A catalyst component for olefin polymerization, a catalyst for olefin polymerization, and use thereof

Abstract

The application discloses an olefin polymerization catalyst component, an olefin polymerization catalyst and application thereof, and the olefin polymerization catalyst component comprises Mg, Ti, halogen and an internal electron donor compound, and the internal electron donor is selected from 2,6-dicarboxylate-4-pyridine ether compounds of general formula (I). The internal electron donor compound of the catalyst component is a 2,6-dicarboxylate-4-pyridine ether compound of general formula (I), the prepared catalyst has the characteristics of high activity, the obtained polymer has high isotacticity, and the overall molecular weight distribution is wide.

Description

TECHNICAL FIELD

[0001] The present application relates to a solid catalyst component for the polymerization of olefins, more particularly, the present application relates to a solid catalyst component of a compound, a catalyst comprising the solid catalyst component and the use of the catalyst in the polymerization of olefins, particularly in the polymerization of propylene. BACKGROUND

[0002] Polyolefins are the largest volume polymer produced and are used in a wide variety of applications due to their low cost, ready processability, and excellent combination of properties. Ziegler-Natta catalysts (Z-N catalysts) still dominate the polyolefin production. Most of the development of Z-N catalysts has focused on the development of highly active and stereospecific catalysts and on improving the copolymerization ability of the catalysts. The traditional Z-N catalysts (transition metal compounds such as titanium bonded to a magnesium-containing support via chemical bonds) have high catalytic efficiency, the produced polymers have good comprehensive properties, and the cost is low. At present, most of the catalysts for producing polyolefins in the world are still based on the Z-N catalyst system, which has the characteristics of high activity, high stereoregularity, long life, and product structure customization. From the development process of Z-N catalysts, it can be seen that as early as the first generation of catalysts, it was found that the addition of a third component (mostly electron donors, also known as Lewis bases, among which, the addition during the preparation of the catalyst is an internal electron donor, and the addition during the polymerization process is an external electron donor) can greatly affect the behavior of olefin polymerization and the properties of the polymer. Changing the internal electron donor in the catalyst can change the properties of the active centers of the catalyst to the greatest extent, thereby changing the performance of the catalyst to the greatest extent. Therefore, the development of new electron donors has always been a hot spot in the research and development of polyolefin catalysts.

[0003] The high performance internal electron donor compounds with distinctive features in the prior art mainly include: 1) fatty acid ester and aromatic acid ester compounds, mainly represented by phthalate compounds; 2) diether compounds (for example, EP0361493, EP0728724); 3) succinate compounds (for example, WO9856834, WO0063261, WO03022894); 4) diol ester compounds (for example, WO9856834, WO0063261, WO03022894); 5) other functional group compounds (CN1105671, CN1242780, US20060128558) and the like. However, in practical applications, the above-mentioned compounds as internal electron donors of olefin polymerization catalysts all have certain problems, for example, the catalyst activity is not high when using binary aromatic carboxylic acid ester compounds as internal electron donors, the relative molecular mass distribution of the prepared polypropylene (PP) is also narrow, and the phthalate compounds as commonly used plasticizers have great harm to human reproductive health and environment; the catalyst activity is relatively high when using 1,3-diether compounds as internal electron donors, and the hydrogen regulation sensitivity of the catalyst is also good, but the relative molecular mass distribution of the prepared PP is narrow, which is not conducive to the development of different grades of PP; the succinate compounds as internal electron donors have the advantages that the relative molecular mass distribution of the synthesized PP is wide, and the disadvantages that the stereoregularity of the PP and the hydrogen regulation sensitivity of the catalyst need to be improved; and the activity of the diol ester catalyst system as a whole is not as ideal as the diether system.

[0004] The most widely used polyolefin internal electron donor in the industry at present is the phthalate compound, and the catalyst prepared therefrom has moderate activity, good stereoselectivity and low price, but the phthalate compound as a commonly used plasticizer has great harm to human reproductive health and environment, and has great substitution demand. Most phthalate substances have been restricted in Europe; therefore, it is one of the common research and development goals in the field of polyolefin catalysts in recent years to develop a new type of electron donor with excellent activity, good stereodirecting property, good comprehensive performance and low cost to replace the widely used phthalate electron donor compound in the prior art and apply it to the preparation of high-efficiency Ziegler-Natta catalyst. SUMMARY

[0005] In order to solve the problems in the prior art, the present application provides an olefin polymerization catalyst component which uses 2,6-dicarboxylate-4-pyridine ether as an internal electron donor compound, can improve the activity of the catalyst, and obtain an olefin polymer with higher stereoregularity.

[0006] Another object of the present application is to provide a preparation method of the olefin polymerization catalyst component.

[0007] Still another object of the present application is to provide an olefin polymerization catalyst.

[0008] It is still another object of the present application to provide the use of the catalyst for the polymerization of olefins in the polymerization of olefins.

[0009] To achieve the objects of the present application, the present application provides a catalyst component for the polymerization of olefins, comprising Mg, Ti, halogen and an internal donor compound selected from 2,6-dicarboxylate-4-pyridine ether compounds of general formula (I):

[0010]

[0011] wherein R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, each independently selected from H, halogen, C1-C 20 hydrocarbon radicals; preferably, R 1 , R 2 , R 3 , R 4 , R 5 may also each contain at least one heteroatom selected from N, O, S, P, Si and halogen.

[0012] Preferably, R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, each independently selected from H, halogen, the following substituents of up to 20 carbon atoms: linear or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatoms alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aryl substituents.

[0013] Preferably, R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, each independently selected from H, halogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20linear or branched or cyclic alkyl, the following substituents of less than 20 carbon atoms: alkenyl, phenyl, meta-chlorophenyl, para-chlorophenyl, ortho-chlorophenyl, meta-methoxyphenyl, para-methoxyphenyl, ortho-methoxyphenyl, para-methylphenyl, meta-methylphenyl, ortho-methylphenyl, meta-trimethylphenyl, para-nitrophenyl, meta-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, indenyl.

[0014] Preferably, the 2,6-dicarboxylate-4-pyridine ether compound in general formula (I) is preferably at least one of 2,6-dicarboxylic acid di-n-butyl ester-4-methoxypyridine, 2,6-dicarboxylic acid diisopropyl ester-4-isopropylpyridine, 2,6-dicarboxylic acid di(dodecyl) ester-4-n-butoxypyridine, 2,6-dicarboxylic acid diphenyl ester-4-methoxypyridine, 2,6-dicarboxylic acid di(meta-chlorophenyl) ester-4-methoxypyridine, 2,6-dicarboxylic acid di(para-methylphenyl) ester-4-methoxypyridine, 2,6-dicarboxylic acid di(para-methoxyphenyl) ester-4-benzyloxy pyridine, 2,6-dicarboxylic acid difuranmethyl ester-4-methoxypyridine, 2,6-dicarboxylic acid dipentenyl ester-3-methyl-5-ethyl-4-methoxypyridine, 2,6-dicarboxylic acid di(para-nitrophenyl) ester-3,5-diethyl-4-methoxypyridine, 2,6-dicarboxylic acid dimethyl ester-3-methyl-5-n-butyl-4-methoxypyridine, 2,6-dicarboxylic acid dibenzyl ester-4-ethoxypyridine, 2-ethyl carboxylate-6-n-butyl carboxylate-4-methoxypyridine, 2-ethyl carboxylate-6-phenyl carboxylate-4-methoxypyridine.

[0015] Preferably, the 2,6-dicarboxylate-4-pyridine ether compound of general formula (I) can be synthesized by the preparation method including but not limited to the following routes 1-3:

[0016]

[0017] Route 1 can be used to synthesize R 1 = R 2 = R 5 ; in route 2, when one alcohol is selected for the second step (R 1 = R 2 ), a single product is obtained; when two alcohols are selected for the second step (R 1 ≠ R 2 ), a mixture of three products is obtained, and the final mixture can be directly used as a mixture of internal electron donor compounds without separation, and the proportion of each component in the mixture can be adjusted by the addition ratio of the two alcohols of the reactants, and the proportion of each component can be determined by chromatography-mass spectrometry and other analytical means; route 3 is a route for synthesizing 2,6-dicarboxylate-4-pyrone from oxalic acid, and then obtaining the final product.

[0018] Preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dicarboxylate-4-pyridine ether compound;

[0019] The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n , MgCl2.mR a OH, R a 2-n MgX n , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alcoholate, wherein m is 0.1-6, 0≤n≤2, X is halogen, R a is a C1-C 20 hydrocarbon group;

[0020] The general formula of the titanium compound is TiX N (OR b ) 4-N , wherein R b is a C1-C 20 hydrocarbon group, X is halogen, and N is 1-4.

[0021] Preferably, the magnesium compound is an alcoholate of a dihalogenated magnesium;

[0022] Alternatively, the magnesium compound is a liquid magnesium compound;

[0023] Alternatively, the magnesium compound is a derivative of a dihalogenated magnesium molecule in which at least one halogen atom is replaced by a hydrocarbon oxy group or a halogenated hydrocarbon oxy group; preferably a hydrocarbon oxy magnesium compound; more preferably an alkyl oxy magnesium and / or an aryl oxy magnesium.

[0024] Preferably, the titanium compound comprises at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, an alkyl oxy halogenated titanium;

[0025] Preferably, the alkyl halogenated titanium comprises at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride;

[0026] Preferably, the titanium compound is titanium tetrachloride.

[0027] Preferably, the molar ratio of the 2,6-dicarboxylate-4-pyridine ether compound to the magnesium compound is 0.01-5.0, preferably 0.05-3.0, calculated as magnesium element.

[0028] The present invention is not particularly limited as to the method of preparing the catalyst component for the polymerization of olefins, which can be prepared according to the following methods:

[0029] Method I: the alcoholate or chlorohydrate of magnesium is reacted with an excess of TiCl4containing at least one 2,6-dicarboxylate-4-pyridine ether compound of general formula (I) in solution at a temperature of 80-135°C. According to the preferred method, the solid catalyst component is prepared by reacting a titanium compound of general formula TiX N (OR b ) 4-N (where R b is a C1-C 20 hydrocarbon group, X is halogen and N is 1-4; preferably TiCl4) with an adduct of general formula MgCl2.mR a OH (where m is a number from 0.1 to 6, preferably from 2 to 4, and R a is a C1-C 20 hydrocarbon group). The adduct can be conveniently made spherical by mixing the alcohol and magnesium chloride in the presence of an inert hydrocarbon which is not miscible with the adduct, rapidly quenching the emulsion and thus solidifying the adduct in the form of spherical particles. Examples of spherical MgCl2.mR a OH adducts prepared according to this process are described in US 4399054 A and US 4469648 A. The adduct thus obtained can be reacted directly with the titanium compound or it can be previously subjected to a controlled thermal dealcoholation (80-130°C) to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5. The reaction with the titanium compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4(generally -25-0°C); the mixture is heated to 80-130°C and kept at this temperature for 0.5-2 hours. The treatment with TiCl4can be carried out once or more than once. The treatment with at least one compound of general formula (I) can be carried out during the treatment with TiCl4and this treatment can be repeated once or more than once.

[0030] Method II: the magnesium compound is dissolved in a solvent system consisting of an organic epoxide compound, an organic phosphine compound and an inert diluent, a homogeneous solution is obtained and mixed with a titanium compound, a solid is precipitated in the presence of a co-precipitant which is one of an organic acid anhydride, an organic acid, an ether, a ketone; this solid is treated with at least one compound of general formula (I) to load it on the solid and, if necessary, treated with titanium tetrachloride and an inert diluent to obtain the final product. The components are used in the following amounts per mole of magnesium halide: organic epoxide compound 0.2-10 moles, organic phosphine compound 0.1-3 moles, co-precipitant 0-1.0 moles, Ti compound 0.5-150 moles.

[0031] Method three: TiCl4or a solution of a hydrocarbyloxytitanium in an aromatic hydrocarbon (e.g., toluene, xylene, etc.) can be reacted with a dihydrocarbyloxymagnesium compound such as a dialkoxy- or diaryloxy-magnesium compound at -25 to 0°C and halogenated at 80 to 130°C. The treatment with the TiCl4in an aromatic hydrocarbon can be repeated one or more times and the at least one compound of formula (I) can be added in one or more portions during the course of the multiple treatments. For example, the preparation of a titanium-containing solid catalyst component can be carried out according to the procedure disclosed in US 5,077,357 A: ethoxymagnesium, titanium tetraethoxide, o-cresol, ethanol and chlorobenzene are added sequentially with stirring; the TiCl4in chlorobenzene solution is added rapidly to the above liquid, and after complete dissolution, the temperature is raised to a specific temperature; after the ethanol reactant is removed by bubbling N2, the stirring is continued for a certain period of time, and then a hot chlorobenzene wash is used once, an isooctane wash is used twice, and then N2drying is used. Alternatively, according to another example: TiCl4, titanium tetraethoxide, ethoxymagnesium and o-cresol are added sequentially to chlorobenzene with stirring; ethanol is added, and after the ethoxymagnesium is dissolved at high temperature, the stirring is continued for 3 h; the hot filtrate is washed once with warm chlorobenzene, once with isooctane, and finally dried with N2.

[0032] Method four: anhydrous magnesium chloride and at least one 2,6-dicarboxylate-4-pyridine ether compound of formula (I) are ground together under conditions to activate the dichloromagnesium. The product thus obtained can be treated one or more times with excess TiCl4at a temperature of 80 to 130°C. After the treatment, the product is washed with a hydrocarbon solvent until it is free of chloride ions. According to a further method, the product obtained by co-grinding anhydrous dichloromagnesium, a titanium compound and at least one 2,6-dicarboxylate-4-pyridine ether compound of formula (I) is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane, etc. The treatment is carried out at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1 to 4 hours. The product is then washed with an inert hydrocarbon solvent such as hexane, etc.

[0033] Method five: dichloromagnesium is pre-activated according to well-known methods and then treated with excess TiCl4at a temperature of about 80 to 135°C, with at least one compound of formula (I) in the solution. The treatment with TiCl4is repeated several times and the solid is washed with hexane to remove any excess TiCl4for the reaction.

[0034] Method six: The solid titanium-containing catalyst component can also be prepared by referring to the method disclosed in CN1208045A: first, a liquid magnesium compound and a liquid titanium compound are contacted in the presence of a compound selected from the group consisting of alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester at a low temperature, generally at -70 - 200°C, preferably at -30 - 130°C, and at least one compound of general formula (I) is used to treat during the contacting process.

[0035] Method seven: A magnesium compound supported on inorganic oxides such as SiO2, alumina or porous resin is used as a carrier to prepare, and then activated by a well-known method, and then treated with excess TiCl4 at a temperature of about 80 - 135°C, and at least one 2,6-dicarboxylate-4-pyridine ether compound of general formula (I) is added during the treatment process.

[0036] The above reactions result in the formation of magnesium halide in an active form (the general crystal magnesium halide structure is regular, and the loadable Ti is little, so the catalytic activity is low, and the magnesium halide must be treated by activation to prepare a high-activity supported catalyst. The activation treatment method includes using physical and / or chemical methods to make it into a microcrystal, so that the active center is loaded on the surface, edge and defect of the magnesium halide. The treated magnesium halide microcrystal suitable for loading Ti is "active magnesium halide"). In addition to these reactions, other methods for forming magnesium halide in an active form from starting materials other than magnesium halide are also known in the literature.

[0037] In any of the preparation methods, the above internal electron donor compound can be directly added as it is or by alternative means, for example, by using a suitable precursor to prepare in situ, which can be converted into the desired internal electron donor compound, for example, by means of known chemical reactions such as esterification, transesterification, etc. Generally, the above electron donor compound is used in a molar ratio of 0.01 - 5, preferably 0.05 - 2.0, relative to MgCl2.

[0038] In any of the preparation methods, at least one compound of general formula (I) can be added simultaneously or separately in any order and any combination in batches or in batches.

[0039] The present application also provides a catalyst for olefin polymerization, which is composed of the above catalyst component and an organic aluminum compound.

[0040] According to a specific embodiment of the present application, preferably, the organic aluminum compound has a general formula of AlR c p X (3-p) , wherein R c is hydrogen or C1-C 20hydrocarbyl group, X is halogen, and p is an integer of 0≤p≤3.

[0041] According to a specific embodiment of the present application, preferably, the organoaluminum compound comprises at least one of a trialkylaluminum compound, an alkylaluminum halide, an alkylaluminum hydride, an alkylaluminum sesquichloride, an alkylaluminoxane.

[0042] According to a specific embodiment of the present application, preferably, the trialkylaluminum compound comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trioctylaluminum; the alkylaluminum halide comprises AlEt2Cl; and the alkylaluminum sesquichloride comprises Al2Et3Cl3.

[0043] According to a specific embodiment of the present application, preferably, the molar ratio of the organoaluminum compound to titanium atoms in the catalyst component is 1-1000:1, more preferably 50-800.

[0044] According to a specific embodiment of the present application, preferably, the raw material composition of the catalyst further comprises an external electron donor.

[0045] According to a specific embodiment of the present application, preferably, the external electron donor is a siloxane compound.

[0046] According to a specific embodiment of the present application, preferably, the siloxane compound has a general formula of R’ t Si(OR”) 4-t wherein R’ and R” are each independently selected from C1-C 18 hydrocarbyl group, and t is an integer of 0≤t≤3; more preferably, R’ and R” each comprises a heteroatom; more preferably, the heteroatom comprises at least one of N, O, S, P, Si.

[0047] Preferably, the siloxane compound is selected from the group consisting of trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n- propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethylsilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n- propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2- ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethyl-ethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclopentyl dimethoxysilane, 3-methylcyclohexyl cyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexyl cyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexyl cyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane. Among these organosilicon compounds, at least one of the following is preferred: di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butytrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyl dimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyl dimethoxysilane, 4-methylcyclohexylcyclopentyl dimethoxysilane, 3,5-dimethylcyclopentyl dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl-tert-butyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyl-tert-methoxysilane, tert-hexyltrimethoxysilane.

[0048] Preferably, the siloxane compound is at least one of cyclohexylmethyldimethoxysilane; diisopropyldimethoxysilane; di-n-butyldimethoxysilane; diisobutyldimethoxysilane; diphenyldimethoxysilane; phenyltriethoxysilane; methyl-tert-butyldimethoxysilane; dicyclopentyldimethoxysilane; 2-ethylpiperidinyl-2-tert-butyldimethoxysilane and (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane and (1,1,1-trifluoro-2-propyl)-methyl-tert-methoxysilane, cyclohexyltrimethoxysilane; tert-butytrimethoxysilane and tert-hexyltrimethoxysilane.

[0049] According to a particular embodiment of the present application, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is in the range of 0.002 to 100, more preferably in the range of 0.01 to 20, further preferably in the range of 0.01 to 5.

[0050] The present application also provides the use of the above-mentioned catalyst in the polymerization of olefins.

[0051] According to a specific embodiment of the present application, preferably, the olefin includes at least one of linear or branched olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, vinylcyclohexene.

[0052] According to a specific embodiment of the present application, preferably, the polymerization includes polymerization of ethylene and / or propylene.

[0053] According to a specific embodiment of the present application, preferably, the polymerization includes homo- or co-polymerization.

[0054] According to a specific embodiment of the present application, preferably, in the catalytic process, the order of adding components in the catalyst is arbitrary, and it is preferred that the organic aluminum compound is first added to the polymerization system, then the external electron donor is added, and finally the catalyst component is added.

[0055] According to a specific embodiment of the present application, preferably, in the above application, the polymerization process can be carried out with or without solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (the polymerization can also be carried out without the molecular weight regulator); both continuous polymerization and batch polymerization processes can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0056] According to a specific embodiment of the present application, preferably, the temperature of the polymerization is ≤200℃, more preferably 20-100℃, and further preferably 40-80℃; the pressure of the polymerization is ≤10MPa, more preferably 0.3-5MPa.

[0057] The internal electron donor compound of the catalyst component of the present application is at least one selected from 2,6-dicarboxylate-4-pyridine ether compounds of general formula (I), and the internal electron donor compound contains various functional groups such as nitrogen hetero, ester, ether or ketone on the six-membered ring structure, and the stereochemical configuration and steric hindrance thereof are conducive to the participation of the functional groups in the formation of active centers. The catalyst prepared by the internal electron donor compounds with various different substituents in the same series has a generally higher activity than the catalysts of the internal electron donors of phthalate esters commonly used in the industry at present, and is higher than the catalysts of diether, and has good stereoselectivity, high isotacticity of the obtained polymer, and wide overall molecular weight distribution. DETAILED DESCRIPTION

[0058] The technical solutions of the present application will be described in detail below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments.

[0059] The operations for preparing the catalyst in the examples were all carried out under high-purity nitrogen protection. The isotacticity of the polymer was determined by heptane extraction method (heptane boiling extraction for 6 hours). After a two-gram dry polymer sample was extracted with boiling heptane for 6 hours in an extractor, the ratio of the weight (g) of the remaining polymer to 2 after drying to constant weight was the isotacticity.

[0060] The bulk density of the polymer was determined by the method of JB / T 2412-2008.

[0061] The molecular weight distribution of the polymer was determined by a PL-220 gel permeation chromatograph with trichlorobenzene as the solvent at 150°C (standard sample: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10um M1Xed-B 300x7.5nm).

[0062] Synthesis of 2,6-dicarboxylate-4-pyridine ether compounds represented by general formula (I)

[0063] Preparation Example 1: Synthesis of 2,6-dibutyldicarboxylate-4-methoxypyridine

[0064] Sodium (23.6 g, 1 mol, 2.04 eq.) was dissolved in anhydrous ethanol (350 mL). A mixture of anhydrous acetone (29 g, 38 mL, 0.5 mol, 1 eq.) and diethyl oxalate (155 g, 144 mL, 1.06 mol, 2.12 eq.) was added to the previous solution in 15 minutes. A yellow precipitate was formed. The reaction mixture was kept at 60°C for one hour. Then, HCl (aq. 37%, 200 mL) and water (100 mL) were added and the solution was stirred at 50°C for 20 hours. The mixture of water and ethanol was removed under reduced pressure. Then a mixture of water (300 mL) and HCl (aq. 37%, 50 mL) was added to the mixture and stirred until the silica gel TLC (eluent: 3 / 7 (v / v) 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered off, washed first with water and then with cold acetone. The crude product was recrystallized to obtain 2,6-dicarboxylic acid-4-pyrone as a white powder.

[0065] In a 1L three-necked flask, 2,6-dicarboxylic acid-4-pyrone (11 g), n-butanol (200 mL), concentrated sulfuric acid (1 mL) were added; heated to reflux for 2 hours; cooled to room temperature; the reaction solution was poured into saturated sodium bicarbonate solution, extracted with ethyl acetate twice (150 mL*2), the combined organic phase was washed with saturated brine (150 mL*2), concentrated and recrystallized to obtain the product 2,6-dibutyldicarboxylate-4-pyrone.

[0066] Di-n-butyl 2,6-dicarboxy-4-hydroxypyridine (10.5 g, 35.7 mmoles) and anhydrous MeOH (500 ml) were added sodium methoxide (4 g, 74 mmoles) gradually to the solution, the reaction mixture was stirred at room temperature for 1 hour, then dimethyl ether (10 mL) was added. The mixture was warmed to 60 °C, stirred for 12 hours, filtered to obtain di-n-butyl 2,6-dicarboxy-4-methoxypyridine.

[0067] Di-n-butyl 2,6-dicarboxy-4-hydroxypyridine (10.5 g, 35.7 mmoles) and anhydrous MeOH (500 ml) were added sodium methoxide (4 g, 74 mmoles) gradually to the solution, the reaction mixture was stirred at room temperature for 1 hour, then dimethyl ether (10 mL) was added. The mixture was warmed to 60 °C, stirred for 12 hours, filtered to obtain di-n-butyl 2,6-dicarboxy-4-methoxypyridine. 1 HNMR (500 MHz, Chloroform-d) δ / ppm: 7.65 (s, 2H), 4.30 (t, J = 8.4 Hz, 4H), 3.82 (s, 3H), 1.80 - 1.69 (m, 4H), 1.52 - 1.41 (m, 4H), 0.97 (t, J = 5.6 Hz, 6H).

[0068] Preparation Example 2-14: Synthesis of other 2,6-dicarboxylic ester-4-pyridine ether compounds

[0069] Compound 1 prepared according to Example 1 was synthesized according to routes 1-3 described above, including but not limited to, and the structure and NMR results of the compound are shown in Table 1.

[0070]

[0071] Table 1: 2,6-dicarboxylic ester-4-pyridine ether compounds prepared according to Examples 1-14

[0072]

[0073]

[0074]

[0075] Preparation of catalyst

[0076] Example 1

[0077] A suspension of 10 g of MgCl2-2.5 C2H5OH microspheres and 150 mL of titanium tetrachloride was prepared in a 500 mL 5 neck flask with stirring, nitrogen sparge, and maintained at -15°C for 1 hour, slowly warmed to 80°C, and 2,6-di-n-butyl-4-methoxypyridine dicarboxylate (3.1 g, 10 mmol) was added, then warmed to 110°C for 1 hour, then the liquid was filtered clean, the liquid was filtered off, and the resulting solid was washed with 120 mL of titanium tetrachloride at 125°C for 3 times. The resulting solid was washed with 150 mL of hexane at 60°C for 4 times, the liquid was filtered off and dried to give the solid catalyst component. The titanium content, internal donor content, and polymerization data of the solid catalyst component are shown in Table 2.

[0078] Example 2-14

[0079] The solid catalyst component was prepared as shown in Example 1, except that 2,6-di-n-butyl-4-methoxypyridine dicarboxylate was replaced by 10 mmol of the compound No. 2-14 prepared in Example 2-14 in Table 1, respectively, in order.

[0080] Example 15

[0081] A suspension of 10 g of MgCl2-2.5 C2H5OH microspheres and 150 mL of titanium tetrachloride was prepared in a 500 mL 5 neck flask with stirring, nitrogen sparge, and maintained at -15°C for 1 hour, slowly warmed to 80°C, and 2,6-di-n-butyl-4-methoxypyridine dicarboxylate (3.1 g, 10 mmol) was added, then warmed to 110°C for 1 hour, then the liquid was filtered clean, the liquid was filtered off, and the resulting solid was washed with 120 mL of titanium tetrachloride at 125°C for 3 times. The resulting solid was washed with 150 mL of hexane at 60°C for 4 times, the liquid was filtered off and dried to give the solid catalyst component. The titanium content, internal donor content, and polymerization data of the solid catalyst component are shown in Table 2.

[0082] Example 16

[0083] A suspension was prepared by adding 8 g of diethoxy magnesium and 100 mL of toluene in a 500 mL 5 neck flask with stirring and nitrogen sparging. 25 mL of titanium tetrachloride was added dropwise at -15 °C. After the dropwise addition was complete, the temperature was slowly increased to 0 °C and 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly increased to 80 °C and 10 mmol of 2,6-di-n-butylate-4-methoxypyridine-2,6-dicarboxylic acid was added. The temperature was then increased to 110 °C and held for 2 hours. The liquid was then filtered off and the resulting solid was washed with 100 mL of titanium tetrachloride at 125 °C for 3 times. The resulting solid was washed with 120 mL of hexane at 60 °C for 4 times. The liquid was filtered off and the resulting solid was dried to give the solid catalyst component.

[0084] Comparative Example 1

[0085] The catalyst component was prepared according to Example 1 except that 2,6-di-n- butylate-4-methoxypyridine-2,6-dicarboxylic acid was replaced by 10 mmol of di-n- butyl phthalate (DN).

[0086] Comparative Example 2

[0087] The catalyst component was prepared according to Example 1 except that 2,6-di-n- butylate-4-methoxypyridine-2,6-dicarboxylic acid was replaced by 10 mmol of 9,9- dimethoxyfluorene (FLU).

[0088] Polymerization

[0089] The solid catalyst was used as a component of a catalyst for olefin polymerization to evaluate polymerization:

[0090] A 5 L stainless steel autoclave was purged with nitrogen and 5 mL of a 0.5 mol / L triethylaluminum hexane solution, 1 mL of a 0.1 mol / L methylcyclohexyldimethoxysilane hexane solution, and 10 mg of the prepared catalyst were added. 10 mL of hexane was then added to flush the feed line, and 2 L (standard state) of hydrogen and 2.5 L of refined propylene were added. The reaction was controlled to pre-polymerize at 25 °C for 5 minutes, and then the temperature was increased to 70 °C. The polymerization reaction was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and the stirring was stopped to discharge the reaction product. The polymer was obtained after drying.

[0091] Table 2

[0092]

[0093]

[0094] As shown in Table 2, the 2,6-dicarboxylate-4-pyridine ether catalysts of Examples 1-14 containing different substituents have higher activity than the phthalate internal electron donor catalyst of Comparative Example 1 and the diether catalyst of Comparative Example 2 under the same preparation conditions, and have good stereoselectivity and high isotacticity of the obtained polymer. The catalysts have regular particle size and high bulk density. Examples 15-16 are catalysts using different preparation methods and 2,6-dicarboxylic acid di-n-butyl ester-4-methoxypyridine, which also show excellent performance of high activity and high stereoselectivity.

[0095] The present application is not limited to the foregoing specific embodiments, and any changes or modifications made by those skilled in the art within the scope of the present application are encompassed by the patent scope of the present application.

Claims

1. A catalyst component for the polymerization of olefins, characterized by, The catalyst component comprises Mg, Ti, halogen and an internal donor compound selected from 2,6-dicarboxylate-4-pyridine ether compounds of general formula (I): General formula (I) wherein R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, each independently selected from H, halogen, a C1-C 20 hydrocarbon group, or a C1-C 20 group containing at least one heteroatom selected from N, O and halogen.

2. The catalyst component for the polymerization of olefins according to claim 1, characterized in that, R 1 , R 2 , R 3 , R 4 , R 5 are the same or different, each independently selected from H, halogen, the following substituents of up to 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O heteroatoms alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aryl substituents.

3. The catalyst component for the polymerization of olefins according to claim 1, characterized in that, R in general formula (I) 1 R 2 R 3 R 4 R 5 are the same or different, each independently selected from the group consisting of H, halogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 linear or branched or cyclic alkyl up to 20 carbon atoms, the following substituents up to 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, m-trimethylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, propenyl, butenyl, pentenyl, hexenyl, indenyl.

4. The catalyst component for the polymerization of olefins according to claim 1, characterized in that, The 2,6-dicarboxylate-4-pyridine ether compound in general formula (I) is selected from at least one of 2,6-dicarbonyl di-n-butyl ester-4-methoxypyridine, 2,6-dicarbonyl diisopropyl ester-4-isopropyl oxypyridine, 2,6-dicarbonyl di(dodecyl) ester-4-n-butoxypyridine, 2,6-dicarbonyl diphenyl ester-4-methoxypyridine, 2,6-dicarbonyl di-m-chlorophenyl ester-4-methoxypyridine, 2,6-dicarbonyl di-p-tolyl ester-4-methoxypyridine, 2,6-dicarbonyl di-p-methoxyphenyl ester-4-benzyloxy pyridine, 2,6-dicarbonyl difurfuryl ester-4-methoxypyridine, 2,6-dicarbonyl dipentenyl ester-3-methyl-5-ethyl-4-methoxypyridine, 2,6-dicarbonyl di-p-nitrophenyl ester-3,5-diethyl-4-methoxypyridine, 2,6-dicarbonyl dimethyl ester-3-methyl-5-n-butyl-4-methoxypyridine, 2,6-dicarbonyl dibenzyl ester-4-ethoxypyridine, 2-ethyl carbonyl-6-n-butyl carbonyl-4-methoxypyridine, 2-ethyl carbonyl-6-phenyl carbonyl-4-methoxypyridine.

5. The catalyst component for the polymerization of olefins according to any one of claims 1-4, characterized in that, The composition of the catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dicarboxylate-4-pyridine ether compound; The precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group; The general formula of the titanium compound is TiX N (OR b ) 4-N , wherein R b is a C1-C 20 hydrocarbon group, X is halogen, and N is 1-4.

6. The catalyst component for the polymerization of olefins according to claim 5, characterized in that, The magnesium compound is an alcoholate of a magnesium dihalide; Alternatively, the magnesium compound is a liquid magnesium compound; Alternatively, the magnesium compound is a derivative of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbyloxy group or a halogenated hydrocarbyloxy group.

7. The catalyst component for the polymerization of olefins according to claim 5, characterized in that, The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy halide titanium.

8. The catalyst component for the polymerization of olefins according to claim 7, characterized in that, The alkoxy halide titanium includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

9. The catalyst component for the polymerization of olefins according to claim 5, characterized in that, The molar ratio of the 2,6-dicarboxylate-4-pyridine ether compound to the magnesium compound is 0.01-5.0, calculated based on the magnesium element.

10. A catalyst for olefin polymerization, comprising the catalyst component of any one of claims 1-9 and an organic aluminum compound.

11. The catalyst of claim 10, wherein The general formula of the organic aluminum compound is AlR c p X (3-p) wherein R c is hydrogen or a C1-C 20 hydrocarbon group, X is halogen, and p is an integer of 0≤p≤3.

12. The catalyst of claim 10, wherein The organic aluminum compound includes at least one of a trialkyl aluminum compound, an alkyl aluminum halide, an alkyl aluminum hydride, an alkyl aluminum sesquichloride, and an alkyl aluminum oxide.

13. The catalyst of claim 10, wherein The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

14. The catalyst of claim 10, wherein The raw material composition of the catalyst further comprises an external donor; The external donor is a siloxane compound.

15. The catalyst of claim 14, wherein The general formula of the siloxane compound is R' t Si(OR'') 4-t wherein R' and R'' are each independently selected from a C1-C 18 hydrocarbon group, and t is an integer of 0 ≤ t ≤ 3.

16. The catalyst of claim 14, wherein The molar ratio of silicon in the external donor to titanium in the catalyst component is 0.002-100.

17. Use of the catalyst of any one of claims 10-16 in olefin polymerization.

18. The use according to claim 17, characterized in that, The olefins include at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, vinylcyclohexene; The polymerization includes homopolymerization or copolymerization; The temperature of the polymerization is ≤200℃, and the pressure of the polymerization is ≤10MPa.

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