Catalyst component for olefin polymerization, catalyst for olefin polymerization and application thereof

Abstract

The invention discloses a catalyst component for olefin polymerization, a catalyst for olefin polymerization and application thereof, the catalyst component for olefin polymerization comprises Mg, Ti, halogen and an internal electron donor compound, and the internal electron donor compound is selected from N-substituent-2, 6-diformate 4-pyridone compounds of a general formula (I). The internal electron donor compound of the catalyst component is selected from at least one of N-substituent-2, 6-diformate 4-pyridone compounds of the general formula (I), the prepared catalyst has the characteristic of high activity, and the obtained polymer is high in isotacticity and wide in overall molecular weight distribution.

Description

Technical Field

[0001] The present invention relates to a solid catalyst component for olefin polymerization, and more specifically, to a solid catalyst component of a compound, a catalyst containing the solid catalyst component and the application of the catalyst in olefin polymerization, especially in propylene polymerization. Background Art

[0002] Polyolefins are a type of polymer material with the largest output and widest application due to their abundant raw materials, low prices, easy processing and excellent comprehensive performance. At present, Ziegler-Natta catalysts (ZN catalysts) still occupy a dominant position in polyolefin production. The development of most ZN catalysts focuses on the development of high-activity and highly stereospecific catalysts and improving the copolymerization ability of catalysts. In addition, due to the high catalytic efficiency of traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to magnesium-containing carriers), the polymers produced have good comprehensive performance and low cost. At present, most catalysts for the production of polyolefins in the world are still based on ZN catalytic systems, which are characterized by high activity, high stereoregularity, long life and customized product structure. It can be seen from the development process of ZN catalysts that as early as the emergence of the first generation of catalysts, it was found that the addition of a third component (mostly an electron donor, also known as a Lewis base, in which the one added during the catalyst preparation process becomes an internal electron donor, and the one added during the polymerization process becomes an external electron donor) will have a great influence on the polymerization behavior of olefins and the properties of polymers. Changing the internal electron donor in the catalyst can change the properties of the catalyst active center to the greatest extent possible, thereby changing the performance of the catalyst to the greatest extent. Therefore, the development of new electron donors has always been a hot topic in the research and development of polyolefin catalysts.

[0003] The relatively distinctive high-performance internal electron donor compounds in the prior art mainly include: 1) fatty acid esters 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) glycol ester compounds (for example, WO9856834, WO0063261, WO03022894); 5) compounds with other functional groups (CN1105671, CN1242780, US20060128558), etc. However, in practical applications, the above compounds have certain problems as internal electron donors for olefin polymerization catalysts. For example, the catalyst activity of divalent aromatic carboxylic acid ester compounds as internal electron donors is not high, and the relative molecular mass distribution of the prepared polypropylene (PP) is also narrow. In addition, phthalate compounds, as commonly used plasticizers, have great harm to human reproductive health and the environment. Although the catalyst activity of 1,3-diether compounds as internal electron donors is relatively high and the catalyst hydrogen adjustment sensitivity is also good, the relative molecular mass distribution of the prepared PP is narrow, which is not conducive to the development of different grades of PP. The advantage of succinate compounds as internal electron donors is that the relative molecular mass distribution of the synthesized PP is relatively wide, but the disadvantage is that the stereoregularity of PP and the hydrogen adjustment sensitivity of the catalyst need to be improved. The activity of the diol ester catalytic system is not as ideal as the diether system as a whole.

[0004] At present, the most widely used polyolefin internal electron donor in industry is phthalate compounds, which have medium activity, good stereoselectivity and low price for the catalysts prepared by them. However, phthalate compounds, as commonly used plasticizers, are very harmful to human reproductive health and the environment, and there is a great demand for replacement. Europe has restricted the use of most phthalate substances; at the same time, the new phthalate restriction policy is bound to affect its use in China. Therefore, it is one of the common research and development goals in the field of polyolefin catalysts in recent years to develop new electron donors with excellent activity, good stereospecificity, good comprehensive performance and low cost to replace the widely used phthalate electron donor compounds in the prior art, and use them to prepare efficient Ziegler-Natta catalysts. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a catalyst component for olefin polymerization, which adopts an internal electron donor compound of N-substituted-2,6-dicarboxylate-4-pyridone, can improve the activity of the catalyst and obtain a higher isotactic olefin polymer.

[0006] Another object of the present invention is to provide a method for preparing the olefin polymerization catalyst component.

[0007] Another object of the present invention is to provide a catalyst for olefin polymerization.

[0008] Another object of the present invention is to provide use of the olefin polymerization catalyst in olefin polymerization.

[0009] In order to achieve the object of the present invention, the present invention provides a catalyst component for olefin polymerization, which comprises Mg, Ti, halogen and an internal electron donor compound, wherein the internal electron donor compound is selected from N-substituted-2,6-dicarboxylate-4-pyridone compounds of general formula (I):

[0010]

[0011] Among them, R in the general formula (I) 1 , R 2 , R 3 , R 4 and R 5’ are the same or different, each independently selected from H, halogen, C 1 -C 20 Preferably, R 1 , R 2 , R 3 , R 4 and R 5’ They may further contain at least one heteroatom selected from N, O, S, P, Si and halogen.

[0012] Preferably, R in the general formula (I) 1 , R 2 , R 3 , R 4 , R 5’ the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

[0013] Preferably, R in the general formula (I) 1 , R 2 , R 3 , R 4 , R 5’ are the same or different and are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20a linear or branched or cyclic alkyl group, or the following substituents having 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, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

[0014] Preferably, the N-substituted-2,6-dicarboxylic acid ester-4-pyridone compound in the general formula (I) is preferably selected from N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone, N-tert-butyl-2,6-dicarboxylic acid didodecyl ester-4-pyridone, N-n-butyl-2,6-dicarboxylic acid di-n-butyl ester-4-pyridone, N-phenyl-2,6-dicarboxylic acid diphenyl ester-4-pyridone, N-m-chlorophenyl-2,6-dicarboxylic acid di-m-chlorophenyl ester-4-pyridone, N-p-chlorophenyl-2,6-dicarboxylic acid di-p-tolyl ester-4 -pyridone, N-o-chlorophenyl-2,6-dicarboxylic acid di-p-methoxyphenyl-4-pyridone, N-p-methoxyphenyl-2,6-dicarboxylic acid difuranyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid dipentenyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid di-p-nitrophenyl ester-3-methyl-5-ethyl-4-pyridone, N-benzyl-2,6-dicarboxylic acid dibenzyl ester-3,5-diethyl-4-pyridone, N-methyl-2-ethyl-6-phenyl-4-pyridone.

[0015] Preferably, the N-substituted-2,6-dicarboxylate-4-pyridone compound of general formula (I) can be synthesized by the preparation methods including but not limited to those shown in the following routes 1 and 2:

[0016]

[0017] In route 1, when an alcohol is selected in the third step (R 1 With R 2 The same) gives a single product. When two alcohols are selected in the third step (R 1 With R 2 The final mixture can be used directly as a mixture as an internal electron donor compound without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols as reactants. The ratio of each component can be determined by chromatography-mass spectrometry, nuclear magnetic resonance and other analytical methods.

[0018] Preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, and the N-substituted-2,6-dicarboxylate-4-pyridone compound;

[0019] The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n MgCl 2 ·mR a OH, R a 2-n MgX n MgCl 2 / SiO 2 MgCl 2 / Al 2 O 3 , at least one of a mixture of magnesium halide and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C 1 -C 20 The hydrocarbon group;

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

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

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

[0023] Alternatively, the magnesium compound is a derivative of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, it is a hydrocarbonoxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0024] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide;

[0025] Preferably, the alkyl titanium halide includes at least one of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride;

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

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

[0028] The present invention does not particularly limit the preparation method of the catalyst component for olefin polymerization, and it can be prepared according to the following preparation methods:

[0029] Method 1: A magnesium alcoholate or chloroalcoholate and an excess of TiCl2 in a solution containing at least one N-substituted-2,6-dicarboxylate-4-pyridone compound of the general formula (I) 4 The reaction temperature is 80-135°C. According to the preferred method, the general formula TiX N (OR b ) 4-N Titanium compounds (where R b C 1 -C 20 A hydrocarbon group, X is a halogen, and N is 1-4; preferably TiCl 4 ) and the general formula is MgCl 2 ·mR a OH (wherein m is a number of 0.1-6, preferably 2-4, and R a C 1 -C 20 The solid catalyst component is prepared by reacting an adduct of an alcohol with an alkyl group of an isocyanate (alkyl group). The adduct can be suitably made into a spherical shape by the following method: in the presence of an inert hydrocarbon that is immiscible with the adduct, an alcohol and magnesium chloride are mixed, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles. The spherical MgCl prepared according to this process 2 ·mR a Examples of OH adducts are described in US Pat. No. 4,399,054 A and US Pat. No. 4,469,648 A. The adduct thus obtained can be reacted directly with the titanium compound, or it can be previously subjected to a thermally controlled dealcoholation (80-130° C.) to obtain an adduct in which the number of moles of alcohol is generally less than 3, preferably between 0.1 and 2.5. The adduct can be prepared by suspending the adduct (dealcoholated or as such) in a cold TiCl 4 The reaction with the titanium compound is carried out in a temperature range of -25-0°C; the mixture is heated to 80-130°C and maintained at this temperature for 0.5-2 hours. 4 The treatment can be performed once or multiple times. 4 During the treatment, at least one compound of the general formula (I) may be added for treatment, and this treatment may be repeated once or multiple times.

[0030] Method 2: Dissolve the magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphine compound and an inert diluent to form a uniform solution, then mix it with a titanium compound, and precipitate a solid in the presence of a precipitation aid; the solid is treated with at least one compound of the general formula (I) to load it on the solid, and if necessary, treated with titanium tetrahalide and an inert diluent to obtain the solid, wherein the precipitation aid is one of an organic anhydride, an organic acid, an ether and a ketone. The components are calculated per mole of magnesium halide, and the organic epoxy compound is 0.2-10 moles, the organic phosphine compound is 0.1-3 moles, the precipitation aid is 0-1.0 moles, and the Ti compound is 0.5-150 moles.

[0031] Method 3: Using TiCl 4 A solution of titanium alkoxide in an aromatic hydrocarbon (e.g., toluene, xylene, etc.) can be reacted with a magnesium dialkoxide compound such as magnesium dialkoxide or magnesium diaryloxide at -25-0°C and halogenated at 80-130°C. 4 The treatment with the aromatic hydrocarbon solution can be repeated once or multiple times, and at least one compound of the general formula (I) can be added once or in batches during multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be referred to: ethoxymagnesium, tetraethoxytitanium, o-cresol, ethanol and chlorobenzene are added in sequence, and stirred; TiCl 4 / chlorobenzene solution is quickly added to the above liquid, and the temperature is raised until it is completely dissolved, and then the temperature is continued to be raised to a specific temperature; using N 2 After bubbling away the ethanol reactant, continue stirring for a certain period of time, then wash once with hot chlorobenzene, wash twice with isooctane, and then N 2 The carrier can be obtained by drying. Or according to another example: TiCl 4 , tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene and stirred; ethanol is added and stirred for 3 hours at high temperature after the ethoxymagnesium is dissolved; hot filtering is then washed once with warm chlorobenzene, once with isooctane, and finally N 2 dry.

[0032] Method 4: Anhydrous magnesium chloride and at least one N-substituted-2,6-dicarboxylate-4-pyridone compound of general formula (I) are ground together under conditions where magnesium dichloride is activated. The product thus obtained can be treated with excess TiCl at a temperature of 80-130°C. 4The product is treated once or more. After the treatment, it is washed with a hydrocarbon solvent until it is free of chloride ions. According to a further method, the product obtained by co-grinding magnesium dichloride, a titanium compound and at least one N-substituted-2,6-dicarboxylate-4-pyridone compound of the general formula (I) in an anhydrous state is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane. 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 to obtain a product.

[0033] Method 5: Magnesium dichloride is pre-activated according to a well-known method, and then an excess of TiCl 4 Treatment, wherein the solution contains at least one compound of the general formula (I). 4 The solid was treated several times and washed with hexane to remove any unreacted TiCl 4 .

[0034] Method 6: The preparation method of the titanium-containing solid catalyst component disclosed in CN1208045A can also be referred to: first, a liquid magnesium compound and a liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid. The contact temperature is generally -70-200°C, preferably -30-130°C, and at least one compound of the general formula (I) is used during the contact process.

[0035] Method 7: You can also use SiO 2 , alumina or other inorganic oxides or a magnesium compound supported on a porous resin as a carrier, then activated by a well-known method, and then heated at a temperature of about 80-135°C with an excess of TiCl 4 The method comprises treating the raw material with at least one N-substituted-2,6-dicarboxylate-4-pyridone compound of the general formula (I) during the treating process.

[0036] The above-mentioned reactions lead to the formation of magnesium halide in an active form (generally, crystalline magnesium halide has a regular structure and can carry very little Ti, so the catalytic activity is low. To prepare a highly active supported catalyst, the magnesium halide must be activated. The activation treatment method includes using physical and / or chemical methods to make it into microcrystals so that the active center is loaded on the surface, edge and defect of the magnesium halide. The treated magnesium halide microcrystals suitable for loading Ti are "active magnesium halide"). In addition to these reactions, there are other well-known methods in the literature to form magnesium halide in an active form from compound starting materials other than magnesium halide.

[0037] In any preparation method, the internal electron donor compound can be added directly or in an alternative manner, such as in situ by using a suitable precursor, which can be converted into the desired internal electron donor compound by known chemical reactions such as esterification, transesterification, etc. Generally, relative to MgCl 2 For example, the inner electron donor compound is used in a molar ratio of 0.01 to 5, preferably 0.05 to 3.0.

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

[0039] The present invention also provides a catalyst for olefin polymerization, the raw material composition of which includes the above catalyst component and an organic aluminum compound.

[0040] According to a specific embodiment of the present invention, preferably, the general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C 1 -C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

[0041] According to a specific embodiment of the present invention, preferably, 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 aluminumoxane.

[0042] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt 2 Cl; the alkylaluminum sesquichloride comprises Al 2 Et 3 Cl 3 .

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

[0044] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst also includes an external electron donor.

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

[0046] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C 1 -C 18 A hydrocarbon group, t is an integer of 0≤t≤3; more preferably, said R' and R" respectively contain heteroatoms; more preferably, said heteroatoms include at least one of N, O, S, P, and 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-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldiethoxysilane, and 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-propyldiethyl Oxysilane, cyclohexyl n-butyldiethoxysilane, amylmethyldimethoxysilane, amylmethyldiethoxysilane, amylethyldimethoxysilane, amylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane , tert-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-dimethylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane. Preferred among these organosilicon compounds are: di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexyl At least one of cyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclopentyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyltert-butyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methylmethoxysilane, and tert-hexyltrimethoxysilane.

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

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

[0050] The invention also provides application of the catalyst in olefin polymerization.

[0051] According to a specific embodiment of the present invention, preferably, the olefin includes at least one of a linear or branched olefin, 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, and vinylcyclohexene.

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

[0053] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0054] According to a specific embodiment of the present invention, preferably, during the catalytic process, the order of adding the components in the catalyst is arbitrary, preferably the organoaluminum 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 invention, preferably, in the above application, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization process 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 invention, preferably, the polymerization temperature is ≤200°C, more preferably 20-100°C, and further preferably 40-80°C; the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

[0057] The internal electron donor compound of the catalyst component of the present invention is at least one selected from the N-substituted-2,6-dicarboxylic acid ester-4-pyridone compounds of the general formula (I), and the internal electron donor compound contains multiple functional groups such as nitrogen, ester, ether or ketone on the six-membered ring structure, and its stereo configuration and steric hindrance are conducive to the functional groups participating in the formation of active centers. The catalyst prepared by the internal electron donor compounds of the same series with multiple different substituents is generally more active than the catalyst of the phthalate internal electron donor commonly used in industry today, and is higher than the diether catalyst, and has good stereoselectivity, the obtained polymer has high isotacticity, and the overall molecular weight distribution is relatively wide. DETAILED DESCRIPTION

[0058] The technical solution of the present invention is described in detail below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the implementation of the present invention, rather than all the embodiments.

[0059] The catalyst preparation operations in the examples were all carried out under the protection of high-purity nitrogen. Determination of polymer isotacticity: Determination by heptane extraction method (6 hours of boiling heptane extraction). Two grams of dry polymer sample are placed in an extractor and extracted with boiling heptane for 6 hours. The ratio of the polymer weight (g) obtained by drying the residue to constant weight to 2 is the isotacticity.

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

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

[0062] Synthesis of N-substituted-2,6-dicarboxylate-4-pyridone compounds represented by general formula (I)

[0063] Preparation Example 1: Synthesis of N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone

[0064] Sodium (14.2 g, 0.6 mol) was dissolved in anhydrous ethanol (200 mL). A mixture of anhydrous acetone (17.4 g, 22.8 mL, 0.3 mol) and diethyl oxalate (93 g, 86.5 mL, 0.64 mol) was added to the previous solution over 15 minutes. A yellow precipitate was formed. The reaction mixture was kept at 60 ° C for one hour. Then, HCl (aq. 37%, 120 mL) and water (60 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 (170 mL) and HCl (aq. 37%, 30 mL) was added to the mixture and stirred until 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 out and washed with water and then with cold acetone. The crude product was recrystallized to give 2,6-dicarboxylic acid-4-pyrone.

[0065] 2,6-dicarboxylic acid-4-pyrone (4.6 g, 25 mmol) was added dropwise to 100 mL of isopropylamine-dichloromethane solution (isopropylamine 1.8 g, 30 mmol) at 0°C. Stir at room temperature for two days. The solvent was removed by rotary evaporation, and the residue was boiled after adding water (50 mL) and activated carbon (1 g). The solution was filtered and then cooled to 5°C. The cold solution was acidified to pH = 1 with HCl (aq. 37%). The solid was filtered, washed three times with ice water, and dried under vacuum at 150°C for 24 hours to obtain N-isopropyl-2,6-dicarboxylic acid-4-pyridone.

[0066] In a 1L three-necked flask, add N-isopropyl-2,6-dicarboxylic acid-4-pyridone (4.5 g, 20 mmol), ethanol (50 mL), and concentrated sulfuric acid (0.3 mL); heat to reflux for 2 hours; cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (100 mL*2), combine the organic phases, wash with saturated brine (100 mL*2), concentrate and recrystallize to obtain the product N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone. 1 H NMR (500MHz, Chloroform-d) δ / ppm: 6.89 (s, 2H), 4.69 (p, J = 4.3Hz, 1H), 4.30 (q, J = 5.1Hz, 4H), 1.35–1.27 (m, 12H).

[0067] Preparation 2-12: Synthesis of other N-substituted-2,6-dicarboxylate-4-pyridone compounds

[0068] Compound 1 was prepared with reference to Example 1, using routes including but not limited to the aforementioned routes 1 and 2. The structure and NMR results of the compound are shown in Table 1.

[0069]

[0070] Table 1 N-substituted-2,6-dicarboxylate-4-pyridone compounds prepared in Examples 1-12

[0071]

[0072]

[0073]

[0074] Catalyst preparation

[0075] Example 1

[0076] In a 500 mL 5-necked flask with stirring and fully replaced with nitrogen, add 10 g MgCl 2 2.5C 2 H 5OH microspheres and 150mL titanium tetrachloride were used to prepare a suspension, then maintained at -15°C for 1 hour, slowly heated to 80°C, N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone (3.1g, 10mmol) was added, and then the temperature was continued to rise to 110°C for 1 hour, and then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 120mL titanium tetrachloride at 125°C. The obtained solid was washed 4 times with 150mL hexane at 60°C, the liquid was filtered off and dried to obtain a solid catalyst component. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 2.

[0077] Example 2-12

[0078] The solid catalyst component preparation process is as shown in Example 1, except that N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone is replaced with 10 mmol of compounds No. 2-12 prepared in Examples 2-12 in Table 1 in sequence.

[0079] Embodiment 13

[0080] In a 500mL 5-necked flask with nitrogen fully replaced and stirred, add 10g anhydrous magnesium chloride, 150mL toluene, 17mL epichlorohydrin and 16mL tributyl phosphate at room temperature, heat to 50℃ with stirring, and maintain for 2 hours, the solid is completely dissolved, then add 2.40g phthalic anhydride and maintain for another hour. Cool the solution to -25℃, add 110mL titanium tetrachloride dropwise within 1 hour, slowly heat to 80℃, and gradually wash out the solid during the heating process. Add 10mmol N-isopropyl-2,6-dicarboxylic acid diethyl ester-4-pyridone and maintain at 80℃ for 1 hour. After filtering, wash twice with 200mL toluene, then add 120mL toluene and 80mL titanium tetrachloride, continue to heat to 110℃, keep the temperature for 2 hours, then filter the liquid clean, and repeat the process once. The liquid was filtered off, and the obtained solid was washed once with 100 mL of dichloroethane and four times with hexane, and then dried to obtain a solid catalyst component. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 2.

[0081] Embodiment 14

[0082] In a 500mL 5-necked flask with nitrogen fully replaced and stirred, 8g of diethoxymagnesium and 100mL of toluene were added to prepare a suspension, 25mL of titanium tetrachloride was added dropwise at -15°C, the temperature was slowly raised to 0°C after the addition was completed, and 50mL of titanium tetrachloride was added dropwise, and then the temperature was slowly raised to 80°C, 10mmol of N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone was added, and then the temperature was continued to rise to 110°C and kept constant for 2 hours, and then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 100mL of titanium tetrachloride at 125°C. The obtained solid was washed 4 times with 120mL of hexane at 60°C, the liquid was filtered off and dried to obtain a solid catalyst component.

[0083] Comparative Example 1

[0084] The catalyst component preparation process is the same as in Example 1, except that N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone is replaced by 10 mmol of di-n-butyl phthalate (DN).

[0085] Comparative Example 2

[0086] The catalyst component preparation process is the same as in Example 1, except that N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone is replaced by 10 mmol of 9,9-dimethoxyfluorene (FLU).

[0087] polymerization

[0088] Polymerization evaluation using solid catalyst as a component of olefin polymerization catalyst:

[0089] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L methylcyclohexyldimethoxysilane hexane solution and 10mg of the prepared catalyst are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and the stirring is stopped to discharge the reaction product, and the polymer is obtained by drying.

[0090] Table 2

[0091]

[0092]

[0093] As can be seen from Table 2, the catalysts of Examples 1 to 12 containing N-substituted-2,6-dicarboxylic acid ester-4-pyridone compounds with different substituents as internal electron donors are more active than the catalyst of the phthalate internal electron donor of Comparative Example 1, and higher than the diether catalyst of Comparative Example 2 under the same preparation conditions, and have good stereoselectivity and high isotacticity of the obtained polymer. The catalyst has regular particle size and high bulk density. Examples 13-14 are catalysts prepared by different preparation methods using N-isopropyl-2,6-dicarboxylic acid diethyl ester-4-pyridone, which also show excellent performance of high activity and high stereoselectivity.

[0094] The present invention is not limited to the aforementioned specific embodiments, and any changes or modifications made by any technician in the field of the present invention are all covered by the patent scope of the present invention.

Claims

1. A catalyst component for olefin polymerization, characterized in that It contains Mg, Ti, halogen and an internal electron donor compound, wherein the internal electron donor compound is selected from the N-substituted-2,6-dicarboxylate-4-pyridone compounds of the general formula (I): Among them, R in the general formula (I) 1 , R 2 , R 3 , R 4 and R 5’ are the same or different, each independently selected from H, halogen, C1-C 20 of hydrocarbon groups.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that R 1 , R 2 , R 3 , R 4 and R 5’ They also each contain at least one heteroatom selected from N, O, S, P, Si and halogen.

3. The catalyst component for olefin polymerization according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 , R 4 , R 5’ the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

4. The catalyst component for olefin polymerization according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 , R 4 , R 5’ are the same or different and are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 a linear or branched or cyclic alkyl group, or the following substituents having 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, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

5. The catalyst component for olefin polymerization according to claim 1, characterized in that The N-substituted-2,6-dicarboxylic acid ester-4-pyridone compound is selected from N-isopropyl-2,6-dicarboxylic acid diethyl ester-4-pyridone, N-tert-butyl-2,6-dicarboxylic acid didodecyl ester-4-pyridone, N-n-butyl-2,6-dicarboxylic acid di-n-butyl ester-4-pyridone, N-phenyl-2,6-dicarboxylic acid diphenyl ester-4-pyridone, N-m-chlorophenyl-2,6-dicarboxylic acid di-m-chlorophenyl ester-4-pyridone, N-p-chlorophenyl-2,6-dicarboxylic acid di-p-tolyl ester-4-pyridone, N - at least one of o-chlorophenyl-2,6-dicarboxylic acid di-p-methoxyphenyl-4-pyridone, N-p-methoxyphenyl-2,6-dicarboxylic acid difuranyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid dipentenyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid di-p-nitrophenyl ester-3-methyl-5-ethyl-4-pyridone, N-benzyl-2,6-dicarboxylic acid dibenzyl ester-3,5-diethyl-4-pyridone, and N-methyl-2-ethyl-6-carboxylic acid phenyl ester-4-pyridone.

6. The catalyst component for olefin polymerization according to any one of claims 1 to 5, characterized in that The catalyst component comprises a titanium compound, a magnesium compound, and the N-substituted-2,6-dicarboxylate-4-pyridone 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 , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 The hydrocarbon group; The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group is: X is halogen, and N is 1-4.

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

8. The catalyst component for olefin polymerization according to claim 6, characterized in that The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

9. The catalyst component for olefin polymerization according to claim 8, characterized in that The alkyl titanium halide includes at least one of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

10. The catalyst component for olefin polymerization according to claim 6, characterized in that The molar ratio of the N-substituted-2,6-dicarboxylate-4-pyridone compound to the magnesium compound is 0.01-5.0, and the magnesium compound is calculated as magnesium element.

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

12. The catalyst according to claim 11, characterized in that The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

13. The catalyst component according to claim 11, characterized in that The organoaluminum compound includes at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

14. The catalyst according to claim 11, characterized in that The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

15. The catalyst according to claim 11, characterized in that The raw material composition of the catalyst also includes an external electron donor; The external electron donor is a siloxane compound.

16. The catalyst according to claim 15, characterized in that The general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 A hydrocarbon group, t is an integer of 0≤t≤3.

17. The catalyst according to claim 16, characterized in that The R' and R" each contain a heteroatom.

18. The catalyst according to claim 17, characterized in that The heteroatom includes at least one of N, O, S, P, and Si.

19. The catalyst according to claim 15, characterized in that The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

20. Use of the catalyst according to any one of claims 11 to 19 in olefin polymerization.

21. The use according to claim 20, 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, and vinylcyclohexene; The polymerization includes homopolymerization or copolymerization; The polymerization temperature is ≤200°C; the polymerization pressure is ≤10MPa.

Images