CN109111537B

CN109111537B - Catalyst component for olefin polymerization and catalyst thereof

Info

Publication number: CN109111537B
Application number: CN201710484889.9A
Authority: CN
Inventors: 张锐; 谭忠; 周奇龙; 徐秀东; 尹珊珊; 李凤奎; 于金华; 宋维玮
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-06-23
Filing date: 2017-06-23
Publication date: 2021-03-16
Anticipated expiration: 2037-06-23
Also published as: CN109111537A

Abstract

The invention relates to a catalyst component for olefin polymerization and a catalyst thereof. The catalyst component comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises at least one 2-carbonate phenyl ketone compound shown in a general formula (I). The catalyst for olefin polymerization provided by the invention has the advantages of good hydrogen regulation performance, high polymerization activity, good stereospecific capacity and the like. When the catalyst is used for olefin polymerization reaction, the obtained polymer has better isotacticity, higher melt index, wider molecular weight distribution and higher bulk density. The novel catalyst provided by the invention has excellent comprehensive performance and wide application prospect.

Description

Catalyst component for olefin polymerization and catalyst thereof

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to a catalyst component for olefin polymerization and a catalyst thereof.

Background

Solid titanium catalyst components based on magnesium, titanium, halogen and an electron donor, known in the art as Ziegler-Natta catalysts, are used in CH2 ═ CHR olefin polymerization, and in particular in the polymerization of alpha olefins having 3 or more carbon atoms, polymers with higher yields and higher stereoregularity can be obtained. Wherein the internal electron donor compound is one of the essential components of the Ziegler-Natta catalyst component. Starting from the second generation of Z-N catalysts, the development of each generation of catalysts is marked by the successful application of a novel internal electron donor, and from monocarboxylic ester compounds such as ethyl benzoate, to currently widely used dicarboxylic ester compounds such as di-N-butyl phthalate or diisobutyl phthalate, to 1, 3-diethers (CN1020448C), succinates (CN1313869) and 1, 3-diol esters (CN1213080C), the internal electron donor can endow the catalysts with different properties, and the development of the internal electron donor promotes the continuous updating of polyolefin catalysts.

In addition to the above several electron donor compounds, in recent years, a class of internal electron donors containing carbonate groups has attracted more and more attention, and CN102762603A and CN102712704A provide polyolefin catalysts containing compounds containing two carbonate groups in the molecule as internal electron donors, mainly bicarbonates of aromatic pyrocatechol, naphthalenediol and biphenyldiol. The internal electron donor in WO2015185495A1 also contains a dicarbonate group and is a dicarbonate of 2, 4-pentanediol structure. In addition to the dicarbonate compounds, internal electron donors containing both carbonate groups and other functional groups in the molecule have also been reported, and CN103764689A provides an internal electron donor containing a carbonate group and an ether bond, wherein two groups are separated by two carbon atoms. EP2636687a1 and WO2015185489a1 respectively report compounds containing both a carbonate group and an alcohol ester group and compounds containing both a carbonate group and an amide ester group as electron donors, which are obtained by reacting aliphatic diols as starting materials. However, these compounds containing carbonate groups have certain disadvantages as internal electron donors, such as higher raw material cost, not broad molecular weight distribution (CN102762603A, CN102712704A), lower melt index (CN103764689A), or too low activity (WO2015185495a1, WO2015185489a 1).

Despite the considerable research work that has been done in the field of Ziegler-Natta catalysts, there is still a need for new or improved processes for the preparation of Ziegler-Natta catalysts with higher performance requirements. Therefore, there is a problem that research and development of a catalyst component for olefin polymerization and a catalyst thereof, which have high activity, good stereospecificity, good hydrogen response, and a wide polymer molecular weight distribution, are urgently required.

Disclosure of Invention

The technical problem to be solved by the present invention is to provide a catalyst component for olefin polymerization and a catalyst thereof, aiming at the defects of the prior art. The present inventors have conducted extensive and intensive experimental studies in the technical fields of olefin polymerization catalyst components and catalysts therefor, and have found that a catalyst excellent in overall performance can be obtained by using a 2-carbonate phenyl ketone compound represented by the general formula (I) as an internal electron donor compound. When the catalyst is used for olefin polymerization reaction, the catalyst has high activity and good hydrogen regulation sensitivity, and the obtained polyolefin resin has good stereospecificity and wide molecular weight distribution.

To this end, the present invention provides in a first aspect a catalyst component for olefin polymerization comprising magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises at least one 2-carbonate phenyl ketone compound represented by the general formula (I);

in the general formula (I), R₁And R₂Identical or different, are each independently selected from substituted or unsubstituted C₁-C₂₀Alkyl of (C)₃-C₂₀Cycloalkyl of, C₆-C₂₀Aryl or C of₇-C₂₀Aralkyl group of (1); preferably R₁And R₂Each independently selected from substituted or unsubstituted C₁-C₆Alkyl of (C)₃-C₁₀Cycloalkyl or C₆-C₁₀Aryl of (a); more preferably R₁And R₂Each independently selected from substituted or unsubstituted C₁-C₆Alkyl groups of (a); further preferred is R₁And R₂Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, or isohexyl.

The term "substituted" as used herein means that the hydrogen of each group is substituted with a halogen atom, an alkyl group or an alkoxy group.

Examples of suitable 2-carbonate phenyl ketones of formula (I) include, but are not limited to:

2-methyl carbonate acetophenone, 2-ethyl carbonate acetophenone, 2-n-propyl carbonate acetophenone, 2-isopropyl carbonate acetophenone, 2-allyl carbonate acetophenone, 2-n-butyl carbonate acetophenone, 2-isobutyl carbonate acetophenone, 2-tert-butyl carbonate acetophenone, 2-n-pentyl carbonate acetophenone, 2-isopentyl carbonate acetophenone, 2-tert-pentyl carbonate acetophenone, 2-n-hexyl carbonate acetophenone, 2-isohexyl carbonate acetophenone, 2-tert-hexyl carbonate acetophenone, 2-n-heptyl carbonate acetophenone, 2-isoheptyl carbonate acetophenone, 2-tert-heptyl carbonate acetophenone; 2-methylcarbonate propiophenone, 2-ethylcarbonate propiophenone, 2-n-propylcarbonate propiophenone, 2-isopropylcarbonate propiophenone, 2-allylcarbonate propiophenone, 2-n-butylcarbonate propiophenone, 2-isobutylcarbonate propiophenone, 2-tert-butylcarbonate propiophenone, 2-n-pentylcarbonate propiophenone, 2-isopentylcarbonate propiophenone, 2-tert-pentylcarbonate propiophenone, 2-n-hexylcarbonate propiophenone, 2-isohexylcarbonate propiophenone, 2-tert-hexylcarbonate propiophenone, 2-n-heptylcarbonate propiophenone, 2-isoheptylcarbonate propiophenone, 2-tert-heptylcarbonate propiophenone; 2-methyl carbonate benzyl ketone, 2-ethyl carbonate benzyl ketone, 2-n-propyl carbonate benzyl ketone, 2-isopropyl carbonate benzyl ketone, 2-allyl carbonate benzyl ketone, 2-n-butyl carbonate benzyl ketone, 2-isobutyl carbonate benzyl ketone, 2-tert-butyl carbonate benzyl ketone, 2-n-pentyl carbonate benzyl ketone, 2-isoamyl carbonate benzyl ketone, 2-tert-pentyl carbonate benzyl ketone, 2-n-hexyl carbonate benzyl ketone, 2-isohexyl carbonate benzyl ketone, 2-tert-hexyl carbonate benzyl ketone, 2-n-heptyl carbonate benzyl ketone, 2-isoheptyl carbonate benzyl ketone, and 2-tert-heptyl carbonate benzyl ketone.

Preferably selected from the group consisting of 2-methyl carbonate acetophenone, 2-ethyl carbonate acetophenone, 2-n-propyl carbonate acetophenone, 2-isopropyl carbonate acetophenone, 2-allyl carbonate acetophenone, 2-n-butyl carbonate acetophenone, 2-isobutyl carbonate acetophenone, 2-n-pentyl carbonate acetophenone, 2-isopentyl carbonate acetophenone, 2-n-hexyl carbonate acetophenone, 2-isohexyl carbonate acetophenone, 2-n-heptyl carbonate acetophenone, 2-isoheptyl carbonate acetophenone; 2-methyl carbonate propiophenone, 2-ethyl carbonate propiophenone, 2-n-propyl carbonate propiophenone, 2-isopropyl carbonate propiophenone, 2-allyl carbonate propiophenone, 2-n-butyl carbonate propiophenone, 2-isobutyl carbonate propiophenone, 2-n-amyl carbonate propiophenone, 2-isoamyl carbonate propiophenone, 2-n-hexyl carbonate propiophenone, 2-isohexyl carbonate propiophenone, 2-n-heptyl carbonate propiophenone, 2-isoheptyl carbonate propiophenone; 2-methyl carbonate benzyl ketone, 2-ethyl carbonate benzyl ketone, 2-n-propyl carbonate benzyl ketone, 2-isopropyl carbonate benzyl ketone, 2-allyl carbonate benzyl ketone, 2-n-butyl carbonate benzyl ketone, 2-isobutyl carbonate benzyl ketone, 2-n-pentyl carbonate benzyl ketone, 2-isoamyl carbonate benzyl ketone, 2-n-hexyl carbonate benzyl ketone, 2-isohexyl carbonate benzyl ketone, 2-n-heptyl carbonate benzyl ketone and 2-isoheptyl carbonate benzyl ketone.

Most preferably selected from the group consisting of 2-methyl carbonate acetophenone, 2-ethyl carbonate acetophenone, 2-n-propyl carbonate acetophenone, 2-isopropyl carbonate acetophenone, 2-allyl carbonate acetophenone, 2-n-butyl carbonate acetophenone, 2-isobutyl carbonate acetophenone, 2-n-pentyl carbonate acetophenone, 2-isopentyl carbonate acetophenone, 2-n-hexyl carbonate acetophenone, 2-isohexyl carbonate acetophenone; 2-methyl carbonate propiophenone, 2-ethyl carbonate propiophenone, 2-n-propyl carbonate propiophenone, 2-isopropyl carbonate propiophenone, 2-allyl carbonate propiophenone, 2-n-butyl carbonate propiophenone, 2-isobutyl carbonate propiophenone, 2-n-amyl carbonate propiophenone, 2-isoamyl carbonate propiophenone, 2-n-hexyl carbonate propiophenone, 2-isohexyl carbonate propiophenone; 2-methyl carbonate benzyl ketone, 2-ethyl carbonate benzyl ketone, 2-n-propyl carbonate benzyl ketone, 2-isopropyl carbonate benzyl ketone, 2-allyl carbonate benzyl ketone, 2-n-butyl carbonate benzyl ketone, 2-isobutyl carbonate benzyl ketone, 2-n-pentyl carbonate benzyl ketone, 2-isoamyl carbonate benzyl ketone, 2-n-hexyl carbonate benzyl ketone and 2-isohexyl carbonate benzyl ketone.

The catalyst component according to the invention, the titanium content is from 1.0% by weight to 8.0% by weight, preferably from 1.6% by weight to 6.0% by weight, based on the total weight of the catalyst component; the content of the magnesium is 10.0 to 70.0 weight percent, and preferably 15.0 to 40.0 weight percent; the content of the halogen is 20.0-90.0 wt%, preferably 30.0-85.0 wt%; the content of the internal electron donor compound is 2.0 wt% -30.0 wt%, preferably 3.0 wt% -20.0 wt%.

The catalyst component comprises a reaction product of a magnesium compound, a titanium compound and an internal electron donor compound, namely the preparation method of the catalyst component can be that the titanium compound, the magnesium compound and the internal electron donor compound are contacted and reacted under certain conditions. The internal electron donor compound comprises at least one 2-carbonate phenyl ketone compound shown in a general formula (I). The amounts of the titanium compound, the magnesium compound and the internal electron donor compound used for preparing the catalyst component are not particularly limited and may be those conventional in the art.

In some embodiments of the present invention, the molar ratio of the internal electron donor compound to the magnesium compound is 0.01 to 3.0, preferably 0.02 to 0.3, based on the internal electron donor compound magnesium.

In some preferred embodiments of the present invention, the magnesium compound includes one or more of a compound represented by general formula (III), a hydrate represented by general formula (IV), and an alcoholate represented by general formula (V);

MgR₅R₆ (III)

MgR₅R₆·qH₂O (IV)

MgR₅R₆·pR₀H₂O (V)。

in the general formulae (III) to (V), R₅And R₆Identical or different, each independently selected from halogen, C₁-C₅Alkyl or alkoxy groups of (a). The halogen is chlorine, bromine or iodine.

In the formula (IV), q is 0.1 to 6.0, preferably 2.0 to 3.5;

in the general formula (V), R₀Is selected from C₁-C₁₈Is preferably C₁-C₅Alkyl groups of (a); p is 0.1 to 6.0, preferably 2.0 to 3.5.

In some more preferred embodiments of the present invention, the magnesium compound is selected from at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutyoxymagnesium, dipentyoxymagnesium, dihexyloxymagnesium, di (2-methyl) hexyloxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymamium bromide, propoxymasium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alkoxide of magnesium dichloride, an alkoxide of magnesium dibromide, and an alkoxide of magnesium diiodide.

In some most preferred embodiments of the invention, the magnesium compound is diethoxymagnesium or magnesium dichloride.

In some preferred embodiments of the present invention, the titanium compound comprises at least one compound represented by the general formula (VI);

TiX_m(OR₇)_4-m (VI)

in the general formula (VI), R₇Is C₁-C₂₀Is preferably C₁-C₅Alkyl groups of (a); x is halogen; m is 1. ltoreq. m.ltoreq.4 and m is an integer, such as 1, 2, 3 or 4. The halogen is chlorine, bromine or iodine.

In some more preferred embodiments of the present invention, the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, and trichloromonoethoxytitanium.

In some most preferred embodiments of the invention, the titanium compound is titanium tetrachloride.

The method of preparing the olefin polymerization catalyst component of the present invention by reacting the titanium compound, the magnesium compound and the internal electron donor compound in the present invention can be performed by a method of preparing an olefin catalyst component, which is conventional in the art. The olefin polymerization 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 CN102453150B method. (1) Contacting a magnesium alkoxide or magnesium alkoxide halide compound with a titanium compound and an internal electron donor compound represented by the formula (1) in the presence of an inert diluent; (2) washing the solid obtained by the step (1) with an inert solvent to obtain a solid catalyst component.

Specific examples of the above-mentioned alkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutyoxymagnesium, dipentyoxymagnesium, dihexomagnesium, di (2-methyl) hexyloxymagnesium, and the like, or a mixture thereof, and diethoxymagnesium or a mixture of diethoxymagnesium and other alkoxymagnesium is preferable. The preparation method of the alkoxy magnesium compound can be prepared by a method known in the art, such as the preparation of metal magnesium and fatty alcohol in the presence of a small amount of iodine.

Specific examples of the alkoxymagnesium halide include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, etc., and ethoxymagnesium chloride is preferable. The alkoxy magnesium halide compound can be prepared by a method known in the art, such as a method of mixing a Grignard reagent of butyl magnesium chloride with tetraethoxy titanium and tetraethoxy silicon to prepare ethoxy magnesium chloride.

In step (1), the inert diluent is selected from C₆～C₁₀Of alkanes orAt least one aromatic hydrocarbon. Specific examples of the inert diluent include one or a mixture of hexane, heptane, octane, decane, benzene, toluene and xylene; toluene is preferred in the present invention. 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 previously diluted with an inert solvent and contacted. The number of times of contact is not particularly limited, and may be once or more.

The solid catalyst component obtained by the above contact reaction may be washed with an inert solvent such as: a hydrocarbon compound. Specific examples of the inert solvent may be selected from one of hexane, heptane, octane, decane, benzene, toluene, xylene, or a mixture thereof. Hexane is preferred in the present invention.

In the present invention, the washing method is not particularly limited, and 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 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 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 is to 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 usually 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the electron donor compound is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.

The contact temperature of each component 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 on the solid to obtain the solid catalyst component.

The secondary precipitant 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 process may be at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and the like, and epichlorohydrin is preferable.

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 may be 0.2 to 10 moles, preferably 0.5 to 4 moles, of the organic epoxy compound per mole of the magnesium halide; the organic phosphorus compound may be present in an amount of 0.1 to 3 moles, preferably 0.3 to 1.5 moles; 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.

Method three, the catalyst component was prepared according to the preparation method of CN 1091748. The magnesium chloride alcoholate melt is stirred and dispersed at high speed in a dispersion system of white oil and silicone oil to form emulsion, and the emulsion is discharged into cooling liquid to be cooled and shaped at a short speed 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 carrier particle size 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 20-200, preferably 30-60; the initial treatment temperature is-30 to 0 ℃, preferably-25 to-20 ℃; the final treatment temperature is 80-136 ℃, preferably 100-130 ℃.

The spherical catalyst obtained has the following characteristics: 1.5-3.5 wt% of titanium, 6.0-20.0 wt% of ester, 52-60 wt% of chlorine, 10-20 wt% of magnesium and 1-6 wt% of inert solvent.

The method four comprises the following steps: the catalyst was prepared with reference to the method disclosed in CN 1506384. Firstly, mixing an organic alcohol compound and a magnesium 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 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 increased to 90-110 ℃ in the presence of a precipitation aid; adding the electron donor compound according to the magnesium/ester molar ratio of 2-10, reacting at the temperature of 100 ℃ and 130 ℃ for 1-3 hours, and filtering to separate solid particles; then (optionally repeating for 2-3 times) contacting and reacting the solid particles with a titanium compound at 100-130 ℃ for 1.5-3 hours according to the titanium/magnesium molar ratio of 20-50, and filtering to separate out the solid particles; finally, washing the solid particles by using an inert solvent with the temperature of 50-80 ℃, and drying to obtain the catalyst component.

In any of the above four methods for preparing the olefin polymerization catalyst component of the present invention, the internal electron donor may be used alone or in combination of two or more.

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 titanium compound.

In a second aspect, the present invention provides a catalyst for olefin polymerization comprising the following components:

component a, a catalyst component according to the first aspect of the present invention;

component b, an alkyl aluminum compound;

wherein the molar ratio of component b to component a, calculated as aluminium to titanium, is (5-5000):1, preferably (20-1000):1, more preferably (50-500): 1.

The alkyl aluminium compound of component b according to the catalyst of the present invention may be any of the various alkyl aluminium compounds commonly used in the field of olefin polymerisation and capable of being used as cocatalysts for Ziegler-Natta type catalysts.

In some preferred embodiments of the present invention, the component b alkyl aluminum compound comprises at least one compound of formula (VII);

AlR'_n'X'_3-n' (VII)

in formula (VII), R' is selected from H, C₁-C₂₀Alkyl or C₆-C₂₀Wherein X ' is halogen, n ' is not less than 1 and not more than 3, and n ' is an integer.

In some more preferred embodiments of the present invention, the alkyl aluminum compound is selected from 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 provided by the invention, the catalyst also comprises a component c and an external electron donor compound. In the present invention, the kind and content of the external electron donor compound are not particularly limited. The external electron donor compound of the component c can be various external electron donor compounds which are commonly used in the field of olefin polymerization and can be used as a cocatalyst of a Ziegler-Natta catalyst.

In some preferred embodiments of the present invention, the molar ratio of component c to component b is 1 (0.1-500) in terms of Si: Al. In some more preferred embodiments of the present invention, the molar ratio of component c to component b is 1 (1-300) in terms of silicon to aluminum. In some further preferred embodiments of the present invention, the molar ratio of component c to component b is 1 (3-100) in terms of silicon to aluminum.

In some preferred embodiments of the present invention, said component c external electron donor compound comprises at least one compound represented by the general formula (VIII):

R^1" _m"R^2" _n"Si(OR^3")_4-m"-n" (VIII)

in the general formula (VIII), R^1"And R^2"Identical or different, each independently selected from H, halogen, C₁-C₂₀Alkyl or haloalkyl of, C₃-C₂₀Cycloalkyl or C₆-C₂₀Aryl of (a); r^3"Is selected from C₁-C₂₀Alkyl or haloalkyl of, C₃-C₂₀Cycloalkyl or C₆-C₂₀Aryl of (a); m 'and n' are integers from 0 to 3, and m '+ n' < 4.

In some more preferred embodiments of the present invention, said component c external electron donor compound is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutylbutylbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl (sec-butyl) dimethoxysilane, tert-butylpentyldimethoxysilane, tert-butyldimethoxysilane, tri-n-butyldimethoxysilane, tri, T-butylnonyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butyldecyldimethoxysilane, methyl-t-butyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylt-butyldimethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentt-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, sec-butyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and at least one of (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane.

In some further preferred embodiments of the present invention, the component c external electron donor compound is selected from at least one of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-t-butyldimethoxysilane and tetramethoxysilane.

In a third aspect, the present invention provides a prepolymerized catalyst for olefin polymerization, which comprises the catalyst component according to the first aspect of the present invention or a prepolymer obtained by prepolymerizing the catalyst according to the second aspect of the present invention with an olefin; wherein the pre-polymerization multiple of the prepolymer is 5-1000g of olefin polymer/g of catalyst component, preferably 10-500g of olefin polymer/g of catalyst component; preferably, the olefin used for the prepolymerization is ethylene or propylene.

In some embodiments of the invention, the temperature of the prepolymerization is from-20 to 80 ℃, preferably from 10 to 50 ℃.

In a fourth aspect, the present invention provides a process for the polymerisation of olefins carried out with the aid of a catalyst component according to the first aspect of the present invention, a catalyst according to the second aspect of the present invention or a prepolymerised catalyst according to the third aspect of the present invention. The olefin has the general formula CH₂Wherein R is hydrogen or C₁-C₆Alkyl or phenyl groups.

The olefin polymerization method provided by the invention can be used for olefin homopolymerization and can also be used for copolymerizing a plurality of olefins. The olefin is selected from 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. Preferably, the olefin is propylene.

In the preparation of polyolefin, the components of the catalyst provided by the invention, namely the catalyst component provided by the invention, the organic aluminum compound used as a cocatalyst and the external electron donor compound can be contacted before being contacted with an olefin monomer, and are referred to as pre-contact or pre-complexing in the industry; it is also possible to add the three components separately to the olefin monomer and then carry out the polymerization, i.e.without "precontacting". According to the olefin polymerization method provided by the invention, the components in the olefin polymerization catalyst are preferably subjected to a pre-contact method. The time of "precontacting" is 0.1 to 30min, preferably 1 to 10 min; the temperature of the "precontacting" is from-20 ℃ to 80 ℃, preferably from 10 to 50 ℃.

The catalyst is firstly prepolymerized to a certain extent in the presence of a small amount of olefin monomer to obtain a prepolymerized catalyst, and then the prepolymerized catalyst is further contacted with the olefin monomer to react to obtain the 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 a prepolymerization process is preferably adopted.

According to the olefin polymerization process of the present invention, the polymerization conditions may be conventional in the art, and the amount of the catalyst may be the amount of various catalysts in the prior art.

The 2-carbonate phenyl ketone compound shown in the general formula (I) is used as an internal electron donor compound, so that the catalyst with excellent comprehensive performance can be obtained. When the catalyst is used for olefin polymerization reaction, the catalyst has high activity and good hydrogen regulation sensitivity, and the obtained polyolefin resin has good stereospecificity and wide molecular weight distribution.

Detailed Description

In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.

The test method used in the present invention is as follows:

(1) the yield (%) of the catalyst component was (mass of the obtained catalyst/mass of magnesium chloride used) × 100%;

(2) titanium content in the catalyst component (wt%): measuring with 721 spectrophotometer;

(3) the purity of the internal electron donor compound is determined by Gas Chromatography (GC);

(4) polymer Melt Index (MI): measured according to GB/T3682-2000;

(5) propylene polymer Isotacticity Index (II): determination by heptane extraction: 2g of dried polymer sample is put in an extractor and extracted by boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer to 2(g) of the residue is dried to constant weight, namely the isotacticity;

(6) polymer molecular weight distribution MWD (MWD ═ Mw/Mn): measured at 150 ℃ using PL-GPC220 and trichlorobenzene as a solvent (standard: polystyrene, flow rate: 1.0mL/min, column: 3 XPlgel 10 μm Ml XED-B300X 7.5 nm);

(7) activity (Ac) calculation: catalyst activity (mass of polyolefin produced)/(mass of solid catalyst component) kg/g;

(8) bulk Density (BD) measurement: the polymer powder obtained in 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/cm³。

Examples

Example 1

Synthesis of internal electron donor compound (compound 1: 2-n-pentylcarbonate acetophenone)

300g of 2-hydroxyacetophenone, 226.3g of anhydrous pyridine, 10g of 4-dimethylaminopyridine were added to a mixed solvent of 300mL of dried tetrahydrofuran and 200mL of chloroform. 397.6g of n-amyl chloroformate is added into 200mL of chloroform, and then the mixture is dripped into a reaction system, and the temperature is kept stable between 10 and 20 ℃ in the dripping process. After the dropwise addition, the temperature is raised to 50 ℃, the mixture is stirred for 3 to 4 hours, and then the reaction is carried out for 8 to 10 hours at 80 ℃. After the reaction was completed, the reaction was cooled, the solid salt was removed by filtration, the solvent was dried by spin-drying, 200mL of ethyl acetate and 400mL of water were added, the pH was adjusted to 5-6 using 10% hydrochloric acid, the aqueous phase was extracted twice (100mL, 80mL) with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was spin-dried to obtain a crude product. Distillation under reduced pressure gave 396.1g of final product in 68% yield and 99.65% purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.9-0.94(t,-O(CH₂)₄CH₃),1.37-1.40(m,-OCH₂CH₂CH₂CH₂CH₃),1.73-1.78(m,-OCH₂CH₂CH₂CH₂CH₃),2.55(s,-C(O)CH₃),4.24-4.29(t,-OCH₂CH₂CH₂CH₂CH₃),7.18-7.81(m,-C₆H₄)。

Preparation of catalyst component

(1) Preparation of alcoholic solution: in a reaction kettle repeatedly replaced by high-purity nitrogen, 15.0g of anhydrous magnesium chloride, 60mL of toluene and 63.5mL of isooctanol are sequentially added, and the mixture reacts for 2.0 hours under the conditions of stirring speed of 300rpm and temperature of 110 ℃ to obtain a stable and uniform solution. Then, 0.8mL of 3, 5-heptanediol dibenzoate and 3.0mL of diisobutyl phthalate were added, and the mixture was reacted at 110 ℃ for 1.5 hours with a stirring speed of 300 rpm. Further, 2.25mL of tetrabutyl titanate was added thereto, and the mixture was reacted at a stirring speed of 300rpm and a temperature of 110 ℃ for 1.5 hours. Then adding 90mL of toluene, reacting for 0.5 hour under the conditions of stirring speed of 300rpm and temperature of 110 ℃, and cooling to room temperature to obtain the alcohol compound solution.

(2) Preparation of catalyst component: 72mL of the above alcohol hydrate solution was charged into a reactor filled with 60mL of titanium tetrachloride and 40mL of toluene, sufficiently contacted at-25 ℃ for 1.5 hours by stirring, then heated to 110 ℃ over 3 hours, kept at a constant temperature for 1 hour, charged with 108mL of toluene and 12mL of titanium tetrachloride, stirred for 1 hour, cooled and pressure-filtered, further charged with 12mL of titanium tetrachloride and 108mL of toluene, heated to 100 ℃ and charged with 1.1g of the compound 1: 2-n-pentylcarbonate acetophenone (molar ratio of compound 1 to magnesium compound 0.083, compound 1: magnesium) was kept at constant temperature for 1 hour. The temperature was raised to 110 ℃, 72mL of toluene and 48mL of titanium tetrachloride were added and stirred for 1 hour, and after filter pressing, the obtained solid was washed 1 time with 120mL of toluene and 4 times with 150mL of hexane. Press-filtering, transferring and drying to obtain the olefin polymerization catalyst component 1.

Polymerization of propylene

The catalyst component 1 prepared above was subjected to propylene polymerization under different conditions. The specific method comprises the following steps: in a 5L autoclave, after sufficient replacement with vapor phase propylene, 5mL of a hexane solution of triethylaluminum (concentration of triethylaluminum: 0.5mmol/mL), L mL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration of CHMMS: 0.10mmol/mL), 10mL of anhydrous hexane, and 10mg of catalyst component 1 were added at room temperature. The autoclave was closed and 0.18mol of hydrogen and 2.4L of liquid propylene were introduced; the temperature was raised to 70 ℃ over 10 minutes with stirring. After polymerization was carried out at 70 ℃ for 1 hour, the stirring was stopped, and the unpolymerized propylene monomer was removed to collect a polymer. Dried under vacuum at 70 ℃ for 1 hour and weighed to calculate the catalyst activity. The polymerization results are shown in Table 1.

Example 2

Synthesis of internal electron donor compound (compound 2: 2-n-butyl carbonate acetophenone)

Using a synthesis similar to that of Compound 1, n-pentyl chloroformate was changed to n-butyl chloroformate to prepare 383.5g of 2-n-butyl carbonate acetophenone, in 73.6% yield and 98.81% purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.94-0.99(t,-O(CH₂)₃CH₃),1.42-1.50(m,-OCH₂CH₂CH₂CH₃),1.72-1.77(m,-OCH₂CH₂CH₂CH₃),2.56(s,-C(O)CH₃),4.26-4.30(m,-OCH₂CH₂CH₂CH₃),7.19-7.53(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 2 in step (2) (the molar ratio of compound 2 to the magnesium compound was 0.088 in terms of compound 2: magnesium) to obtain catalyst component 2.

Thirdly, the process for propylene polymerization was the same as in example 1 except that catalyst component 1 was replaced with catalyst component 2 and the polymerization results were as shown in table 1.

Example 3

Synthesis of internal electron donor compound (compound 3: 2-isobutyl carbonate acetophenone)

Using a synthesis similar to that of Compound 1, n-pentyl chloroformate was changed to isobutyl chloroformate to prepare 282.6g of 2-isobutylcarbonate acetophenone, in 55.6% yield and 98.7% purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.98-1.00(t,-OCH₂CH(CH₃)₂),(m,-OCH₂CH(CH₃)₂),2.53(s,-C(O)CH₃),4.04-4.06(d,-OCH₂CH(CH₃)₂),7.17-7.80(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 3 (the molar ratio of compound 3 to the magnesium compound was 0.088 in terms of compound 3: magnesium) to obtain catalyst component 3.

Thirdly, a propylene polymerization process was carried out in the same manner as in example 1 except that catalyst component 1 was replaced with catalyst component 3 and the polymerization results were as shown in Table 1.

Example 4

Synthesis of internal electron donor compound (compound 4: 2-n-propyl carbonate acetophenone)

Using a synthesis method similar to that of Compound 1, n-pentyl chloroformate was changed to n-propyl chloroformate to prepare 152.3g of acetophenone, 2-n-propyl carbonate, 58.3% in yield and 99.85% in purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.98-1.03(t,-O(CH₂)₂CH₃),1.74-1.81(m,-OCH₂CH₂CH₃),2.56(s,-C(O)CH₃),4.21-4.25(m,-OCH₂CH₂CH₃),7.18-7.82(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 4 (the molar ratio of compound 4 to the magnesium compound was 0.093 in terms of compound 4: magnesium) to obtain catalyst component 4.

Thirdly, a propylene polymerization process was carried out in the same manner as in example 1 except that catalyst component 1 was replaced with catalyst component 4 and the polymerization results were as shown in Table 1.

Example 5

Firstly, synthesizing an internal electron donor compound (compound 5: 2-allyl carbonate acetophenone):

using a synthesis similar to that of compound 1, n-pentyl chloroformate was changed to allyl chloroformate to prepare 187.3g of 2-allyl carbonate acetophenone, in 61.3% yield and 99.2% purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):2.55(s,-C(O)CH₃)，4.73-4.76(m,-OCH₂CH＝CH₂),5.29-5.46(m,-OCH₂CH＝CH₂),5.93-6.05(m,-OCH₂CH＝CH₃),7.18-7.82(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 5 (the molar ratio of compound 5 to the magnesium compound was 0.094 in terms of compound 5: magnesium) to obtain catalyst component 5.

Thirdly, a propylene polymerization process was carried out in the same manner as in example 1 except that catalyst component 1 was replaced with catalyst component 5 and the polymerization results were as shown in Table 1.

Example 6

Firstly, synthesizing an internal electron donor compound (compound 6: 2-isopropyl carbonate acetophenone):

using a synthesis similar to that of compound 1, n-pentyl chloroformate was changed to isopropyl chloroformate to prepare 207.3g of 2-isopropyl carbonate acetophenone, in 52.6% yield and 98.9% purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):1.39-1.41(d,-OCH(CH₃)₂),2.57(s,-C(O)CH₃),4.97-5.02(m,-OCH(CH₃)₂),7.20-7.83(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 6 (the molar ratio of compound 6 to the magnesium compound was 0.093 in terms of compound 6: magnesium) to obtain catalyst component 6.

Thirdly, a propylene polymerization method was the same as in example 1 except that the catalyst component 1 was replaced with the catalyst component 6, and the polymerization results were as shown in table 1.

Example 7

Firstly, synthesizing an internal electron donor compound (compound 7: 2-n-butyl carbonate propiophenone):

using a synthesis method similar to that of compound 1, 2-hydroxyacetophenone was changed to 2-hydroxypropiophenone, and n-pentyl chloroformate was changed to n-butyl chloroformate, to prepare 243.8g of 2-n-butyl carbonate phenylpropanone in a yield of 63.7% and a purity of 99.0% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.95-0.99(t,-O(CH₂)₃CH₃),1.16-1.19(t,-C(O)CH₂CH₃),1.44-1.49(m,-OCH₂CH₂CH₂CH₃)，1.71-1.78(m,-OCH₂CH₂CH₂CH₃),2.90-2.95(q,-C(O)CH₂CH₃),4.27-4.30(t,-OCH₂CH₂CH₂CH₃),7.19-7.79(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 7 (the molar ratio of compound 7 to magnesium compound was 0.083 in terms of compound 7: magnesium) to obtain a polymerization catalyst component 7.

Thirdly, a propylene polymerization process was carried out in the same manner as in example 1 except that catalyst component 1 was replaced with catalyst component 7 and the polymerization results were as shown in Table 1.

Example 8

Firstly, synthesizing an internal electron donor compound (compound 8: 2-n-butyl carbonate phenyl butanone):

using a synthesis method similar to that of compound 1, 181.6g of 2-n-butylcarbonate butanone was prepared by replacing 2-hydroxyacetophenone with 2-hydroxybenzenebutanone and n-pentyl chloroformate with n-butyl chloroformate, in a yield of 50.4% and a purity of 99.2% (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.95-0.99(t,-O(CH₂)₃CH₃,-(O)CCH₂CH₂CH₃),1.42-1.51(t,-OCH₂CH₂CH₂CH₃),1.68-1.78(m,-OCH₂CH₂CH₂CH₃,-(O)CCH₂CH₂CH₃)，2.86-2.89(m,-(O)CCH₂CH₂CH₃),4.26-4,30(q,-OCH₂CH₂CH₂CH₃₃),7.19-7.78(m,-C₆H₄)。

Secondly, the catalyst component was prepared by the same method as in example 1 except that compound 1 was replaced with compound 8 (the molar ratio of compound 8 to the magnesium compound was 0.079 in terms of compound 8: magnesium) to obtain catalyst component 8.

Thirdly, a propylene polymerization method was the same as in example 1 except that the catalyst component 1 was replaced with the catalyst component 8, and the polymerization results are shown in table 1.

Example 9

Firstly, synthesizing an internal electron donor compound (compound 9: 2-allyl carbonate phenyl butanone):

using a synthesis method similar to that of compound 1, 2-hydroxyacetophenone was changed to 2-hydroxybenzenebutanone and n-pentyl chloroformate was changed to allyl chloroformate, to prepare 192.8g of 2-allyl carbonate phenylbutanone in 61.3% yield and 98.9% purity (GC).

¹H NMR(CDCl₃/TMS,300MHz)δ(ppm):0.92-0.97(t,-C(O)CH₂CH₂CH₃)，1.66-1.74(m,-C(O)CH₂CH₂CH₃)，2.83-2.88(t,-C(O)CH₂CH₂CH₃)，4.72-4.74(d,-OCH₂CH＝CH₂),5.27-5.44(m,-OCH₂CH＝CH₂),5.94-5.99(m,-OCH₂CH＝CH₃),7.17-7.76(m,-C₆H₄)。

Second, a catalyst component was prepared in the same manner as in example 1 except that compound 1 was replaced with compound 9 (the molar ratio of compound 9 to the magnesium compound was 0.084 in terms of compound 9: magnesium) to obtain catalyst component 9.

Thirdly, a propylene polymerization process was carried out in the same manner as in example 1 except that the catalyst component 1 was replaced with the catalyst component 9, and the polymerization results were as shown in Table 1.

Comparative example 1

First, the preparation method of the catalyst component is the same as that of example 1, except that the internal electron donor is replaced with di-n-butyl phthalate (DNBP) to obtain the catalyst component 10.

Secondly, the propylene polymerization process was the same as in example 1 except that the catalyst component 1 was replaced with the catalyst component 10, and the polymerization results were as shown in Table 1.

TABLE 1

As can be seen from the data in Table 1, the catalyst prepared by using the 2-carbonate phenyl ketone compound shown in the general formula (I) with the specific structure as the catalyst component of the internal electron donor compound is a non-phthalate catalyst, so that the safety of the catalyst is improved, the activity is high, the bulk density and the melt index of the obtained polymer are high (namely the hydrogen regulation of the catalyst is high), and the molecular weight distribution is wide.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims

1. A catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises at least one 2-carbonate phenyl ketone compound shown in a general formula (I);

in the general formula (I), R₁And R₂Identical or different, each independently selected from C which is unsubstituted or substituted by halogen atoms, alkyl groups or alkoxy groups₁-C₁₀Alkyl, unsubstituted or substituted by halogen atoms, alkyl or alkoxy₃-C₁₀Or C which is unsubstituted or substituted by halogen atoms, alkyl groups or alkoxy groups₆-C₁₀Aryl group of (1).

2. The catalyst component according to claim 1 in which in the formula (I) R is₁And R₂Each independently selected from C which is unsubstituted or substituted by halogen atoms, alkyl groups or alkoxy groups₁-C₆Alkyl group of (1).

3. The catalyst component according to claim 1 or 2, characterized in that the titanium content is from 1.0 wt% to 8.0 wt%, based on the total weight of the catalyst component; the content of the magnesium is 10.0-70.0 wt%; the content of the halogen is 20.0-90.0 wt%; the content of the internal electron donor compound is 2.0 wt% -30.0 wt%.

4. The catalyst component according to claim 3, characterized in that the titanium content is from 1.6% to 6.0% by weight, based on the total weight of the catalyst component; the content of the magnesium is 15.0-40.0 wt%; the content of the halogen is 30.0-85.0 wt%; the content of the internal electron donor compound is 3.0 wt% -20.0 wt%.

5. The catalyst component according to claim 1 or 2, characterized in that it comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound comprising at least one 2-carbonate phenyl ketone compound of general formula (I);

wherein the molar ratio of the internal electron donor compound to the magnesium compound is 0.01-3.0 in terms of the internal electron donor compound and magnesium.

6. The catalyst component according to claim 5, wherein the molar ratio of the internal electron donor compound to the magnesium compound is 0.02-0.3 in terms of internal electron donor compound to magnesium.

7. The catalyst component according to claim 5, characterized in that the magnesium compound comprises one or more of a compound of formula (III), a hydrate of formula (IV) and an alcoholate of formula (V);

MgR₅R₆ (III)

MgR₅R₆·qH₂O (IV)

MgR₅R₆·pR₀H₂O (V)

in the general formulae (III) to (V), R₅And R₆Identical or different, each independently selected from halogen, C₁-C₅Alkyl or alkoxy of (a);

in the general formula (IV), q is 0.1 to 6.0;

in the general formula (V), R₀Is selected from C₁-C₁₈A hydrocarbon group of (a); p is 0.1-6.0.

8. The catalyst component according to claim 7 characterized in that in the general formula (IV), q is from 2.0 to 3.5;

in the general formula (V), R₀Is C₁-C₅Alkyl groups of (a); p is 2.0-3.5.

9. The catalyst component according to claim 5 in which the titanium compound comprises at least one compound of formula (VI);

TiX_m(OR₇)_4-m (VI)

in the general formula (VI), R₇Is C₁-C₂₀A hydrocarbon group of (a); x is halogen; m is not less than 1 and not more than 4, and m is an integer.

10. The catalyst component according to claim 9, characterized in that in the general formula (VI), R₇Is C₁-C₅Alkyl group of (1).

11. A catalyst for the polymerization of olefins comprising the following components:

component a, the catalyst component of any one of claims 1 to 10;

component b, an alkyl aluminum compound;

wherein the molar ratio of the component b to the component a is (5-5000):1 in terms of aluminum: titanium.

12. The catalyst of claim 11 wherein the molar ratio of component b to component a is (20-1000):1, calculated as aluminum to titanium.

13. The catalyst of claim 11 wherein the molar ratio of component b to component a is (50-500):1, calculated as aluminum to titanium.

14. The catalyst according to claim 11, characterized in that the alkyl aluminum compound of component b comprises at least one compound of general formula (VII);

AlR'_n'X'_3-n' (VII)

15. The catalyst according to any one of claims 11 to 14, further comprising a component c and an external electron donor compound, wherein the molar ratio of the component c to the component b is 1 (0.1-500) in terms of Si to Al.

16. The catalyst of claim 15 wherein the molar ratio of component c to component b is 1 (1-300) in terms of Si to Al.

17. The catalyst of claim 15 wherein the molar ratio of component c to component b is 1 (3-100) in terms of Si to Al.

18. The catalyst of claim 15, wherein the component c external electron donor compound comprises at least one of the compounds represented by the general formula (VIII):

R¹"_m"R²"_n"Si(OR^3")_4-m"-n" (VIII)

in the general formula (VIII), R¹"and R²"identical or different, each independently selected from H, halogen, C₁-C₂₀Alkyl or haloalkyl of, C₃-C₂₀Cycloalkyl or C₆-C₂₀Aryl of (a); r³Is selected from C₁-C₂₀Alkyl or haloalkyl of, C₃-C₂₀Cycloalkyl or C₆-C₂₀Aryl of (a); m 'and n' are integers from 0 to 3, and m '+ n' < 4.

19. A prepolymerized catalyst for the polymerization of olefins comprising the catalyst component according to any of claims 1 to 10 or a prepolymer obtained by prepolymerizing the catalyst according to any of claims 11 to 18 with olefins; wherein the pre-polymerization multiple of the prepolymer is 5-1000g of olefin polymer/g of catalyst component.

20. The prepolymerized catalyst according to claim 19 wherein the prepolymer has a prepolymerization multiple of 10 to 500g olefin polymer/g catalyst component.

21. The prepolymerized catalyst according to claim 19 wherein the olefin used for the prepolymerization is ethylene or propylene.

22. A process for the polymerization of olefins having the general formula CH, by polymerization of olefins in the presence of a catalyst component according to any of claims 1 to 10, a catalyst according to any of claims 11 to 18 or a prepolymerised catalyst according to any of claims 19 to 21₂Wherein R is hydrogen or C₁-C₆Alkyl or aryl of (a).