halogen, hydrogen atom and C1-C20Alkyl, cycloalkyl, aryl, haloalkyl or amino.
23. Use of a catalyst as claimed in any one of claims 20 to 22 in the polymerisation of olefins.
24. Use according to claim 23, wherein the olefin is selected from the general formula CH2Olefins of CHR, whichIn which R is hydrogen or C1-C12A hydrocarbyl or aryl group of (a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810401572.9A CN110407963B (en) | 2018-04-28 | 2018-04-28 | Catalyst component for olefin polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810401572.9A CN110407963B (en) | 2018-04-28 | 2018-04-28 | Catalyst component for olefin polymerization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110407963A CN110407963A (en) | 2019-11-05 |
| CN110407963B true CN110407963B (en) | 2021-09-21 |
Family
ID=68357229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810401572.9A Active CN110407963B (en) | 2018-04-28 | 2018-04-28 | Catalyst component for olefin polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110407963B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456285B (en) * | 2020-10-22 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization and olefin polymerization method |
| CN114456287B (en) * | 2020-10-22 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst component and catalyst and method for homo-polymerization of ethylene or copolymerization of ethylene and alpha-olefin |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580035A (en) * | 2003-08-06 | 2005-02-16 | 中国石油化工股份有限公司 | Glycol ester compound for preparing catalyst for olefinic polymerization |
| EP1626976B1 (en) * | 2003-05-13 | 2007-10-17 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system |
| CN104513328A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Catalyst composition used in olefin polymerization reaction and application thereof |
| CN104558293A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
| CN104884477A (en) * | 2012-12-27 | 2015-09-02 | 陶氏环球技术有限责任公司 | An enhylene based polymer |
| CN107840909A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
| CN107880189A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
-
2018
- 2018-04-28 CN CN201810401572.9A patent/CN110407963B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1626976B1 (en) * | 2003-05-13 | 2007-10-17 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system |
| CN1580035A (en) * | 2003-08-06 | 2005-02-16 | 中国石油化工股份有限公司 | Glycol ester compound for preparing catalyst for olefinic polymerization |
| CN104884477A (en) * | 2012-12-27 | 2015-09-02 | 陶氏环球技术有限责任公司 | An enhylene based polymer |
| CN104513328A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Catalyst composition used in olefin polymerization reaction and application thereof |
| CN104558293A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
| CN107840909A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
| CN107880189A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and evaluation of 1,3-diethyl-2,2-dimethoxymethylcyclohexane, an external electron donor in Ziegler–Natta catalysis;Grison C et al.;《Comptes Rendus de l"Academie des Sciences Series IIC Chemistry》;20011231;第4卷(第12期);第893-898页 * |
| 以不同结构的2,4-戊二醇酯为内给电子体的催化剂的性能;孙赵娜 等;《石油化工》;20101231;第39卷(第11期);第1236-1240页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110407963A (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6523271B2 (en) | Catalyst component for olefin polymerization, method for preparing the same and catalyst containing the same | |
| KR101419757B1 (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| JP5623535B2 (en) | Catalyst composition for olefin polymerization and catalyst comprising the same | |
| EP3059263A1 (en) | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor | |
| RU2525402C2 (en) | Catalytic component for polymerisation of olefins and catalyst, including thereof | |
| JP2013510941A (en) | Method for producing solid catalyst for propylene polymerization | |
| CN107428995B (en) | Oxalic acid diamides as modifiers for polyolefin catalysts | |
| CN110407963B (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| CN102234338B (en) | Catalyst component for olefin polymerization and catalyst comprising same | |
| JP2010132904A (en) | ELECTRON DONOR COMPOSITION FOR SOLID CATALYST, SOLID CATALYST COMPOSITION FOR USE IN POLYMERIZING alpha-OLEFIN, AND PROCESS FOR PRODUCING POLYMER COMPRISING alpha-OLEFIN UNIT USING THE SOLID CATALYST COMPOSITION | |
| US10808048B2 (en) | Process of manufacture of catalyst and propylene polymer that use this or copolymer for propylene polymerization | |
| CN110407964B (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| CN114805647A (en) | Catalyst composition for olefin polymerization and application thereof | |
| CN110903419B (en) | Solid catalyst component for olefin polymerization, catalyst and application thereof | |
| CN109678996B (en) | Catalyst component and catalyst system for olefin polymerization, prepolymerized catalyst system and olefin polymerization method | |
| CN110903418B (en) | Solid catalyst component for olefin polymerization, catalyst and application thereof | |
| CN109553704B (en) | Catalyst component for olefin polymerization, catalyst and application | |
| CN107840905A (en) | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization | |
| CN107840906A (en) | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization | |
| KR102785613B1 (en) | Polymerization Method of Ultrahigh Molecular Weight Polyethylene and method for preparing catalyst thereof | |
| CN109678998B (en) | Catalyst component and catalyst system for olefin polymerization, prepolymerized catalyst system and olefin polymerization method | |
| CN109679004B (en) | Catalyst component and catalyst system for olefin polymerization, prepolymerized catalyst system and olefin polymerization method | |
| CN111234073B (en) | Catalyst component, catalyst system and prepolymerized catalyst for olefin polymerization, use thereof and olefin polymerization process | |
| CN111234070B (en) | Catalyst component, catalyst system and prepolymerized catalyst for olefin polymerization, use thereof and olefin polymerization process | |
| CN110903420B (en) | Solid catalyst component for olefin polymerization, catalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |