西班牙专利ES2557178A2 Catalyst component for use in olefin polymerization reaction, catalyst, and application

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专利摘要:
Provided in the present invention is a solid catalyst component for use in an olefin polymerization reaction, comprising magnesium, titanium, a halogen, and an electron donor. The electron donor is at least one selected from glycol ester compounds as represented by formula (I) as follows. A catalyst provided on the basis of the present invention is provided with greatly increased polymerization activity, hydrogen-modulation sensitivity, and stereospecificity. Based on the present invention, a catalyst system employing the glycol ester compounds as represent by formula (I) provided in the present invention is for use in olefin polymerization, provides great comprehensive performance, and is of high catalytic activity, particularly in a high hydrogen concentration, while the hydrogen-modulation sensitivity of the catalyst is increased and/or the isotactic index of a polymer acquired is increased significantly, thus facilitating preparation and acquisition of polymers of high melt flow index and high isotacticity and facilitating the development of polymers of different material designations.
公开号:ES2557178A2
申请号:ES201590123
申请日:2014-05-21
公开日:2016-01-22
发明作者:Changxiu Li；Mingzhi Gao；Haitao Liu；Jianhua Chen；Jing Ma；Jixing Ma；Xiaoxia Cai；Jun Wang；Xiaofan Zhang；Jianjun Hu
申请人:Sinopec Beijing Research Institute of Chemical Industry；China Petroleum and Chemical Corp；
IPC主号:

专利说明:

Catalyst component for the polymerization of olefins, catalyst and use thereof 5 Field of the invention
The present disclosure relates to a catalyst component, in particular to a catalyst component for preparing olefinic polymers of high fluidity index and high isotacticity. The present disclosure also relates to a catalyst comprising the
10 catalyst component, and the use of the catalyst in the polymerization of olefins.
Background of the invention
As is well known, a catalyst component based on solid titanium with magnesium,
Titanium, halogens and electron donors as basic ingredients can be used in the polymerization of olefins, in particular, in the polymerization of -olefins having three or more carbon atoms, to produce polymers with a high degree of stereoregularity. Electron donor compounds are a necessary ingredient of the catalyst component. With the development of internal electron donor compounds, the
20 catalysts for the polymerization of olefins are continuously updated. At present, a plurality of electron donor compounds, such as polycarboxylic acids, monocarboxylic esters or polycarboxylic esters, anhydrides, ketones, monoethers or polyethers, alcohols, amines and derivatives thereof have been disclosed.
In the prior art, there is a mention of a diol diester compound, which, when acting as an electron donor, enables a catalyst with excellent overall performance in olefin polymerization. When the catalyst is used in the polymerization of propylene, it has a high activity and stereoselectivity of the polymerization, producing polymers with a wide molecular weight distribution. However, the
The activity, response to hydrogen or stereoselectivity of the catalyst are not really satisfactory, especially in the production of polymers of high flow rates in the presence of highly concentrated hydrogen, in which the isotactic indices of the obtained polymers can still be improved.
The present disclosure provides a catalyst component and a catalyst, which uses a diol diester as an internal electron donor compound, wherein said diester of

Diol is obtained by reacting a non-terminal group diol having more than 6 carbon atoms in the linear chain with benzoic acid having at least one hydrocarbyl group, that is, substituted Cm (m≥2). The catalyst of the present disclosure has a high polymerization activity and response to hydrogen. When the catalyst of the present disclosure
5 is used in the polymerization of olefins, especially in the polymerization of propylene, polymers with greater isotacticity or a higher flow rate can be obtained.
Summary of the invention
To eliminate the defects of the prior art, the inventor of the present disclosure has investigated in the art and has unexpectedly discovered that a catalyst component containing a 1,3-diol benzoate compound with a certain structure (a diol diester obtained by reacting a non-terminal group diol having more than 6 carbon atoms in the linear chain with benzoic acid having at least
A hydrocarbyl group, that is, Cm (m≥2) substituted) as an internal electron donor compound shows excellent overall performance, such as high polymerization activity and hydrogen response in the polymerization of olefins, especially propylene, or It can produce polymers with a high flow rate and satisfactory high isotacticity.
According to one aspect of the present disclosure, it provides a solid catalyst component for the polymerization of olefins, which comprises magnesium, titanium, a halogen and an electron donor, wherein the electron donor is at least one selected from the group consisting of diol diester compounds shown in Formula (I):
wherein, R1 to R4, identical or different from each other, may be independently selected from hydrogen, halogens, and substituted or unsubstituted C1 to C10 hydrocarbyl groups, at least one of R1 and R2 being a substituted C1 to C10 hydrocarbyl group or not

substituted, and R3 and R4 being optionally joined to form a ring;
wherein R5 is selected from substituted or unsubstituted C2 to C10 hydrocarbyl groups,where n is an integer in the range of 1 to 5; Y5wherein R6 is selected from C1 to C15 substituted or unsubstituted hydrocarbyl groups.
As regards the catalyst component (also referred to as the solid catalyst component or solid catalyst component) of the present disclosure, the term
"Substituted" means that the hydrogen in the corresponding groups may be optionally substituted with alkyl groups or halogen atoms. For example, said substituted C1 to C10 linear alkyl groups, C3 to C15 branched alkyl groups, C3 to C15 cycloalkyl groups, C6 to C20 aryl groups, or C7 to C20 alkaryl or aralkyl groups means that the hydrogen in said alkyl, aryl groups, alkaryl or aralkyl may optionally be
15 substituted with groups or alkyl or halogen atoms. In the present disclosure, aryl hydrocarbyl groups comprise aralkyl, aryl alkenyl groups, etc. and hydrocarbyl aryl groups comprise alkaryl groups, alkenyl aryl groups, etc.
In a specific embodiment of the above catalyst component, in the compounds of
Diol diesters shown in Formula (I), R1 to R4, identical or different from each other, may be independently selected from hydrogen, halogens, substituted or unsubstituted linear C1 to C10 alkyl groups, branched C3 to C10 alkyl groups , C3 to C10 cycloalkyl groups, C6 to C10 aryl groups, C7 to C10 alkaryl groups and C7 to C10 aralkyl groups;
Wherein R5 is selected from substituted or unsubstituted C2 to C10 linear alkyl groups, C3 to C10 branched alkyl groups, C3 to C10 cycloalkyl groups, C6 to C10 aryl groups, C7 to C10 alkaryl groups and C7 to C10 aralkyl groups; and wherein R6 is selected from substituted or unsubstituted C1 to C10 linear alkyl groups, C3 to C10 branched alkyl groups, C3 to C10 cycloalkyl groups, C6 to C10 aryl groups, groups
30 C7 to C15 hydrocarbyl and C7 to C15 hydrocarbyl groups.
In another specific embodiment of the above catalyst component, in the diol diester compounds shown in Figure (I), R1 and R2 are selected from hydrogen, linear C1 to C6 alkyl groups (for example C1 to C3 linear alkyl groups) and alkyl groups
C3 to C6 branched halogenated or non-halogenated;

wherein R3 and R4 are selected from hydrogen, halogens, and C1 to linear alkyl groupsC6 and halogenated or non-halogenated C3 to C6 branched alkyl groups;wherein R5 is selected from C2 to C6 linear alkyl groups and branched alkyl groupsC3 to C6 halogenated or non-halogenated, n being equal to 1 or 2, preferably, being n 1, andR5 being a para-or ortho-substituted group; Ywherein R6 is selected from linear or branched C4 to C10 alkyl groups, groupsC5 to C10 cycloalkyl, C6 to C10 aryl groups, C8 to C15 aryl alkenyl groups, C7 to alkaryl groupsC15, and halogenated or non-halogenated C7 to C15 aralkyl groups, preferably aryl groupsC8 to C12 alkenyl, C7 to C15 alkaryl groups and halogenated or non-halogenated C7 to C15 alkyl groupshalogenated
According to the present disclosure, at least one of R1 and R2 is a C1 hydrocarbyl groupto C10 substituted or unsubstituted. That is, R1 and R2 are not selected simultaneously fromhydrogen and halogens. In other words, at most one of R1 and R2 (that is, R1 or R2)It is selected from hydrogen and halogens. Such halogens for example canUnderstand chlorine, bromine and iodine atoms.
In a specific embodiment according to the catalyst component of the presentdisclosure, the diol diester compounds shown in Formula (I) are one ormost selected from the group consisting of2,4-hexanediol bis (4-ethyl benzoate),2,4-hexanediol bis (4-n-propyl benzoate),2,4-hexanediol bis (4-n-butyl benzoate),2,4-hexanediol bis (4-iso-butyl benzoate),2,4-hexanediol bis (4-tert-butyl benzoate),2,4-hexanediol bis (4-hexyl benzoate),3-methyl-2,4-hexanediol bis (4-ethyl benzoate),3-methyl-2,4-hexanediol bis (4-n-propyl benzoate),3-methyl-2,4-hexanediol bis (4-n-butyl benzoate),3-methyl-2,4-hexanediol bis (4-iso-butyl benzoate),3-methyl-2,4-hexanediol bis (4-tert-butyl benzoate),3-methyl-2,4-hexanediol bis (4-hexyl benzoate),3-ethyl-2,4-hexanediol bis (4-ethyl benzoate),3-ethyl-2,4-hexanediol bis (4-n-propyl benzoate),3-ethyl-2,4-hexanediol bis (4-n-butyl benzoate),3-ethyl-2,4-hexanediol bis (4-iso-butyl benzoate),

3-ethyl-2,4-hexanediol bis (4-tert-butyl benzoate),3-ethyl-2,4-hexanediol bis (4-hexyl benzoate),3,5-heptanediol bis (4-ethyl benzoate),3,5-heptanediol bis (4-n-propyl benzoate),
5 bis (4-iso-propyl benzoate) of 3,5-heptanediol,3,5-heptanediol bis (4-n-butyl benzoate),3,5-heptanediol bis (4-iso-butyl benzoate),3,5-heptanediol bis (4-tert-butyl benzoate),3,5-heptanediol bis (4-pentyl benzoate),
10-3,5-heptanediol, 3,5-heptanediol cinnamic acid bis (4-hexyl benzoate), 4-methyl-3,5-heptanediol bis (4-ethyl benzoate), bis (4 -n-propyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-iso-propyl benzoate) of 4-methyl-3,5-heptanediol,
15 bis (4-n-butyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-iso-butyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-pentyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-hexyl benzoate) of 4-methyl-3,5-heptanediol,
4-Ethyl-3,5-heptanediol-cinnamic acid 4-ethyl-3,5-heptanediol bis (4-n-propyl benzoate) 4-ethyl- 4-ethyl benzoate 3,5-heptanediol, 4-ethyl-3,5-heptanediol bis (4-n-butyl benzoate), 4-ethyl-3,5-heptanediol bis (4-n-butyl benzoate),
25 bis (4-iso-butyl benzoate) of 4-ethyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-ethyl-3,5-heptanediol, bis (4-pentyl benzoate) of 4 -ethyl-3,5-heptanediol, 4-ethyl-3,5-heptanediol bis (4-hexyl benzoate), 4-ethyl-3,5-heptanediol cinnamic acid 4-ethyl benzoate
30 bis (4-tert-butyl benzoate) of 4-n-propyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-n-butyl-3,5-heptanediol, bis (4-tert -butyl benzoate) of 4,4-dimethyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-methyl-4-ethyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-methyl-4-n-propyl-3,5-heptanediol,
35-3-methyl-2,4-heptanediol bis (4-n-propyl benzoate), 3-methyl-2,4-heptanediol bis (4-iso-propyl benzoate),

4-methyl-3,5-octanediol bis (4-tert-butyl benzoate),4-ethyl-3,5-octanediol bis (4-tert-butyl benzoate),4-n-propyl-3,5-octanediol bis (4-tert-butyl benzoate),4-n-butyl-3,5-octanediol bis (4-tert-butyl benzoate),4,4-dimethyl-3,5-octanediol bis (4-tert-butyl benzoate),4,4-diethyl-3,5-octanediol bis (4-n-propyl benzoate),4,4-di-n-propyl-3,5-octanediol bis (4-tert-butyl benzoate),4-methyl-4-ethyl-3,5-octanediol bis (4-tert-butyl benzoate),4,6-nonanodiol bis (4-ethyl benzoate),4,6-nonanodiol bis (4-n-propyl benzoate),4,6-nonanodiol bis (4-n-butyl benzoate),4,6-nonanodiol bis (4-iso-butyl benzoate),4,6-nonanodiol bis (4-tert-butyl benzoate),4,6-nonanodiol bis (4-hexyl benzoate),4,6-Nonanodiol cinnamic acid 4-ethyl benzoate,5-methyl-4,6-nonanodiol bis (4-ethyl benzoate),5-methyl-4,6-nonanodiol bis (4-n-propyl benzoate),5-methyl-4,6-nonanodiol bis (4-n-butyl benzoate),5-methyl-4,6-nonanodiol bis (4-iso-butyl benzoate),5-methyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5-methyl-4,6-nonanodiol bis (4-hexyl benzoate),5-ethyl-4,6-nonanodiol bis (4-ethyl benzoate),5-ethyl-4,6-nonanodiol bis (4-n-propyl benzoate),5-ethyl-4,6-nonanodiol bis (4-n-butyl benzoate),5-ethyl-4,6-nonanodiol bis (4-iso-butyl benzoate),5-ethyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5-ethyl-4,6-nonanodiol bis (4-hexyl benzoate),5-n-propyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5-n-butyl-4,6-nonanodiol bis (4-n-butyl benzoate),5,5-dimethyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5,5-diethyl-4,6-nonanodiol bis (4-hexyl benzoate),5,5-di-n-propyl-4,6-nonanodiol bis (4-pentyl benzoate), and5,5-dibutyl-4,6-nonanodiol bis (4-tert-butyl benzoate).
In the present disclosure, the process for preparing electron donor compounds shown in Formula (I) is known. For example, compounds 10

Electron donors can be prepared by reacting the corresponding diols with chlorides or acyl anhydrides. Reference may be made to the synthesis procedure disclosed in US20050096389.
In the above catalyst component, based on the total weight of the catalyst component, the content of the diol diester compounds shown in Formula (I) represents from 1% to 25% by weight, the titanium content from 0.5% to 8% by weight, and the magnesium content from 3% to 25% by weight. Preferably, the content of the diol diester compounds shown in Formula (I) represents 5% to 20% by weight, the titanium content 1% to 6% by weight, and the magnesium content 10% to 20% by weight. More preferably, the content of the diol diester compounds shown in Formula (I) represents 8% to 12% by weight, the titanium content 2% to 4% by weight, and the magnesium content 15% at 19% by weight. The content of diol diesters shown in Formula (I) can be measured by liquid chromatography, in which a Waters-600E high resolution liquid chromatography is adopted, with a C-18 column, a temperature of the 30 ° C column, a mobile methanol-water phase at a flow rate of 1.0 ml / min, and an ultraviolet detector. The titanium content can be measured by a 752S ultraviolet-visible spectrophotometer, with 1 mol / l sulfuric acid as a white solution. And the magnesium content can be measured by titration with an EDTA solution of 0.02 mol / l.
In accordance with another specific embodiment of the present disclosure, the catalyst component is prepared by reacting magnesium compounds, titanium compounds and diol diester compounds shown in Formula (I).
In the catalyst component of the present disclosure, based on one mole of magnesium compounds, the dosage of the titanium compounds is in the range of 0.5 mol to 150 mol, and the dosage of the diol diester compounds it is in the range of 0.01 mol to 5 mol, preferably 0.02 mol to 2 mol, and more preferably 0.02 mol to 0.4 mol.
In accordance with the present disclosure, the magnesium compounds are selected from the group consisting of magnesium dihalides, magnesium alkoxy compounds, magnesium alkyl compounds, magnesium dihalide hydrates or alcoholates and magnesium dihalide derivatives with halogen atoms of they are substituted with alkoxy groups or halogenated alkoxy groups, preferably magnesium dihalides and

alcoholates thereof, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.
According to the present disclosure, the titanium compounds preferably have a general formula of TiXm (OR1) 4-m, in which R1 is a C1 to C20 hydrocarbyl group, X is a halogen, and 1≤m≤ 4. Titanium compounds may, for example, be selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxy titanium, tetraethoxy titanium, triethoxy titanium chloride, diethoxy titanium dichloride and ethoxy titanium trichloride, preferably tetrachloride Titanium
It should be particularly noted that in a specific embodiment, the reaction comprises dissolving magnesium compounds in a solvent system composed of organic epoxides, organic phosphorus compounds and an inert diluent to form a homogeneous solution, which is to be mixed with titanium compounds. Next, a solid precipitates in the presence of a coprecipitation agent. Finally, the solid is treated with compounds shown in Formula (I), so that the compounds shown in Formula (I) will be loaded onto the solid. The solid can then be treated with a titanium tetrahalide and an inert diluent when deemed necessary, on which reference can be made to CN 85100997. In the catalyst component prepared as before, the content of the diol diester compounds to be shown in Formula (I) varies in the range of 1% to 25% by weight, the titanium content in the range of 0.5% to 8% by weight, and the magnesium content in the range of 3% to 25% by weight. Preferably, the content of the diol diester compounds shown in Formula (I) varies in the range of 5% to 20% by weight, the content of titanium in the range of 1% to 6% by weight, and the magnesium content in the range of 10% to 20% by weight. More preferably, the content of the diol diester compounds shown in Formula (I) varies in the range of 8% to 12% by weight, the content of titanium in the range of 2% to 4% by weight, and the magnesium content in the range of 15% to 19% by weight.
According to the present disclosure, based on one mole of the magnesium compounds, the dosage of the organic peroxides varies in the range of 0.2 mol to 10 mol, the dosage of the organic phosphorus compounds in the range of 0 , 1 mol to 3 mol, and the dosage of the coprecipitation agent in the range of 0 mol to 1.0 mol.
In accordance with the present disclosure, organic epoxides may comprise compounds that are selected from the group consisting of aliphatic olefins, dienes,

halogenated aliphatic olefins, oxides of dienes, glycidyl ethers and internal ethers having 2 to 8 carbon atoms. Specific compounds thereof include ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, glycidyl methyl ether, diglycidyl ether and tetrahydrofuran.
According to the present disclosure, the organic phosphorus compounds may be hydrocarbyl esters or halogenated orthophosphoric acid or phosphorous acid hydrocarbyl esters. Specific compounds thereof include trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and triphenyl phosphite.
In accordance with the present disclosure, the coprecipitation agent may be selected from the group consisting of organic anhydrides, organic acids, ethers and ketones. Specific compounds thereof comprise 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, dimethyl ether, diethyl ether dipropyl ether, dibutyl ether, diamil ether, etc.
In accordance with the present disclosure, the magnesium compounds can also be dissolved in a solvent system containing organic alcohol compounds, which can be monohydric alcohols with 2 to 8 carbon atoms. For example, the reaction may comprise dissolving the magnesium compounds in an inert solvent containing hydrocarbon compounds and alcohol compounds to form a solution, which is to be mixed with titanium compounds at, for example, from -40 ° C to 40 ° C , followed by the addition of electron donor compounds at, for example, from -40 ° C to 150 ° C. After washing with an inert diluent, a solid catalyst component is obtained. The electron donor compounds may be at least one selected from the group consisting of the diol diester compounds shown in Formula (I). In the catalyst component prepared above, based on the total weight of the catalyst component, the content of the diol diester compounds shown in Formula (I) varies in the range of 3% to 25% by weight, the titanium content in the range of 0.5% to 8% by weight, and the magnesium content in the range of 8% to 25% by weight. Preferably, the content of the diol diester compounds shown in Formula (I) varies in the range of 5% to 20% by weight, the content of titanium in the range of 1% to 6% by weight, and the magnesium content in the range of 10% to 20% by weight.

The hydrocarbon compounds may comprise compounds that are selected from the group consisting of linear or branched C6 to C12 alkanes and C6 to C15 aromatic hydrocarbon compounds, specifically including hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, etc. The alcohol compounds may comprise those selected from the group consisting of aliphatic alcohols, cycloaliphatic alcohols and aromatic alcohols, wherein the aliphatic alcohols may be linear and branched C1 to C10 aliphatic alcohols; the cycloaliphatic alcohols can be C3 to C10 cycloaliphatic alcohols; and the aromatic alcohols may be C6 to C20 aryl alcohols or alkaryl alcohols, specifically including ethanol, propanol, butanol, pentanol, hexanol, octanol, iso-octanol, etc., or mixtures thereof. The inert diluent may be selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene, and xylene.
The catalyst component of the present disclosure can also be prepared by the following procedures.
Procedure 1: The catalyst component can be prepared by the process disclosed in CN 1040379. First, a magnesium compound and organic alcohol compound with a molar ratio in the range of 2: 1 to 5: 1 between they are mixed with an inert diluent. The temperature of the resulting mixture rises to the range of 120 ° C to 150 ° C, which precedes the addition of an anhydride in an amount that allows the molar ratio of magnesium to the anhydride to be in the range of 5: 1 to 10 : 1, followed by reaction for 1 to 5 hours. Next, a cooled alcoholate is added to room temperature in a solution of the titanium compound that is precooled to a temperature in the range of -15 ° C to -40 ° C, at a rate of amounts between them such that it allows the molar ratio from titanium to magnesium be in the range of 20: 1 to 50: 1. The temperature rises to 90 ° C to 110 ° C, after which a compound shown in Formula (I) is added in such an amount that allows the magnesium to internal electron donor molar ratio is in the range of 2: 1 to 10: 1, followed by reaction at a temperature in the range of 100 ° C to 130 ° C for 1 to 3 hours. Then the solid particles are filtered off. The solid particles are added to a solution of titanium compound in an amount such that it allows the molar ratio of titanium to magnesium to be in the range of 20: 1 to 50: 1, which precedes the reaction at a temperature in the range from 100 ° C to 130 ° C under stirring for 1.5 to 3 hours. The solid particles are obtained by filtration, washed with an inert diluent at a temperature in the range of 50 ° C to 80 ° C, and

they are dried to obtain the catalyst component.
Procedure 2: The solid catalyst component can be prepared by reacting the titanium compound of the present disclosure, specifically TiCl4, for example, with an adduct having a general formula of MgCl2 · pROH. In the formula MgCl2 · pROH, "p" is a number in the range of 0.1 to 6, preferably 2 to 3.5, and "R" is a hydrocarbyl group having 1 to 18 carbon atoms. The adduct can be adequately prepared in spheres as follows. In the presence of an inert hydrocarbon compound that is immiscible with the adduct, an alcohol (ROH) is mixed with MgCl2 to form an emulsion, which is inactivated, so that the adduct can solidify in the form of spherical particles. The adduct thus obtained can be reacted directly with a titanium compound. Alternatively, before reacting with the titanium compound, the alcohol can first be removed from the adduct under thermal control at a temperature in the range of 80 ° C to 130 ° C, after which they will generally have less than 3 mol , preferably 0.1 to 2.7 mol of alcohol per mol of adduct. The adduct, whether alcohol-free or not, can be suspended in cold TiCl4 (usually 0 ° C) to form a mixture, which is heated to a temperature in the range of 80 ° C to 130 ° C by temperature programming and kept constant. for 0.1 to 2 hours for the reaction between the adduct and the titanium compound. Previous treatment with TiCl4 may be carried out one or more times during which a compound shown in Formula (I) of the present disclosure may be added for treatment, which may also be carried out one or more times.
The catalyst component can be prepared specifically by the process disclosed in CN 1091748. A melt of magnesium chloride alcoholate is dispersed in a dispersing system of white oil and silicone oil at a mixing rate to form an emulsion, which is left in a liquid refrigerant to cool and harden in microspheres of magnesium chloride alcoholate. The liquid refrigerant may be an inert hydrocarbon solvent having a low boiling temperature, such as petroleum ether, pentane, hexane, heptane, etc. The magnesium chloride alcoholate microspheres obtained are washed and dried to form a spherical support, in which the molar ratio of the alcohol to magnesium chloride varies in the range of 2: 1 to 3: 1, preferably 2: 1 to 2.5: 1, and the support has a grain size in the range of 10 μm to 300 μm, preferably 30 μm to 150 μm.
The anterior spherical support is treated with an excess amount of titanium tetrachloride at a low temperature. Although the temperature rises gradually, a donor of

electrons shown in Formula (I) of the present disclosure. After the above treatment, the spherical support is washed a plurality of times with an inert solvent and then dried to obtain the catalyst component in the form of a spherical solid powder. The molar ratio of titanium tetrachloride to magnesium chloride varies in the range of 20: 1 to 200: 1, preferably 30: 1 to 60: 1. The initial treatment temperature varies in the range of -30 ° C to 0 ° C, preferably from -25 ° C to -20 ° C, and final treatment temperature varies in the range of 80 ° C to 136 ° C, preferably 100 ° C to 130 ° C .
Procedure 3: A dialkoxy magnesium compound is added to an aromatic hydrocarbon compound under stirring to form a suspension, which is treated with titanium tetrachloride at a temperature in the range of -20 ° C to 100 ° C. The reaction between them is carried out at a temperature in the range of 0 ° C to 130 ° C, during which an electron donor shown in Formula (I) of the present disclosure is added at a temperature in the range from -20 ° C to 130 ° C, to obtain a solid. The solid is then washed with an aromatic hydrocarbon compound, treated with titanium tetrachloride in an aromatic solvent at a temperature in the range of 0 ° C to 130 ° C, washed with an inert solvent and pumped dry to obtain the component of catalyst. Based on one mole of the dialkoxy magnesium compound, the dosage of titanium tetrachloride varies in the range of 0.5 mol to 100 mol, and the dosage of the electron donor varies in the range of 0.01 mol to 10 mol.
Procedure 4: Titanium tetrachloride or a solution of an aromatic hydrocarbon compound may be used to halogenate a dihydroxycarbyloxy magnesium compound such as a dialkoxy magnesium compound or a diaryloxy magnesium compound at a temperature in the range of 80 ° C to 130 ° C. The above halogenation may be repeated once or a plurality of times, during which a compound shown in Formula (I) of the present disclosure may be added.
Procedure 5: The procedure disclosed in US 4540679 is used to prepare the catalyst component of the present disclosure. To begin, a magnesium alcoholate is reacted with carbon dioxide to prepare a magnesium hydrocarbyl carbonate support. A transition metal compound (preferably a tetravalent titanium compound) is reacted with the magnesium hydrocarbyl carbonate support, and an electron donor shown in Formula (I) of the present disclosure in an inert solvent to a certain reason, where the molar ratio of the transition metal to magnesium is at least 0.5: 1, and the dosage of the electron donor that

Shown in Formula (I) of the present disclosure is a maximum of 1.0 mol per gram of titanium atoms. The inert solvent will be purified to remove substances such as water, oxygen and carbon dioxide that easily cause catalyst poisoning. The reaction is carried out at a temperature in the range of -10 ° C to 170 ° C for a period of several minutes to several hours.
The catalyst component of the present disclosure can also be prepared by forming an emulsion with a magnesium compound, an electron donor, etc., in a diluent, followed by the addition of a titanium compound to be fixed to form a spherical solid, which It is then treated to obtain the catalyst component.
In any one of the aforementioned procedures, the electron donors shown in Formula (I) can be added either in the form of compounds or in other forms. For example, a suitable precursor of an electron donor shown in Formula (I) can be used to obtain the electron donor in-situ by, for example, known chemical reactions such as esterification reactions, etc.
In accordance with another aspect of the present disclosure, a catalyst for the polymerization of olefins is provided, comprising the following components:
component a): the catalyst component according to the first aspect of the present disclosure; and component b): alkylaluminum compounds.
In the above catalysts, the alkyl aluminum compounds have the general formula of AlRnX3-n, in which R can be selected from the group consisting of hydrogen, and hydrocarbyl groups C1 to C20, and 1≤n≤3. More specifically, the alkyl aluminum compounds may be selected from the group consisting of triethylaluminum, tripropyl aluminum, tri-n-butylaluminum, tri-iso-butylaluminum, tri-n-octylaluminum, tri-iso-octylaluminum, diethylaluminium hydride, dihydride hydride. iso-butylaluminum, diethylaluminium chloride, di-iso-butylaluminum chloride, ethylaluminum sesquichloride and ethylaluminium dichloride, preferably triethylaluminum and tri-iso-butylaluminum.
The dosage of the alkyl aluminum compounds may be a conventional dosage in the art. In accordance with a preferred embodiment of the present disclosure, the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum varies

in the range of 1: 5 to 1: 1000, for example from 1:20 to 1: 250.
In the above catalyst, the catalyst further comprises component c): an external electron donor, which is selected from the group consisting of organosilicon compounds, ethers, esters and mixtures thereof. When the external electron donor is added, olefinic polymers with high stereoregularity can be obtained, for example, organolysicon compounds having a general formula of RnSi (OR ′) 4-n, in which 0≤n≤3; R and R ', identical or different from each other, can be alkyl, cycloalkyl, aryl, halogenated alkyl and amino groups; and R can also be a halogen or hydrogen atom. Specific compounds thereof may be selected from the group consisting of trimethyl methoxy silane, trimethyl ethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, phenyl triethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silyl, vinyl trimethoxy silyl dimethoxy silane and methyl tert-butyl dimethoxy silane, preferably cyclohexyl methyl dimethoxy silane and diphenyl dimethoxy silane. The external electron donor compounds can also be ether compounds such as 1,3-diether, ester compounds such as monobenzoate, dibenzoate and diol diester compounds, and mixtures of organosilicon compounds, ethers and esters.
In the above catalyst, the dosage of the external electron donor compound may be a conventional dose in the art. According to a preferred embodiment of the present disclosure, the molar ratio of component c) to component a) based on silicon (or ethers or esters) to titanium varies in the range of 0: 1 to 500: 1, for example, 0 , 1: 1 to 500: 1, 0.1: 1 to 100: 1, or 1: 1 to 50: 1.
The catalyst of the present disclosure can be added directly to the reactor for polymerization. Alternatively, the catalyst may first participate in a prepolymerization reaction before polymerization. In the present disclosure, the term "prepolymerization" refers to polymerization at lower conversion. In accordance with the present disclosure, the prepolymerization catalyst comprises the above solid catalyst component and prepolymers obtained in the prepolymerization between the solid catalyst component and olefins, the multiple prepolymerizations thereof being in the range of 0.1 g to 1000 g of olefinic polymers per g of catalyst component.
The same -olefins mentioned above, preferably ethylene or propylene, can be used for prepolymerization. Specifically, polymerization is preferred

particularly a mixture of ethylene or propylene with one or a plurality of -olefins representing a maximum of 20 mol%. Preferably, the conversion of the catalyst component in the prepolymerization is about 0.2 g to 800 g of polymers per g of solid catalyst component.
The prepolymerization process can be carried out in the liquid or gas phase at a temperature in the range of -40 ° C to 80 ° C, preferably from -20 ° C to 50 ° C. The prepolymerization steps can be carried out in line as a portion of a continuous polymerization, or they can be carried out independently in a discontinuous operation. In order to prepare 0.5 to 20 g of polymers per g of solid catalyst component used, propylene prepolymerization and the catalyst of the present disclosure are particularly preferred. The polymerization pressure varies in the range of 0.01 MPa to 10 MPa.
In accordance with yet another aspect of the present disclosure, a polymerization process is provided, in which the olefins are polymerized in the presence of the above solid catalyst component, the prepolymerization catalyst or catalyst.
The catalyst of the present disclosure can be added directly to the reactor for polymerization. Alternatively, the olefin prepolymerization can first be carried out in the presence of the catalyst to obtain a prepolymerization catalyst, which will be added to the reactor for polymerization.
The olefin polymerization of the present disclosure can be carried out by a known process for the polymerization in liquid or gas phase, or in a combination of liquid phase and gas phase. A routine technique such as a suspension process, or a gas phase fluidized bed, etc., can also be used. Preferably, a polymerization temperature is adopted in the range of 0 ° C to 150 ° C, preferably 60 ° C to 90 ° C.
The olefins of the present disclosure have a general formula of CH2 = CHR, wherein R is hydrogen or a C1 to C12 alkyl or aryl group. For example, olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, preferably selected from ethylene and propylene. For example, homopolymerization of propylene or copolymerization of propylene and other olefins can be carried out. The procedure of the present disclosure can also be applied in, for example, the

homopolymerization of ethylene, and the copolymerization of ethylene and -olefins such as propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.
It should be noted that, the catalyst component of the present disclosure contains a diol diester shown in Formula (I) which contains a special structure. The diol diester is obtained by reacting a non-terminal group diol having more than 6 carbon atoms in the linear chain with benzoic acid containing at least one hydrocarbyl group, that is, substituted Cm (m≥2). The diol diester containing a special structure can further improve the response to hydrogen and the polymerization activity of the catalyst, and produces olefins having a high flow rate and high isotacticity. That is, when the polymers obtained in the present disclosure have the same flow rate, that is, an equal hydrogen response, than the polymers obtained using diol diesters of other structures, the polymers of the present disclosure would certainly have a greater isotacticity, while when the polymers obtained in the present disclosure have the same isotacticity as the polymers obtained using diol esters of other structures, the polymers of the present disclosure would certainly have a higher flow rate, that is, a greater response to hydrogen.
In accordance with the present disclosure, when the catalyst system containing a diol diester compound shown in Formula (I) of the present disclosure is used in the polymerization of olefins, the catalyst shows good overall performance, including high catalytic activity In particular, in the presence of highly concentrated hydrogen, the catalyst has an improved hydrogen response and / or the isotacticity of the polymers obtained can be significantly improved. The catalyst of the present disclosure is beneficial for obtaining polymers with high fluidity index and high isotacticity, and for the development of polymers of different qualities.
Detailed description of the achievements
The following examples are used to explain and describe the present disclosure, and not to limit the present disclosure in any way.
Test Procedures:
1. The isotactic index of a polymer is tested by heptane extraction (6 hours of boiling heptane extraction): 2 g of a dried polymer sample is placed in a

extractor to extract with boiling heptane for 6 hours. Then, the rest is dried to a constant weight (g), which is divided by 2 to obtain the isotactic index of the polymer.
5 2. The melt index (MI) of a polymer is tested by the standardized GB / T test3682-2000.
3. Measurement by nuclear magnetic resonance: A resonance spectrometer is used
magnetic magnetic Bruke dmx 300 for the measurement of 1 H NMR (300 MHz; the solvent: 10 CDCl3; internal standard: TMS; measuring temperature: 300 K)
Synthesis of electron donor compounds
The synthesis of compound ID3, ie bis (4-n-propyl benzoate) of 3,5-heptanediol, is taken as an example.
A solution in methanol of 3,5-heptadione (14.2 g of 3,5-heptadione / 30 ml of methanol) is added dropwise to a mixture of 2.5 g of sodium borohydride, 0.05 g of sodium hydroxide and 25 ml of water at a temperature in the range of 0 ° C to 10 ° C. After completion, the solvent is removed by distillation under reduced pressure and the residue thereof is extracted with ethyl acetate. Then, solvent removal is carried out again and 3,5-heptanediol is obtained in a yield of 92%. For infrared characterization, the Nicolet 6700 Fourier transform infrared spectrometer is used. The IR spectra thereof indicate a strong adsorption peak at 3400 cm -1, and absence of
25 adsorption peak around 1700 cm -1, which is evidence of complete reduction reaction.
In 0.03 mol of 3,5-heptanediol, 30 ml of tetrahydrofuran and 0.09 mol of pyridine are added. Then, 0.075 mol of 4-n-propyl-benzoyl chloride is added under stirring. The reaction is heated at reflux for 4 hours. After cooling, 20 ml of saturated saline are added. The reaction mixture is extracted with ethyl acetate. The extract of this is then dried with anhydrous sodium sulfate and then filtered. After removal of the solvent, a crude product is purified with a chromatographic column to obtain a colorless viscous liquid, that is, 3,5-heptanediol bis (4-n-propyl benzoate),
35 whose characterization data are listed below.

1H NMR (TMS ， CDCl3, ppm): δ 0.92 ~ 1.03 (12H, m, -CH3); 1.62 ~ 1.71 (4H, m, -CH2);
1.74 ~ 1.81 (4H, m, -CH2); 1.94 ~ 2.28 (2H, m, -CH2); 2.59 ~ 2.70 (4H, m, -CH2); 5.18 ~ 5.25 (2H, m, -CH); 7.15 ~ 7.30 (4H, m, -C6H4-); 7.88 ~ 8.04 (4H, m, -C6H4-).
UPLC: Waters Acquity high resolution liquid chromatography, with a BEH C-18 column, a column temperature of 30 ° C, a mobile phase of acetonitrile-water at a flow rate of 0.5 ml / min, and a ultraviolet detector The observation is carried out at a position of 229 nm. The data obtained from it are as follows: residence time 9,931 min (37.7%), bis (4-n-propyl benzoate) peaks of (3S, 5S) -3,5-heptanediol and bis (4- (3R, 5R) -3,5-heptanediol n-propyl benzoate); residence time 11,160 min, bis (4-n-propyl benzoate) peak of meso-3,5-heptanediol.
Examples 1 to 5
Preparation of a catalyst component
In a reactor in which the air has been suitably replaced with high purity nitrogen, 6.0 g of magnesium chloride, 119 ml of toluene, 5 ml of epoxy chloropropane and 15.6 ml of tributyl phosphate (TBP) are successively added ). The temperature rises to 50 ° C under stirring and remains constant for 2.5 hours until the solid dissolves completely. Next, 1.7 g of phthalic anhydride are added, and the temperature is maintained for 1 hour. The temperature is then reduced to below -25 ° C, followed by the addition of 70 ml of TiCl4 in one hour. After this, the temperature rises slowly to 80 ° C, during which a solid precipitates gradually. Next, 4.6 mmol of the diol diester compound (I) is added as shown in Table 1 and the temperature is kept constant for one hour. After filtration, 80 ml of toluene is added to the reactor and a wash is performed twice to obtain a solid precipitate.
Then, 60 ml of toluene and 40 ml of TiCl4 are added in the reactor and the temperature is raised to 108 ° C, followed by 2 hours of treatment. The filtrate is separated, which precedes the addition of another 60 ml of toluene and 40 ml of TiCl4. The temperature is then raised again to 108 ° C, followed by another 2 hours of treatment and then the filtrate is separated. After this, another 60 ml of toluene are added, and a wash is performed once in a boiling state. Then 60 ml of hexane are added, followed by two washes. After the addition of another 60 ml of hexane, another wash is carried out twice at room temperature to obtain the catalyst component. Diester compounds

Specific diol are shown in Table 1.
Comparative Examples 1 to 2
5 The steps are similar to those in Examples 1 to 5, except that different ones are addeddiol diester compounds in the corresponding reactors. Table 1 showsspecific diol diester compounds.
Examples 6 to 9
10 Under nitrogen protection, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol and 19.5 g of decane as solvent are added in a 500 ml reactor. The temperature rises to 130 ° C, followed by a 1.5 hour reaction until the magnesium chloride is completely dissolved. 1.1 g of phthalic anhydride are added to the reactor and the
The temperature is kept constant at 130 ° C, followed by a one hour reaction to obtain an alcoholate, which is then cooled to room temperature.
Under nitrogen protection, the above alcoholate in 120 ml of a previously cooled TiCl4 solution is added dropwise to -22 ° C. The temperature is slowly raised 20 to 100 ° C, followed by the addition of 10 mmol of diol diester compounds shown in Formula (I) respectively. The temperature rises to 110 ° C and remains constant for 2 hours, which precedes a hot filtration. Next, 120 ml of TiCl4 are added and the temperature is raised to 110 ° C and kept constant for 1 hour, followed by filtration. The solid particles are washed with anhydrous hexane
25 four times and then dried to obtain the catalyst component. Specific diol diester compounds are shown in Table 1.
Comparative Examples 3 to 4
The steps are similar to those of Examples 6 to 9, except that different diol diester compounds are added in the corresponding reactors. Specific diol diester compounds are shown in Table 1.
Propylene polymerization experiments
35 The catalyst components prepared in the examples and comparative examples

The above are used respectively in the polymerization of propylene, which is carried out in the following steps. In a 5-liter stainless steel reactor in which the air has been suitably replaced by gaseous propylene, 2.5 mmol of AlEt3, 0.1 mmol of cyclohexylmethyldimethoxysilane (CHMMS), 8 mg to 10 mg of the components are added catalyst
5 solids prepared as before and a certain amount of hydrogen. After feeding 2.3 liters of liquid propylene to the reactor, the temperature rises to 70 ° C and remains constant for one hour. Then, cooling and reducing the pressure to obtain the PP powders of Examples 1 to 9, and Comparative Examples 1 to 4, are carried out. The data is as shown in Table 1.
10 Table 1 Propylene polymerization result
Number Diol diester compoundPolymerization activity (kg of PP / g catalyst)Fluency rate (g / 10min)Isotactic index (%)
1.2 NL Hydrogen 7.2 NL Hydrogen 1.2 NL Hydrogen7.2 NL Hydrogen 1.2 NL Hydrogen7.2 NL Hydrogen
Example 1 ID157.568.51.730.198.996.6
Example 2 ID258.569.81.731.998.896.6
Example 3 ID360.571.01.936.598.596.1
Example 4 ID452.960.42.455.898.395.5
Comparative Example 1 ID550.958.61.728.398.295.0
Comparative Example 2 ID660.069.00.915.198.897.1
Example 5 ID752.2/1.6/97.2/
Example 6 ID856.1/2.6/98.1/
Example 7 ID958.270.52.645.798.896.5
Example 8 ID1057.568.42.549.998.596.4
Example 9 ID1154.862.02.750.998.296.0
Comparative Example 3 ID550.058.02.330.098.395.1
Comparative Example 4 ID1263.173.64.972.494.785.4
ID1: 2,4-hexanediol bis (4-n-propyl benzoate) ID2: 3,5-heptanediol bis (4-tert-butyl benzoate) ID3: 3,5- bis (4-n-propyl benzoate) heptanediol ID4: 3,5-heptanediol bis (4-n-butyl benzoate) 3,5-heptanediol bis-benzoate ID6: 2,4-pentanediol bis (4-n-propyl benzoate)

ID7: 3,5-heptanediol cinnamic acid 4-n-propyl benzoate
ID8: 4-ethyl-3,5-heptanediol bis (4-tert-butyl benzoate)
ID9: 3,5-octanediol bis (4-n-butyl benzoate)
ID10: 4-methyl-3,5-heptanediol bis (4-n-butyl benzoate)
ID11: 3,5-heptanediol bis (4-iso-butyl benzoate)
ID12: 2,6-dimethyl-3,5-heptanediol bis (4-n-propyl benzoate)
The above data indicates that the catalyst having a special structure (shown in Formula (I) that is obtained by reacting a non-terminal group diol having more than 6 carbon atoms in the linear chain with benzoic acid having At least one hydrocarbyl group, that is, Cm (m≥2) substituted) provided by the present disclosure has a fairly good overall performance. Compared to the diol diesters of the comparative examples obtained by reacting a non-terminal group diol with benzoic acid (as adapted in Comparative Examples 1 and 3), the diol diester compound having a special structure (which It is shown in the Formula
(I) that is obtained by reacting a non-terminal group diol having more than 6 carbon atoms in the linear chain with benzoic acid having at least one hydrocarbyl group, that is, substituted Cm (m≥2)) that is provides for the present disclosure not only significantly improves the activity of the catalyst, but also improves the hydrogen response of the catalyst (i.e., the polymer obtained has a high flow rate) and isotacticity of the polymer, especially in the presence of highly concentrated hydrogen. Compared to the pentyl diol diester that is adopted in Comparative Example 2, the diol diester compound of the present disclosure significantly improves the melt flow rate of the polymer, especially the melt flow rate of the polymer in the presence of highly hydrogen. concentrated, provided that a high isotacticity of the polymer is maintained. That is, the diol diester compound of the present disclosure improves the hydrogen response of the catalyst. Compared to the diol diester used in Comparative Example 4, which contains a side chain at the position  of the main chain (i.e., does not contain position  between two hydroxyl groups), the diol diester compound of the This disclosure greatly improves the isotacticity of the polymer provided that a high activity of the catalyst is maintained.
It should be noted that the above examples are used only to explain, and not to limit the present disclosure in any way. Although the present disclosure has been described with reference to preferable examples, it is understood that the terms and expressions adopted are to describe and explain rather than limit the present disclosure. The present

Disclosure may be modified within the scope of the claims, or may be amended without departing from the scope or spirit of the present disclosure. Although the present disclosure is described with specific procedures, materials and examples, the scope of the present disclosure in this document will not be limited by the examples disclosed in particular that have been described above, but may extend to other procedures and uses that have the same functions.

权利要求:
Claims (13)
[1]
1. A catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen and an electron donor, wherein the electron donor is at least one selected from the group consisting of diol diester compounds shown in Formula (I):
wherein, R1 to R4, identical or different from each other, can be independently selected from hydrogen, halogens, and C1 to C10 hydrocarbyl groups substituted or not
10 substituted, with at least one of R1 and R2 being a substituted or unsubstituted C1 to C10 hydrocarbyl group, and R3 and R4 being optionally linked to form a ring; wherein R5 is selected from substituted or unsubstituted C2 to C10 hydrocarbyl groups, where n is an integer in the range of 1 to 5; and wherein R6 is selected from substituted or unsubstituted C1 to C15 hydrocarbyl groups.
[2]
2. The catalyst component according to claim 1, wherein in the diol diester compounds shown in Formula (I), R1 to R4, identical or different from each other, can be independently selected from hydrogen, halogens, C1 to C10 linear alkyl groups, C3 to C10 branched alkyl groups, C3 to C10 cycloalkyl groups, C6 aryl groups
20 to C10, C7 to C10 alkaryl groups and substituted or unsubstituted C7 to C10 aralkyl groups; wherein R5 is selected from C2 to C10 linear alkyl groups, C3 to C10 branched alkyl groups, C3 to C10 cycloalkyl groups, C6 to C10 aryl groups, C7 to C10 alkaryl groups and substituted or unsubstituted C7 to C10 aralkyl groups; and wherein R6 is selected from C1 to C10 linear alkyl groups, C3 branched alkyl groups
25 to C10, C3 to C10 cycloalkyl groups, C6 to C10 aryl groups, C7 to C15 aryl hydrocarbyl groups, and C7 to C15 substituted or unsubstituted aryl hydrocarbyl groups.
[3]
3. The catalyst component according to claim 1, wherein in the compounds of
diol diesters shown in Formula (I), R1 and R2 are selected from hydrogen and C1 to C6 linear alkyl groups and C3 to C6 branched alkyl groups halogenated or not

halogenated; wherein R3 and R4 are selected from hydrogen, halogens and C1 to C6 linear alkyl groups and halogenated or non-halogenated C3 to C6 branched alkyl groups; wherein R5 is selected from C2 to C6 linear alkyl groups and halogenated or non-halogenated C3 to C6 branched alkyl groups, n being equal to 1 or 2, preferably, being n 1 and R5 being a para-or ortho-substituted group; and wherein R6 is selected from C4 to C10 linear or branched alkyl groups, C5 to C10 cycloalkyl groups, C6 to C10 aryl groups, C8 to C15 aryl groups, C7 to C15 alkaryl groups, and halogenated C7 to C15 alkylalkyl groups, preferably C8 to C12 alkenyl groups, C7 to C15 alkaryl groups and halogenated or non-halogenated C7 to C15 aralkyl groups.
[4]
4. The catalyst component according to any one of claims 1 to 3, whereinthe diol diester compounds shown in Formula (I) are one or moreselected from the group consisting of2,4-hexanediol bis (4-ethyl benzoate),2,4-hexanediol bis (4-n-propyl benzoate),2,4-hexanediol bis (4-n-butyl benzoate),2,4-hexanediol bis (4-iso-butyl benzoate),2,4-hexanediol bis (4-tert-butyl benzoate),2,4-hexanediol bis (4-hexyl benzoate),3-methyl-2,4-hexanediol bis (4-ethyl benzoate),3-methyl-2,4-hexanediol bis (4-n-propyl benzoate),3-methyl-2,4-hexanediol bis (4-n-butyl benzoate),3-methyl-2,4-hexanediol bis (4-iso-butyl benzoate),3-methyl-2,4-hexanediol bis (4-tert-butyl benzoate),3-methyl-2,4-hexanediol bis (4-hexyl benzoate),3-ethyl-2,4-hexanediol bis (4-ethyl benzoate),3-ethyl-2,4-hexanediol bis (4-n-propyl benzoate),3-ethyl-2,4-hexanediol bis (4-n-butyl benzoate),3-ethyl-2,4-hexanediol bis (4-iso-butyl benzoate),3-ethyl-2,4-hexanediol bis (4-tert-butyl benzoate),3-ethyl-2,4-hexanediol bis (4-hexyl benzoate),3,5-heptanediol bis (4-ethyl benzoate),3,5-heptanediol bis (4-n-propyl benzoate),3,5-heptanediol bis (4-iso-propyl benzoate),3,5-heptanediol bis (4-n-butyl benzoate),

3,5-heptanediol bis (4-iso-butyl benzoate),3,5-heptanediol bis (4-tert-butyl benzoate),3,5-heptanediol bis (4-pentyl benzoate),3,5-heptanediol bis (4-hexyl benzoate),
3,5-heptanediol cinnamic acid 5 4-ethyl benzoate,4-methyl-3,5-heptanediol bis (4-ethyl benzoate),4-methyl-3,5-heptanediol bis (4-n-propyl benzoate),4-methyl-3,5-heptanediol bis (4-iso-propyl benzoate),4-methyl-3,5-heptanediol bis (4-n-butyl benzoate),
10 bis (4-iso-butyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-methyl-3,5-heptanediol, bis (4-pentyl benzoate) of 4 -methyl-3,5-heptanediol, 4-methyl-3,5-heptanediol bis (4-hexyl benzoate), 4-methyl-3,5-heptanediol cinnamic acid 4-ethyl benzoate
15-4-ethyl-3,5-heptanediol bis (4-n-propyl benzoate) 4-ethyl-3,5-heptanediol bis (4-iso-propyl benzoate) bis (4-ethyl-3,5-heptanediol) -ethyl-3,5-heptanediol, 4-ethyl-3,5-heptanediol bis (4-iso-butyl benzoate), 4-ethyl-3,5-heptanediol bis (4-iso-butyl benzoate),
20-4-ethyl-3,5-heptanediol bis (4-pentyl benzoate) 4-ethyl-3,5-heptanediol bis (4-hexyl benzoate) 4-ethyl bis (4-tert-butyl benzoate) -3,5-heptanediol, 4-ethyl-3,5-heptanediol-cinnamic acid 4-n-propyl-3,5-heptanediol, 4-ethyl-3,5-heptanediol-cinnamic acid bis (4-tert-butyl benzoate),
25 bis (4-tert-butyl benzoate) of 4-n-butyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4,4-dimethyl-3,5-heptanediol, bis (4-tert -butyl benzoate) of 4-methyl-4-ethyl-3,5-heptanediol, bis (4-tert-butyl benzoate) of 4-methyl-4-n-propyl-3,5-heptanediol, bis (4-n -propyl benzoate) of 3-methyl-2,4-heptanediol,
30 bis (4-iso-propyl benzoate) of 3-methyl-2,4-heptanediol, bis (4-tert-butyl benzoate) of 4-methyl-3,5-octanediol, bis (4-tert-butyl benzoate) 4-ethyl-3,5-octanediol, 4-n-propyl-3,5-octanediol bis (4-tert-butyl benzoate), 4-n-butyl-3 bis (4-tert-butyl benzoate) , 5-octanediol,
4,4-dimethyl-3,5-octanediol bis (4-n-propyl benzoate) 4,4-diethyl-3,5-octanediol bis (4-tert-butyl benzoate),

4,4-di-n-propyl-3,5-octanediol bis (4-tert-butyl benzoate),4-methyl-4-ethyl-3,5-octanediol bis (4-tert-butyl benzoate),4,6-nonanodiol bis (4-ethyl benzoate),4,6-nonanodiol bis (4-n-propyl benzoate),4,6-nonanodiol bis (4-n-butyl benzoate),4,6-nonanodiol bis (4-iso-butyl benzoate),4,6-nonanodiol bis (4-tert-butyl benzoate),4,6-nonanodiol bis (4-hexyl benzoate),4,6-Nonanodiol cinnamic acid 4-ethyl benzoate,5-methyl-4,6-nonanodiol bis (4-ethyl benzoate),5-methyl-4,6-nonanodiol bis (4-n-propyl benzoate),5-methyl-4,6-nonanodiol bis (4-n-butyl benzoate),5-methyl-4,6-nonanodiol bis (4-iso-butyl benzoate),5-methyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5-methyl-4,6-nonanodiol bis (4-hexyl benzoate),5-ethyl-4,6-nonanodiol bis (4-ethyl benzoate),5-ethyl-4,6-nonanodiol bis (4-n-propyl benzoate),5-ethyl-4,6-nonanodiol bis (4-n-butyl benzoate),5-ethyl-4,6-nonanodiol bis (4-iso-butyl benzoate),5-ethyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5-ethyl-4,6-nonanodiol bis (4-hexyl benzoate),5-n-propyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5-n-butyl-4,6-nonanodiol bis (4-n-butyl benzoate),5,5-dimethyl-4,6-nonanodiol bis (4-tert-butyl benzoate),5,5-diethyl-4,6-nonanodiol bis (4-hexyl benzoate),5,5-di-n-propyl-4,6-nonanodiol bis (4-pentyl benzoate), and5,5-dibutyl-4,6-nonanodiol bis (4-tert-butyl benzoate).
[5]
5. The catalyst component according to any one of claims 1 to 4, wherein the catalyst component is prepared by reacting magnesium compounds, titanium compounds, and the diol diester compounds shown in Formula (I).
[6]
6. The catalyst component according to claim 5, wherein the magnesium compounds are selected from the group consisting of magnesium dihalides, magnesium alkoxy compounds, magnesium alkyl compounds, magnesium dihalide hydrates or alcoholates, and dihalide derivatives of magnesium with halogen atoms thereof that

they are substituted with halogenated alkoxy groups or alkoxy groups, preferably magnesium dihalides and alcoholates thereof; and wherein the titanium compounds have a general formula of TiXm (OR1) 4-m, R1 being a C1 to C20 hydrocarbyl group, X a halogen, and 1≤m≤ 4, preferably titanium tetrachloride.
[7]
7. The catalyst component according to claim 5 or 6, wherein based on one mole of the magnesium compounds, the dosage of the titanium compounds varies in the range of 0.5 mol to 150 mol, and that of the diol diester compounds shown in the Formula
(I) in the range of 0.01 mol to 5 mol, preferably 0.02 mol to 2 mol, and more preferably 0.02 mol to 4 mol.
[8]
8. A catalyst for olefin polymerization, comprising the following components: component a): the catalyst component according to any one of claims 1 to 7; and component b): alkylaluminum compounds.
[9]
9. The catalyst according to claim 8, further comprising component c): an external electron donor, which is selected from the group consisting of organosilicon compounds, ethers and esters.
[10]
10. The catalyst according to claim 8 or 9, wherein the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum varies in the range of 1: 5 to 1: 1000, and / or the ratio molar from component c) to component a) varies in the range of 0: 1 to
500: 1
[11]
eleven. A prepolymerization catalyst for polymerization of olefins, comprising the catalyst according to any one of claims 8 to 10, and a prepolymer generated by prepolymerization between said catalyst and olefins, the multiple prepolymerizations thereof being 0.1 g to 1000 g of olefinic polymers per g of catalyst component.
[12]
12. A process for olefin polymerization, in which the polymerization of olefins is carried out in the presence of the catalyst component according to any one of claims 1 to 7, the catalyst according to any one of claims 8 to 10, or the

prepolymerization catalyst according to claim 11.
[13]
13. The process according to claim 12, wherein the olefins have a general formula of CH2 = CHR, where R is hydrogen or a C1 to C12 alkyl or aryl group, preferably selected from propylene and ethylene.

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CN107129547A|2017-09-05|Ingredient of solid catalyst, catalyst and application for olefinic polymerization

CN106478846B|2019-05-31|For the catalyst carrier of olefinic polymerization, catalytic component and catalyst

CN107129549A|2017-09-05|Ingredient of solid catalyst, catalyst and application for olefinic polymerization

CN105085730B|2018-12-28|It is a kind of for the catalytic component of olefinic polymerization, preparation method and its catalyst

CN105085748B|2018-05-11|A kind of catalytic component and its catalyst for propylene polymerization

CN104177520B|2018-06-12|It is used to prepare the ingredient of solid catalyst of olefin polymer

CN104177521B|2016-08-17|Prepare method and the catalyst of solid catalyst component for olefine polymerization

CN109111536A|2019-01-01|Catalytic component and its catalyst for olefinic polymerization

BR112016007091B1|2021-10-05|CATALYST COMPOSITION FOR POLYMERIZATION OF OLEFINS AND USE OF IT

同族专利:

公开号 | 公开日

KR102174946B1|2020-11-05|

TW201446734A|2014-12-16|

SG11201509482XA|2015-12-30|

BR112015028908A2|2017-07-25|

RU2015154533A3|2018-03-30|

ES2557178R1|2016-04-07|

WO2014187323A1|2014-11-27|

US20160115257A1|2016-04-28|

RU2673083C2|2018-11-22|

TWI644896B|2018-12-21|

US9751960B2|2017-09-05|

ES2557178B2|2017-07-05|

GB2530212B|2020-08-19|

KR20160010616A|2016-01-27|

GB201522379D0|2016-02-03|

DE112014002517T5|2016-02-25|

GB2530212A|2016-03-16|

RU2015154533A|2017-06-22|

BR112015028908B1|2020-10-06|

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优先权:

申请号 | 申请日 | 专利标题

CN201310190424.4A|CN104177520B|2013-05-21|2013-05-21|It is used to prepare the ingredient of solid catalyst of olefin polymer|

CN201310190424|2013-05-21|

CN201310190990.5A|CN104177521B|2013-05-21|2013-05-21|Prepare method and the catalyst of solid catalyst component for olefine polymerization|

CN201310190990|2013-05-21|

PCT/CN2014/078050|WO2014187323A1|2013-05-21|2014-05-21|Catalyst component for use in olefin polymerization reaction, catalyst, and application|

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