NL2021838B1 - Catalyst component, catalyst, and prepolymerization catalyst for olefin polymerization, and method for olefin polymerization - Google Patents
Catalyst component, catalyst, and prepolymerization catalyst for olefin polymerization, and method for olefin polymerization Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/00—Polymerisation catalysts
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Abstract
Provided are a catalyst component for olefin polymerization, a catalyst for olefin polymerization, a prepolymerization catalyst obtained by prepolymerization of the catalyst, and a method for olefin polymerization. The catalyst component for olefin polymerization includes magnesium, titanium, halogen, Lewis base compound A as shown in formula (I), and another Lewis base compound B, wherein a molar ratio of a total amount of compound A and compound B to magnesium is in a range of (0.03—O.20):1. When the catalyst is used in olefin polymerization, in particular propylene polymerization, the catalyst has a high activity.
Description
-1- CATALYST COMPONENT, CATALYST, AND PREPOLYMERIZATION CATALYST FOR OLEFIN POLYMERIZATION, AND METHOD FOR OLEFIN POLYMERIZATION CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the priority of Chinese patent application CN 201610846996.7, entitled “Catalyst component, catalyst, and prepolymerization catalyst for olefin polymerization, and method for olefin polymerization” and filed on October 19, 2017, the entirety of which is incorporated herein by reference.
FIELD OF THE DISCLOSURE The present disclosure relates to the technical field of olefin polymerization, and in particular, to a catalyst component for olefin polymerization, a catalyst for olefin polymerization, a prepolymerization catalyst obtained by prepolymerization of the catalyst, and a method for olefin polymerization.
BACKGROUND OF THE DISCLOSURE A Ziegler-Natter catalyst is generally composed of magnesium, titanium, halogen, and a Lewis base and so on. The Lewis base is an organic compound containing oxygen, nitrogen, phosphorus, silicon, and the like. Sometimes, in order to improve overall performance of a catalyst, two or more Lewis base compounds are added during preparation of the catalyst. For example, it is disclosed in Chinese patents 201310517877.3, 201310518069.9, 201310518086.2, and 201310518285.3 that overall performance of a catalyst can be improved by using malonate compounds together with other Lewis base compounds, but activity of the catalyst is not high enough, which is not beneficial for energy-saving and efficiency-increasing. It is disclosed in Chinese patents CN201510708748.1 and CN201510708579.1 that phthalic anhydride is introduced in the above system, and activity of a catalyst is improved. However, introduction of phthalic anhydride will result in that a final catalyst obtained comprises more or less a phthalate compound, and residue of the phthalate compound will eventually stay in a polymer. The phthalate compound is an environmental hormone, which will influence human health, such as fertility and development, and thus it is not desirable that the polymer comprises such a substance. Although research and development on the Ziegler-Natter catalyst have been carried out for -1-
-2- decades, how to further improve the function of the catalyst is still a pursuit in the field, especially how to achieve a balance among various properties of the catalyst. For example, how to avoid presence of a phthalate compound in the catalyst while maintaining high catalytic activity is pursued.
SUMMARY OF THE DISCLOSURE The present disclosure aims to provide a catalyst component, a catalyst, and a prepolymerization catalyst for olefin polymerization, and a method for olefin polymerization. When used for olefin polymerization, especially for propylene polymerization, the catalyst component or the catalyst provided herein has a high catalytic activity, and does not comprise a phthalate compound. According to a first aspect of the present disclosure, provided is a catalyst component for olefin polymerization, comprising magnesium, titanium, halogen, Lewis base compound A as shown in formula (1), and another Lewis base compound B, wherein a molar ratio of a total amount of compound A and compound B to magnesium is in a range of (0.03-0.20):1, °° Ra Re ; R, b (1) in formula (1), R. and R, may be identical to or different from each other, selected from substituted or unsubstituted C:-Ca9alkyl, substituted or unsubstituted C-C29 alkenyl, substituted or unsubstituted C3-Cy cycloalkyl, substituted or unsubstituted Cs-Cy aryl, substituted or unsubstituted CC alkaryl, substituted or unsubstituted C7-C29 aralkyl or substituted or unsubstituted C19-C2 polycyclic aromatic groups, preferably selected from substituted or unsubstituted linear or branched C,-Cyo alkyl, substituted or unsubstituted Cs-Cg cycloalkyl, substituted or unsubstituted Cs-Ci9 aryl, substituted or unsubstituted C7-C9 alkaryl, or substituted or unsubstituted C;-Cyg aralkyl, and further preferably selected from substituted or unsubstituted linear or branched C,-Cg alkyl; R. and Ry may be identical to or different from each other, selected from hydrogen, substituted or unsubstituted linear or branched Ci-Cy alkyl, substituted or unsubstituted C,-Cyo alkenyl, substituted or unsubstituted Cs-Cyp cycloalkyl, substituted or unsubstituted Cs-C29 aryl, substituted or unsubstituted C7-C20 alkarvi, 22
-3- substituted or unsubstituted C;-C‚0 aralkyl or substituted or unsubstituted Ci9-C29 polycyclic aromatic groups, preferably selected from substituted or unsubstituted linear or branched CC alkyl, substituted or unsubstituted C:-C:9 alkenyl, substituted or unsubstituted C:-C19 cycloalkyl, substituted or unsubstituted Cs-Cy aryl, substituted or unsubstituted C;-Cyy alkaryl, substituted or unsubstituted CC aralkyl or substituted or unsubstituted Ci9-C1s polycyclic aromatic groups, further preferably selected from substituted or unsubstituted linear or branched C,-Cs alkyl, substituted or unsubstituted C3-Cs alkenyl, substituted or unsubstituted Cs-Cs aryl or substituted or unsubstituted CC aralkyl, and most preferably linear or branched C,-Cq alkyl or C3-Cs alkenyl; and R and Ry may optionally be bonded together to form a ring.
After an entensive study, inventors of the present invention found that when the molar ratio of a total amount of compound A and compound B to magnesium in the catalyst component is controlled in a range of (0.03-0.20): 1, preferably in a range of (0.03-0.17): 1, and more preferably in a range of (0.04-0.14): 1, the catalytic activity thereof can be significantly improved. According to some embodiments, the molar ratio of a total amount of compound A and compound B to magnesium may be 0.03:1,0.04: 1, 0.05: 1, 0.06: 1, 0.07: 1, 0.08: 1, 0.09: 1, 0.10: 1, 0.11: 1, 0.12: 1, 0.13: 1, 0.14: 1,
0.15:1,0.16:1,0.17:1,0.18:1, 0.19: 1, or 0.20: 1 and so on.
Further, the inventors found that when a molar ratio of compound A to compound B is controlled in a specific range, the catalytic activity thereof can be significantly improved. According to a preferred embodiment of the present disclosure, in the catalyst component, the molar ratio of compound A to compound B is in a range of (0.21-2.0):1, preferably (0.3-1.6):1, further preferably (0.4-1.5):1, and most preferably {0.5-1.4}:1. According to some embodiments, the molar ratio of compound A to compound B may be 0.3:1,0.4:1,05:1,0.6:1,0.7:1,0.8:1,0.9:1,1.0: 1, 1.1: 1, 1.2: 1,1.3:1,1.4:1,15:1,1.6:1,1.7:1,1.8:1,0r 1.9: 1 and so on.
In the present disclosure, the term *C:-C29 alkyl” refers to linear alkyl of C4-Cy or branched alkyl of C:-C9, and includes, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
In the present disclosure, examples of C3-Cy cycloalkyl include, but not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
In the present disclosure, examples of Cs-C9 aryl include, but not limited to, phenyl, -3-
-4- 4-methylphenyl, 4-ethylphenyl, dimethyiphenyl, vinylphenyl.
In the present disclosure, the term “C:-C29 alkenyl” refers to linear alkenyl of C:-C0r branched alkenyl of C3-C29, and includes, but not limited to, vinyl, allyl, and butenyl.
In the present disclosure, examples of C;-Cy aralkyl include, but not limited to, phenylmethyi, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl and phenyl-tert-butyl.
In the present disclosure, examples of C;-C9 alkaryl include, but not limited to, tolyl, ethylphenyt, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl.
In the present disclosure, examples of C19-C29 polycyclic aromatic groups include, but not limited to, naphthyl, anthracenyl, phenanthryl, fluorenyl.
Specifically, the compound as shown in formula (1) is preferably selected from a group consisting of diethyl dipropyimalonate, dipropyl dipropylmalonate, diethyl diisobutylmalonate, diethyl di-n-butylmalonate, diethyl di-tert-butyimalonate, diethyl dibenzyimalonate, diethyl phenylethylmalonate, dipropyl diisobutylmalonate, dipropyl di-n-butylmalonate, dipropyl di-tert-butylmalonate, dibutyl diisobutylmalonate, dibutyl di-n-butylmalonate, dibutyl di-tert-butylmalonate, dipentyl diisobutylmalonate, dipentyl di-n-butylmalonate, dipentyl di-tert-butylmalonate, dihexyl diisobutylmalonate, dihexyl di-n-butylmalonate, dihexyl di-tert-butylmalonate, diheptyl diisobutylmalonate, diheptyl di-n-butylmalonate, diheptyl di-tert-butylmalonate, dipropyl diisoamylmalonate, dipropyl di-n-pentyimalonate, dipropyl dihexylmalonate, dipropyl phenylethylmalonate, dipropyl phenyimethylmalonate, dipropyl phenylpropylmalonate, dipropyl phenyl-n-butylmalonate, dipropyl phenylisobutylmalonate, dipropyl phenylisopentyimalonate, dipropyl phenyi-n-pentylmalonate, dipropyl diphenylmalonate, dipropyl benzylethyimalonate, dipropyl benzylmethylmalonate, dipropyl benzylpropylmalonate, dipropyl benzyl-n-butylmalonate, dipropyl benzylisobutylmalonate, dipropyl benzylisopentyimalonate, dipropyl benzyl-n-pentylmalonate, dipropyt dibenzylmalonate, dibutyl phenylethylmalonate, dibutyl phenylmethyimalonate, dibutyl phenylpropylmalonate, dibutyl phenyl-n-butylmalonate, dibutyl phenylisobutylmalonate, dibutyl phenylisopentylmalonate, dibutyl phenyl-n-pentylmalonate, dibutyl diphenylmalonate, dibutyl benzylethylmalonate, dibutyl benzylmethylmalonate, dibutyl benzylpropylmalonate, dibutyl benzyl n-butylmalonate, dibutyl benzylisobutylmalonate, dibutyl benzylisopentylmalonate, dibutyl benzyl-n-pentylmalonate, dibutyl dibenzylmalonate, dipentyl phenylethylmalonate, dipentyl phenylmethyimalonate, dipentyl phenylpropylmalonate, dipentyl -4-
-5.- phenyl-n-butylmalonate, dipentyl phenylisobutylmalonate, dipentyl phenylisopentylmalonate, dipentyl phenyi-n-pentylmalonate, dipentyl diphenylmalonate, dipentyl benzylethyimalonate, dipentyl benzylmethyimalonate, dipentyl benzylpropylmalonate, dipentyl benzyl-n-butylmalonate, dipentyl benzylisobutylmalonate, dipentyl benzylisopentylmalonate, dipentyl benzyl-n-pentylmalonate, dipentyl dibenzylmalonate, dicyclohexyl phenylethylmalonate, dicyclohexyl phenylmethyimalonate, dicyclohexyl phenylpropyimalonate, dicyclohexyl phenyl-n-butylmalonate, dicyclohexyl phenylisobutyimalonate, dicyclohexyl phenylisopentylmalonate, dicyclohexyl phenyl-n-pentyl malonate, dicyclohexyl diphenylmalonate, dicyclohexyl benzylethyimalonate, dicyclohexyl benzylmethylmalonate, dicyclohexyl benzylpropylmalonate, dicyclohexyl benzyl-n-butylmalonate, dicyclohexyl benzylisobutylmalonate, dicyclohexyl benzylisopentyimalonate, dicyclohexyl benzyl-n-pentylmalonate, dicyciohexyl dibenzylmalonate, diphenyl phenylmethyimalonate, diphenyl phenylpropyimalonate, diphenyl phenyin-butylmalonate, diphenyl phenylisobutylmalonate, diphenyl phenylisopentylmalonate, diphenyl phenyl-n-pentylmalonate, diphenyl diphenylmalonate, diphenyl benzylethylmalonate, diphenyl benzylmethyimalonate, diphenyl benzylpropylmalonate, diphenyl benzyl-n-butylmalonate, diphenyl benzylisobutylmalonate, diphenyl benzylisopentyl malonate, diphenyl benzyl-n-pentylmalonate, diphenyl dibenzylmalonate, dicyclohexyl fluorenylmethylmalonate, dicyclohexyl fluorenylpropylmalonate,dicyclohexyl fluorenyl-n-butylmalonate, dicyclohexyl fluorenylisobutyimalonate, dicyclohexyl fluorenylisopentylmalonate, dicyclohexyl fluorenyi-n-pentylmalonate, dicyclohexyl difluorenyl malonate, diphenyl allyimethyimalonate, diphenyl allyl propyimalonate, diphenyl allyl-n-butylmalonate, diphenyl allylisobutylmalonate, diphenyl allylisopentylmalonate,diphenyl allyl-n-pentylmalonate, diphenyl diallylmalonate, dimethyl allylmethylmalonate, dimethyl allylpropylmalonate, dimethyl allyl-n-butylmalonate, dimethyl allylisobutylmalonate, dimethyl allylisopentylmalonate, dimethyl allyl-n-pentylmalonate, dimethyl diallylmalonate, diethyl allylmethylmalonate, diethyl allylpropyimalonate, diethyl allyl-n-butylmalonate, diethyl allylisobutylmalonate, diethyl allylisopentylmalonate, diethyl allyl-n-pentylmalonate, diethyl diallylmalonate, dipropyl allylmethylmalonate, dipropyl allylpropylmalonate, dipropyl allyl-n-butylmalonate, dipropyl allylisobutyimalonate, dipropyl allylisopentylmalonate, dipropyl allyl-n-pentyimalonate, dipropyl diallylmalonate, dibutyl allylmethylmalonate, dibutyl allylpropylmalonate, dibutyl allyl-n-butylmalonate, dibutyl allylisobutylmalonate, dibutyl allylisopentylmalonate, dibutyl allyl-n-pentylmalonate, dibutyl diallyimalonate, dipentyl allylmethylmalonate, dipentyl allylpropylmalonate, dipentyl allyl-n-butylmalonate, dipentyl allylisobutylmalonate, dipentyl allylisopentylmalonate, dipentyl allyl-n-pentyimalonate, dipentyl diallylmalonate, dicyclohexyl allylmethylmalonate, dicyclohexyl allylpropylmalonate, dicyclohexyl allyl-n-butylmalonate, dicyclohexyl allylisobutylmalonate, dicyclohexyl allylisopentylmalonate, -5-
-6- dicyclohexyl allyln-pentylmalonate and dicyclohexyl diallylmalonate, further preferably selected from diethyl diisobutylmalonate, diethyl di-n-butyl-malonate, diethyl di-tert-butylmalonate, dipropyl diisobutylmalonate, dipropyl di-n-butylmalonate, dipropyl di-tert-butyimalonate, diethyl dibenzyimalonate, dipropyl dibenzylmalonate, diethyl phenylethyimalonate, dipropyl phenylethylmalonate, diethyl dipropyimalonate, dipropyl dipropylmalonate, diethyl diallylmalonate anddipropyl diallylmalonate. According to the present disclosure, the another Lewis base compound B refers to another Lewis base different from compound A.
According to an embodiment of the present disclosure, compound B is at least one of an ether compound, a monocarboxylic ester compound, and a dicarboxylic ester compound. Preferably, compound B is at least one of 1,3-diether compound, a polyol (polyphenol) ester compound, and a succinic acid ester compound.
Further preferably, compound B is at least one compound as shown in formula (li), ; 3 R~¢—O—M—0—C—R, (1) wherein Ry; and R; are identical to or different from each other, selected from substituted or unsubstituted C;-Cyg alkyl, substituted or unsubstituted C,-Cyo alkenyl, substituted or unsubstituted C3-Cyg cycloalkyl, substituted or unsubstituted Cs-C‚9 aryl, substituted or unsubstituted C;-C29 alkaryl, substituted or unsubstituted C;-C9 aralkyl or substituted or unsubstituted Cio-C29 polycyclic aromatic groups; and M is a divalent linking group, preferably selected from a group consisting of C1-C2 alkylene, C3-C;0 cycloalkylene, Cs-C9 arylene and a combination thereof. The alkylene, cycloalkylene, and/or arylene is optionally substituted with C;-Cyo alkyl, and the substituent is optionally bonded to from one ring or a plurality of rings. A carbon atom or/and a hydrogen atom in M is optionally substituted with nitrogen, oxygen, sulfur, silicon, phosphorus or a halogen atom. According to a preferred embodiment of the present disclosure, M is selected from at least one of the divalent groups as shown in formula (Hi), formula (IV), formula (V), formula (VI), and formula (Vi): Ru, R's oe i, R! R* D D CQ R'7 . _ _ R's Rs R2 RO “Ra “Ry “Rs -6-
-7- Formula (If) Formula (IV) Formula (V) Formula (VI) Formula (VII.
in formula (II), R’s-R’s are identical to or different from each other, selected from hydrogen, halogen, substituted or unsubstituted C:-Ca9 alkyl, substituted or unsubstituted C,-Cyp alkenyl, substituted or unsubstituted C;-Cyo cycloalkyl, substituted or unsubstituted Cs-C29 aryl, substituted or unsubstituted C;-Cyy alkaryl, substituted or unsubstituted C,-Cyo aralkyl, substituted or unsubstituted C10-Cyo polycyclic aromatic groups, or substituted or unsubstituted C;-C,q ester, and R'y and R's are optionally bonded to form a ring or a plurality of rings.
In formula (IV), R!-R° are identical to or different from each other, selected from substituted or unsubstituted C;-Cyg alkyl, substituted or unsubstituted C,-Cyo alkenyl, substituted or unsubstituted C3-Ca9 cycloalkyl, substituted or unsubstituted Cs-C29 aryl, substituted or unsubstituted C7-C29 alkarvi, substituted or unsubstituted C;-Cyg aralkyl, or substituted or unsubstituted C19-C29 polycyclic aromatic groups, and R™-R* are bonded to one ring or a plurality of rings.
In formula (V), formula (VI), and formula {VII}, Rs, Rs, and Rs are independently selected from hydrogen, halogen, substituted or unsubstituted C:-C9 alkyl, substituted or unsubstituted C:-C2 alkenyl, substituted or unsubstituted Cs-Co cycloalkyl, substituted or unsubstituted Cs-Co aryl, substituted or unsubstituted C+-C29 alkaryl, substituted or unsubstituted C;-Cyp aralkyl, or substituted or unsubstituted C19-C20 polycyclic aromatic groups.
in the present disclsure, the term “substituted or unsubstituted” means a hydrogen atom which is bonded to a carbon of the described group can be substituted by a group which is selected from a group consisting of C;-Cyp alkyl, C:-C:9 alkenyl, C:-C9 alkynyl, halogen, nitro group, cyano group, amino-Cy-Cypalkyl and other common substitute groups.
Specifically, the compound as shown in formula (II) is preferably selected from a group consisting of 2,4-pentanediol dibenzoate, 2,4-pentanediol di-n-propyl dibenzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-n-propyl dibenzoate, 4-ethyl3,5 heptanediol dibenzoate, 3,5-heptanediol di-p-methy! benzoate, 3,5-heptanediol di-o-methy! benzoate, 3,5-heptanediol di-p-chloro benzoate, 3,5-heptanediol di-o-chloro benzoate, 3,5-heptanediol di-p-methoxy! benzoate, 3,5-heptanediol di-o-methoxyl benzoate, 3,5-heptanediol di-m-methoxyl benzoate, 2-methyi-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol -7-
-8- dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyi-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyi-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di-(p-chlorobenzoic acid)ester, 6-methyl-2,4-heptanediol di-(p-methylbenzoic acid )ester, 6-methyi-2,4-heptanediol di(m-methylbenzoic acid)ester, 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyi-3,5-octanediol dibenzoate, 2-methyl-6-ethyi-3,5-octanediol dibenzoate, 5-methyl-4,6 nonanediol dibenzoate, 5-ethyl-4,6 nonanediol dibenzoate, 5-propyl-4,6 nonanediol dibenzoate, 5-butyl-4,6 nonanediol dibenzoate, 5,5-dimethyl-4,6 nonanediol dibenzoate, 5-methyl-4-ethyl-4,6 nonanediol dibenzoate, 5-phenyl-4,6 nonanediol dibenzoate, 4,6-nonanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate, dibenzoic acid-1,8-naphthylate, di-4-methyl benzoic acid-1,8-naphthylate, di-3-methyl benzoic acid-1,8-naphthylate, di-2-methyl benzoic acid-1,8-naphthylate, di-4-ethyl benzoic acid-1,8-naphthylate, di-4-n-propyl benzoic acid-1,8-naphthylate, di-4- isopropyl benzoic acid-1,8-naphthylate, di-4-n-butyl benzoic acid-1,8-naphthylate, di-4-isobutyl benzoic acid-1,8-naphthylate, di-4-tert-butyl benzoic acid-1,8-naphthylate, di-4-phenyl benzoic acid-1,8-naphthylate, di-4-fluorobenzoic acid-1,8-naphthylate, di-3-fluorobenzoic acid-1,8-naphthylate, and di-2-fluorobenzoic acid-1,8-naphthylate.
According to a preferred embodiment of the present disclosure, in the catalyst component, a content of magnesium measuring by magnesium element is 10-25wt%; a content of titanium measuring by titanium element is 1-7wt%; a content of compound A is 1-20wt%; and a content of compound B is 1-20wt%. According to a preferred embodiment of the present disclosure, when compound A is di-n-butyl diethyl malonate, and compound B is 2,4-pentanediol di-n-propyl benzoate, the molar ratio of compound A to compound B is (0.6-1.0}:1, and the molar ratio of a total amount of compound A and -8-
-9. compound B to magnesium is (0.1-0.14):1, the obtained catalyst has an extremely high catalytic activity. The catalyst component in the present disclosure can be prepared by a method comprising following steps of contacting a magnesium compound, a titanium compound, the compound as shown in formula (I}, and the compound as shown in formula (Il) with each other so as to obtain the catalyst component. In a specific embodiment of the present disclosure, the catalyst component is prepared by a method comprising following steps.
1) A magnesium compound is dissolved into a system comprising compound A, and a precipitation agent is added so as to precipitate solids.
2) The solids precipitated in step 1) are treated with a titanium compound, and compound B is added therein and/or before a process of treating the solids with the titanium compound.
In step 1), “A magnesium compound being dissolved into a system comprising compound A” comprises two circumstances: a magnesium compound is first dissolved into a solvent system to obtain a solution, and then compound A is added; and a magnesium compound is dissolved into a system made up of compound A and a solvent system together.
in the present disclosure, the magnesium compound may be selected from a group consisting of magnesium dihalide, alkoxy magnesium, alkyl magnesium, a hydrate or an alcohol adduct of magnesium dihalide, or a derivative formed by replacing a halogen atom of the magnesium dihalide with alkoxy or haloalkoxy; and preferably, the magnesium compound is selected from a group consisting of magnesium dihalide or alcohol adduct of magnesium dihalide, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcohol adduct thereof.
In the present disclosure, the titanium compound may be a titanium compound represented by formula TiX„(OR’}4n. in the formula, R' is C:-C‚o hydrocarbyl, X is halogen, and 1sm<4. The titanium compound is preferably selected from a group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxylate, titanium tetraethoxylate, titanium monochlorotriethoxylate, titanium dichlorodiethoxylate, or titanium trichloromonoethoxylate, and is further preferably titanium tetrachloride.
-9-
-10- In the present disclosure, the precipitation agent may be selected from metal halides, such as titanium halides, iron halides, or zinc halides; preferably, the precipitation agent is a titanium halide, such as a titanium tetrachloride or a titanium tetrabromide; and more preferably, the precipitation agent is a titanium tetrachloride.
A solid catalyst component of the present disclosure can be prepared according to a following method, but a method for preparing the catalyst component involved in the present disclosure is not limited to this.
First, a magnesium compound is dissolved into a solvent system consisting of an organic epoxide compound, an organic phosphorus compound, and an inert diluent so as to form a uniform solution. After that, in the presence of a coprecipitation agent having a special structure, i.e., in the presence of compound A as shown in formula (I), the uniform solution obtained is mixed with a precipitation agent (such as a titanium compound). Then, temperature is increased, and a solid precipitates. The solid is treated with an electron donor compound so that the electron donor compound is loaded on the solid. Then, the solid is treated with titanium tetrahalide or with titanium tetrahalide and the inert diluent.
The organic epoxide compound, the organic phosphorus compound, and the coprecipitation agent are disclosed in Chinese Patent CN85100997, and relevant content is hereby cited for reference.
Specifically, the magnesium compound can be dissolved a solvent system consisting of the organic epoxide compound and the organic phosphorus compound. The organic epoxide compound comprises at least one of aliphatic olefin with 2 to 8 carbon atoms, dialkene, halogenated aliphatic olefin, oxide of dialkene, glycidyl ethers and inner ethers. Specific compounds are as follows: ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene dioxide, epoxy chloropropane, methyl glycidyl ether, diglycidyl ether, and terahydrofuran.
The organic phosphorus compound is at least one selected from trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenylmethy! phosphate.
-10-
-11- In a specific embodiment, the solid catalyst component of the present disclosure is prepared according to a method disclosed in patent CN85100997. First, a magnesium compound is dissolved into a solvent system consisting of an organic epoxide compound, an organic phosphorus compound, and an inert diluent so as to form a uniform solution. After that, the uniform solution obtained is mixed with a titanium compound in the presence of a coprecipitation agent having a special structure, i.e, in the presence of compound A as shown in formula (I). At a temperature in a range of -40-50 °C, at best in a range of -35-0 °C, the titanium compound is dripped into the above magnesium halide solution. Then, temperature of reaction mixture is increased to a range of 60-80 °C, and an electron donor compound is added therein. A suspension liquid is stirred for 0-3 hours at this temperature, and then mother liquor is filtered off. After washing with an inert diluent is performed, a solid is obtained. Then, treating with a mixture of a titanium halide and an inert diluent at a temperature in a range of 60-130 °C is performed for 1 to 5 times. A solid obtained is washed with an inert diluent, and a solid catalyst is obtained after drying is performed. Measuring by magnesium per mole, a dosage of the organic epoxide compound is in a range of 0.2-10 mol; a dosage of the organic phosphorus compound is in a range of 0.1-3 mol; the compound as shown in formula {I} is in a range of 0.001-30 mol, preferably in a range of 0.05-15 mol; a dosage of the titanium compound is in a range of 3-40 mol, preferably in a range of 5-30 mol; and a dosage of the electron donor compound is in a range of
0.005-15 mol, preferably in a range of 0.05-5 mol.
According to a second aspect of the present disclosure, provided is a catalyst for olefin polymerization, comprising a reaction product of the following components.
a. the above catalyst component ; b. an alkylaluminium compound, which is preferably an alkylaluminium compound represented by formula AIR” Xs.,, wherein R” is hydrogen or hydrocarbyl of C;-Cy; X is halogen; and 0<ns3, the alkylaluminium compound can be specifically selected from a group consisting of triethylaluminium, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethyl aluminum chloride, ethylaluminum dichloride, and is preferably selected from triethylaluminium and triisobutylaluminum; -11-
-12- c. optionally, an external electron donor component, which is preferably an organosilicon compound represented by formula (R°>kSi(OR°)a1. In the formula, Osks3; R® is selected from halogen, hydrogen atom, linear or branched alkyt or haloalkyl, C:-C29 cycloalkyl, Cs-C29 aryl or amino; and R° is linear or branched alkyl or haloalkyl, C3-C9 cycloalkyl, Cs-Cyp aryl or amino.
The expression of “optionally, an external electron donor component” means that the external electron donor component can be selected or not as required. When an olefin polymer with high stereoregularity is needed, it is required to add the external electron donor. Specifically, the organosilicon compound includes, but not limited to, trimethylmethoxysilicane, trimethylethyoxyisilicane, dimethyldimethoxysilicane, dimethyldiethyoxylsilicane, diphenyl dimethoxysilicane, diphenyl diethyoxylsilicane, phenyl triethyoxylsilicane, phenyl trimethoxysilicane, and vinyltrimethoxysilicane, cyclohexylmethyldimethoxysilicane and methyltert-butyldimethoxysilicane, preferably selected from cyclohexyimethyldimethoxysilicane and diphenyl dimethoxysilicane.
in the above catalyst system, preferably, a molar ratio of component a and component b measuring by titanium to aluminum is in a range of 1: (5-1000), preferably 1: (25-100); and a molar ratio of component c and component a measuring by the external electron donor to titanium is (0-500}:1, preferably (25-100):1.
According to a third aspect of the present disclosure, provided is a prepolymerization catalyst for olefin polymerization, comprising a prepolymer obtained by prepolymerization of the above catalyst component and/or the above catalyst with olefin. Multiple of the prepolymerization is 0.1-1000 g olefin prepolymer/g catalyst component, and preferably multiple of the prepolymerization is 0.2-500 g prepolymer/g solid catalyst component.
A process of the prepolymerization can be performed at a temperature in a range of -20-80 °C, preferably in a range of 0-50 °C, in gas phase or liquid phase. Steps of the prepolymerization as a part of a process of continuous polymerization can be performed on line, and also can be separately performed in batches.
-12-
-13- According to a fourth aspect of the present disclosure, provided is a method for olefin polymerization, performed in the presence of at least one of the above catalyst component, the above catalyst, and the above prepolymerization catalyst. Preferably, olefin is represented by formula CH,=CHR’. In the formula, R’”’ is hydrogen, C;-Cy; alkyl or Cs-C; aryl. The olefin includes, but not limited to, ethylene, propylene, 1-butylene, 4-methyl-1-amylene, and 1-hexene, and more preferably olefin is ethylene or propylene. The method for olefin polymerization is especially suitable for homopolymerization of propylene or for copolymerization of propylene and other olefin.
The catalyst of the present disclosure can be directly added into a reactor to be used in a polymerization process; or the catalyst can be subjected to prepolymerization so as to obtain a prepolymerization catalyst, in the presence of which subsequent polymerization of olefin can be performed.
The olefin polymerization in the present disclosure can be carried out, according to the known technique, in a liquid phase or a gas phase, or in a stage combination thereof. Common techniques such as a slurry polymerization process and a gas phase fluidized bed process can be used. It is better to use the following reaction conditions: a polymerization temperature is in a range of 0-150°C, preferably in a range of 60-90°C; and a polymerization pressure is in a range of 0.01-10 MPa.
According to the present disclosure, in a process of preparing the catalyst component, when compound A as shown in formula (I} and another Lewis base compound B, in particular a diol ester compound, are added, an obtained catalyst has good fluidity, good particle morphology, uniform particle size distribution and excellent comprehensive performance. When the catalyst is used in olefin polymerization, in particular propylene polymerization, the catalyst has high activity, and an obtained polymer does not contain a phthalate compound.
Other features and advantages of the present disclosure will be further explained in the subsequent detailed description of the embodiments.
-13-
-14-
DETAILED DESCRIPTION OF THE EMBODIMENTS Preferred embodiments will be explained in details in the following description. Although preferred embodiments of the present disclosure are described in the following description, it should be understand that the present disclosure can be implemented in various manners and should not be limited to embodiments elaborated herein. Measuring Method Measurement of xylene soluble substance (XS): Xylene soluble substance is measured according to GB/T24282-2009 standard. Measurement of a content of Lewis base compounds (including compound A and compound B) is as follows. A content of Lewis base compounds in the catalyst is measured by using a waters 600E high performance liquid chromatograph. First, a pretreatment is performed to a sample using an ethyl acetate - dilute hydrochloric acid solution system so as to extract the Lewis base compounds. High performance liquid chromatograph is used to separate the Lewis base compounds and measure a peak area thereof, and an external standard curve is used for correction. Calculation is performed so as to obtain a percentage content of the Lewis base compounds in the sample.
Propylene Polymerization
32.5 mmol of AlEt; and 0.01 mmol of methyl cyclohexyl dimethoxy silicane (CHMMS) were placed into a stainless reactor having a volume of 5 L and replaced sufficiently with propylene gas, and then 10 mg of solid catalyst component prepared according to the following examples and comparative examples and 1.2 L of hydrogen gas were added. Into the resulting mixture was introduced 2.3 L of liquid propylene. The resulting mixture was heated to 70°C and maintained at 70°C for 1 hour. Then, cooling and pressure releasing were performed, so that a PP powder could be obtained. See Table 1 for specific data.
Examples 1-10 and Comparative Examples 1-4 Preparation of Catalyst Component
5.0 g of magnesium chloride, 98 mL of methylbenzene, 4.2 mL of epoxy chloropropane, and 13.0 -14-
-15- mb of tributyl phosphate (TBP} were placed one by one into a reactor replaced sufficiently with high-purity nitrogen.
Under stirring, the resulting mixture was heated to 50°C and kept at this temperature for 2.5 hours.
After a complete dissolution of the solid, a certain amount of compound A was added to the obtained solution.
The solution was kept for 1 hour.
Then, the solution was cooled to a temperature below -25°C. 47 mL of TiCl, was added dropwise to the solution within 1 hour, and the solution was slowly heated to 80°C to precipitate the solid.
Then, a certain amount of compound B was added to the solid.
The obtained mixture was kept for 1 hour at 80°C.
Then, the obtained mixture was filtered, and after that the obtained mixture was washed twice using 70 mL of methylbenzene respectively to obtain solid precipitate.
A solution of 40 mL TiCl,/60mL methylbenzene was added to the solid precipitate.The obtained mixture was heated to 110°C, maintained for 1 hour, and filtered; and same operations were repeated for three times.
Then the obtained mixture was washed twice with hexane at 70°C, and washed twice with hexane at room temperature, respectively, so as to obtain a (solid) catalyst component.
See Table 1 for specific components and dosage of compound A and compound B.
Table 1 Number Compound A Compound B Activity | XS A/B (A+B}/Mg KgPP/gcat/ | % | mol/mol | mol/mol hr Example 1 diethyl 2,4-pentanediol 92.3 1.5 0.13 di-n-butylmalonate | di-n-propyl benzoate Example 2 diethyl di-n-butyl 2,4-pentanediol 80.3 2.3 0.5 0.08 malonate dibenzoate Example3 diethyl di-n-butyl 3,5-heptanediol 74.7 2.5 1.4 0.20 malonate dibenzoate Example4 diethyl diallyl 3,5-heptanediol 79.0 1.9 0.14 malonate dibenzoate Examples diethyl diisobutyl 3,5-heptanediol me fis ae | ow -15-
-16- Example6 diethyl 3,5-heptanediol 2.8 0.4 0.05 di-n-butylmalonate dibenzoate Example? diethyl 3,5-heptanediol 70.5 2.9 1.0 0.05 diisobutylmalonate dibenzoate Example 8 diethyl diisobutyl 3,5-heptanediol 68.7 2.3 1.0 0.14 malonate dibenzoate Example 9 diethyl diisobutyl 3,5-heptanediol 67.8 2.5 0.5 malonate dibenzoate Example 10 | diethyl di-n-butyl | 4-ethyl-3,5-heptane 65.1 2.7 0.7 0.10 malonate diol dibenzoate Comparative diethyl 3,5-heptanediol 39.2 2.0 1.0 0.28 Example 1 | diisobutylmalonate dibenzoate Comparative diethyl 3,5-heptanediol 35.4 3.5 1.0 0.02 Example 2 | diisobutyimalonate dibenzoate Comparative diethyl 3,5-heptanediol 53.7 2.7 0.05 Example 3 | diisobutyimalonate dibenzoate Comparative diethyl 3,5-heptanediol 38.2 2.9 0.3 0.015 Example 4 | diisobutylmalonate dibenzoate Comparative diethyl 3,5-heptanediol 32.1 2.6 2.3 0.21 Example 5 | diisobutylmalonate dibenzoate In Table 1, A/B represents a molar ratio of compound A to compound B, and (A+B)/Mg -16-
217 - represents a molar ratio of a total amount of compound A and compound B to magnesium. It can be seen from data in Table 1 that a catalyst having high activity is obtained by controling the molar ratio of the total content of the malonate compound and another internal electron donor compound to magnesium in the catalyst component in the specific range, a catalyst having a higher activity can be obtained. Furthermore, by controling the molar ratio of the malonate compound to the another internal electron donor compound in the catalyst component in the specific range, the activity of the catalyst can be improved also. In addition, the ploymer obtained by using the catalyst component or the according to catalyst does not contain a phthalate compound.
it should be noted that the embodiments above are provided only for illustrating the present disclosure, rather than restricting the present disclosure. Amendments can be made to the present disclosure based on the disclosure of the claims and within the scope and spirit of the present disclosure. While the above descriptions about the present disclosure involve particular methods, materials, and implementing examples, it does not means that the present disclosure is limited to the presently disclosed examples. On the contrary, the present disclosure can be extended to other methods and applications having same functions as those of the present disclosure. -17-
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| CN1006071B (en) | 1985-04-01 | 1989-12-13 | 中国石油化工总公司 | Catalyst system for olefin polymerization and copolymerization |
| US8211819B2 (en) * | 2009-12-21 | 2012-07-03 | Basf Corporation | Internal and external donor compounds for olefin polymerization catalysts |
| US20130131290A1 (en) * | 2010-08-05 | 2013-05-23 | Basell Poliolefine Italia, s.r.l. | Catalyst components for the polymerization of olefins |
| WO2014132806A1 (en) * | 2013-02-27 | 2014-09-04 | 東邦チタニウム株式会社 | Production method for solid catalyst component for polymerizing olefins, catalyst for polymerizing olefins, and production method for polymerized olefins |
| KR102060850B1 (en) * | 2013-02-27 | 2020-02-11 | 도호 티타늄 가부시키가이샤 | Production method for solid catalyst component for polymerizing olefins, catalyst for polymerizing olefins, and production method for polymerized olefins |
| TWI639626B (en) * | 2013-09-30 | 2018-11-01 | 中國石油化工科技開發有限公司 | Catalyst composition for olefin polymerization and application thereof |
| CN104558293B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst |
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