CN110407964B - Catalyst component for olefin polymerization and preparation method thereof - Google Patents
Catalyst component for olefin polymerization and preparation method thereof Download PDFInfo
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- CN110407964B CN110407964B CN201810402018.2A CN201810402018A CN110407964B CN 110407964 B CN110407964 B CN 110407964B CN 201810402018 A CN201810402018 A CN 201810402018A CN 110407964 B CN110407964 B CN 110407964B
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Abstract
The invention discloses a catalyst component for olefin polymerization, which comprises or consists of a 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) an oxygen-containing titanium-containing compound; (6) a titanium tetrahalide. In the preparation process of the catalyst component, the acyl halide compound and the compound containing two hydroxyl groups generate diol ester, the obtained catalyst and an organic silicon compound are compounded to obtain the catalyst with excellent comprehensive performance, and when the catalyst is used for olefin polymerization, the obtained polymer has high stereospecificity and high activity.
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
In recent years, the development of olefin polymerization processes has been accelerated, and at the same time, the development of catalysts compatible with olefin polymerization has been accelerated. The Ziegler-Natta catalyst system is the predominant catalyst 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. Researches prove that the phthalate ester compound can bring harm to the reproductive system, the immune system, the digestive system and the like of a human body, such as damage to the reproductive capacity of males, promotion of precocious puberty of females and the like. 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
In the research process, the invention discovers that during the preparation process of the olefin polymerization catalyst, diol compounds and acyl halide compounds can be utilized to react in situ to generate diol ester compounds and directly participate in the synthesis of catalyst components. 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. The preparation process does not need to use epoxy cosolvent and phthalic anhydride settling aid, and can avoid the generation of phthalate compounds in the reaction process. 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.
According to a first aspect of the present invention, there is provided a catalyst component for olefin polymerization.
The invention provides a catalyst component for olefin polymerization, which comprises or consists of a 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) an oxygen-containing titanium-containing compound; (6) a titanium tetrahalide.
According to a preferred embodiment of the invention, the magnesium compound is of the general formula MgR1 nX2-nWherein X is halogen, preferably chlorine, bromine or iodine, most preferably Cl, R1Is C1-C20 alkyl, alkoxy or halogenated alkoxy, preferably C1-C5 alkyl, alkoxy or halogenated alkoxy, n is more than or equal to 0 and less than or equal to 2, preferably, the magnesium compound is selected from magnesium dihalide (including magnesium dichloride and dibromide)Magnesium, 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 furyl 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, phthaloyl chloride, oxalyl chloride and furoyl chloride, and more preferably, from one or more of benzoyl chloride, phthaloyl 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 respectively and independently selected from H, halogen, C1-C20 linear or branched alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkylene or condensed ring aryl, R is1-R6Cannot be simultaneously hydrogen; 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. .
R1-R6The choice of groups may be exemplified by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, alkyl substituted phenyl, naphthyl, ethenyl, propenyl, and the like.
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.
According to a preferred embodiment of the present invention, 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 dibenzoate, 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, (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, 4-pentanediol, 3-butanediol, 3-pentanediol, 3-butanediol, 3-pentanediol, 3, 2-dimethyl-pentanediol, 2, 4-pentanediol, and 3-pentanediol, 2, 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, 2-allyl-1, 3-pentanediol, 2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 3-hexanediol, 2, 3-methyl-hexanediol, 2,4, 6, 6-pentamethyl-3, 5-hexanediol, 2-methyl-hexanediol, 2, 4-hexanediol, 3-hexanediol, 2-methyl-hexanediol, 3-hexanediol, 2, 3-hexanediol, 3-methyl-hexanediol, 2, 3-methyl-hexanediol, 2, 3-hexanediol, 2, 6, 2-hexanediol, 2, 6, 2, 3, 2, 3, 2, 3, 2, 3, 2, 3, 2, 3, 2, 3, 2, 6-heptene-2, 4-heptanediol, 2-methyl-6-heptene-2, 4-heptanediol ester, 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, 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, a mixture of these, and a mixture of these, 3, 5-diethyl-6-heptene-2, 4-heptanediol, 3, 5-dipropyl-6-heptene-2, 4-heptanediol, 3, 5-dibutyl-6-heptene-2, 4-heptanediol ester, 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, 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, 2, 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, 4-dimethyl-3, 5-heptanediol, 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-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, a mixture thereof, and a solvent, 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, 6-heptene-2, 4-heptanediol, 2-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, a salt thereof, and a salt thereof, One or more of 5-phenyl-4, 6-nonanediol, 4-butyl-3, 5-heptanediol, and 3-methyl-3-butyl-2, 4-pentanediol.
According to a preferred embodiment of the invention, the oxygen-containing titanium-containing compound is of the formula Ti (OR ")pX4-pThe compound shown in the specification, wherein X is halogen, preferably chlorine, bromine and iodine, R' is C1-C20 hydrocarbon group, preferably C1-C14 alkyl, such as methyl, ethyl, propyl, butyl, pentyl and the like, and p is more than 0 and less than or equal to 4.
According to a preferred embodiment of the invention, the oxygen-containing titanium-containing compound is selected from one or more of tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium. Titanium tetrabutoxide is preferred.
According to a preferred embodiment of the present invention, the titanium tetrahalide is one or more of titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide and titanium tetraiodide. Titanium tetrachloride is preferred.
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 20 moles, preferably 0.2 to 12 moles, for example, 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4, 5, 6, 7, 8, 9, 10, 11, 12 moles and any value therebetween, per mole of the magnesium compound; the amount of the compound having two hydroxyl groups is 0.1 to 10mol, preferably 0.25 to 1mol, and may be, for example, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1mol or any value therebetween; the amount of the oxygen-containing titanium-containing compound is 0.1 to 10mol, preferably 1.0 to 5mol, and may be, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 mol or any value therebetween; 1 to 5 moles, for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 5.0 moles and any value therebetween; the acid halide compound is 0.1 to 10, preferably 0.5 to 4.0 moles, more preferably 1 to 2 moles, and may be, 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.
According to a preferred embodiment of the present invention, the presence of an alcohol in the catalyst component is disadvantageous, that is to say does not contain a compound containing two hydroxyl groups, and it is advantageous for the present invention that the molar ratio of the acid halide compound to the compound containing two hydroxyl groups is from 2 to 3, and may for example be from 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 and any value in between, preferably from 2.2 to 2.6.
Another aspect of the present invention is to provide a process for the preparation of the above catalyst component.
According to the present invention, the preparation method of the above catalyst component comprises the steps of:
(i) contacting and reacting a magnesium compound, a Lewis base compound, a compound containing two hydroxyl groups and an oxygen-containing titanium-containing compound to obtain a contact reaction product;
(ii) mixing the contact reaction product with an acyl halide compound to obtain a mixture;
(iii) and (3) carrying out contact reaction on the transparent solution and titanium tetrahalide to obtain a solid precipitate, namely the catalyst component.
According to a preferred embodiment of the present invention, in the preparation method of the catalyst component, the step (i) is a mixed dissolution process of a magnesium compound, a lewis base compound and a compound having two hydroxyl groups, an oxygen-containing titanium-containing compound. In step (i), the magnesium compound, Lewis base compound, compound containing two hydroxyl groups and oxygen-containing titanium compound are contacted, optionally in the presence of an inert diluent, at 0 to 200 ℃, e.g., 0 ℃, 1 ℃,4 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 98 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and any temperature in between, preferably at 25 to 150 ℃. The inert diluent may be exemplified by benzene, toluene, xylene, isobutane, pentane, hexane, heptane, cyclohexane, 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.
According to a preferred embodiment of the present invention, 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 dropwise added to the contact reaction product to sufficiently react the acid halide compound with the compound having two hydroxyl groups, preferably at-30 to 150 ℃.
According to a preferred embodiment of the present invention, after obtaining the mixture in step (ii), the method further comprises heating the mixture to 80-200 ℃ to obtain a clear solution, which is usually carried out at a relatively high temperature, but should be carried out below the decomposition temperature of the reactants. After a clear solution is formed, it may be further mixed with an inert diluent. The inert diluent may be, for example, an aliphatic or aromatic hydrocarbon selected from benzene, toluene, xylene, isobutane, pentane, hexane, heptane, cyclohexane, etc., or a mixture thereof. In one embodiment of the present invention, toluene or hexane is preferred as the inert diluent. And (5) after obtaining the transparent solution, carrying out step (iii), and carrying out contact reaction on the transparent solution and titanium tetrahalide to obtain solid precipitate.
According to a preferred embodiment of the present invention, in step (iii), the mixed solution is contacted with the 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 25 ℃, and the process may be performed by slowly dropping the titanium compound into the mixed solution or dropping the mixed solution into the titanium compound, preferably, the dropping process is controlled within a range of 10min to 1 h. Optionally, during the contacting of the mixture with the titanium compound, other electron donor compounds such as alkoxysilanes may be added. After the dropwise addition is completed, the temperature is raised to-30-150 ℃, preferably 20-130 ℃, the mixed solution is reacted with the titanium compound to separate out a solid, and the temperature is gradually raised to the reaction temperature preferably within 30min-5h, preferably within 30min-1 h.
In the present invention, the preparation method of the catalyst component further comprises a step (iv) of post-treating the catalyst component, and the post-treatment of the solid precipitate comprises aging, washing and drying. According to a preferred embodiment of the invention, the solid precipitate is subjected to a maturation treatment with a titanium tetrahalide, preferably titanium tetrachloride. In this step, the titanium tetrahalide may be added at once or in portions. According to a preferred embodiment of the present invention, in this step, in order to bring the titanium tetrahalide into sufficient contact with the solid precipitate, the reaction temperature conditions at the time of adding the titanium tetrahalide are in the range of 70 to 150 ℃, preferably in the range of 90 to 130 ℃, and the specific number of aging times is 1 to 5, preferably 2 to 3.
In the present invention, after the solid precipitate aging treatment reaction using titanium tetrahalide in step (iv) is completed, excess reactants and by-products formed during the preparation are removed by washing, followed by drying to obtain a solid particulate catalyst component. In the present invention, the washing solvent used in the washing step is not particularly limited, and any inert solvent may be selected, and for example, isobutane, pentane, hexane, heptane, cyclohexane, toluene and the like may be selected as the washing solvent.
The present invention also provides a catalyst for olefin polymerization, comprising:
(1) the above catalyst components;
(2) an alkyl aluminum compound; preferably of the 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;
(3) optionally, an external electron donor component.
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, di (cyclobutylmethyl) dimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisoisobutyldimethoxysilaneButyl dimethoxysilane, di-n-butyl dimethoxysilane, dicyclopentyl dimethoxysilane and di (cyclobutylmethyl) dimethoxysilane.
Preferably, 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 external electron donor component is silicon; preferably 1: 25-100:25-100.
The invention also provides the catalyst component or the application of the catalyst in olefin polymerization, wherein the olefin is preferably in 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 catalyst component provided by the invention utilizes the in-situ reaction of the diol-containing compound and the acyl halide compound to generate the diol ester compound and directly participates in the synthesis of the catalyst component. 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. The preparation process does not need to use epoxy cosolvent and phthalic anhydride settling aid, and can avoid the generation of phthalate compounds in the reaction process. 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.
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, 35mL (0.10mol) of titanium tetra-n-butoxide, 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, and the mixture is maintained for 2.5 hours; then heating to 140 ℃, and stirring for reaction until the magnesium chloride is completely dissolved; then cooling the solution to below-25 ℃, and dripping TiCl within 1 hour436mL (0.32 mol); slowly heating to 80 ℃, maintaining for 1 hour, filtering, adding 70mL of toluene, and washing once; then 60mL of toluene and TiCl are added440mL, heating to 110 ℃, maintaining for 2 hours, and filtering; the same operation was repeated 1 time, 60mL of toluene was added and the mixture was washed at 110 ℃ for 5 minutes, filtered, 60mL of hexane was added and the mixture was washed at 68 ℃ twice for 5 minutes each, and 60mL of hexane was added and the mixture was washed at room temperature twice for 5 minutes each, to obtain a solid procatalyst 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 benzoyl chloride was replaced by t-butyl chloride.
Example 10
The same as in example 1, except that 2-ethyl-2, 4-pentanediol was used instead of 2, 4-pentanediol.
Example 11
The same as in example 1, except that 2-ethyl-1, 3-pentanediol was used instead of 2, 4-pentanediol.
Example 12
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 13
The same as in example 1 except that 2, 4-pentanediol was used in an amount of 0.0125 mol.
Example 14
The same as in example 1 except that benzoyl chloride was used in an amount of 0.065 mol.
Example 15
The same as in example 1, except that benzoyl chloride was used in an amount of 0.075 mol.
Example 16
The same as in example 1 except that benzoyl chloride was used in an amount of 0.10 mol.
Example 17
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 18
The same as in example 1 except that magnesium diethoxide was used in place of magnesium chloride.
Example 19
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 20
The same as in example 1 except that 4-methyl-4-ethyl-3, 5-heptanediol was used instead of 2, 4-pentanediol.
Example 21
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 above were separately 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 (29)
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) an oxygen-containing titanium-containing compound; (6) titanium tetrahalide;
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;
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 chain or branched chain alkyl, C3-C20 cycloalkylC6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkylene or condensed ring aryl, R1-R6Cannot be simultaneously hydrogen;
the preparation method of the catalyst component comprises the following steps:
(i) contacting and reacting a magnesium compound, a Lewis base compound, a compound containing two hydroxyl groups and an oxygen-containing titanium-containing compound to obtain a contact reaction product;
(ii) mixing the contact reaction product with an acyl halide compound to obtain a mixture;
(iii) and (3) carrying out contact reaction on the mixture and titanium tetrahalide to obtain a solid precipitate, namely 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 R is1Is C1-C5 alkyl, alkoxy or halogenated alkoxy.
4. 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.
5. The catalyst component according to any of claims 1 to 4, wherein R is2Is phenyl, C1-C4 alkyl or furyl, which is substituted or unsubstituted by halogen.
6. The catalyst component according to claim 5 wherein 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.
7. The catalyst component according to any of claims 1 to 4 in which R is1、R2At least one of which is not H.
8. The catalyst component according to claim 7 in which 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-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, 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, 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, 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, 5-propyl-6-heptene-2, 4-heptanediol, 6-propyl-6-heptene-2, 4-heptanediol, 3-butyl-6-heptene-2, 4-heptanediol, a mixture of these, and a mixture of these, 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-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, 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, 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, 4-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-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, a salt thereof, and a salt thereof, One or more of 5-phenyl-4, 6-nonanediol, 4-butyl-3, 5-heptanediol, and 3-methyl-3-butyl-2, 4-pentanediol.
9. The catalyst component according to claim 8 in which the 2, 4-pentanediol comprises (2S, 4S) - (+) -2, 4-pentanediol and (2R, 4R) - (+) -2, 4-pentanediol.
10. The catalyst component according to any of claims 1 to 4, characterized in that the oxygen-containing titanium-containing compound is of the general formula Ti (OR ")pX4-pThe compound is shown in the specification, wherein X is halogen, R' is C1-C20 alkyl, and p is more than 0 and less than or equal to 4; and/or
The titanium tetrahalide is one or more of titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide and titanium tetraiodide.
11. The catalyst component according to claim 10 in which R "is a C1-C4 alkyl group.
12. The catalyst component according to claim 10 wherein the oxygen containing titanium compound is selected from one or more of tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
13. The catalyst component according to any of claims 1 to 4 wherein the catalyst component is fed with the Lewis base compound in an amount of 0.01 to 20 moles per mole of the magnesium compound; and/or 0.1 to 10mol of a compound containing two hydroxyl groups; and/or 0.1-10 mol of oxygen-containing titanium-containing compound; and/or 1-5 mol of titanium tetrahalide; and/or the acid halide compound is 0.1 to 10 mol.
14. The catalyst component according to claim 13 in which the lewis base compound is present in an amount of 0.2 to 12 moles; and/or 0.25 to 1 mole of a compound containing two hydroxyl groups; and/or 1.0-5 mol of oxygen-containing titanium-containing compound; and/or the acid halide compound is 0.5 to 4 mol.
15. The catalyst component according to claim 13 characterized in that the acid halide compound is 1 to 2 moles.
16. The catalyst component according to claim 13 characterized in that the molar ratio of the acid halide compound to the compound containing two hydroxyl groups is 2 to 3.
17. The catalyst component according to claim 16 wherein the molar ratio of the acid halide compound to the compound containing two hydroxyl groups is from 2.2 to 2.6.
18. A process for the preparation of the catalyst component of any of claims 1 to 17, comprising the steps of:
(i) contacting and reacting a magnesium compound, a Lewis base compound, a compound containing two hydroxyl groups and an oxygen-containing titanium-containing compound to obtain a contact reaction product;
(ii) mixing the contact reaction product with an acyl halide compound to obtain a mixture;
(iii) and (3) carrying out contact reaction on the mixture and titanium tetrahalide to obtain a solid precipitate, namely the catalyst component.
19. The method of claim 18, wherein the temperature of the contact reaction is between 0 ℃ and 200 ℃.
20. The method of claim 18, wherein the temperature of the contact reaction is between 25 ℃ and 150 ℃.
21. The method of claim 18, wherein the mixing is performed at-30-150 ℃ to obtain the mixture.
22. The method according to any one of claims 18 to 21, wherein after obtaining the mixture in step (ii), further comprising heating the mixture to 80-200 ℃ to obtain a clear solution, and then performing step (iii).
23. A catalyst for olefin polymerization, comprising:
(1) a catalyst component as claimed in any one of claims 1 to 17, or a catalyst component produced by a process as claimed in any one of claims 18 to 22;
(2) an alkyl aluminum compound;
(3) optionally, an external electron donor component.
24. The catalyst according to claim 23, characterized in that 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, and q is more than 0 and less than or equal to 3.
25. The catalyst of claim 23, wherein the external electron donor component 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.
26. The catalyst of claim 23, wherein 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 external electron donor component is silicon.
27. The catalyst of claim 26, wherein the molar ratio of the catalyst component (1), the alkyl aluminum compound (Al) and the external electron donor component (Si) is 1: 25-100:25-100.
28. Use of a catalyst as claimed in any one of claims 23 to 27 in the polymerisation of olefins.
29. Use according to claim 28, wherein the olefin is of the formula CH2Olefins of CHR, wherein R is hydrogen or C1-C12A hydrocarbyl or aryl group of (a).
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