CN115806635A - 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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CN115806635A
CN115806635A CN202111083877.8A CN202111083877A CN115806635A CN 115806635 A CN115806635 A CN 115806635A CN 202111083877 A CN202111083877 A CN 202111083877A CN 115806635 A CN115806635 A CN 115806635A
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electron donor
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magnesium
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CN115806635B (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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China Petroleum and Chemical Corp
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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 a reaction product of the following components: 1) A solid catalyst component comprising titanium, magnesium, a halogen, and an internal electron donor compound; 2) An alkyl aluminum compound; 3) A composite external electron donor compound comprising tetravinyl silane and hydrocarbyl dihydrocarbyloxy silane; the structure of the alkyl dialkoxyl silane is shown as a formula (I), wherein R in the formula (I) 1 ″‑R 4 "identical or different, each being selected from C 1 ‑C 20 Straight chain alkyl group of (1), C 3 ‑C 20 Branched alkyl of (2), C 3 ‑C 20 Cycloalkyl of, C 6 ‑C 20 Aryl or C of 7 ‑C 20 An alkylaryl group of (2).

Description

Catalyst system for olefin polymerization and olefin polymerization method
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly 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: a main catalyst (solid catalyst component), (2) a cocatalyst (usually an alkyl aluminum 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 stereoregularity of the polymer and also affects the activity, hydrogen response and the like of the catalyst to different degrees.
Although a variety of compounds are known to be useful as external electron donors, the use of different external electron donors for a particular catalyst may result in different polymer properties. The choice of a suitable external electron donor may be particularly compatible with the specific catalyst system, i.e. finding a suitable external electron donor may significantly improve certain properties of the polymer product, such as isotacticity, molecular weight distribution and hydrogen response, while having no or little effect on other properties. It is therefore essential to find external electron donors which provide polymers with a good combination of properties for a particular catalyst.
Patent document US5100981 discloses a catalyst system consisting of a main catalyst and a mixture of two external electron donors, cyclohexyl methyl dimethoxy silane (CHMMS) and phenyl triethoxy silane.
Patent document JP19820199728 also describes a catalyst system which is constructed 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, and when the catalyst components are used for propylene polymerization, the external electron donor used is an external electron donor commonly used in industry at present, such as C-donor. Although patent document CN03109781.2 also uses different external electron donors for comparison, such as diisobutyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), bis (cyclobutylmethyl) dimethoxysilane, etc., in addition to C-donor, it is found from the patent document disclosed that such catalyst systems have poor hydrogen response.
Patent documents with application numbers CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN200410073623.8 and CN200410073621.9 respectively describe catalyst components using polyol ester compounds and o-phthalic ester compounds to compound internal electron donors, and when the catalyst components are used for propylene polymerization, the used external electron donor hydrocarbyl dialkoxy silane is an external electron donor commonly used in the industry at present, such as CHMMS and the like. In addition, patent document CN03109781.2 also uses different external electron donors as comparison, for example, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane (DCPMS), bis (cyclobutylmethyl) dimethoxysilane, etc. in addition to CHMMS, and the catalyst system shows high activity, high orientation ability and wide molecular weight distribution of the prepared polymer.
Patent documents CN1091748A, CN1330086A, CN101050245A, US6020279A, CN1580136A and CN1463990A describe preparation of spherical magnesium halide alcoholate carrier and synthesis method of catalyst, and the patent documents generally use external electron donor hydrocarbyl dialkoxy silane as external electron donor.
The research of the existing olefin polymerization catalyst mainly focuses on improving the olefin polymerization activity and the properties of polymer such as the tacticity and the like. However, in the case that the kind of the external electron donor is not changed, it is difficult to control the properties (e.g., isotacticity and melt index) of the polymer to some extent by adjusting the amount of the external electron donor, so that the application of the olefin polymerization catalyst is limited. For this reason, it is necessary to develop a new catalyst to solve the problem.
Disclosure of Invention
The present inventors have unexpectedly found that a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound can be combined with a specific solid catalyst component under the same polymerization conditions to obtain a polymer having excellent overall properties by adding tetraenylsilane and a hydrocarbyl dihydrocarbyloxysilane compound as the external electron donor compound during olefin polymerization. By adjusting the polymerization conditions and the proportion of the composite external electron donor, the obtained catalyst system has the concrete characteristics of 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 adjusted by adjusting the proportion of the external electron donor. The present invention has been made based on this finding.
A first aspect of the present invention provides a catalyst system for the polymerisation of olefins, the catalyst system comprising the reaction product of:
1) A solid catalyst component comprising titanium, magnesium, a halogen, and an internal electron donor compound;
2) An alkyl aluminum compound;
3) A composite external electron donor compound comprising tetravinylsilane and hydrocarbyl dihydrocarbyloxysilane;
the structure of the alkyl dialkoxyl silane is shown as the formula (I):
Figure BDA0003264023320000031
in the formula (I), R 1 ″-R 4 "identical or different, each being selected from C 1 -C 20 Straight chain alkyl of (1), C 3 -C 20 Branched alkyl of C 3 -C 20 Cycloalkyl of (C) 6 -C 20 Aryl or C of 7 -C 20 An alkylaryl group of (2).
A second aspect of the present invention provides an olefin polymerisation process comprising: contacting one or more olefins with the catalyst system described above under olefin polymerization conditions.
Compared with the conventional external electron donors such as C-donor D-donor the like, the composite external electron donor compound in the catalyst system is combined with a specific solid catalyst component, and a polymer with more excellent comprehensive performance can be obtained under the same polymerization conditions. By adjusting the polymerization conditions and the proportion of the composite external electron donor, the obtained catalyst system has the concrete characteristics of 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 adjusted 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 in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention there is provided a catalyst system for the polymerisation of olefins, the catalyst system 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 comprising tetravinylsilane and hydrocarbyl dihydrocarbyloxysilane;
the structure of the hydrocarbyl dialkoxyl silane is shown as the formula (I):
Figure BDA0003264023320000041
in the formula (I), R 1 ″-R 4 "identical or different, each being selected from C 1 -C 20 Straight chain alkyl of (1), C 3 -C 20 Branched alkyl of (2), C 3 -C 20 Cycloalkyl of, C 6 -C 20 Aryl or C of 7 -C 20 An alkylaryl group of (a).
In the present invention, C 1 -C 20 Straight chain alkyl group of (1), C 3 -C 20 Non-limiting examples of branched alkyl groups of (a) 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 the alkylaryl group of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl and isopropylphenyl.
Preferably, in the formula (I), R 1 ″-R 4 Each is selected from C 1 -C 20 Straight chain alkyl of (1), C 3 -C 20 Branched alkyl of C 3 -C 20 Cycloalkyl of (2), preferably R 1 "and R 2 "are the same.
Specific examples of the hydrocarbyl dihydrocarbyloxysilane in the present invention include, but are not limited to: the hydrocarbyl dialkoxysilane is selected from at least one of methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, methylcyclohexyldiethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldiethoxysilane, methylcyclohexyldipropoxysilane, diisopropyldipropoxysilane, diisobutyldropoxysilane, dicyclopentyldipropoxysilane, methylcyclohexyldibutoxysilane, diisopropyldibutoxysilane, diisobutyldibutoxysilane, dicyclohexyldibutoxysilane, and dicyclopentyldibutoxysilane.
Preferably, the hydrocarbyl dialkoxysilane is methylcyclohexyldimethoxysilane and/or dicyclopentyldimethoxysilane.
The tetravinylsilane in the invention can be prepared by a conventional synthesis method, and can also be purchased by a general chemical product purchasing method.
According to the invention, the tetravinylsilane is used in an amount of 0.001 to 1.0 mole, the hydrocarbyldihydrocarbyloxysilane in an amount of 0.001 to 1.0 mole per mole of aluminum in the aluminum alkyl compound, and the molar ratio of tetravinylsilane to hydrocarbyldihydrocarbyloxysilane 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 respectively 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 the following method one or method two:
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 with a titanium compound and an internal electron donor compound to react in the presence of a precipitation assisting agent to obtain the solid catalyst component.
In the first method of the present invention, the magnesium compound may be at least one selected from magnesium halide, water or alcohol complex of magnesium halide, and derivative in which one halogen atom in magnesium halide molecule is substituted by hydrocarbyloxy group or halohydrocarbyloxy group. Preferably, the magnesium compound is a magnesium halide, e.g., 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, dienes, halogenated aliphatic olefins, oxides of dienes, glycidyl ethers, and internal ethers. 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 selected from at least one of 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, ethyl ether, propyl ether, butyl ether and pentyl ether.
The inert diluent may be a conventional choice in the art. The inert diluent can adopt benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbon compounds; toluene and/or xylene are preferred.
The specific operation of the first process according to the present invention can be carried out according to the preparation process of the solid catalyst component disclosed in patent documents CN102464746A, CN1258684A, the relevant disclosure of which is incorporated herein by reference in its entirety.
The second method comprises the following steps: and (3) carrying out contact reaction on a titanium compound, a magnesium compound and an internal electron donor compound to obtain a solid catalyst component.
The second process can be carried out according to conventional methods in the prior art. According to a preferred embodiment, it comprises the following steps:
1) Mixing a titanium compound with a spherical magnesium halide alcoholate 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 obtain 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 alcoholate 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 The linear alkyl group of (1); p is 0.1 to 6.
The preparation method of the spherical magnesium halide alcoholate carrier can comprise the following steps: mixing magnesium halide and low-carbon alcohol, heating to react to generate magnesium halide alcoholate melt, wherein the reaction temperature is 90-140 ℃, putting the magnesium halide alcoholate melt into a cooled inert medium after high shear action in a dispersion medium to form spherical magnesium halide alcoholate particles, and washing and drying to obtain the spherical carrier. The high shear effect can be obtained by a conventional method such as a high-speed stirring method (for example, patent document CN 00109216.2), a spraying method (for example, patent document US 6020279), and a super-gravity rotating bed (for example, patent document CN 1580136) and an emulsifier method (for example, patent document CN 1463990). The dispersant system (dispersion medium) can be hydrocarbon inert solvent such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert cooling medium can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.
The spherical magnesium halide alcoholate carrier of the invention can be obtained by the preparation methods of patent documents CN1036011C, CN1151183C, CN100491410, US6020279, CN1267508C and CN1463990, the relevant contents of the disclosure of which are incorporated herein by reference in their entirety.
According to the invention, in the first method and the second method, the internal electron donor compound comprises a mono-element or multi-element aliphatic carboxylic ester compound and an aromatic carboxylic ester compound, a phosphate ester compound, an acid anhydride, a ketone, an alcohol, an amine, an ether compound and a derivative thereof, a glycol ester compound, or a complex ligand of any component 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, 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 naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl hemimellitate, tributyl hemimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate. More preferably, the internal electron donor compound is dibutyl phthalate and/or diisobutyl phthalate.
<xnotran> , 2- (2- ) -1,3- ,2- -1,3- ,2- -1,3- ,2- -1,3- ,2- -1,3- ,2- -1,3- ,2- (2- ) -1,3- ,2- (2- ) -1,3- ,2- ( ) -1,3- ,2- ( ) -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- , </xnotran> <xnotran> 2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2,2- (2- ) -1,3- ,2- -2- -1,3- ,2- -2- (2- ) -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- ( ) -1,3- ,2- -2- -1,3- ,2- (1- ) -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- , </xnotran> 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-isoamyl-1, 3-dimethoxypropane.
When the internal electron donor compound is a glycol ester-based compound, non-limiting examples of the internal electron donor compound include: 2-isopropyl-2-isoamyl-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.
When the internal electron donor compound is an acid anhydride 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 than 2 internal electron donors are contained, the used internal electron donor compounds can be used together in various ways, can be used in different steps and under different conditions, and can also be added simultaneously, and the addition of the used internal electron donor compounds is not in sequence.
According to the invention, in the first and second processes, 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 of 0 to 4.
Preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium.
According to the present invention, the titanium compound may be used in an amount of 0.5 to 150 moles per mole of magnesium in the solid catalyst component.
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 radical, X 1 Is a halogen atom, 0 < d.ltoreq.3, and when two or three R' "are contained, they may be the same or different. Preferably, the alkyl aluminum compound is triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, 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 aluminium in the aluminium alkyl compound to titanium in the solid catalyst component is in the range of from 1 to 1000: 1, more preferably in the range of 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 either individually or as a mixture of the two components.
According to different requirements on polymer properties, the catalyst system can be directly used for the polymerization reaction of olefin; or the catalyst can be prepolymerized with olefin to produce prepolymerized catalyst, and then the prepolymerized catalyst is polymerized with olefin.
According to a second aspect of the present invention, there is provided an olefin polymerisation process comprising: contacting one or more olefins with the catalyst system described above 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 alkene isThe hydrocarbon is propylene and/or ethylene; more preferably, the olefin is propylene.
In addition, the olefin may be polymerized in the presence of small amounts of diolefins, depending on the particular application.
In the present invention, the olefin polymerization reaction 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 an operation in which liquid-phase and gas-phase polymerization stages are combined. The olefin polymerization may be carried out according to 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 from 0 to 150 ℃ and preferably from 60 to 90 ℃ and the polymerization pressure is atmospheric or higher.
The parameters not defined in the present invention are all the conventional technical means in the field.
The present invention is further illustrated by the following examples. But is not limited by these examples.
In the following examples and comparative examples:
1) The isotactic index of the polymer is determined by the n-heptane extraction method, according to GB/T2412-2008, 2g of a dried polymer sample is placed in an extractor, and after extraction with boiling n-heptane for 6 hours, the residue is dried to constant weight; the ratio of the obtained polymer weight (g) 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 to 3 are intended to illustrate the preparation of the solid catalyst component of the present invention.
Preparation example 1
100mL of titanium tetrachloride was charged into a 300mL stirred glass reaction flask sufficiently purged with high-purity nitrogen, cooled to-20 ℃ and 8g of a spherical magnesium chloride alcoholate (prepared by the method of example 1 in patent document CN1151183C, the molar ratio of ethanol to magnesium chloride in the carrier was 2.62) was added. Slowly raising the temperature to 110 ℃ in stages, adding 2.5mmol of 2, 4-pentanediol dibenzoate and 3.9mmol of dibutyl phthalate in the temperature raising process, keeping the temperature at 110 ℃ for 0.5h to obtain solid precipitates, filtering out liquid, adding 100mL of titanium tetrachloride for treatment twice each time, washing with hexane five times, and drying in vacuum to obtain the solid catalyst component A.
Preparation example 2
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 50 ℃ under stirring, the mixture is maintained for 2.5 hours to completely dissolve the solid, 1.4g of phthalic anhydride is added, and the mixture is maintained for 1 hour. Cooling the solution to below-25 ℃, and dripping TiCl within 1 hour 4 And (2) slowly heating to 80 ℃, gradually separating out a solid in the heating process, adding 6mmol of 2, 4-pentanediol dibenzoate, maintaining the temperature for 1 hour, filtering, adding 70mL of toluene, and washing twice to obtain a solid precipitate. Toluene 60mL was then added to the solid 4 40mL, warmed to 100 ℃ and treated for 2 hours, after draining the filtrate, the treatment was repeated again. Adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, and washing for two times in the boiling state to obtain a solid catalyst component B.
Preparation example 3
A300 mL stirred glass reaction flask fully purged with high-purity nitrogen was charged with 100mL of titanium tetrachloride, cooled to-20 ℃ and charged with 8g of spherical magnesium chloride alcoholate (prepared by the method of example 1 in patent document CN1151183C, molar ratio of ethanol to magnesium chloride in the carrier was 2.62). Slowly raising the temperature to 110 ℃ in stages, adding 3.9mmol of dibutyl phthalate in the temperature raising process, keeping the temperature at 110 ℃ for 0.5h to obtain a solid precipitate, filtering out liquid, adding 100mL of titanium tetrachloride for treatment twice, washing with hexane five times, and drying in vacuum to obtain the titanium-containing solid catalyst component C.
Examples 1-17 are intended 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 stream at 70 ℃ for 1 hour, then the polymerizer was replaced with vapor-phase propylene 3 times, and 5mL of a hexane solution of triethylaluminum (concentration of triethylaluminum: 0.5 mmol/mL), a hexane solution of a compound external electron donor compound (concentration of external electron donor: 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 an appropriate amount of hydrogen and 1.0kg of liquid propylene were introduced; the temperature in the kettle was rapidly raised to 70 ℃ with stirring. After polymerization at 70 ℃ for 1 hour, the stirring was stopped, the unpolymerized propylene monomer was removed, and the polymer was collected and vacuum-dried at 70 ℃ for 2 hours, to thereby obtain polypropylene. Wherein the composite external electron donor is Tetravinylsilane (TVS) and methylcyclohexyldimethoxysilane (C-donor/C) or Tetravinylsilane (TVS) and dicyclopentyldimethoxysilane (D-donor/D). The compounding 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 conducted in the same manner as in examples 1 to 6 except that the solid catalyst component B was used as a main catalyst in the polymerization and the composite external electron donor was Tetravinylsilane (TVS) and methylcyclohexyldimethoxysilane (C-donor/C) or Tetravinylsilane (TVS) and dicyclopentyldimethoxysilane (D-donor/D). The compounding 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 conducted in the same manner as in examples 1 to 6, except that the solid catalyst component C was used as a main catalyst in the polymerization, and the composite external electron donor was either Tetravinylsilane (TVS) and methylcyclohexyldimethoxysilane (C-donor/C) or Tetravinylsilane (TVS) and dicyclopentyldimethoxysilane (D-donor/D). The compounding 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 method is the same as that of examples 1-6, except that the composite external electron donor is replaced by separately adding methylcyclohexyldimethoxysilane (C-doror/C) or dicyclopentyldimethoxysilane (D-doror/D) to prepare polypropylene. The polymerization activity of the catalyst, the properties of polypropylene, and the like are shown in Table 1.
Comparative examples 3 to 4
The polymerization method is the same as that of examples 1-6, except that the solid catalyst component B is used as a main catalyst during polymerization, and the composite external electron donor is changed into methyl cyclohexyl dimethoxy silane (C-doror/C) or dicyclopentyl dimethoxy silane (D-doror/D) which is added separately, so as to prepare the polypropylene. The polymerization activity of the catalyst, the properties of polypropylene, and the like are shown in Table 1.
Comparative examples 5 to 6
The polymerization method is the same as that of examples 1-6, except that the solid catalyst component C is used as a main catalyst during polymerization, and the composite external electron donor is changed to be methyl cyclohexyl dimethoxy silane (C-donor/C) or dicyclopentyl dimethoxy silane (D-donor/D) which is added separately, so as to prepare the polypropylene. The polymerization activity of the catalyst, the properties of polypropylene, and the like are shown in Table 1.
TABLE 1
Figure BDA0003264023320000141
Figure BDA0003264023320000151
* : al stands for triethylaluminum and Si stands for an external electron donor.
As can be seen from the data in Table 1, under the same polymerization conditions, the catalyst of the present invention can obtain polymers with excellent comprehensive properties, and the hydrogen response of the catalyst can be improved by adjusting the proportion of the catalyst of the present invention under the condition that the total amount of external electron donors is not changed. For the main catalyst A, the isotactic index of the polymer can be effectively adjusted by adjusting the proportion of the external electron donor under the condition that the melt index of the obtained polymer is basically unchanged.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 described embodiments.

Claims (10)

1. A catalyst system for the polymerization of olefins, the catalyst system comprising the reaction product of:
1) A solid catalyst component comprising titanium, magnesium, a halogen, and an internal electron donor compound;
2) An alkyl aluminum compound;
3) A composite external electron donor compound comprising tetravinyl silane and hydrocarbyl dihydrocarbyloxy silane;
the structure of the alkyl dialkoxyl silane is shown as the formula (I):
Figure FDA0003264023310000011
in the formula (I), R 1 ″-R 4 "identical or different, each being selected from C 1 -C 20 Straight chain alkyl group of (1), C 3 -C 20 Branched alkyl of C 3 -C 20 Cycloalkyl of, C 6 -C 20 Aryl or C of 7 -C 20 An alkylaryl group of (a).
2. The catalyst system for olefin polymerization according to claim 1, wherein in the formula (I), R is 1 ″-R 4 Each is selected from C 1 -C 20 Straight chain alkyl of (1), C 3 -C 20 Branched alkyl of (2), C 3 -C 20 Cycloalkyl of (2), preferably R 1 "and R 2 "same;
preferably, the hydrocarbyl dialkoxysilane is selected from at least one of methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, methylcyclohexyldiethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldiethoxysilane, methylcyclohexyldipropoxysilane, diisopropyldipropoxysilane, diisobutyldropoxysilane, dicyclohexyldipropoxysilane, dicyclopentyldipropoxysilane, methylcyclohexyldibutoxysilane, diisopropyldibutoxysilane, diisobutyldibutoxysilane, dicyclohexyldibutoxysilane and dicyclopentyldibutoxysilane, more preferably methylcyclohexyldimethoxysilane and/or dicyclopentyldimethoxysilane.
3. The catalyst system for olefin polymerization according to claim 1 or 2, wherein the tetravinylsilane is used in an amount of 0.001 to 1.0 mole, the hydrocarbyldialkoxysilane is used in an amount of 0.001 to 1.0 mole, and the molar ratio of tetravinylsilane to hydrocarbyldialkoxysilane is 1: 100 to 100: 1, preferably 1: 20 to 20: 1, per mole of aluminum in the aluminum alkyl compound.
4. The catalyst system for olefin polymerization according to claim 1, wherein the solid catalyst component is prepared by the following method one or method two:
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 in the presence of a precipitation assistant, contacting and reacting the uniform solution with a titanium compound and an internal electron donor compound to obtain a solid catalyst component;
the second method comprises the following steps: the method comprises the following steps of (1) carrying out contact reaction on a titanium compound, a magnesium compound and an internal electron donor compound to obtain a solid catalyst component;
preferably, method two comprises the steps of:
1) Mixing a titanium compound with a spherical magnesium halide alcoholate 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 obtain a solid precipitate;
3) And washing and drying the solid precipitate to obtain the solid catalyst component.
5. The catalyst system for olefin polymerization according to claim 1 or 4, wherein the internal electron donor compound comprises mono-or poly-aliphatic carboxylic acid ester compounds and aromatic carboxylic acid ester compounds, phosphoric acid ester compounds, acid anhydrides, ketones, alcohols, amines, ether compounds and derivatives thereof, glycol ester compounds, or double ligands of any component thereof;
preferably, the internal electron donor compound is selected from the group consisting 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, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl adipate, diethyl naphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl hemimellitate, tributyl hemimellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-dimethoxybutyl 1, 3-dimethoxybutyl 2-dimethoxypropyl propane, 2-1, 2-dimethoxybutyl-1, 2-dimethoxypropyl propane, 2-1, 2-dimethoxybutyl propane, 2-1, 2-dimethoxycyclohexyl propane, 2-ethyl-1, 2-1, 3-dimethoxyphenyl-ethyl-1, 2-dimethoxypropane, 2-1, 2-dimethoxyphenyl-1, 2-dimethoxypropane, 2-dimethoxyphenyl-cyclohexylpropane, 1, 2-ethyl-1, 2-diisopropylpropane, 1, 2-dimethoxypropane, <xnotran> 3- ,2- ( ) -1,3- ,2- ( ) -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2,2- (2- ) -1,3- ,2- -2- -1,3- ,2- -2- (2- ) -1,3- , </xnotran> <xnotran> 2,2- -1,3- ,2,2- -1,3- ,2,2- -1,3- ,2,2- ( ) -1,3- ,2- -2- -1,3- ,2- (1- ) -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,2- -2- -1,3- ,9,9- , </xnotran> At least one of 2-isopropyl-2-isoamyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 9-bis (phenylmethylcarboxymethyl) fluorene, and phthalic anhydride;
further preferably, the internal electron donor compound is at least one of dibutyl phthalate, diisobutyl phthalate, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2, 4-pentanediol dibenzoate and phthalic anhydride;
in the solid catalyst component, the dosage of the internal electron donor compound is 0.01-5 mol per mol of magnesium.
6. The catalyst system for the polymerization of olefins according to claim 1 OR 4, wherein 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 of 0 to 4; preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium;
the titanium compound is used in an amount of 0.5 to 150 moles per mole of magnesium in the solid catalyst component.
7. The catalyst system for olefin polymerization according to claim 4, wherein, in the first process,
the magnesium compound is selected from at least one of magnesium halide, water or alcohol complex of magnesium halide, and derivatives of magnesium halide, wherein one halogen atom in the magnesium halide molecule is substituted by hydrocarbonoxy or halohydrocarbonoxy; the magnesium compound is preferably a magnesium halide, more preferably magnesium chloride;
the organic epoxy compound is selected from aliphatic olefin with 2-8 carbon atoms, diene, halogenated aliphatic olefin, oxide of diene, glycidyl ether or internal ether; preferably at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran;
the precipitation aid is selected from at least one of 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, ethyl ether, propyl ether, butyl ether, and amyl ether.
8. The catalyst system for olefin polymerization according to claim 4, wherein in the second process,
said halogenationThe carrier of magnesium alcoholate has the general formula of MgX 2 P (ROH), X is Cl, br or I, preferably Cl; r is C 1 -C 18 Alkyl, preferably C 2 -C 4 The linear alkyl group of (1); p is 0.1 to 6.
9. Catalyst system for the polymerization of olefins according to claim 1 in which the alkylaluminum compound has the general formula AlR' d X 1 3-d Wherein R' "is C 1 -C 8 Alkyl radical, X 1 Is a halogen atom, 0 < d.ltoreq.3, which may be the same or different when two or three R' "are present;
preferably, the alkyl aluminum compound is triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, 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 aluminium in the aluminium alkyl compound to titanium in the solid catalyst component is in the range of from 1 to 1000: 1, more preferably in the range of from 1 to 500: 1.
10. A process for the polymerization of olefins, the process comprising: contacting one or more olefins with the catalyst system of any of claims 1-9 under olefin polymerization conditions; the olefin has a general formula of CH 2 ＝CH-R V Wherein R is V Is hydrogen or C 1 -C 6 An alkyl group;
preferably, the olefin is propylene and/or ethylene; more preferably, the olefin is propylene.
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