CN111072815A - Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method - Google Patents
Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method Download PDFInfo
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- CN111072815A CN111072815A CN201811224580.7A CN201811224580A CN111072815A CN 111072815 A CN111072815 A CN 111072815A CN 201811224580 A CN201811224580 A CN 201811224580A CN 111072815 A CN111072815 A CN 111072815A
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Abstract
The invention belongs to the field of catalysts, and relates to a catalyst component and a catalyst for olefin polymerization, application thereof and an olefin polymerization method. The catalyst component comprises the reaction product of: (1) a solid component containing a magnesium compound and an alkylene oxide compound, (2) at least one titanium compound; and (3) an internal electron donor compound; the internal electron donor compound comprises an internal electron donor compound a and an internal electron donor compound b, wherein the internal electron donor compound a is a monocarboxylic acid ester compound, and the internal electron donor compound b is a diether compound. When the internal electron donor simultaneously contains a diether compound and a monobasic aromatic carboxylic ester compound, and the solid component contains a magnesium compound and an alkylene oxide compound in a specific ratio, the hydrogen regulation sensitivity and the stereospecificity of the catalyst can be effectively improved.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, application of the catalyst component and the catalyst, and an olefin polymerization method.
Background
In plastic processing, melt flow rate is an important index for measuring the fluidity of plastic melt, and is an important reference for selecting plastic processing materials and grades. The melt flow rate is largely dependent on the molecular weight of the polymer, with low molecular weight polymers having high melt flow rates. In order to obtain an olefin polymer having a high melt flow rate, it is generally necessary to add a large amount of hydrogen during polymerization to reduce the molecular weight of the polymer. However, the upper limit of the amount of hydrogen that can be added is limited by the pressure resistance of the polymerization reactor. The partial pressure of the olefin gas to be polymerized has to be lowered in order to add more hydrogen, in which case the productivity is lowered. In addition, the high-volume use of hydrogen also causes the obtained polypropylene to have low isotacticity, thereby causing the problem of unqualified product quality. Therefore, it is highly desirable to develop a catalyst having high hydrogen response (a small amount of hydrogen can provide a polymer having a high melt flow rate) and high stereospecificity (the polymer can maintain a high isotacticity under polymerization conditions with a large amount of hydrogen).
US4298718 and US4495338 disclose Ziegler-Natta catalysts using magnesium halides as support. The catalyst formed by the action of the carrier and titanium tetrachloride shows higher catalytic activity in catalyzing propylene polymerization, but the isotacticity of the obtained polypropylene is lower, which indicates that the stereospecific capacity of the catalyst is poorer. Then, researchers add an electron donor compound (such as ethyl benzoate or phthalate) in the preparation process of the Ziegler-Natta catalyst to form a solid titanium catalyst, and add another electron donor (an alkoxysilane compound) during olefin polymerization to obtain polypropylene with higher isotacticity during propylene polymerization catalysis, which indicates that the addition of the electron donor compound improves the stereotactic ability of the catalyst. However, the hydrogen regulation sensitivity of the catalyst is insufficient, and the direct hydrogen regulation method is difficult to produce products with high melt index. Moreover, it is found that the phthalate compound (plasticizer) can cause serious damage to the growth and development of animals and reproductive systems, and simultaneously, the phthalate compound can also have similar influence on human beings.
CN1580034A, CN1580035A, CN1580033A, CN1436766A and CN1552740A disclose that glycol ester compounds are used as electron donors of Ziegler-Natta catalysts for propylene polymerization, which are characterized by wider molecular weight distribution and higher polymerization activity, but when a spherical catalyst containing carboxylic glycol ester internal electron donor is used for propylene polymerization, the stereotactic ability is poorer, and the isotacticity of the obtained polypropylene is lower.
In addition, catalysts for olefin polymerization are mostly prepared by supporting titanium halide on active anhydrous magnesium chloride. Among these, one common method for preparing active magnesium chloride is to use anhydrous MgCl2With an alcohol to form MgCl2·mROH·nH2The solid component of the olefin polymerization catalyst is prepared by the magnesium chloride-alcohol adduct of O and then supporting a titanium halide with this adduct. Such alcoholsThe compounds may be prepared by spray drying, spray cooling, high pressure extrusion or high speed stirring. Such as: magnesium chloride alcoholates as disclosed in US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US 6323152. The preparation process of the magnesium chloride alcoholate carrier generally needs high-temperature melting and then low-temperature cooling molding, the energy consumption of the process is large, and the obtained alcoholate carrier needs dealcoholization treatment, so that the process is complex. The activated magnesium chloride carrier can also be prepared by taking alkoxy magnesium as a raw material. The alkoxy magnesium compound is mostly prepared by taking magnesium powder or alkyl magnesium as a raw material, and compared with magnesium chloride, the alkoxy magnesium compound has high raw material price and complex preparation process. In order to solve the above problems, CN102040681A discloses a compound useful as a support for olefin polymerization catalysts, which has the following structure:
wherein R is1Is C1-C12Linear or branched alkyl of (a); r2And R3Identical or different and is hydrogen or C1-C5Straight or branched chain alkyl, wherein the hydrogen on the alkyl group is optionally substituted with a halogen atom; x is chlorine or bromine, one of which may also be C1-C14Alkyl or alkoxy, C6-C14Aryl or aryloxy substituted; m is 0.1-1.9, n is 0.1-1.9, p + m + n is 2. The preparation steps of the compound are as follows: in the presence of an inert dispersion medium, MgX2General formula R1Heating an alcohol compound represented by OH to 30-160 ℃ for reaction to form a magnesium halide alcohol compound solution; then reacting the carrier with an ethylene oxide compound at 30-160 ℃ to form a carrier; wherein X is chlorine or bromine, R1Is C1-C12Linear or branched alkyl. CN102040680A also discloses an olefin polymerization catalyst prepared using the compound of the aforementioned patent application which can be used as a support for an olefin polymerization catalyst. Although the technical proposal disclosed by the technical proposal reduces the raw material cost for preparing the carrier and simplifies the carrier preparation process, the single kettle yield of the carrier is reduced because a large amount of inert dispersion medium is required to be used in the carrier preparation process,and the recovery of the inert dispersion medium increases the solvent recovery cost; in addition, the stereoregularity of the polymer obtained in the olefin polymerization process by the olefin polymerization catalyst using the support of this patent application is yet to be further improved.
Therefore, it is urgently required to develop a catalyst having high hydrogen response and high stereospecificity and containing no phthalate compound (plasticizer).
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, the use of the catalyst component and the catalyst, and a process for olefin polymerization. The catalyst component has high hydrogen regulation sensitivity and stereospecificity, and does not contain phthalate compounds (plasticizers).
The inventor of the present invention unexpectedly found in the research process that when the internal electron donor contains a diether compound and a monocarboxylic ester compound at the same time, and the solid component contains a magnesium compound represented by formula i and an alkylene oxide compound represented by formula ii in a specific ratio (the molar ratio of the two compounds is 1: 0.01-0.8), the molar ratio of the monocarboxylic ester compound to the diether compound is controlled to be 0.065-0.7: when 1, the hydrogen response and stereospecificity of the catalyst can be effectively improved. Further, the inventors of the present invention have also found that, when a catalyst component for olefin polymerization is prepared using a mono-aromatic carboxylic acid ester compound and a diether compound as internal electron donors and the molar ratio of the mono-aromatic carboxylic acid ester compound to the diether compound is controlled to be 0.15 to 0.35: 1, the two internal electron donors can be perfectly matched, so that the hydrogen response and the stereospecificity of the catalyst are more effectively improved.
In this regard, a first aspect of the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component comprising the reaction product of:
(1) a solid component containing a magnesium compound represented by formula I and an alkylene oxide compound represented by formula II, the content of the alkylene oxide compound represented by formula II being 0.01 to 0.8 mole per mole of the magnesium compound represented by formula I;
(2) at least one titanium compound; and
(3) an internal electron donor compound;
wherein R is1Is C1-C12Linear or branched alkyl of (a); r2And R3Are the same or different and are each independently hydrogen or C1-C5Wherein the hydrogen on the alkyl group is optionally substituted with halogen; x is halogen; m is 0.1-1.9, n is 0.1-1.9, and m + n is 2;
the internal electron donor compound comprises an internal electron donor compound a and an internal electron donor compound b, wherein the internal electron donor compound a is a monocarboxylic acid ester compound, and the internal electron donor compound b is a diether compound shown as a formula III; the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.065-0.7: 1;
the monocarboxylic acid ester compound is a monocarboxylic aromatic carboxylic acid ester and/or a monocarboxylic aliphatic carboxylic acid ester;
in the formula III, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is one of substituted or unsubstituted alkaryl groups.
In the present invention, C1-C20Examples of the linear or branched alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, n-eicosyl.
In the present invention, C3-C20Examples of the substituted or unsubstituted cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, cyclododecyl.
In the present invention, C6-C20The substituted or unsubstituted aryl group of (1) includes C6-C20Substituted or unsubstituted phenyl of, also including C10-C20Examples of the substituted or unsubstituted fused ring aryl group of (a) may include, but are not limited to: phenyl, halogen substituted phenyl, alkoxy substituted phenyl, naphthyl, methyl naphthyl, ethyl naphthyl, anthryl, methyl anthryl, ethyl anthryl, phenanthryl, methyl phenanthryl and ethyl phenanthryl, pyrenyl, indenyl.
In the present invention, C7-C20The substituted or unsubstituted aralkyl group of (2) means an alkyl group having an aryl substituent and having 7 to 20 carbon atoms. C7-C20Examples of the substituted or unsubstituted aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl-isopropyl, phenyl-n-pentyl.
In the present invention, C7-C20The substituted or unsubstituted alkylaryl group of (2) means an aryl group having an alkyl substituent and having 7 to 20 carbon atoms. C7-C20Examples of substituted or unsubstituted alkaryl groups of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl, isopropylphenyl and n-pentylphenyl.
In the present invention, the above-mentioned groups in other carbon number ranges can be selected correspondingly within the carbon number range defined, and are not described in detail herein.
According to the present invention, it is preferable that the aliphatic monocarboxylic acid ester is a monoester comprising an aliphatic monocarboxylic acid having 2 to 10 carbon atoms and a monohydric or polyhydric aliphatic alcohol having 1 to 15 carbon atoms or an aromatic alcohol having 6 to 15 carbon atoms; the monobasic aromatic carboxylic ester is formed by monobasic aromatic carboxylic acid with 7-10 carbon atoms and monobasic or polybasic aliphatic alcohol with 1-15 carbon atoms or aromatic alcohol with 6-15 carbon atoms. The aliphatic monocarboxylic acid and the aromatic monocarboxylic acid may optionally have a substituent, and the substituent may be a hydroxyl group and/or an alkoxy group.
Further preferably, the aromatic monocarboxylic acid ester is at least one of benzoate, orthohydroxybenzoate, orthomethoxybenzoate and orthoethoxybenzoate.
According to the invention, preferably, the internal electron donor compound b is a1, 3-diether compound shown in formula IV,
in the formula IV, R9' and R10' same or different, each independently hydrogen, halogen, C1-C18Straight or branched alkyl of (2), C3-C18Substituted or unsubstituted cycloalkyl of (A), C6-C18Substituted or unsubstituted aryl and C7-C18Or one of substituted or unsubstituted aralkyl, or R9' and R10' bonding to each other to form a ring; r11' and R12' same or different, each independently C1-C10Linear or branched alkyl.
According to the present invention, examples of the internal electron donor compound b may include, but are not limited to: 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-isopropylphenyl-1, 3-dimethoxypropane, 2-isopropyl, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-methyl, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene.
Most preferably, the internal electron donor compound b is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.
In the present invention, the 1, 3-diether compound can be synthesized by the methods disclosed in CN1020448C, CN100348624C and CN 1141285A. The disclosure of which is incorporated herein by reference in its entirety. This is not described in detail herein.
According to the present invention, when the internal electron donor comprises a monocarboxylic acid ester compound and a diether compound, a certain synergistic effect can be generated, and the total amount of the monocarboxylic acid ester compound and the diether compound is preferably 70 to 100 wt%, more preferably 80 to 100 wt%, even more preferably 90 to 100 wt%, and most preferably 100 wt%, based on the amount of the internal electron donor.
The inventor of the present invention has found that, when the molar ratio of the monocarboxylic acid ester compound to the diether compound is 0.15 to 0.35: 1, the two can be better blended cooperatively, so that the catalyst with higher hydrogen regulation sensitivity and stereotactic ability is obtained.
In the solid component, preferably, R1Is C1-C8More preferably C2-C5Such as ethyl, propyl, butyl or pentyl.
In the solid component, preferably, R2And R3Are the same or different and are each independently hydrogen or C1-C3Wherein the hydrogen on the alkyl group is optionally substituted with halogen. Specifically, R2And R3Each independently is preferably hydrogen, methyl, ethyl, propyl, chloromethyl, chloroethyl, chloropropyl, bromomethyl, bromoethyl or bromopropyl.
In the solid component, preferably, X is bromine, chlorine or iodine, more preferably chlorine.
In the solid component, preferably, m is 0.5 to 1.5, n is 0.5 to 1.5, and m + n is 2. Most preferably, m is 1 and n is 1.
In the solid component, preferably, the alkylene oxide compound represented by the formula II is at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.
According to the present invention, it is preferred that the content of the alkylene oxide compound represented by the formula II is 0.02 to 0.5 mol, preferably 0.02 to 0.3 mol, per mol of the magnesium compound represented by the formula I in the solid component.
In the present invention, the solid component is preferably present in the form of spherical particles, the average particle diameter (D50) of which is preferably 30 to 125 μm, more preferably 40 to 85 μm. The solid component preferably has a particle size distribution value (SPAN ═ D90-D10)/D50) of 0.6 to 2.5, more preferably 0.6 to 0.85. In the present invention, the average particle diameter and the particle size distribution value of the solid component particles are measured using a Masters Sizer 2000 particle Sizer (manufactured by Malvern Instruments Ltd).
In the present invention, the titanium compound may be various titanium compounds conventionally used in the art, for example, the titanium compound may be selected from the group consisting of titanium compounds having a general formula of Ti (OR)4)4-aXaWherein R is4Can be C1-C14Is preferably C1-C8Alkyl groups of (a), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; x may be a halogen, such as F, Cl, Br, I, or any combination thereof; a is an integer of 0 to 4. Preferably, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxyAt least one of titanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloro-monoethoxytitanium.
The contents of magnesium, titanium and an internal electron donor in the catalyst component are not particularly limited, and may be any value in the catalyst component conventional in the art, and preferably, the content of the magnesium element is 2 to 15 parts by weight, preferably 3 to 12 parts by weight, and more preferably 4 to 10 parts by weight, per part by weight of the titanium element; the content of the internal electron donor is 2 to 10 parts by weight, preferably 3 to 8 parts by weight, and more preferably 4 to 7 parts by weight.
The second aspect of the present invention provides a method for producing the above catalyst component, which comprises the steps of:
(1) preparing a solid component, comprising:
(a) in a closed container, magnesium halide MgX is added in the presence of at least one high molecular dispersion stabilizer2And an organic alcohol R1Reacting the mixture of OH at 30-160 ℃ to form a magnesium halide alcoholate solution;
(b) reacting the magnesium halide alcoholate solution with an alkylene oxide compound shown as a formula II at 30-160 ℃ to generate a solid component;
wherein X is halogen, R1Is C1-C12Linear or branched alkyl of (a);
wherein R is2And R3Are the same or different and are each independently hydrogen or C1-C5Wherein the hydrogen on the alkyl group is optionally substituted with halogen;
wherein, the dosage of the organic alcohol is 3-30 mol and the dosage of the alkylene oxide compound shown in the formula II is 1-10 mol based on each mol of magnesium; the dosage of the macromolecular dispersion stabilizer is 0.1 to 10 weight percent of the total dosage of the magnesium halide and the organic alcohol;
(2) the solid component prepared in the step (1) is contacted with a titanium compound for reaction, and an internal electron donor is added in one or more time periods before, during and after the reaction, wherein the internal electron donor contains a monocarboxylic ester compound and a diether compound shown as a formula III.
In step (1), preferably, the organic alcohol is used in an amount of 4 to 20 moles per mole of magnesium; the dosage of the alkylene oxide compound shown in the formula (2) is 2-6 mol; the amount of the polymeric dispersion stabilizer is 0.2 to 5% by weight of the total amount of the magnesium halide and the organic alcohol.
In magnesium halide MgX2In (b), X is preferably bromine, chlorine or iodine. More preferably, the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, most preferably magnesium dichloride.
In an organic alcohol R1In OH, R1Preferably C1-C8More preferably C2-C5Such as ethyl, propyl, butyl or pentyl. Specifically, the organic alcohol may be selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethyl-1-hexanol, for example.
In the alkylene oxide compounds of the formula II, R2And R3Each independently preferably hydrogen or C1-C3Wherein the hydrogen on the alkyl group is optionally substituted by halogen, in particular, R2And R3Each independently is preferably hydrogen, methyl, ethyl, propyl, chloromethyl, chloroethyl, chloropropyl, bromomethyl, bromoethyl or bromopropyl. Specifically, the alkylene oxide compound may be selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.
In the present invention, the "polymer" in the polymer dispersion stabilizer is not particularly limited in terms of molecular weight, but is defined as a polymer (or macromolecule) in IUPAC (International Union of Pure and Applied Chemistry ), that is, a "molecule of relatively high molecular mass whose structure is mainly composed of multiple repetitions of units derived from molecules of relatively low molecular mass in practice or in concept". In the present invention, the weight average molecular weight of the polymeric dispersion stabilizer in the step (a) is preferably more than 1000, more preferably more than 3000, and further preferably 6,000-2,000,000. Specifically, the polymeric dispersion stabilizer may be selected from the group consisting of polyacrylate, styrene-maleic anhydride copolymer, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkyl phenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinyl benzyl trimethylamine salt, at least one of polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone vinyl acetate copolymer, polyethylene glycol (PEG), alkyl phenyl polyoxyethylene ether and polyalkylmethacrylate compounds, preferably at least one of polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer and polyethylene glycol.
In the preparation of the solid component, the magnesium halide, the organic alcohol and the high molecular dispersion stabilizer in the step (a) may participate in the formation of the magnesium halide alcoholate solution in the form of containing a slight amount of water. These trace amounts of water are water that is inevitably introduced in industrial production or during storage or transportation, and not water that is artificially added.
In the process of preparing the solid component, the magnesium halide, the organic alcohol and the polymeric dispersion stabilizer in step (a) may be added in any order without any order of addition.
In the preparation of the solid component, the reaction time in the step (a) may be 0.1 to 5 hours, preferably 0.5 to 2 hours.
In the preparation of the solid component, the reaction time in the step (b) may be 0.1 to 5 hours, preferably 0.2 to 1 hour.
In the preparation of the solid component, an inert dispersion medium is preferably not added in steps (a) and (b). The inert dispersion medium is an inert dispersion medium conventionally used in the art, and may be, for example, at least one selected from liquid aliphatic, aromatic hydrocarbons, cycloaliphatic hydrocarbons, and silicone oils, and specifically, may be, for example, at least one of linear or branched liquid alkanes having a carbon chain length of more than 6 carbons, kerosene, paraffin oil, vaseline oil, white oil, and methyl silicone oil.
In a preferred embodiment, the preparation of the solid component comprises:
(i) heating a mixture of magnesium halide, organic alcohol and at least one polymeric dispersion stabilizer to 30-160 ℃, preferably 40-120 ℃ for 0.1-5 hours, preferably 0.5-2 hours, while stirring, in a closed container to form a magnesium halide alcoholate solution, wherein the organic alcohol is used in an amount of 3-30 moles, preferably 4-25 moles, per mole of magnesium; the amount of the polymeric dispersion stabilizer is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total amount of the magnesium halide and the organic alcohol.
(ii) Adding the alkylene oxide compound represented by the formula (2) into the magnesium halide alcoholate solution under stirring, and reacting at 30-160 ℃ (preferably 40-120 ℃) for 0.1-5 hours, preferably 0.2-1 hour to form solid component particles, wherein the amount of the alkylene oxide compound is 1-10 moles, preferably 2-6 moles per mole of magnesium.
Preferably, the solid component particles obtained in the above-mentioned process for preparing the solid component are washed with an inert hydrocarbon solvent (e.g., hexane, heptane, octane, decane, toluene, etc.), dried, and then used in the subsequent step (2) to prepare the catalyst component for olefin polymerization.
In the step (2), the process of contacting the solid component prepared in the step (1) with a titanium compound to react preferably comprises: suspending the solid component in a titanium compound raw material at the temperature of-30 ℃ to 0 ℃, and then heating to 40 ℃ to 130 ℃ for reaction for 0.1 hour to 5 hours. More preferably, the process of contacting the solid component prepared in step (1) with a titanium compound comprises: suspending the solid component in a titanium compound raw material at the temperature of-20 ℃ to 0 ℃, and then heating to 50 ℃ to 130 ℃ for reaction for 0.5 hour to 2 hours. The titanium compound starting material may be a pure titanium compound or a mixture of a titanium compound and an inert solvent. The inert solvent may be selected from aliphatic and aromatic hydrocarbons, for example, hexane, heptane, octane, decane, toluene, and the like.
In one embodiment, in order to obtain a more isotactic olefin polymer when the prepared catalyst component is used in an olefin polymerization process, step (2) includes adding an internal electron donor containing at least a monocarboxylic acid ester compound and a diether compound in one or more time periods before, during and after the solid component reacts with the titanium compound, and the internal electron donor containing at least a monocarboxylic acid ester compound and a diether compound may be added together or may be separately added at different time periods. Preferably, the internal electron donor comprising at least the monocarboxylic acid ester compound and the diether compound is added during the heating of the mixture of the solid component and the titanium compound (i.e., before the start of the reaction).
Preferably, the method for preparing the catalyst component further comprises, after reacting the solid component with the titanium compound, filtering off the liquid and recovering the solid, and treating the recovered solid one or more times, preferably 2 to 4 times, with a liquid titanium compound (such as titanium tetrachloride); the obtained solid catalyst component is then washed several times with a hydrocarbon solvent. The hydrocarbon solvent may be selected from aliphatic, aromatic or alicyclic hydrocarbons, for example, hexane, heptane, octane, decane, toluene, and the like.
In the step (2), the titanium compound may be used in an amount of 5 to 200 moles, preferably 10 to 50 moles, per mole of magnesium; the amount of the internal electron donor may be 0.04 to 0.6 mol, preferably 0.07 to 0.5 mol, and more preferably 0.1 to 0.4 mol.
The types and amounts of the monocarboxylic acid ester compounds and the diether compounds, and the types of the titanium compounds have been described above, and are not described herein again.
A third aspect of the invention provides the use of the above catalyst component in the preparation of a catalyst for the polymerisation of olefins.
A fourth aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:
(1) the above catalyst components;
(2) an alkylaluminum compound as a cocatalyst; and
(3) optionally an external electron donor compound.
In the catalyst for olefin polymerization, the aluminum alkyl compound may be various aluminum alkyl compounds conventionally used in the art, for example, the aluminum alkyl may have a general formula of AlR16R16′R16", wherein R16、R16' and R16Each independently is C1-C8And wherein one or both of the groups may be halogen, and the hydrogen on the alkyl group may also be substituted by halogen; said C is1-C8Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl and the halogen may be fluorine, chlorine, bromine, iodine. In particular, the alkyl aluminium compound may be chosen, for example, from one or more of triethylaluminium, triisobutylaluminium, tri-n-butylaluminium, tri-n-hexylaluminium, diethylaluminium monochloride, diisobutylaluminium monochloride, di-n-butylaluminium monochloride, di-n-hexylaluminium monochloride, ethylaluminium dichloride, isobutylaluminium dichloride, n-butylaluminium dichloride and n-hexylaluminium dichloride.
In the catalyst for olefin polymerization, the external electron donor may be various external electron donors commonly used in the art, and for example, the external electron donor may be selected from carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organic phosphorus compounds, and organic silicon compounds. Preferably, the external electron donor contains at least one Si-OR bond and has the general formula (R)17)x(R18)ySi(OR19)zWherein R is17、R18And R19Is C1-C18Optionally containing heteroatoms, x andy is each independently an integer from 0 to 2, z is an integer from 1 to 3, and the sum of x, y and z is 4. Preferably, R17、R18Is C3-C10Alkyl, cycloalkyl, optionally containing heteroatoms; r19Is C1-C10Optionally containing heteroatoms. Specifically, the external electron donor may be selected from, for example, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.
Further, in general, in the catalyst for olefin polymerization, the molar ratio of the catalyst component for olefin polymerization in terms of titanium element to the amount of aluminum alkyl in terms of aluminum element may be 1: 1-2000, preferably 1: 20-500; the molar ratio of the external electron donor to the aluminum alkyl in terms of aluminum element may be 1: 2-200, preferably 1: 2.5-100.
According to the present invention, in the preparation process of the catalyst for olefin polymerization, the alkylaluminum and the optional external electron donor compound may be respectively mixed with the catalyst component for olefin polymerization and then reacted, or the alkylaluminum and the optional external electron donor compound may be mixed in advance and then mixed with the catalyst component for olefin polymerization and reacted.
According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor may be added into the polymerization reactor separately, or may be added into the polymerization reactor after mixing, or may be added into the polymerization reactor after olefin prepolymerization by a prepolymerization method known in the art.
A fifth aspect of the present invention provides the use of a catalyst for olefin polymerization as described above in an olefin polymerization reaction.
A sixth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions. The improvement of the present invention is that a new catalyst component and catalyst for olefin polymerization are used, so that the specific kind of olefin, the polymerization reaction method and conditions of olefin can be the same as those in the prior art.
According to the invention, the above-mentioned catalysts are particularly suitable for use with catalysts of the formula CH2CHR (wherein R is hydrogen, C)1-C6Alkyl or C6-C12Aryl) by homopolymerization and copolymerization of olefins.
According to the present invention, the polymerization of the olefin can be carried out according to the existing methods, specifically, under the protection of inert gas, in a liquid phase monomer or an inert solvent containing a polymeric monomer, or in a gas phase, or by a combined polymerization process in a gas-liquid phase. The polymerization temperature may be generally 0 to 150 ℃ and preferably 60 to 90 ℃. The pressure of the polymerization reaction may be normal pressure or higher; for example, it may be in the range of 0.01 to 10MPa, preferably 0.01 to 6MPa, more preferably 0.1 to 4 MPa. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen may be added to the reaction system as a polymer molecular weight regulator to regulate the molecular weight and melt index of the polymer. In addition, the kinds and amounts of the inert gas and the solvent are well known to those skilled in the art during the polymerization of olefins, and will not be described herein.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the following examples and comparative examples:
(1) polymer melt index: measured according to the method of ASTM D1238-99.
(2) Polymer isotactic index: the determination is carried out by adopting a heptane extraction method (boiling extraction for 6 hours by heptane), namely, a 2g dried polymer sample is taken and placed in an extractor to be extracted for 6 hours by boiling heptane, then, the residue is dried to constant weight, and the ratio of the weight (g) of the obtained polymer to 2 is the isotactic index.
Preparation of the solid component
The solid components, designated as A1-A2, were prepared as described in CN104558284A, preparations 1-2, respectively. The solid components A1-A2 of the invention have the same contents and structures as A1-A2 prepared by the method disclosed in CN 104558284A.
Example 1
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
(1) Preparation of the catalyst component
In a 300mL glass reaction flask, 90mL (820mmol) of titanium tetrachloride was added, cooled to-20 ℃ and 8g (45mmol) of the above solid component A1 was added and the temperature was raised to 110 ℃. Adding 2mmol of ethyl benzoate and 7mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane in the temperature rising process, maintaining the temperature at 110 ℃ for 30min, filtering out the liquid, washing twice with titanium tetrachloride and five times with hexane, and drying in vacuum to obtain a solid catalyst component Cat-1.
(2) Liquid phase bulk polymerization of propylene
The liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. To the reaction vessel were added 1ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 0.1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1mmol/ml) and 6mg of the above solid catalyst Cat-1 in this order under a nitrogen blanket. The autoclave was closed and 6.5L of hydrogen (normal volume) and 2.3L of liquid propylene were added. The temperature is raised to 70 ℃, after 1 hour of reaction, the temperature is reduced, the pressure is relieved, the material is discharged, the obtained propylene homopolymer is weighed and analyzed after being dried, and the results are shown in table 1.
Example 2
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
(1) Preparation of the catalyst component
In a 300mL glass reaction flask, 90mL (820mmol) was added, cooled to-20 ℃ and 8g (45mmol) of the above solid component A1 was added and the temperature was raised to 110 ℃. Adding 2mmol of ethyl o-methoxybenzoate and 9mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane during the temperature rising process, maintaining the temperature at 110 ℃ for 30min, filtering out the liquid, washing twice with titanium tetrachloride, washing five times with hexane, and drying in vacuum to obtain a solid catalyst component Cat-2.
(2) Liquid phase bulk polymerization of propylene
The liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. To the reaction vessel were added 1ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 0.1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1mmol/ml) and 6mg of the above solid catalyst Cat-2 in this order under a nitrogen blanket. The autoclave was closed and 6.5L of hydrogen (normal volume) and 2.3L of liquid propylene were added. The temperature is raised to 70 ℃, after 1 hour of reaction, the temperature is reduced, the pressure is relieved, the material is discharged, the obtained propylene homopolymer is weighed and analyzed after being dried, and the results are shown in table 1.
Example 3
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
(1) Preparation of the catalyst component
In a 300mL glass reaction flask, 184.4mL of titanium tetrachloride (1680mmol) was added, cooled to-20 ℃ and 10g (56mmol) of the above solid component A2 was added and the temperature was raised to 110 ℃. Adding 0.6mmol of ethyl o-methoxybenzoate and 8.8mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane during the temperature rising process, maintaining the temperature at 110 ℃ for 30min, filtering the liquid, washing the liquid twice with titanium tetrachloride and five times with hexane, and drying the liquid in vacuum to obtain a solid catalyst component Cat-3.
(2) Liquid phase bulk polymerization of propylene
The liquid-phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. To the reaction vessel were added 1ml of a hexane solution of triethylaluminum (concentration: 0.5mmol/ml), 0.1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1mmol/ml) and 6mg of the above solid catalyst Cat-3 in this order under a nitrogen blanket. The autoclave was closed and 6.5L of hydrogen (normal volume) and 2.3L of liquid propylene were added. The temperature is raised to 70 ℃, after 1 hour of reaction, the temperature is reduced, the pressure is relieved, the material is discharged, the obtained propylene homopolymer is weighed and analyzed after being dried, and the results are shown in table 1.
Example 4
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in accordance with the procedure of example 2, except that the amounts of ethyl o-methoxybenzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane added during the temperature rise were 5.6mmol and 8mmol, respectively, to obtain a catalyst component Cat-4 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Example 5
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 2, except that 1.1mmol of o-ethoxybenzoate and 7.3mmol of 9, 9-dimethoxymethylfluorene were added during the temperature increase, without adding o-methoxybenzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, to give a catalyst component Cat-5 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Example 6
This example is intended to illustrate the catalyst component for olefin polymerization and the preparation method thereof, and the catalyst for olefin polymerization and the application thereof according to the present invention.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 2, except that 2.8mmol of o-methoxybenzoate and 8mmol of 9, 9-dimethoxymethylfluorene were added during the temperature rise to obtain a catalyst component Cat-6 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 1
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and a liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that, in the preparation of the catalyst component, the ethyl benzoate was replaced with the same parts by weight of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to give a catalyst component for olefin polymerization, DCat-1; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 2
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and a liquid-phase bulk polymerization of propylene was carried out in accordance with the procedure of example 2, except that, in the preparation of the catalyst component, 37mmol, in terms of magnesium element, of a magnesium halide support (prepared as disclosed in CN1330086A example 1) was added thereto in place of the solid component A1, and the 2mmol of ethyl o-methoxybenzoate was replaced with the same weight part of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane to give a catalyst component DCat-2 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 3
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
Preparing a catalyst component and carrying out liquid-phase bulk polymerization of propylene according to the method of comparative example 2, except that, in the preparation of the catalyst component, the 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was replaced with the same weight part of ethyl o-methoxybenzoate to obtain a catalyst component DCat-3 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 4
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 1, except that in the preparation of the catalyst component, the amounts of ethyl benzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added in an amount of 0.5mmol and 9mmol, respectively, to give a catalyst component DCat-4 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 5
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
A catalyst component was prepared and liquid-phase bulk polymerization of propylene was carried out in the same manner as in example 2, except that in the preparation of the catalyst component, ethyl o-methoxybenzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added in amounts of 7mmol and 9mmol, respectively, to give a catalyst component DCat-5 for olefin polymerization; the resulting propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.
Comparative example 6
This comparative example serves to illustrate a reference catalyst component for the polymerization of olefins and a process for its preparation and a catalyst for the polymerization of olefins and its use.
Liquid bulk polymerization of propylene was carried out in the same manner as in example 1, except that the catalyst component Cat-1 was replaced with the same parts by weight of a DQ catalyst component (hereinafter referred to as DCat-6, and the internal electron donor is diisobutyl phthalate) commercially available from Odada catalyst division, petrochemical, China, and the resulting propylene homopolymer was dried, weighed, and analyzed, and the results are shown in Table 1.
TABLE 1
As can be seen from the results of the examples and comparative examples in Table 1, when the internal electron donor contains both the monocarboxylic acid ester compound and the diether compound, and the molar ratio of the monocarboxylic acid ester compound to the diether compound in the catalyst component is 0.065-0.7: 1, in particular between 0.15 and 0.35: 1, the prepared polypropylene has a high melt index under a high isotactic index, namely, the polypropylene can have both a high isotactic index and a high melt flow index; the catalyst without the phthalate ester compound (plasticizer) has the characteristics of high stereospecificity and high hydrogen regulation sensitivity.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (16)
1. A catalyst component for the polymerization of olefins, the catalyst component comprising the reaction product of:
(1) a solid component containing a magnesium compound represented by formula I and an alkylene oxide compound represented by formula II, the content of the alkylene oxide compound represented by formula II being 0.01 to 0.8 mole per mole of the magnesium compound represented by formula I;
(2) at least one titanium compound; and
(3) an internal electron donor compound;
wherein R is1Is C1-C12Linear or branched alkyl of (a); r2And R3Are the same or different and are each independently hydrogen or C1-C5Wherein the hydrogen on the alkyl group is optionally substituted with halogen; x is halogen; m is 0.1-1.9, n is 0.1-1.9, and m + n is 2;
the internal electron donor compound comprises an internal electron donor compound a and an internal electron donor compound b, wherein the internal electron donor compound a is a monocarboxylic acid ester compound, and the internal electron donor compound b is a diether compound shown as a formula III; the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.065-0.7: 1;
the monocarboxylic acid ester compound is a monocarboxylic aromatic carboxylic acid ester and/or a monocarboxylic aliphatic carboxylic acid ester;
in the formula III, R1’、R2’、R3’、R4’、R5' and R6' same or different, each independently hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20One of substituted or unsubstituted alkaryl groups; or, R1’、R2’、R3’、R4’、R5' and R6' two or more of which are bonded to each other to form a ring;
R7' and R8' same or different, each independently C1-C20Straight or branched alkyl of (2), C3-C20Substituted or unsubstituted cycloalkyl of (A), C6-C20Substituted or unsubstituted aryl of (1), C7-C20Substituted or unsubstituted aralkyl and C7-C20Is one of substituted or unsubstituted alkaryl groups.
2. The catalyst component according to claim 1 in which the monoaliphatic carboxylic acid ester is a monoaliphatic ester formed from a monoaliphatic carboxylic acid having from 2 to 10 carbon atoms and a monohydric or polyhydric aliphatic alcohol having from 1 to 15 carbon atoms or an aromatic alcohol having from 6 to 15 carbon atoms;
the monobasic aromatic carboxylic ester is formed by monobasic aromatic carboxylic acid with 7-10 carbon atoms and monobasic or polybasic aliphatic alcohol with 1-15 carbon atoms or aromatic alcohol with 6-15 carbon atoms.
3. The catalyst component of claim 1 in which the internal electron donor compound b is a1, 3-diether compound of formula IV,
in the formula IV, R9' and R10' same or different, each independently hydrogen, halogen, C1-C18Straight or branched alkyl of (2), C3-C18Substituted or unsubstituted cycloalkyl of (A), C6-C18Substituted or unsubstituted aryl and C7-C18Substituted or unsubstituted aralkyl ofOr R is9' and R10' bonding to each other to form a ring; r11' and R12' same or different, each independently C1-C10Linear or branched alkyl.
4. The catalyst component of claim 1, wherein the molar ratio of the internal electron donor compound a to the internal electron donor compound b in the catalyst component is 0.15-0.35: 1.
5. the catalyst component according to any of claims 1 to 4 in which R is in the solid component1Is C1-C8Linear or branched alkyl of (a); r2And R3Are the same or different and are each independently hydrogen or C1-C3Wherein the hydrogen on the alkyl group is optionally substituted with halogen; x is chlorine; m is 0.5-1.5, n is 0.5-1.5, and m + n is 2.
6. The catalyst component according to any of claims 1 to 4 in which the amount of the alkylene oxide compound of formula II in the solid component is 0.02 to 0.5 mole, preferably 0.02 to 0.3 mole per mole of the magnesium compound of formula I.
7. The catalyst component according to any of claims 1 to 4 in which the amount of magnesium is from 2 to 15 parts by weight, preferably from 3 to 12 parts by weight, and more preferably from 4 to 10 parts by weight, per part by weight of titanium; the content of the internal electron donor is 2 to 10 parts by weight, preferably 3 to 8 parts by weight, and more preferably 4 to 7 parts by weight.
8. A process for the preparation of the catalyst component according to any one of claims 1 to 7, comprising the steps of:
(1) preparing a solid component, comprising:
(a) in a closed container, in at least one high fractionMagnesium halide MgX in the presence of a molecular dispersion stabilizer2And an organic alcohol R1Reacting the mixture of OH at 30-160 ℃ to form a magnesium halide alcoholate solution;
(b) reacting the magnesium halide alcoholate solution with an alkylene oxide compound shown as a formula II at 30-160 ℃ to generate a solid component;
wherein X is halogen, R1Is C1-C12Linear or branched alkyl of (a);
wherein R is2And R3Are the same or different and are each independently hydrogen or C1-C5Wherein the hydrogen on the alkyl group is optionally substituted with halogen;
wherein, the dosage of the organic alcohol is 3-30 mol and the dosage of the alkylene oxide compound shown in the formula II is 1-10 mol based on each mol of magnesium; the dosage of the macromolecular dispersion stabilizer is 0.1 to 10 weight percent of the total dosage of the magnesium halide and the organic alcohol;
(2) the solid component prepared in the step (1) is contacted with a titanium compound for reaction, and an internal electron donor is added in one or more time periods before, during and after the reaction, wherein the internal electron donor contains a monocarboxylic ester compound and a diether compound shown as a formula III.
9. The production method according to claim 8, wherein, in the step (1), the organic alcohol is used in an amount of 4 to 20 moles per mole of magnesium; the dosage of the alkylene oxide compound shown in the formula II is 2-6 mol; the amount of the polymeric dispersion stabilizer is 0.2 to 5% by weight of the total amount of the magnesium halide and the organic alcohol.
10. The production method according to claim 8 or 9, wherein the magnesium halide MgX2Wherein X is bromine, chlorine or iodine; organic alcohol R1In OH, R1Is C1-C8Linear or branched alkyl of (a); in the alkylene oxide compounds of the formula II, R2And R3Each independently is hydrogen or C1-C3Wherein the hydrogen on the alkyl group is optionally substituted with halogen.
11. The production method according to claim 8 or 9, wherein the weight average molecular weight of the polymer dispersion stabilizer is preferably more than 1000, more preferably more than 3000, and further preferably 6,000-;
the macromolecular dispersion stabilizer is selected from at least one of polyacrylate, styrene-maleic anhydride copolymer, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkyl phenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, 1-dodeca-4-vinylpyridine bromide polymer, polyvinyl benzyl trimethylamine salt, polyvinyl alcohol, polyacrylamide, ethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, polyethylene glycol, alkyl phenyl polyoxyethylene ether and polyalkylmethacrylate compound, and preferably at least one of polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer and polyethylene glycol.
12. The production method according to claim 8 or 9, wherein an inert dispersion medium selected from at least one of liquid aliphatic, aromatic hydrocarbons, cycloaliphatic hydrocarbons and silicone oils is not added in steps (a) and (b).
13. Use of the catalyst component according to any one of claims 1 to 12 for the preparation of a catalyst for the polymerization of olefins.
14. A catalyst for the polymerization of olefins, the catalyst comprising:
(1) the catalyst component of any one of claims 1 to 12;
(2) an alkyl aluminum compound; and
(3) optionally an external electron donor compound.
15. Use of the catalyst of claim 14 in olefin polymerization reactions.
16. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of claim 14 under olefin polymerization conditions.
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811224580.7A CN111072815A (en) | 2018-10-19 | 2018-10-19 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| EP19874270.2A EP3868796B1 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| PCT/CN2019/111252 WO2020078352A1 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| JP2021520594A JP7479361B2 (en) | 2018-10-19 | 2019-10-15 | Olefin polymerization catalyst components, catalysts and their applications |
| FIEP19874270.2T FI3868796T3 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| KR1020217015086A KR20210080466A (en) | 2018-10-19 | 2019-10-15 | Catalyst components for olefin polymerization, catalysts and uses thereof |
| SG11202103779QA SG11202103779QA (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| BR112021006289A BR112021006289A2 (en) | 2018-10-19 | 2019-10-15 | catalyst component and catalyst for olefin polymerization and application thereof |
| PT198742702T PT3868796T (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| US17/286,776 US11970510B2 (en) | 2018-10-19 | 2019-10-15 | Catalyst component and catalyst for olefin polymerization, and application thereof |
| TW108137362A TWI851609B (en) | 2018-10-19 | 2019-10-17 | Catalyst components for olefin polymerization, catalysts and their applications |
| SA521421681A SA521421681B1 (en) | 2018-10-19 | 2021-04-07 | Catalyst component and catalyst for olefin polymerization, and application thereof |
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|---|---|---|---|
| CN201811224580.7A CN111072815A (en) | 2018-10-19 | 2018-10-19 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
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