CN115806635B - Catalyst system for olefin polymerization and olefin polymerization method - Google Patents

Catalyst system for olefin polymerization and olefin polymerization method Download PDF

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CN115806635B
CN115806635B CN202111083877.8A CN202111083877A CN115806635B CN 115806635 B CN115806635 B CN 115806635B CN 202111083877 A CN202111083877 A CN 202111083877A CN 115806635 B CN115806635 B CN 115806635B
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dimethoxypropane
silane
compound
catalyst system
olefin polymerization
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CN115806635A (en
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张天一
夏先知
周俊领
段瑞林
万真
赵瑾
刘月祥
凌永泰
胡建军
马长友
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention belongs to the technical field of olefin polymerization catalysts, and discloses a catalyst system for olefin polymerization and an olefin polymerization method, wherein the catalyst system comprises the reaction products of the following components: 1) A solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; 2) An alkyl aluminum compound; 3) A composite external electron donor compound containing tetravinyl silane and hydrocarbyldialkyloxy silane; the structure of the hydrocarbyloxysilane is shown as a formula (I), wherein R is 1 ″‑R 4 "same or different, each selected from C 1 ‑C 20 Straight chain alkyl, C 3 ‑C 20 Branched alkyl, C 3 ‑C 20 Cycloalkyl, C 6 ‑C 20 Aryl or C of (2) 7 ‑C 20 Alkylaryl groups of (a).

Description

Catalyst system for olefin polymerization and olefin polymerization method
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and in particular relates to a catalyst system for olefin polymerization and an olefin polymerization method.
Background
It is well known that catalyst systems used in the polymerization of ethylene, alpha-olefins and mixtures thereof generally consist of three parts, including in particular: (1) a main catalyst (solid catalyst component), (2) a cocatalyst (usually an alkylaluminum-based compound) and (3) an external electron donor compound added during polymerization.
One or more external electron donor compounds are used during the polymerization to control the stereoregularity and morphology of the polymer. The external electron donor affects the activity of the catalyst, the sensitivity of hydrogen regulation, and the like to different degrees in addition to the stereoregularity of the polymer.
While a variety of compounds are known to be useful as external electron donors, the use of different external electron donors with a particular catalyst may result in different polymer properties. The selection of a suitable external electron donor may be particularly compatible with the particular catalyst system, that is, the finding of a suitable external electron donor may significantly improve certain properties of the polymer product, such as isotacticity, molecular weight distribution, hydrogen sensitivity, etc., while having no or little effect on other properties. Thus, it is highly desirable to find external electron donors for specific catalysts that provide polymers with a good combination of properties.
Patent document US5100981 discloses a catalyst system consisting of a main catalyst and a mixture of two external electron donors, the external electron donors being Cyclohexylmethyldimethoxysilane (CHMMS) and phenyltriethoxysilane.
Patent document JP19820199728 also describes a catalyst system which is constituted by using a ziegler-natta catalyst in which two external electron donors are mixed, which may be methyl benzoate and tetraethoxysilane.
Patent documents CN02100900.7 and CN03109781.2 describe catalyst components using polyol ester compounds as internal electron donors, which are external electron donor hydrocarbyloxysilanes used in propylene polymerization, such as C-donor and the like, which are currently commonly used in industry. Although patent document CN03109781.2 also uses different external electron donors as a comparison, for example, diisobutyldimethoxy silane, dicyclopentyl dimethoxy silane (D-donor), bis (cyclobutylmethyl) dimethoxy silane, etc. are used in addition to C-donor, it is found from the disclosed patent document that the hydrogen sensitivity of such catalyst systems is poor.
Patent documents with application numbers CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN200410073623.8, CN200410073621.9 respectively describe catalyst components using a polyol ester compound and a phthaloyl ester compound as internal electron donors, and when the catalyst components are used for propylene polymerization, the external electron donor hydrocarbyloxysilane used is an external electron donor commonly used in industry at present, such as CHMMS and the like. In addition, in patent document CN03109781.2, as a comparison, for example, diisobutyldimethoxy silane, dicyclopentyl dimethoxy silane (DCPMS), bis (cyclobutylmethyl) dimethoxy silane, etc. are used in addition to CHMMS, and the catalyst system exhibits high activity, high orientation ability, and a broad molecular weight distribution of the polymer produced.
Patent documents CN1091748A, CN1330086A, CN101050245A, US6020279A, CN1580136a and CN1463990a describe the preparation of spherical magnesium halide alkoxide supports and the synthesis of catalysts, and generally use an external electron donor hydrocarbyloxysilane as an external electron donor.
The research of the existing olefin polymerization catalyst mainly expands around the performance of improving the polymerization activity of olefin, the tacticity of polymer and the like. However, in the case of these catalysts, the properties (e.g., isotacticity, melt index) of the polymer are difficult to control to some extent by adjusting the amount of the external electron donor without changing the kind of the external electron donor, resulting in limited applications of the olefin polymerization catalyst. For this reason, it is necessary to develop a new catalyst to solve the problem.
Disclosure of Invention
The present inventors have unexpectedly found in the research work that a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound, when an olefin is polymerized, is compounded with a hydrocarbyldialkylalkoxysilane compound as an external electron donor compound by adding a tetravinylsilane, and can be combined with a specific solid catalyst component under the same polymerization conditions to give a polymer excellent in overall properties. By adjusting the polymerization conditions and the ratio of the composite external electron donor, the obtained catalyst system is embodied as improved hydrogen regulation sensitivity, improved polymerization activity and improved isotactic index of the obtained polymer. Under the condition of keeping the hydrogen regulation sensitivity of the catalyst basically unchanged, the isotactic index of the polymer can be effectively regulated by adjusting the proportion of the external electron donor. Based on this finding, the present invention has been proposed.
In a first aspect the present invention provides a catalyst system for the polymerization of olefins comprising the reaction product of:
1) A solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound;
2) An alkyl aluminum compound;
3) A composite external electron donor compound containing tetravinyl silane and hydrocarbyldialkyloxy silane;
the structure of the hydrocarbyloxysilane is shown as a formula (I):
in the formula (I), R 1 ″-R 4 "same or different, each selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl or C of (2) 7 -C 20 Alkylaryl groups of (a).
In a second aspect, the present invention provides a process for the polymerization of olefins, the process comprising: one or more olefins are contacted with the above-described catalyst system under olefin polymerization conditions.
Compared with conventional external electron donors such as C-donor D-donor, the composite external electron donor compound in the catalyst system disclosed by the invention is combined with a specific solid catalyst component, so that a polymer with better comprehensive performance can be obtained under the same polymerization condition. The catalyst system obtained by adjusting the polymerization conditions and the compounding ratio of the external electron donor is characterized by improved hydrogen regulation sensitivity, improved polymerization activity and improved isotactic index of the polymer. Under the condition of keeping the hydrogen regulation sensitivity of the catalyst basically unchanged, the isotactic index of the polymer can be effectively regulated by adjusting the proportion of the external electron donor.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention there is provided a catalyst system for the polymerization of olefins comprising the reaction product of:
1) A solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound;
2) An alkyl aluminum compound;
3) A composite external electron donor compound containing tetravinyl silane and hydrocarbyldialkyloxy silane;
the structure of the hydrocarbyloxysilane is shown as a formula (I):
in the formula (I), R 1 ″-R 4 "same or different, each selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl or C of (2) 7 -C 20 Alkylaryl groups of (a).
In the invention, C 1 -C 20 Straight chain alkyl, C 3 -C 20 Non-limiting examples of branched alkyl groups of (2) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, dimethylhexyl, n-decyl.
C 3 -C 20 Examples of cycloalkyl groups of (a) include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C 6 -C 20 Examples of aryl groups of (a) may include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl.
C 7 -C 20 Examples of alkylaryl groups of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl, isopropylphenyl.
Preferably, in formula (I), R 1 ″-R 4 "each selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl of (C), preferably R 1 "and R 2 "same".
In the present invention, specific examples of the hydrocarbyloxysilane include, but are not limited to: the hydrocarbyloxysilane is selected from at least one of methylcyclohexyldimethoxy silane, diisopropyldimethoxy silane, diisobutyldimethoxy silane, dicyclohexyldimethoxy silane, dicyclopentyldimethoxy silane, methylcyclohexyldiethoxy silane, diisopropyldiethoxy silane, diisobutyldiethoxy silane, dicyclohexyldiethoxy silane, methylcyclohexyldipropoxy silane, diisopropyldipropoxy silane, diisobutyldipropoxy silane, dicyclohexyldipropoxy silane, dicyclopentyldipropoxy silane, methylcyclohexyldibutoxy silane, diisopropyldibutoxy silane, diisobutyldibutoxy silane, dicyclohexyldibutoxy silane, and dicyclopentyldibutoxy silane.
Preferably, the hydrocarbyloxysilane is methylcyclohexyldimethoxy silane and/or dicyclopentyl dimethoxy silane.
The tetravinyl silane can be prepared by adopting a conventional synthesis method, and can also be purchased according to a general chemical product purchasing method.
According to the invention, the amount of the tetravinyl silane is 0.001 to 1.0 mol per mol of aluminum in the aluminum alkyl compound, the amount of the hydrocarbyloxysilane is 0.001 to 1.0 mol, and the molar ratio of the tetravinyl silane to the hydrocarbyloxysilane is 1:100 to 100:1, preferably 1:20 to 20:1.
In the polymerization process, the composite external electron donor compound can be added after being pre-contacted with the solid catalyst component for a period of time, can be added after being mixed with the solid catalyst component for a short time, and can also be added at different stages of polymerization. The components in the compound external electron donor compound can be added separately or simultaneously.
The solid catalyst component of the present invention can be prepared by any preparation method known in the art.
Preferably, the solid catalyst component is prepared by one or both of the following methods:
the method comprises the following steps: in an inert diluent, a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an optional silane compound are contacted to form a uniform solution, and then the uniform solution is contacted and reacted with a titanium compound and an internal electron donor compound in the presence of a precipitation aid to obtain a solid catalyst component.
In the method one of the present invention, the magnesium compound may be selected from at least one of magnesium halide, a water or alcohol complex of magnesium halide, and a derivative in which one halogen atom in the magnesium halide molecule is replaced with a hydrocarbyloxy group or a halohydrocarbonoxy group. Preferably, the magnesium compound is a magnesium halide, for example, magnesium chloride, magnesium bromide, magnesium iodide. The magnesium compound is more preferably magnesium chloride.
The organic epoxy compound may be selected from aliphatic olefins having 2 to 8 carbon atoms, diolefins, halogenated aliphatic olefins, oxides of diolefins, glycidyl ethers, internal ethers, and the like. Specific examples include, but are not limited to: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, and the like.
The precipitation aid can be at least one selected from organic acid anhydride, organic acid, ether and ketone; preferably at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether and pentyl ether.
The inert diluent may be a conventional choice in the art. The inert diluent can be benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbon or halogenated hydrocarbon compounds; toluene and/or xylene are preferred.
According to the present invention, the specific operation of the first method may be carried out according to the preparation method of the solid catalyst component disclosed in patent document CN102464746A, CN1258684a, the disclosure of which is incorporated herein by reference in its entirety.
The second method is as follows: and (3) carrying out contact reaction on the titanium compound and the magnesium compound and the internal electron donor compound to obtain the solid catalyst component.
Method two may be carried out according to methods conventional in the art. According to a preferred embodiment, it comprises the following steps:
1) Mixing a titanium compound with a spherical magnesium halide alkoxide carrier at a temperature of-30 ℃ to 0 ℃ to obtain a carrier suspension;
2) Heating the carrier suspension to 80-130 ℃, adding an internal electron donor compound in the heating process, and reacting for 0.2-2h at constant temperature to prepare a solid precipitate;
3) And washing and drying the solid precipitate to obtain the solid catalyst component.
In the second process of the invention, optionally, in step 3), the solid precipitate is treated with a titanium compound before washing. The treatment may be performed one or more times. The inert solvent used for washing can be one or more selected from hexane, heptane, octane, decane and toluene.
In step 1), the mixing is optionally carried out in the presence of an inert solvent.
The general formula of the spherical magnesium halide alkoxide carrier is MgX 2 P (ROH), X is Cl, br or I, preferably Cl; r is C 1 -C 18 Alkyl, preferably C 2 -C 4 A linear alkyl group of (a); p is 0.1-6.
The preparation method of the spherical magnesium halide alkoxide carrier can comprise the following steps: mixing magnesium halide and low-carbon alcohol, heating to react to obtain magnesium halide alcohol compound melt, placing the magnesium halide alcohol compound melt into a cooled inert medium after high shearing action in a dispersion medium at the reaction temperature of 90-140 ℃ to form spherical magnesium halide alcohol compound particles, and washing and drying to obtain the spherical carrier. The high shearing action can be obtained by conventional methods such as a high-speed stirring method (for example, patent document CN 00109216.2), a spraying method (for example, patent document US 6020279), a super gravity rotating bed (for example, patent document CN 1580136), an emulsifying machine method (for example, patent document CN 1463990), and the like. The dispersant system (dispersion medium) may be hydrocarbon inert solvent such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The cooled inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, and the like.
The spherical magnesium halide alkoxide carrier of the present invention can be obtained by the preparation methods of patent documents CN1036011C, CN1151183C, CN100491410, US6020279, CN1267508C and CN1463990, the disclosures of which are incorporated herein by reference in their entirety.
According to the present invention, in the first and second methods, the internal electron donor compound includes a mono-or polybasic aliphatic carboxylic acid ester compound and an aromatic carboxylic acid ester compound, a phosphoric acid ester compound, an acid anhydride, a ketone, an alcohol, an amine, an ether compound and derivatives thereof, a glycol ester compound, or a complex of any of the components thereof.
When the internal electron donor compound is a carboxylate compound, the internal electron donor compound may be selected from benzoate, phthalate, malonate, succinate, glutarate, and the like. Preferably, the internal electron donor compound is selected from at least one of ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 2-dimethylbuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, tetraethyl trimellitate and tetrabutyl trimellitate. More preferably, the internal electron donor compound is dibutyl phthalate and/or diisobutyl phthalate.
When the internal electron donor compound is a diether compound, the internal electron donor compound may be selected from 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentanyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane 2, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, at least one of 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane and 9, 9-dimethoxymethylfluorene. The internal electron donor compound is preferably 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.
When the internal electron donor compound is a glycol ester compound, non-limiting examples of the internal electron donor compound include: 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 9-bis (benzylcarboxymethyl) fluorene. Preferably, the internal electron donor compound is 2, 4-pentanediol dibenzoate.
In addition, when the internal electron donor compound is an acid anhydride-based compound, the internal electron donor compound is preferably phthalic anhydride.
According to the present invention, the internal electron donor compound may be used in an amount of 0.01 to 5 moles per mole of magnesium in the solid catalyst component.
In the preparation process of the solid catalyst component of the present invention, if 2 or more kinds of internal electron donors are contained, the internal electron donor compounds used may be used together in various ways, may be used in different steps and under different conditions, may be added simultaneously, and may be added in a non-sequential order.
According to the invention, in the first and second methods, the titanium compound has the general formula Ti (OR w ) 4-k X′ k Wherein R is w Is C 1 -C 20 Alkyl, X' is Cl, br or I, and k is an integer from 0 to 4.
Preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide.
According to the invention, the amount of the titanium compound used in the solid catalyst component may be 0.5 to 150 moles per mole of magnesium.
In the invention, the general formula of the alkyl aluminum compound is AlR'. d X 1 3-d Wherein R' "is C 1 -C 8 Alkyl, X 1 Is a halogen atom, 0 < d.ltoreq.3, which may be the same or different when two or three R' "are contained. Preferably, the alkyl aluminum compound is triethylaluminumAluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, al (n-C) 6 H 13 ) 3 、Al(n-C 8 H 17 ) 3 And AlEt 2 At least one of Cl.
Preferably, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the solid catalyst component is from 1 to 1000:1, more preferably from 1 to 500:1.
In the present invention, the alkyl aluminum compound and the external electron donor compound may be contacted with the solid catalyst component alone or as a mixture of both components.
According to different requirements on polymer properties, the catalyst system disclosed by the invention can be directly used for the polymerization reaction of olefin; or the catalyst can be pre-polymerized with the pre-polymerized olefin to generate a pre-polymerized catalyst, and then the pre-polymerized catalyst is polymerized with the olefin.
According to a second aspect of the present invention there is provided a process for the polymerisation of olefins, the process comprising: one or more olefins are contacted with the above-described catalyst system under olefin polymerization conditions.
In the present invention, the olefin may have the general formula CH 2 ＝CH-R V Wherein R is V Is hydrogen or C 1 -C 6 An alkyl group. Non-limiting examples of the olefins include: ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene. Preferably, the olefin is propylene and/or ethylene; more preferably the olefin is propylene.
In addition, the olefin may be polymerized in the presence of a small amount of diene, depending on the particular application requirements.
In the present invention, the olefin polymerization may be carried out in a liquid phase (liquid phase monomer or monomer dissolved in an inert solvent) or a gas phase, or may be carried out in a combination of liquid phase and gas phase polymerization stages. The olefin polymerization may be carried out according to well-known polymerization techniques, for example, using conventional techniques such as slurry processes, gas-phase fluidized beds, and the like.
In the present invention, the olefin polymerization conditions include: the polymerization temperature is 0 to 150 ℃, preferably 60 to 90 ℃, and the polymerization pressure is normal pressure or higher.
Parameters not defined in the present invention are all conventional in the art.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
In the following examples and comparative examples:
1) The isotactic index of the polymer was determined by n-heptane extraction, 2g of a dried polymer sample was placed in an extractor according to GB/T2412-2008, extracted with boiling n-heptane for 6 hours, and the residue was dried to constant weight; the ratio of the weight (g) of the obtained polymer to 2 is the isotactic index.
2) Polymer melt index: measured according to GB3682-2000 at 230℃under a load of 2.16 kg.
Preparation examples 1-3 are provided to illustrate the preparation of the solid catalyst component of the present invention.
Preparation example 1
Into a 300mL glass reaction flask with stirring, which had been sufficiently replaced with high-purity nitrogen gas, 100mL of titanium tetrachloride was added, cooled to-20℃and 8g of spherical magnesium chloride alkoxide (prepared in the same manner as in example 1 of CN1151183C, the molar ratio of ethanol to magnesium chloride in the carrier was 2.62) was added. Slowly heating to 110 ℃ in stages, adding 2.5mmol of 2, 4-pentanediol dibenzoate and 3.9mmol of dibutyl phthalate in the heating process, keeping the temperature at 110 ℃ for 0.5h to obtain a solid precipitate, filtering the liquid, adding 100mL of titanium tetrachloride for two times each time, washing with hexane for five times, and vacuum drying to obtain the solid catalyst component A.
Preparation example 2
To the reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were added in this order, the temperature was raised to 50℃with stirring, and the mixture was maintained for 2.5 hours, so that the solid was completely dissolved, and 1.4g of phthalic anhydride was added, and the reaction was continued for 1 hour. Cooling the solution to below-25 ℃, and dripping TiCl in 1 hour 4 56mL, slowly heating to 80 ℃, gradually precipitating solid matters in the heating process, adding 6mmol of 2, 4-pentanediol dibenzoate,after maintaining the temperature for 1 hour and filtering, 70mL of toluene was added and washed twice to obtain a solid precipitate. 60mL of toluene, tiCl, was then added to the solid 4 40mL was warmed to 100℃and treated for 2 hours, and after the filtrate was drained, the treatment was repeated again. 60mL of toluene is added, the mixture is washed three times in a boiling state, 60mL of hexane is added, and the mixture is washed twice in a boiling state, so that the solid catalyst component B is obtained.
Preparation example 3
Into a 300mL glass reaction flask with stirring, which had been sufficiently replaced with high-purity nitrogen gas, 100mL of titanium tetrachloride was added, cooled to-20℃and 8g of spherical magnesium chloride alkoxide (prepared in the same manner as in example 1 of CN1151183C, the molar ratio of ethanol to magnesium chloride in the carrier was 2.62) was added. Slowly heating to 110 ℃ in stages, adding 3.9mmol of dibutyl phthalate in the heating process, keeping the temperature at 110 ℃ for 0.5h to obtain a solid precipitate, filtering out liquid, adding 100mL of titanium tetrachloride for twice each time, washing with hexane for five times, and vacuum drying to obtain the titanium-containing solid catalyst component C.
Examples 1-17 are provided to illustrate the catalyst system and olefin polymerization process of the present invention.
Examples 1 to 6
In a 5-liter autoclave, purged with a nitrogen gas stream at 70℃for 1 hour, then the polymerization vessel was replaced with propylene in a gas phase 3 times, and 5mL of a hexane solution of triethylaluminum (triethylaluminum concentration: 0.5 mmol/mL), a hexane solution of a compound external donor compound (external donor concentration: 0.1 mmol/mL), 10mL of anhydrous hexane and 8mg of solid catalyst component A (main catalyst) were introduced under nitrogen protection. The autoclave was closed and a suitable amount of hydrogen and 1.0kg of liquid propylene were introduced; the temperature in the kettle was quickly raised to 70 ℃ with stirring. After polymerization at 70℃for 1 hour, stirring was stopped, unpolymerized propylene monomer was removed, and the polymer was collected and dried under vacuum at 70℃for 2 hours, thereby obtaining polypropylene. Wherein the composite external electron donor is tetravinyl silane (TVS) and methylcyclohexyl dimethoxy silane (C-donor/C) or tetravinyl silane (TVS) and dicyclopentyl dimethoxy silane (D-donor/D). The ratio of the composite external electron donor, the polymerization activity of the catalyst system, the polypropylene performance and the like are shown in Table 1.
Examples 7 to 11
Propylene polymerization was carried out in the same manner as in examples 1 to 6 except that solid catalyst component B was used as a main catalyst in the polymerization, and that the added composite external electron donor was tetravinyl silane (TVS) and methylcyclohexyldimethoxy silane (C-donor/C) or tetravinyl silane (TVS) and dicyclopentyl dimethoxy silane (D-donor/D). The ratio of the composite external electron donor, the polymerization activity of the catalyst system, the polypropylene performance and the like are shown in Table 1.
Examples 12 to 17
Propylene polymerization was carried out in the same manner as in examples 1 to 6 except that solid catalyst component C was used as a main catalyst in the polymerization, and that the incorporated composite external electron donor was tetravinyl silane (TVS) and methylcyclohexyldimethoxy silane (C-donor/C) or tetravinyl silane (TVS) and dicyclopentyl dimethoxy silane (D-donor/D). The ratio of the composite external electron donor, the polymerization activity of the catalyst system, the polypropylene performance and the like are shown in Table 1.
Comparative examples 1 to 2
The polymerization process was the same as in examples 1 to 6 except that the composite external donor was changed to methyl cyclohexyl dimethoxy silane (C-donor/C) or dicyclopentyl dimethoxy silane (D-donor/D) alone to prepare polypropylene. The polymerization activity of the catalyst and the properties of polypropylene are shown in Table 1.
Comparative examples 3 to 4
The polymerization method was the same as in examples 1 to 6 except that solid catalyst component B was used as a main catalyst in the polymerization, and the composite external donor was changed to methylcyclohexyldimethoxy silane (C-donor/C) or dicyclopentyl dimethoxy silane (D-donor/D) alone to prepare polypropylene. The polymerization activity of the catalyst and the properties of polypropylene are shown in Table 1.
Comparative examples 5 to 6
The polymerization method was the same as in examples 1 to 6 except that solid catalyst component C was used as a main catalyst in the polymerization, and the composite external donor was changed to methylcyclohexyldimethoxy silane (C-donor/C) or dicyclopentyl dimethoxy silane (D-donor/D) alone to prepare polypropylene. The polymerization activity of the catalyst and the properties of polypropylene are shown in Table 1.
TABLE 1
* : al represents triethylaluminum, si represents an external electron donor.
From the data in Table 1, it is understood that polymers excellent in overall properties can be obtained by using the catalyst of the present invention under the same polymerization conditions, and that the hydrogen regulation sensitivity of the catalyst can be improved by adjusting the ratio of the catalyst without changing the total amount of the external electron donor. For the main catalyst A, the isotactic index of the polymer can be effectively regulated by adjusting the proportion of the external electron donor under the condition that the melt index of the obtained polymer is basically unchanged.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.

Claims (26)

1. A catalyst system for the polymerization of olefins, characterized in that the catalyst system comprises the reaction product of:
1) A solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound;
2) An alkyl aluminum compound;
3) A composite external electron donor compound containing tetravinyl silane and hydrocarbyldialkyloxy silane;
the structure of the hydrocarbyloxysilane is shown as a formula (I):
(I)
In the formula (I), R 1 ''-R 4 ' are identical or different and are each selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl or C of (2) 7 -C 20 Alkylaryl groups of (a);
the internal electron donor compound is selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl biphenyl triacid, tributyl biphenyl triacid, tetraethyl pyromellitate, tetrabutyl pyromellitate, 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane 2, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethyl-2-isopropyl-1, 3-dimethoxybenzoate, 2-isopropyl-4-diol, 5-diethylbenzoate, 4-diethylbenzoate, 5-diol, 5-diethylbenzoate, 5-diethylbenzhydryl-3-dimethoxypropane, at least one of 9, 9-bis (benzylcarboxymethyl) fluorene and phthalic anhydride;
the dosage of the tetravinyl silane is 0.001-1.0 mol, the dosage of the hydrocarbyloxy silane is 0.001-1.0 mol, and the mol ratio of the tetravinyl silane to the hydrocarbyloxy silane is 1:100-100:1.
2. The catalyst system for olefin polymerization according to claim 1, wherein in the formula (I), R 1 ''-R 4 ' are each selected from C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl, C 3 -C 20 Cycloalkyl groups of (a).
3. The catalyst system for olefin polymerization according to claim 2, wherein R 1 ' and R 2 ' same.
4. The catalyst system for olefin polymerization according to claim 2, wherein the hydrocarbyloxysilane is selected from at least one of methylcyclohexyldimethoxy silane, diisopropyldimethoxy silane, diisobutyldimethoxy silane, dicyclohexyldimethoxy silane, dicyclopentyldimethoxy silane, methylcyclohexyldiethoxy silane, diisopropyldiethoxy silane, diisobutyldiethoxy silane, dicyclohexyldiethoxy silane, dicyclopentyldiethoxy silane, methylcyclohexyldipropoxy silane, diisopropyldipropoxy silane, diisobutyldipropoxy silane, dicyclohexyldipropoxy silane, dicyclopentyldipropoxy silane, methylcyclohexyldibutoxy silane, diisobutyldibutoxy silane, dicyclohexyldibutoxy silane, and dicyclopentyldibutoxy silane.
5. The catalyst system for olefin polymerization according to claim 4, wherein the hydrocarbyloxysilane is methylcyclohexyldimethoxy silane and/or dicyclopentyl dimethoxy silane.
6. The catalyst system for olefin polymerization according to claim 1, wherein the molar ratio of tetravinyl silane to hydrocarbyloxysilane is 1:20-20:1.
7. The catalyst system for olefin polymerization according to claim 1, wherein the solid catalyst component is produced by one or two of the following methods:
the method comprises the following steps: in an inert diluent, contacting a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an optional silane compound to form a uniform solution, and then contacting the uniform solution with a titanium compound and an internal electron donor compound in the presence of a precipitation aid to react to obtain a solid catalyst component;
the second method is as follows: and (3) carrying out contact reaction on the titanium compound and the magnesium compound and the internal electron donor compound to obtain the solid catalyst component.
8. The catalyst system for olefin polymerization according to claim 7, wherein the second method comprises the steps of:
1) Mixing a titanium compound with a spherical magnesium halide alkoxide carrier at a temperature of-30 ℃ to 0 ℃ to obtain a carrier suspension;
2) Heating the carrier suspension to 80-130 ℃, adding an internal electron donor compound in the heating process, and reacting for 0.2-2h at constant temperature to prepare a solid precipitate;
3) And washing and drying the solid precipitate to obtain the solid catalyst component.
9. The catalyst system for olefin polymerization according to claim 1, wherein the internal electron donor compound is at least one of di-n-butyl phthalate, diisobutyl phthalate, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2, 4-pentanediol dibenzoate, and phthalic anhydride;
the solid catalyst component comprises 0.01-5 mol of the internal electron donor compound per mol of magnesium.
10. The catalyst system for olefin polymerization according to claim 7 OR 8, wherein the titanium compound has the general formula of Ti (OR w ) 4-k X' k Wherein R is w Is C 1 -C 20 Alkyl, X' is Cl, br or I, and k is an integer from 0 to 4;
the amount of the titanium compound used in the solid catalyst component is 0.5 to 150 moles per mole of magnesium.
11. The catalyst system for olefin polymerization according to claim 10, wherein the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide.
12. The catalyst system for olefin polymerization according to claim 7, wherein in the first process,
the magnesium compound is selected from at least one of magnesium halide, water or alcohol complex of magnesium halide, derivative of magnesium halide with one halogen atom replaced by alkoxy or halogen alkoxy;
the organic epoxy compound is selected from aliphatic olefin, diene, halogenated aliphatic olefin, oxide of diene, glycidyl ether or internal ether with 2-8 carbon atoms;
the precipitation aid is at least one selected from the group consisting of organic acid anhydrides, organic acids, ethers and ketones.
13. The catalyst system for olefin polymerization according to claim 12, wherein the magnesium compound is magnesium halide.
14. The catalyst system for olefin polymerization according to claim 13, wherein the magnesium compound is magnesium chloride.
15. The catalyst system for olefin polymerization according to claim 12, wherein the organic epoxy compound is at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.
16. The catalyst system for olefin polymerization according to claim 12, wherein the precipitation aid is at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether and pentyl ether.
17. The catalyst system for olefin polymerization according to claim 8, wherein, in the second method,
the general formula of the magnesium halide alkoxide carrier is MgX 2 P (ROH), X is Cl, br or I; r is C 1 -C 18 An alkyl group; p is 0.1-6.
18. The catalyst system for the polymerization of olefins according to claim 17 in which X is Cl.
19. The catalyst system for the polymerization of olefins according to claim 17 in which R is C 2 -C 4 Straight chain alkyl of (a).
20. The catalyst system for olefin polymerization according to claim 1, wherein the alkyl aluminum compound has a general formula of AlR ' ' '. d X 1 3-d Wherein R' "is C l -C 8 Alkyl, X 1 Is a halogen atom, 0 < d.ltoreq.3, which may be the same or different when two or three R ' ''s are contained.
21. The catalyst system for olefin polymerization according to claim 20, wherein the alkyl aluminum compound is triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, al (n-C) 6 H 13 ) 3 、Al(n-C 8 H 17 ) 3 And AlEt 2 At least one of Cl.
22. The catalyst system for olefin polymerization according to claim 20, wherein the molar ratio of aluminum in the alkyl aluminum compound to titanium in the solid catalyst component is 1-1000:1.
23. The catalyst system for olefin polymerization according to claim 22, wherein the molar ratio of aluminum in the alkyl aluminum compound to titanium in the solid catalyst component is 1-500:1.
24. A process for the polymerization of olefins, comprising: contacting one or more olefins with the catalyst system of any of claims 1-23 under olefin polymerization conditions; the general formula of the olefin is CH 2 =CH-R V Wherein R is V Is hydrogen or C 1 -C 6 An alkyl group.
25. The olefin polymerization process of claim 24 wherein the olefin is propylene and/or ethylene.
26. The olefin polymerization process of claim 25 wherein the olefin is propylene.
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