CN112661883B - Solid catalyst component for preparing polyolefin, catalyst system and application thereof - Google Patents
Solid catalyst component for preparing polyolefin, catalyst system and application thereof Download PDFInfo
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Abstract
The invention provides a solid catalyst component for preparing polyolefin, which comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a first internal electron donor compound and a second internal electron donor compound, the first internal electron donor compound is cis-4-cyclohexene-1, 2-diformyl ester compound shown in a formula (I), and the second internal electron donor compound is a diester compound shown in a formula (II). The solid catalyst component provided by the invention is used in different Z-N catalyst systems, and the hydrogen regulation sensitivity is improved.
Description
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a solid catalyst component for preparing polyolefin, a catalyst system and application thereof.
Background
With magnesium, titanium, halogenAnd an internal electron donor as an essential component, i.e., a Ziegler-Natta (Z-N) catalyst known in the art, can be used for CH 2 = CHR olefin polymerization polymer with higher yield and higher stereoregularity can be obtained especially in alpha-olefin polymerization having 3 or more carbon atoms. In recent years, the development of fifth generation Ziegler-Natta catalysts, i.e., non-phthalate Z-N catalysts, has been a hotspot in the polypropylene industry and academia. The fifth generation catalyst uses a novel non-phthalate internal electron donor as a main sign. Compared with the phthalate internal electron donor used in the traditional fourth-generation Z-N catalyst, the fifth-generation catalyst not only avoids the use of phthalate (plasticizer), but also can endow the catalyst and resin with unique performances. However, most of the existing non-plasticizer propylene polymerization catalysts are suitable for producing polypropylene grades with special properties such as narrow or wide molecular weight distribution, insensitive hydrogen regulation and the like.
The internal electron donor plays a role in the development of the polypropylene catalyst, and different internal electron donors can endow the catalyst with different properties, for example, succinate internal electron donors can bring wide molecular weight distribution and high weight average molecular weight to the polymer; the 1, 3-diol ester internal electron donor has the characteristic of high activity, and the molecular weight distribution of the obtained polymer is wide; when the existing diesters such as 2,2' -dialkyl diethyl malonate compounds are used as internal electron donors for olefin polymerization, the hydrogen regulation sensitivity is not high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a Z-N catalyst, which uses two compounds with specific structures of cis-4-cyclohexene-1, 2-diformate compound and diester compound shown in a formula (II) as an internal electron donor, and when the catalyst is used for olefin polymerization, the hydrogen regulation sensitivity is improved compared with that when only the internal electron donor of the diester compound is used.
In a first aspect, the present invention provides a solid catalyst component for the preparation of polyolefins, comprising magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a first internal electron donor compound and a second internal electron donor compound,
the first internal electron donor compound is cis-4-cyclohexene-1, 2-diformate compound shown in formula (I), the second internal electron donor compound is diester compound shown in formula (II),
in the formula (I), R 1 And R 2 Are the same or different and are each independently selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl or cycloalkyl, C 6 -C 20 Aryl radical, C 7 -C 20 Alkylaryl and C 7 -C 20 Aralkyl, any of said alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups being optionally substituted by one or more substituents selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino and bis-C 1 -C 10 An alkylamino group; or R 1 And R 2 Can be connected into a ring in any mode; r a 、R b 、R c 、R d 、R e And R f The same or different, each independently selected from hydrogen and C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy and halogen;
in the formula (II), R 3 And R 4 The same or different, each independently selected from hydrogen and C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl or cycloalkyl, C 6 -C 20 Aryl radical, C 7 -C 20 Alkylaryl and C 7 -C 20 Aralkyl, any of said alkyl, cycloalkyl, aryl, alkaryl and aralkyl groups being optionally substituted by one or more substituents selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino and bis-C 1 -C 10 Alkylamino, the carbon atoms of the backbone optionally being substituted with heteroatoms; or R 3 And R 4 May be linked to form a ring in any manner, and may contain a double bond or a hetero atom in the resulting ring skeleton; r is 5 And R 6 Are the same or different and are each independently selected from C 1 -C 10 Alkyl radical, C 6 -C 15 Aryl and C 7 -C 15 An alkaryl group.
According to a preferred embodiment of the invention, in formula (I), R 1 And R 2 Identical or different, R 1 And R 2 Each independently selected from C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl or cycloalkyl, C 6 -C 10 And (3) an aryl group.
According to a preferred embodiment of the invention, in formula (I), R 1 And R 2 Is selected from C 1 -C 6 Straight-chain or branched alkyl, in particular selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, cyclopentyl and phenyl.
According to some embodiments of the invention, the cis-4-cyclohexene-1, 2-dicarboxylate is selected from at least one of cis-4-cyclohexene-1, 2-dicarboxylic acid methyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid ethyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid n-propyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid isopropyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid n-butyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid isobutyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid n-pentyl ester, and cis-4-cyclohexene-1, 2-dicarboxylic acid isoamyl ester.
According to a preferred embodiment of the present invention, said cis-4-cyclohexene-1, 2-dicarboxylate is selected from at least one of cis-4-cyclohexene-1, 2-dicarboxylate, cis-4-cyclohexene-1, 2-dicarboxylate n-propyl ester, cis-4-cyclohexene-1, 2-dicarboxylate n-butyl ester and cis-4-cyclohexene-1, 2-dicarboxylate.
According to a preferred embodiment of the present invention, said cis-4-cyclohexene-1, 2-dicarboxylate is selected from at least one of cis-4-cyclohexene-1, 2-dicarboxylate, n-propyl cis-4-cyclohexene-1, 2-dicarboxylate, isopropyl cis-4-cyclohexene-1, 2-dicarboxylate, n-butyl cis-4-cyclohexene-1, 2-dicarboxylate and isobutyl cis-4-cyclohexene-1, 2-dicarboxylate.
According to some embodiments of the invention, in formula (II), R 3 And R 4 Is selected from C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl or cycloalkyl, C 6 -C 10 And (3) an aryl group.
According to a preferred embodiment of the invention, in formula (II), R 3 And R 4 Is selected from C 1 -C 6 Straight-chain or branched alkyl, in particular selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl and phenyl.
According to a preferred embodiment of the invention, in formula (II), R 5 And R 6 Is selected from C 1 -C 6 Alkyl, preferably selected from methyl, ethyl and isopropyl.
According to some embodiments of the invention, the diester-based compound is selected from at least one of diethyl 2,2 '-dimethylmalonate, diethyl 2,2' -diethylmalonate, diethyl 2,2 '-di-n-propylmalonate, diethyl 2,2' -diisopropylmalonate, diethyl 2,2 '-diallylmalonate, diethyl 2,2' -di-n-butylmalonate, diethyl 2,2 '-diisobutyl malonate, diethyl 2,2' -di-n-pentylmalonate, diethyl 2,2 '-diisopentylmalonate, diethyl 2,2' -dicyclopentylmalonate, diethyl 2,2 '-diphenylmalonate, diethyl 2,2' -dipropylmalonate, diethyl 2,2 '-ethylphenyl-2' -malonate and diethyl 2-benzylmalonate.
According to a preferred embodiment of the present invention, the diester-based compound is at least one selected from the group consisting of diethyl 2,2' -diethylmalonate, diethyl 2,2' -di-n-propylmalonate, diethyl 2,2' -diisopropylmalonate, diethyl 2,2' -diallylmalonate, diethyl 2,2' -di-n-butylmalonate, diethyl 2,2' -di-isobutylmalonate, diethyl 2,2' -di-n-pentylmalonate, diethyl 2,2' -diisopentylmalonate, diethyl 2,2' -diphenylmalonate, diethyl 2,2' -dibenzylmalonate, diethyl 2-ethyl-2 ' -phenylmalonate and diethyl 2-benzylmalonate.
According to some embodiments of the invention, the diester-based compound is selected from at least one of diethyl 2,2' -di-n-propylmalonate, diethyl 2,2' -diallylmalonate, diethyl 2,2' -di-n-butylmalonate, diethyl 2,2' -di-isobutylmalonate, diethyl 2-ethyl-2 ' -phenylmalonate and diethyl 2-benzylmalonate.
According to some embodiments of the present invention, the molar ratio of the first internal electron donor compound and the second internal electron donor compound is from 0.1.
According to some embodiments of the present invention, the titanium atom is present in an amount of 1.0 to 8.0wt%, preferably 1.6 to 6.0wt%, based on the total amount of the catalyst components; the content of magnesium atoms is 10 to 70wt%, preferably 15 to 40wt%; the content of halogen atoms is 20 to 90wt%, preferably 30 to 85 wt%; the total internal electron donor compound content is 2-30wt%, preferably 3-20wt%.
The preparation method of the solid catalyst component can be that a magnesium compound, a titanium compound and an internal electron donor are contacted and reacted under certain conditions. The amounts of the titanium compound, the magnesium compound and the internal electron donor used for preparing the solid catalyst component are not particularly limited and may be those conventional in the art, respectively.
According to a preferred embodiment of the present invention, the magnesium compound may be at least one of a magnesium compound represented by formula (III), a hydrate of the magnesium compound represented by formula (III), and an alcohol adduct of the magnesium compound represented by formula (III),
MgR 7 R 8 (III)
in the formula (III), R 7 And R 8 Each independently selected from at least one of halogen, a linear or branched alkoxy group having 1 to 5 carbon atoms and a linear or branched alkyl group having 1 to 5 carbon atoms, preferably, R 7 And R 8 Each selected from halogens, for example at least one selected from chlorine, bromine and iodine.
In the solid catalyst component of the present invention, the hydrate of the magnesium compound represented by the formula (III) is MgR 5 R 6 ·qH 2 O, wherein q is in the range of 0.1 to 6, preferably 2 to 3.5; the alcohol adduct refers to MgR 5 R 6 ·pR 0 OH, wherein R 0 Is a hydrocarbon group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, more preferably at least one of a methyl group, an ethyl group, an n-propyl group and an isopropyl group; p is in the range of 0.1 to 6, preferably 2 to 3.5.
According to a preferred embodiment of the present invention, the magnesium compound is selected from at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentyloxymagnesium, dihexomagnesium, di (2-methyl) hexyloxymagnesium, methoxymethylmagnesium chloride, methoxymethylmagnesium bromide, methoxymethylmagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymasium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dichloride, an alcohol adduct of magnesium dibromide, and an alcohol adduct of magnesium diiodide. Most preferably, the magnesium compound is diethoxymagnesium or magnesium dichloride.
The solid catalyst component according to the invention in which the titanium compound is a compound of formula (IV),
TiX m (OR 9 ) 4-m (IV)
in formula (IV), X is a halogen, for example selected from chlorine, bromine and iodine; r 9 Is a hydrocarbon group with 1-20 carbon atoms, preferably an alkyl group with 1-5 carbon atoms; m isAn integer from 0 to 4, for example m may be 0, 1,2, 3 or 4.
According to a preferred embodiment of the present invention, the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxyxide, titanium dichlorodiethoxytitanium and titanium trichloromonoethoxyxide. Most preferably, the titanium compound is titanium tetrachloride.
In the present invention, the method of preparing the olefin polymerization solid catalyst component of the present invention by reacting a titanium compound, a magnesium compound and an internal electron donor may be performed by a method of preparing an olefin catalyst component, which is conventional in the art. The solid catalyst component of the present invention can be prepared, for example, by the following method.
Method one, the catalyst component was prepared according to the following procedure with reference to the method of CN 102453150B. (1) Contacting a magnesium alkoxide or magnesium alkoxide halide compound with a titanium compound and an internal electron donor compound in the presence of an inert diluent; (2) Washing the solid obtained in the step (1) with an inert solvent to obtain a solid catalyst component.
The magnesium alkoxide compound used in the first process may be selected from one or a mixture of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, diisobutyoxy magnesium, dipentyoxy magnesium, dihexyl magnesium, di (2-methyl) hexyl magnesium, preferably diethoxy magnesium or a mixture of diethoxy magnesium and other alkoxy magnesium. The alkoxy magnesium compound can be prepared by a method known in the art, such as the preparation of metallic magnesium and fatty alcohol in the presence of a small amount of iodine.
The alkoxy magnesium halide compound used in the first process may be selected from at least one of methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride and butoxy magnesium chloride, preferably ethoxy magnesium chloride. The alkoxy magnesium halide compound can be prepared by a method well known in the art, such as preparing magnesium ethoxy chloride by mixing grignard reagent butyl magnesium chloride with tetraethoxy titanium and tetraethoxy silicon.
In step (1) of method one, the inert diluent is selected from C 6 -C 10 At least one of an alkane or an arene. Specific examples of the inert diluent may employ one or a mixture of hexane, heptane, octane, decane, benzene, toluene, xylene, and preferably toluene. The order of contacting is not particularly limited, and for example, the components may be contacted in the presence of an inert diluent, or the components may be diluted with an inert solvent and then contacted. The number of times of contact is not particularly limited, and may be once or more.
In step (2) of the first process, the inert solvent washing is selected from hydrocarbon compounds, for example, one selected from hexane, heptane, octane, decane, benzene, toluene, xylene or a mixture thereof, preferably hexane.
In the step (2) of the first process, the washing method is not particularly limited, but a method such as decantation or filtration is preferable. The amount of the inert solvent to be used, the washing time and the number of washing times are not particularly limited, and the amount of the inert solvent to be used is usually 1 to 1000 mol, preferably 10 to 500 mol, based on 1 mol of the magnesium compound, and the washing time is usually 1 to 24 hours, preferably 10 to 6 hours. In addition, from the viewpoint of washing uniformity and washing efficiency, it is preferable to carry out stirring during the washing operation. It should be noted that the obtained solid catalyst component may be stored in a dry state or in an inert solvent.
The amount of each component used in the first process is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the internal electron donor compound is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.
The contact temperature of the components in the first method is usually-40-200 ℃, and preferably-20-150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.
Secondly, referring to the method of patent CN85100997, the magnesium dihalide is dissolved in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, and then the uniform solution is mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation assistant; then the solid is contacted with an internal electron donor to be carried and attached on the solid to obtain the solid catalyst component.
The precipitation assistant used in the second method may be at least one of an organic acid anhydride, an organic acid, an ether, and a ketone. Specific examples of the organic acid anhydride may be at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, and the like, specific examples of the organic acid may be at least one of acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, and the like, specific examples of the ether may be at least one of methyl ether, ethyl ether, propyl ether, butyl ether, and pentyl ether, and the ketone may be at least one of acetone, methyl ethyl ketone, and benzophenone.
The organic epoxy compound used in the second method may be at least one selected from ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and the like, and epichlorohydrin is preferred.
The organophosphorus compound used in the second process may be a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid or phosphorous acid, and specific examples of the organophosphorus compound include: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, or the like, with tributyl orthophosphate being preferred.
The inert diluent used in the second method may employ at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.
The amount of each component used in the second method is 0.2 to 10 moles, preferably 0.5 to 4 moles, of the organic epoxy compound per mole of the magnesium halide; 0.1 to 3 moles, preferably 0.3 to 1.5 moles of an organophosphorus compound; the titanium compound may be in the range of 0.5 to 20 moles, preferably 5 to 15 moles; the precipitation-assisting component may be 0.01 to 0.3 mol, preferably 0.02 to 0.08 mol; the total amount of the electron donor compound may be 0 to 10 moles, preferably 0.02 to 0.3 moles.
According to the third method, the catalyst component is prepared by the method of CN1091748, the magnesium chloride alcoholate melt is stirred and dispersed at a high speed in a dispersion system of white oil and silicone oil to form emulsion, and the emulsion is unloaded into cooling liquid to be cooled and shaped at a short time to form the magnesium chloride alcoholate microspheres. The cooling liquid is inert hydrocarbon solvent with low boiling point, such as petroleum ether, pentane, hexane, heptane, etc. The obtained magnesium chloride alcoholate microspheres are washed and dried to form spherical carriers, and the molar ratio of alcohol to magnesium chloride is 2-3, preferably 2-2.5. The particle size of the carrier is 10-300 microns, preferably 30-150 microns.
Treating the spherical carrier with excessive titanium tetrachloride at low temperature, gradually heating, adding electron donor during the treatment, washing with inert solvent for several times, and drying to obtain solid powdered spherical catalyst. The molar ratio of titanium tetrachloride to magnesium chloride is 20 to 200, preferably 30 to 60; the initial treatment temperature is-30-0 ℃, preferably-25-20 ℃; the final treatment temperature is 80-136 deg.C, preferably 100-130 deg.C.
The spherical catalyst obtained has the following characteristics: 1.5-3.5% of titanium, 6.0-20.0% of ester, 52-60% of chlorine, 10-20% of magnesium and 1-6% of inert solvent.
The method four comprises the following steps: the catalyst component was prepared with reference to the method disclosed in CN 1506384. Firstly, mixing a magnesium compound and an organic alcohol compound with an inert solvent according to a molar ratio of 2-5, heating to 120-150 ℃ to form a uniform solution, and selectively adding phthalic anhydride used as a precipitation aid, a silicon-containing compound or other assistants which are beneficial to obtaining good particles; then, according to the molar ratio of titanium to magnesium of 20-50, an alcohol compound and a titanium compound are contacted and reacted for 2-10h, the reaction temperature is-15 ℃ to-40 ℃, and the temperature is raised to 90-110 ℃ in the presence of a precipitation aid; adding an internal electron donor compound according to the molar ratio of magnesium/ester of 2-10, reacting for 1-3 hours at 100-130 ℃, and filtering to separate solid particles; then (optionally repeating for 2-3 times) contacting and reacting the solid particles with a titanium compound at a titanium/magnesium molar ratio of 20-50 at 100-130 ℃ for 1.5-3 hours, and filtering to separate out the solid particles; finally washing the solid particles by using an inert solvent at the temperature of 50-80 ℃, and drying to obtain the catalyst component.
In any of the above four methods for preparing the solid catalyst component of the present invention, the first internal electron donor and the second internal electron donor may be used alone or in combination.
In any of the above four methods for preparing the olefin polymerization catalyst component of the present invention, the internal electron donor can also be added before or during the contact between the magnesium compound and the titanium compound, for example, in the first method, the internal electron donor is added to the suspension of the magnesium alkoxide or magnesium alkoxide halide in the inert diluent, and then mixed with the titanium compound to prepare the olefin polymerization catalyst; in the second method, the internal electron donor is added into the magnesium halide solution before the magnesium halide solution contacts with the titanide.
In the preparation of the above-mentioned olefin polymerization catalyst component, the molar ratio of the sum of the amounts of the internal electron donor compounds represented by the formula (I) and the formula (II) as internal electron donors to magnesium atoms may be usually 0.01 to 3, preferably 0.02 to 0.3.
In the catalyst component provided by the invention, based on the total amount of the catalyst component, the catalyst component preferably contains 1-3.5wt% of titanium, 10-20wt% of magnesium, 50-70wt% of chlorine and 6-20wt% of an internal electron donor compound, and more preferably contains 1.8-3.2wt% of titanium, 15-20wt% of magnesium, 52-60wt% of chlorine and 7-11wt% of an internal electron donor compound.
In a second aspect, the present invention provides a catalyst system for the polymerization of olefins comprising the reaction product of:
1) The solid catalyst component according to the first aspect,
2) An alkyl-aluminium compound, which is a mixture of,
3) Optionally, an external electron donor compound.
The amount of the aluminum alkyl compound used in the catalyst system according to the invention may be the amount conventionally used in the art. Preferably, the alkyl aluminium compound is calculated as aluminium, the catalyst component is calculated as titanium, the molar ratio of the alkyl aluminium compound to the catalyst component is between 5 and 5000:1, preferably 20 to 1000:1, more preferably 50 to 500:1.
in the present invention, the aluminum alkyl compound may be any of various aluminum alkyl compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst for a Ziegler-Natta type catalyst. Preferably, the alkyl aluminum compound may be a compound represented by formula (V),
AlR' n 'X' 3-n ' (V)，
in the formula (V), R' is selected from hydrogen and C 1 -C 20 Alkyl or C 6 -C 20 X 'is halogen and n' is an integer of 1 to 3. Preferably, specific examples of the alkyl aluminum compound may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride.
According to the catalyst system of the present invention, the kind and content of the external electron donor compound are not particularly limited. Preferably, the molar ratio of the alkylaluminum compound to the external electron donor compound, expressed as aluminum, is from 0.1 to 500, preferably from 1 to 300, more preferably from 3 to 100.
According to the catalyst system of the present invention, the external electron donor compound may be any of various external electron donor compounds commonly used in the field of olefin polymerization, which can be used as a co-catalyst of a ziegler-natta type catalyst. Preferably, the external electron donor compound may be an organosilicon compound represented by formula (VI),
R 1 ” m” R 2 ” n” Si(OR 3 ”) 4-m”-n” (VI)，
in the formula (VI), R 1 "and R 2 "may be the same or different and each is independently selected from halogen, hydrogen atom, C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 20 Aryl and C 1 -C 20 One of the haloalkyl groups of (a); r 3 "is selected from C 1 -C 20 Alkyl of (C) 3 -C 20 Cycloalkyl of, C 6 -C 20 Aryl and C 1 -C 20 One of the haloalkyl groups of (a); m 'and n' are each an integer of 0 to 3, and m "+ n"<4。
<xnotran> , , , , , , , , , , , , , , , , , , , () , , , , , , , , , , , , , , , , , , , , (2- ) , , </xnotran> At least one member selected from the group consisting of diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1, 1-trifluoro-2-propyl) -methyldimethoxysilane. More preferably, the external electron donor compound may be at least one of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-t-butyldimethoxysilane, and tetramethoxysilane.
In a third aspect, the present invention provides the use of a solid catalyst component according to the first aspect and/or a catalyst system according to the second aspect in the polymerisation of olefins.
According to some embodiments of the present invention, the solid catalyst component and/or the catalyst system of the present invention may be used for homopolymerization of olefins, or for copolymerization of a plurality of olefins. At least one of the olefins is represented by the general formula CH 2 Olefin represented by = CHR where R is hydrogen or C 1 -C 6 The alkyl group of (1). Specific examples of the olefin may include: at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene. Preferably, the olefin may be at least one of ethylene, propylene, 1-n-butene, 4-methyl-1-pentene, and 1-n-hexene. More preferably, the olefin is propylene.
In a fourth aspect, the present invention provides a process for the polymerisation of olefins, the process comprising: contacting one or more olefins, at least one of which is represented by the general formula CH, with the solid catalyst component provided according to the first aspect or/and the catalyst system provided according to the second aspect under olefin polymerization conditions 2 An olefin represented by = CHR, wherein R is hydrogen or C 1 -C 6 Alkyl group of (1).
The method for polymerizing the olefin can be used for homopolymerization of the olefin and copolymerization of a plurality of olefins. Specific examples of the olefin may include: at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene. Preferably, the olefin may be at least one of ethylene, propylene, 1-n-butene, 4-methyl-1-pentene, and 1-n-hexene. More preferably, the olefin is propylene.
According to the present invention, the solid catalyst component, the alkylaluminum compound as cocatalyst and the external electron donor compound may be contacted prior to contacting the olefin monomer, referred to in the art as "precontacting" or "preconlexoring"; it is also possible to add the three components separately to the olefin monomer and then carry out the polymerization, i.e.without "precontacting". In accordance with the olefin polymerization process provided by the present invention, it is preferred that the components of the olefin polymerization catalyst system be "precontacted". The "precontacting" time is between 0.1 and 30 minutes, preferably between 1 and 10 minutes; the temperature of the "precontacting" is from-20 ℃ to 80 ℃, preferably from 10 ℃ to 50 ℃.
According to the invention, the catalyst system is polymerized to a certain extent in the presence of a small amount of olefin monomer to obtain a prepolymerized catalyst, and the prepolymerized catalyst is further contacted with olefin monomer to react to obtain an olefin polymer. This technique, known in the industry as a "prepolymerization" process, contributes to, among other things, increasing the polymerization activity of the catalyst and increasing the bulk density of the polymer. According to the olefin polymerization method provided by the invention, a prepolymerization process can be adopted, a prepolymerization process can also be not adopted, and the prepolymerization process is preferably adopted. When the olefin monomer is propylene, the rate of the "prepolymerization" is 5-1000g PP/g Cat, preferably 10-500g PP/g Cat; the temperature of the "prepolymerization" is from-20 ℃ to 80 ℃, preferably from 10 ℃ to 50 ℃.
According to the polymerization method for preparing polyolefin of the present invention, the polymerization conditions may be conventional in the art. The amount of catalyst used may be any of the various catalysts known in the art.
Detailed Description
The present invention will be described in detail below by way of examples. However, the present invention is not limited to the following examples.
In the following examples, the test methods involved are as follows:
1. yield of catalyst component (%) = (mass of catalyst obtained/mass of magnesium chloride used) × 100%;
2. titanium content in catalyst component: measuring with 721 spectrophotometer;
3. particle size distribution of the solids of the catalyst component: measuring by a Malvern 2000 laser particle size analyzer according to a normal hexane dispersing agent laser diffraction method;
4. purity of internal electron donor compound: measuring by gas chromatography;
5. polymer Melt Index (MI): measured according to GB/T3682-2000;
6. propylene polymer Isotacticity Index (II): measuring by adopting a heptane extraction method; extracting 2g of dried polymer sample in an extractor with boiling heptane for 6 hours, and drying the residue to constant weight to obtain the ratio of the weight (g) of the polymer to 2 (g), namely the isotacticity;
7. polymer molecular weight distribution MWD (MWD = Mw/Mn): using PL-GPC220 and trichlorobenzene as a solvent, the measurement was carried out at 150 ℃ (standard: polystyrene, flow rate: 1.0mL/min, column: 3xPlgel 10um MlxED-B300x7.5nm).
8. And (3) activity calculation: catalyst Activity = (quality of polyolefin produced)/(quality of catalyst solid component) g/g
9. And (3) measuring the bulk density: the polymer powder obtained by the preparation was allowed to freely fall from a height of 10cm in a funnel into a 100mL container, and the weight of the polymer powder in the container was weighed to M g, whereby the bulk density of the polymer was M/100g/cm 3 。
1. Synthesis of internal electron donor compound:
a compound A: cis-4-Cyclohexenyl-1, 2-dicarboxylic acid ethyl ester
50.0g of cis-4-cyclohexenyl-1, 2-dicarboxylic acid and 2.5g of tetrabutylammonium bromide were dissolved in a dried mixed solvent of 500mL of N, N' -dimethylformamide and 100mL of acetone, and stirred until completely dissolved. 101.6g of potassium carbonate was added, and the mixture was stirred until no bubble was released. 76.9g of bromoethane was added thereto, and the reaction was carried out at 20 ℃ for 1 hour. The temperature is raised to 35 ℃ for reaction for 4 hours, and the temperature is raised to 50 ℃ for reaction for 4 hours. The reaction was stopped, cooled, filtered to remove the solid, washed clean solvent, added with 300mL of water, extracted with ethyl acetate (180mL, 100mL, 80mL) three times, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, washed free of solvent, and distilled under reduced pressure to obtain 54.5g of cis-4-cyclohexenyl-1, 2-dicarboxylic acid ethyl ester as a final product, in 82.1% yield and 99.2% purity (GC).
Compound B: cis-4-Cyclohexenyl-1, 2-dicarboxylic acid n-butyl ester
Using a synthetic method analogous to that for Compound A, conversion of bromoethane to n-bromobutane gave cis-4-cyclohexenyl-1, 2-dicarboxylic acid n-butyl ester 54.3g, yield: 78.4% and 99.6% pure (GC).
2. Preparation of solid catalyst component
Example 1
(1) Preparation of alcohol compound solution
Sequentially adding 20g of anhydrous magnesium chloride, 80mL of toluene and 80mL of isooctanol into a reaction kettle repeatedly substituted by high-purity nitrogen, reacting for 3.0 hours under the conditions of stirring speed of 300rpm and temperature of 110 ℃, adding 3.0mL of tetrabutyl titanate, continuing to react for 1.5 hours, and adding 120mL of toluene to obtain a stable and uniform alcohol compound solution.
(2) Preparation of the catalyst component
75mL of the alcohol hydrate solution and 2.4g of 2, 4-pentanediol benzoate were added dropwise into a reactor which was sufficiently replaced with nitrogen and which was charged with 60mL of titanium tetrachloride and 40mL of toluene, and were sufficiently contacted with each other at-25 ℃ for 1.5 hours by stirring, followed by heating to 110 ℃ over 3.5 hours, holding the temperature for 1 hour, adding 108mL of toluene and 12mL of titanium tetrachloride, stirring for 1 hour, cooling and pressure-filtering, adding 12mL of titanium tetrachloride and 108mL of toluene, heating to 100 ℃, adding 1.2g of a mixture of compound A and diethyl di-n-propylmalonate (mass ratio: 1), and holding the temperature for 1 hour. The temperature was raised to 110 ℃ and 96mL of toluene and 24mL of titanium tetrachloride were added and stirred for 1 hour, and the liquid was removed by pressure filtration and repeated twice. After stirring for 1 hour with 108mL of toluene and 12mL of titanium tetrachloride, the resulting solid was washed 4 times with 150mL of hexane after pressure filtration. And (3) carrying out filter pressing, transferring and drying to obtain the olefin polymerization catalyst component.
Example 2
Using the same preparation method as in example 1, the internal electron donor was replaced with 1.2g of a mixture of compound a and diethyl diallylmalonate (mass ratio 1.
Example 3
Using the same preparation method as in example 1, the internal electron donor was changed to 1.2g of a mixture of compound a and diethyl di-n-butylmalonate (mass ratio 1.
Example 4
Using the same preparation method as in example 1, the internal electron donor was changed to 1.2g of a mixture of compound a and diethyl diisobutyl malonate (mass ratio 1.
Example 5
Using the same preparation method as in example 1, the internal electron donor was changed to 1.2g of a mixture of compound a and diethyl ethylphenylmalonate (mass ratio 1.
Example 6
Using the same preparation method as in example 5, the internal electron donor was changed to 1.2g of a mixture of compound a and diethyl benzylmalonate (mass ratio 1.
Example 7
Using the same preparation method as in example 5, the internal electron donor was changed to a mixture of 1.2g of a mixture of compound B and diethyl di-n-propylmalonate (mass ratio 1).
Example 8
Using the same preparation method as in example 5, the internal electron donor was replaced with 1.2g of a mixture of compound B and diethyl diallylmalonate (mass ratio 1.
Example 9
Using the same preparation method as in example 1, the internal electron donor was changed to 1.2g of a mixture of compound B and diethyl di-n-butylmalonate (mass ratio 1.
Example 10
Using the same preparation method as in example 1, the internal electron donor was replaced with 1.2g of a mixture of compound B and diethyl diisobutyl malonate (mass ratio 1.
Example 11
Using the same preparation method as in example 1, the internal electron donor was changed to 1.2g of a mixture of compound B and diethyl ethylphenylmalonate (mass ratio 1.
Example 12
Using the same preparation method as in example 5, the internal electron donor was replaced with 1.2g of a mixture of compound B and diethyl benzylmalonate (mass ratio 1.
Example 13
A catalyst solid component was prepared using the same preparation method as example 1, using only 1.2g of Compound A as an internal electron donor.
Comparative example 1
The same preparation method as in example 1 was used, and only 1.2g of diethyl di-n-propylmalonate was used as an internal electron donor to prepare a catalyst solid component.
3. Polymerization of propylene
In a 5L autoclave, after sufficient replacement with propylene in the gas phase, 5mL of a hexane solution of triethylaluminum (the concentration of triethylaluminum was 0.5 mmol/mL), L mL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (the concentration of CHMMS was 0.10 mmol/mL), 10mL of anhydrous hexane, and 10mg of the solid catalyst component were added at room temperature. The autoclave was closed and a quantity of hydrogen and 1.2kg of liquid propylene were introduced. 4.5L of hydrogen is added, the polymerization temperature is 70 ℃, and the material is discharged after the polymerization time is 1 hour.
TABLE 1 Performance of the catalyst
As can be seen from the data in Table 1, the Z-N catalyst prepared by compounding the cis-4-cyclohexene-1, 2-diformate compound and the diester compound shown in the formula (II) and serving as an internal electron donor has high activity, excellent hydrogen regulation performance and high stereospecific capacity, and the obtained polymer has moderate molecular weight distribution. Therefore, the polypropylene catalyst compounded by the two internal electron donors provided by the invention is very suitable for preparing a general polypropylene brand without plasticizer.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (21)
1. A solid catalyst component for the preparation of polyolefins comprising magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a first internal electron donor compound and a second internal electron donor compound, the molar ratio of the first internal electron donor compound to the second internal electron donor compound being from 0.1 to 1;
the first internal electron donor compound is cis-4-cyclohexene-1, 2-diformate compound shown in formula (I), the second internal electron donor compound is diester compound shown in formula (II),
in the formula (I), R 1 And R 2 Are the same or different and are each independently selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl or cycloalkyl, C 6 -C 20 Aryl radical, C 7 -C 20 Alkylaryl and C 7 -C 20 Aralkyl, any of which may be optionally substituted with one or more substituents selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino and bis-C 1 -C 10 An alkylamino group; or R 1 And R 2 Connecting to form a ring in an arbitrary mode; r a 、R b 、R c 、R d 、R e And R f The same or different, each independently selected from hydrogen and C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy and halogen;
in the formula (II), R 3 And R 4 The same or different, each independently selected from hydrogen and C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl or cycloalkyl, C 6 -C 20 Aryl radical, C 7 -C 20 Alkaryl and C 7 -C 20 Aralkyl, any of which may be optionally substituted with one or more substituents selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino and bis-C 1 -C 10 Alkylamino, the carbon atoms of the backbone optionally being substituted with heteroatoms; or R 3 And R 4 Linked to form a ring in any manner and containing a double bond or a heteroatom in the resulting ring skeleton; r 5 And R 6 Are the same or different and are each independently selected from C 1 -C 10 Alkyl radical, C 6 -C 15 Aryl and C 7 -C 15 An alkaryl group.
2. The solid catalyst component according to claim 1 in which in formula (I), R is 1 And R 2 Identical or different, R 1 And R 2 Each independently selected from C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl or cycloalkyl, C 6 -C 10 An aryl group; and/or, in the formula (II), R 5 And R 6 Are the same or different and are each independently selected from C 1 -C 6 An alkyl group.
3. The solid catalyst component according to claim 2, characterized in that in formula (I), R is 1 And R 2 Is selected from C 1 -C 6 Straight chain alkyl or C 3 -C 6 Branched alkyl or C 6 -C 10 An aryl group; and/or, in the formula (II), R 5 And R 6 Identical or different, each independently selected from methyl, ethyl and isopropyl.
4. The solid catalyst component according to claim 2 in which in formula (I), R is 1 And R 2 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, cyclopentyl, and phenyl.
5. The solid catalyst component according to any one of claims 1 to 4, wherein the cis-4-cyclohexene-1, 2-dicarboxylate is selected from at least one of cis-4-cyclohexene-1, 2-dicarboxylate, n-propyl cis-4-cyclohexene-1, 2-dicarboxylate, isopropyl cis-4-cyclohexene-1, 2-dicarboxylate, n-butyl cis-4-cyclohexene-1, 2-dicarboxylate, isobutyl cis-4-cyclohexene-1, 2-dicarboxylate, n-pentyl cis-4-cyclohexene-1, 2-dicarboxylate and isopentyl cis-4-cyclohexene-1, 2-dicarboxylate.
6. The solid catalyst component according to claim 5 wherein the cis-4-cyclohexene-1, 2-dicarboxylate is selected from at least one of cis-4-cyclohexene-1, 2-dicarboxylic acid methyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid ethyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid n-propyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid isopropyl ester, cis-4-cyclohexene-1, 2-dicarboxylic acid n-butyl ester and cis-4-cyclohexene-1, 2-dicarboxylic acid isobutyl ester.
7. The solid catalyst component according to claim 6 wherein the cis-4-cyclohexene-1, 2-dicarboxylate is selected from at least one of cis-4-cyclohexene-1, 2-dicarboxylate, cis-4-cyclohexene-1, 2-dicarboxylate and cis-4-cyclohexene-1, 2-dicarboxylate.
8. The solid catalyst component according to claim 1, characterized in that in formula (II), R 3 And R 4 Is selected from C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl or cycloalkyl, C 6 -C 10 And (4) an aryl group.
9. The solid catalyst component according to claim 8 in which in formula (II), R 3 And R 4 Is selected from C 1 -C 6 Straight chain alkyl or C 3 -C 6 Branched alkyl or C 6 -C 10 And (4) an aryl group.
10. The solid catalyst component according to claim 9 in which in formula (II), R 3 And R 4 Selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl and phenyl.
11. The solid catalyst component according to claim 1, wherein the diester-based compound is at least one selected from the group consisting of diethyl 2,2 '-dimethylmalonate, diethyl 2,2' -diethylmalonate, diethyl 2,2 '-di-n-propylmalonate, diethyl 2,2' -diisopropylmalonate, diethyl 2,2 '-di-n-butylmalonate, diethyl 2,2' -di-isobutylmalonate, diethyl 2,2 '-di-n-pentylmalonate, diethyl 2,2' -diisopentylmalonate, diethyl 2,2 '-dicyclopentylmalonate, diethyl 2,2' -diphenylmalonate, diethyl 2,2 '-dibenzylmalonate, diethyl 2-ethyl-2' -phenylmalonate, and diethyl 2-benzylmalonate.
12. The solid catalyst component according to claim 11, characterized in that the diester-based compound is at least one selected from the group consisting of diethyl 2,2 '-diethylmalonate, diethyl 2,2' -di-n-propylmalonate, diethyl 2,2 '-diisopropylmalonate, diethyl 2,2' -di-n-butylmalonate, diethyl 2,2 '-di-isobutylmalonate, diethyl 2,2' -di-n-pentylmalonate, diethyl 2,2 '-diisopentylmalonate, diethyl 2,2' -diphenylmalonate, diethyl 2,2 '-dibenzylmalonate, diethyl 2-ethyl-2' -phenylmalonate, and diethyl 2-benzylmalonate.
13. The solid catalyst component according to claim 12, characterized in that the diester-based compound is at least one selected from the group consisting of diethyl 2,2 '-di-n-propylmalonate, diethyl 2,2' -di-n-butylmalonate, diethyl 2,2 '-di-isobutylmalonate, diethyl 2-ethyl-2' -phenylmalonate and diethyl 2-benzylmalonate.
14. The solid catalyst component according to claim 1, characterized in that the molar ratio of the first internal electron donor compound and the second internal electron donor compound is 0.2.
15. The solid catalyst component according to claim 14, characterized in that the molar ratio of the first internal electron donor compound and the second internal electron donor compound is between 0.3 and 1 and 0.3.
16. The solid catalyst component according to any one of claims 1 to 4, characterized in that the total content of the components in the catalyst component is 100wt% and the content of titanium atoms is 1.0 to 8.0wt%, based on the total amount of the catalyst component; the content of magnesium atoms is 10-70wt%; the content of halogen atoms is 20-90wt%; the total internal electron donor compound content is 2-30wt%.
17. The solid catalyst component according to claim 16, wherein the total content of each component in the catalyst component is 100wt% and the content of titanium atom is 1.6 to 6.0wt% based on the total amount of the catalyst component; the content of magnesium atoms is 15-40wt%; the content of halogen atoms is 30-85%; the total content of the internal electron donor compound is 3-20wt%.
18. A catalyst system for the polymerization of olefins comprising the reaction product of:
1) The solid catalyst component of any of claims 1 to 17,
2) An alkyl-aluminium compound, which is a mixture of,
3) Optionally, an external electron donor compound.
19. Use of the solid catalyst component according to any one of claims 1 to 17 or the catalyst system according to claim 18 in olefin polymerization reactions.
20. A process for the polymerization of olefins having the general formula CH, in the presence of the solid catalyst component according to any of claims 1 to 17 or the catalyst system according to claim 18 2 = CHR, wherein R is hydrogen or C1-C6 alkyl; the olefin polymerization is homopolymerization of a single olefin or copolymerization of a plurality of olefins.
21. The method of claim 20, wherein the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.
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| JP2003040918A (en) * | 2001-07-25 | 2003-02-13 | Toho Catalyst Co Ltd | Solid catalyst component and catalyst for polymerizing olefins |
| CN102212154A (en) * | 2011-04-19 | 2011-10-12 | 中国科学院化学研究所 | Catalyst solid component for olefin polymerization and preparation method thereof |
| CN104558292A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for olefin polymerization |
| CN105504110A (en) * | 2015-12-30 | 2016-04-20 | 神华集团有限责任公司 | Preparation method of catalyst solid component for olefin polymerization |
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| JP2003040918A (en) * | 2001-07-25 | 2003-02-13 | Toho Catalyst Co Ltd | Solid catalyst component and catalyst for polymerizing olefins |
| CN102212154A (en) * | 2011-04-19 | 2011-10-12 | 中国科学院化学研究所 | Catalyst solid component for olefin polymerization and preparation method thereof |
| CN104558292A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for olefin polymerization |
| CN105504110A (en) * | 2015-12-30 | 2016-04-20 | 神华集团有限责任公司 | Preparation method of catalyst solid component for olefin polymerization |
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