CN111057168B - Catalyst for olefin polymerization and preparation method and application thereof - Google Patents
Catalyst for olefin polymerization and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention relates to a catalyst for olefin polymerization, a preparation method and application thereof, belonging to the field of olefin polymerization catalysts. The catalyst for olefin polymerization comprises the following components: (A) a solid catalyst component prepared by a process comprising the steps of: reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound to form a uniform solution, and then mixing the uniform solution with an aromatic ester compound, a halide of transition metal titanium or a derivative thereof and a halogenated hydrocarbon compound to obtain a solid catalyst component; (B) a co-catalyst component; the olefin polymerization catalyst obtained by the invention not only can show good activity and copolymerization performance, but also can show high polymerization activity and high polymer melt index under the polymerization condition of high hydrogen-ethylene ratio. The catalyst has simple preparation process, and is very suitable for slurry polymerization process of ethylene and combined polymerization process of catalyst with high copolymerization performance and high hydrogen regulation sensitivity.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to a catalyst for olefin polymerization and a preparation method and application thereof.
Background
Through the development of the last 60 years, the Ziegler-Natta type polyethylene catalyst has made good progress in the aspects of activity, bulk density of powder, fine powder content, oligomer and the like, and basically meets the requirements of the existing industrial production. With the development of new products, when a resin product with a double-peak mark is produced, a large amount of comonomer needs to be added into the existing catalyst, so that the problems of resin stickiness, reactor scaling and short safe operation period of a device are easily caused. In order to better meet the requirements of industrial production and produce resin products with more excellent performance, a catalyst product with excellent copolymerization performance needs to be provided on the premise of ensuring the basic performance of the existing catalyst.
In the prior art, some electron donors are introduced into olefin polymerization catalysts to improve the hydrogen regulation performance of the catalysts, for example, silane electron donors and benzoate electron donors are introduced into Chinese patents with publication numbers of CN1958620A and CN103772536A respectively. The introduction of other electron donors can improve the copolymerization performance of the catalyst, for example, Chinese patents with publication numbers of CN1726230A, CN1798774A and CN101050248A respectively introduce electron donors such as alcohol, ketone, amine, amide, nitrile, alkoxy silane, aliphatic ether and aliphatic carboxylic ester. The activity of the catalyst can be improved by introducing certain electron donors into the catalyst, such as halogenated alkane introduced in Chinese patent with the publication number of CN 102977232A.
The above-mentioned electron donors can only improve the performance of the olefin polymerization catalyst in a certain aspect, and cannot meet the requirements of industrial production. A class of electron donors needs to be found, so that the hydrogen regulation performance and the copolymerization performance of the polyolefin catalyst can be improved simultaneously, and the requirement of an industrial production device for producing series-brand products is met.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a catalyst for olefin polymerization. In particular to a catalyst for olefin polymerization and a preparation method and application thereof. The inventor finds out through research that: in the preparation process of the catalyst, an aromatic ester compound and a halogenated hydrocarbon compound are introduced as internal electron donors, and the olefin polymerization catalyst not only can show good activity and copolymerization performance, but also can show high polymer melt index under the polymerization condition of high hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure is more than or equal to 1.5). The present invention has been made based on this finding.
One of the objects of the present invention is to provide a catalyst for olefin polymerization, which catalyst may comprise the following components:
(A) solid catalyst component:
the solid catalyst component is prepared by a method comprising the following steps: reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound to form a uniform solution, and then mixing the uniform solution with an aromatic ester compound, a halide of transition metal titanium or a derivative thereof and a halogenated hydrocarbon compound to obtain a solid catalyst component;
(B) the cocatalyst component:
the cocatalyst component is selected from an organic aluminum compound with the general formula of AlR1 aX1 bHcIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1Is a halogen atom, preferably fluorine, chlorine or bromine, a, b and c are each an integer of 0 to 3, and a + b + c is 3; preferably AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl, and the like.
The ratio of the cocatalyst component to the solid catalyst component is (5-500): 1, preferably (20-200) in terms of the molar ratio of aluminum in the cocatalyst component to titanium in the solid catalyst component: preferably 1, more preferably (50 to 200):1, more preferably (100 to 150): 1.
wherein the addition ratio of the magnesium halide, the organic epoxy compound, the organic phosphorus compound, the organic alcohol compound, the aromatic ester compound, the halide of the transition metal titanium or the derivative thereof, and the halogenated hydrocarbon compound is 0.2 to 10 mol, preferably 0.3 to 4.0 mol, more preferably 0.5 to 1.2 mol of the organic epoxy compound, and 0.1 to 10 mol, preferably 0.2 to 4.0 mol, more preferably 0.4 to 1.0 mol of the organic phosphorus compound per mol of the magnesium halide; 0 to 6 moles, preferably 0 to 2 moles, more preferably 1 to 2 moles of an organic alcohol compound; 0.1 to 1 mol, preferably 0.2 to 0.7 mol of an aromatic ester compound; 1 to 20 moles, preferably 1 to 15 moles, more preferably 6 to 15 moles, and further preferably 6 to 11 moles of a halide of a transition metal titanium or a derivative thereof; the amount of the halogenated hydrocarbon compound is 0.1 to 1.5 mol, preferably 0.2 to 1.2 mol, more preferably 0.4 to 0.8 mol, and still more preferably 0.5 to 0.7 mol.
In the catalyst component obtained in the present invention, the molar ratio of titanium: 3 to 10% by weight, preferably 3 to 7% by weight.
Wherein the content of the first and second substances,
the magnesium halide is magnesium dihalide, and the magnesium dihalide is at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide. Among them, magnesium dichloride is preferred.
The organic epoxy compound comprises at least one of aliphatic olefin with 2-8 carbon atoms, diene or halogenated aliphatic olefin or oxide, glycidyl ether, internal ether and the like of the diene. Specific compounds may be selected from: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, and the like. Among these, at least one of ethylene oxide, propylene oxide, epichlorohydrin and tetrahydrofuran is preferable, and tetrahydrofuran and/or epichlorohydrin are more preferable.
The organophosphorus compound is selected from hydrocarbyl esters of orthophosphoric acid or hydrocarbyl esters or halogenated hydrocarbyl esters of phosphorous acid. In particular, it may be selected from: at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, benzyl phosphite, etc. Among them, at least one of trimethyl orthophosphate, triethyl orthophosphate and tributyl orthophosphate is preferable, and tributyl orthophosphate is most preferable.
The organic alcohol compound is selected from straight chain, branched chain or naphthenic alcohol with 1-10 carbon atoms or alcohol containing aryl with 6-20 carbon atoms; the organic alcohol compound is preferably an aliphatic alcohol compound containing 1-10 carbon atoms. Specifically, the fatty alcohol: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, glycerol, hexanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, decanol, etc.; cycloalkanols such as cyclohexanol, methylcyclohexanol, etc.; aromatic alcohols, such as benzyl alcohol, methyl benzyl alcohol, α -methyl benzyl alcohol, α -dimethyl benzyl alcohol, and the like. Ethanol, butanol, 2-ethylhexanol, and glycerol are preferred. There is no particular limitation on the proportion of each alcohol in the alcohol composition.
Wherein the general formula of the aromatic ester compound is R1 nR2 mC6H5-n-m-x[(CH2)yCOOR3]xWherein R is1，R2Selected from alkyl, aryl, alicyclic group or alkoxy with 1-20 carbon atoms, R3Selected from alkyl, aryl and alicyclic groups with 1-20 carbon atoms, n is more than or equal to 0 and less than 5, m is more than or equal to 0 and less than 5, 0<x is less than 5, y is more than or equal to 0 and less than or equal to 9, n, m, x and y are integers, and n + m + x is less than 5; the aromatic ester compound can be selected from: methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, t-butyl benzoate, hexyl benzoate, octyl benzoate, cyclohexyl benzoate, 2-methylcyclohexyl benzoate, ethyl o-methylbenzoate, ethyl p-methylbenzoate, ethyl 2, 4-dimethylbenzoate, ethyl 2, 6-dimethylbenzoate, ethyl 3, 5-dimethylbenzoate, ethyl 2, 4, 6-triisopropylbenzoate, methoxyethyl benzoate, methoxypropyl benzoate, methoxybutyl benzoate, methoxyhexyl benzoate, methoxyoctyl benzoate, ethoxyethyl benzoate, ethoxypropyl benzoate, ethoxybutyl benzoate, ethoxyhexyl benzoate, ethoxyoctyl benzoate, butoxyethyl benzoate, butoxybutyl benzoate, butoxyhexyl benzoate, ethyl 5-acetyl-2-ethoxybenzoate, ethyl 2, 4-dimethylbenzoate, 2, 6-dimethylbenzoate, 3, 5-dimethylbenzoate, ethoxybutyl benzoate, ethoxyhexyl benzoate, ethoxyoctyl benzoate, butoxyethyl benzoate, butoxybutyl benzoate, butoxyhexyl benzoate, 5-acetyl-2-ethoxyethyl benzoate, ethoxybutyl benzoate, and ethoxybutyl benzoate, 3-, 4, 5-trimethoxybenzoic acid ethyl ester, phenylacetic acid methyl ester, phenylacetic acid ethyl ester, phenylacetic acid propyl ester, phenylacetic acid isopropyl ester, phenylacetic acid butyl ester, phenylacetic acid tert-butyl ester, phenylacetic acid hexyl ester, phenylacetic acid octyl ester, phenylacetic acid cyclohexyl ester, phenylacetic acid 2-methyl cyclohexyl ester, o-methyl phenylacetic acid ethyl ester, p-methyl phenylacetic acid ethyl ester, 2, 4-dimethyl phenylacetic acid ethyl ester, 2, 6-dimethyl phenylacetic acid ethyl ester, 3, 5-dimethyl phenylacetic acid ethyl ester, 2, 4, 6-tri-isopropyl phenylacetic acid ethyl ester, phenylacetic acid methoxy propyl ester, phenethyl acetateAt least one of methoxybutyl acetate, methoxyhexyl phenylacetate, methoxyoctyl phenylacetate, ethoxyethyl phenylacetate, ethoxypropyl phenylacetate, ethoxybutyl phenylacetate, ethoxyhexyl phenylacetate, ethoxyoctyl phenylacetate, butoxyethyl phenylacetate, butoxybutyl phenylacetate, butoxyhexyl phenylacetate, 5-acetyl-2-ethoxyethyl phenylacetate, 3-, 4, 5-trimethoxyethyl phenylacetate, methyl phenylpropionate and ethyl phenylpropionate. At least one of ethyl benzoate, propyl benzoate, ethoxyethyl benzoate, ethyl phenylacetate and propyl phenylacetate is preferable.
Wherein the halogenated hydrocarbon compound has the general formula Rm 1XaR2 nXbR3 pXcWherein R is1、R2、R3Each independently is alkyl or aryl, m, n and p can be integers of 0-10 but not 0 at the same time, a, b and c are integers of 0-4 but not 0 at the same time, a + b + c is less than or equal to 4, and X is selected from F, Cl or Br; specifically, the halogenated hydrocarbon compound may be selected from at least one of trichloromethane, dichloromethane, methyl bromide, ethyl chloride, propyl chloride, butyl chloride, pentyl chloride, hexyl chloride, ethyl bromide, 1, 2-dichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, 1, 3-dichloropropane, 1,2, 3-trichloropropane, 1, 4-dichlorobutane, 1, 5-dichloropentane, 1, 6-dichlorohexane, chlorocyclopentane, chlorocyclohexane, monochlorobenzene, dichlorobenzene, and bromobenzene. At least one of 1,2, 3-trichloropropane, trichloromethane, 1, 2-dichloroethane and 1,1, 1-trichloroethane is preferable.
The halide of the transition metal titanium or the derivative thereof has the general formula of Ti (OR)aXbWherein R is C1～C14A hydrocarbon group of (2), preferably C1～C8An alkyl group; x is a halogen atom, a, b are integers from 1 to 4, and a + b is 3 or 4. In particular, it may be selected from: TiCl (titanium dioxide)3、TiCl4、TiBr4、TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4、Ti(OC4H9)4And so on. Preference is given to TiCl3、TiCl4、TiBr4、Ti(OC2H5)2Cl2、Ti(OC2H5)Cl3、Ti(OC2H5)3Cl、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC4H9)4. With TiCl4Is most preferred.
Another object of the present invention is to provide a process for preparing the catalyst for olefin polymerization.
The preparation method of the solid catalyst component of the catalyst for olefin polymerization can comprise the following steps:
dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound under stirring to form a uniform transparent solution, wherein the dissolving temperature is 50-90 ℃, adding an organic alcohol compound during the solution forming process or after the solution forming process, and reacting for a certain time (specifically reacting for 1.5-4 hours) to obtain a reaction solution; mixing the reaction solution with an aromatic ester compound, a halide of transition metal titanium or a derivative thereof and a halogenated hydrocarbon compound at-30-0 ℃; and slowly heating the mixture to 50-120 ℃, separating out the solid to form particles, filtering, removing the mother liquor, and washing the solid with an inert solvent to obtain the solid catalyst component.
Wherein, regarding the preparation of the magnesium halide solution: the magnesium halide solution is a uniform solution obtained by dissolving magnesium halide in a solvent system consisting of an organic epoxy compound and an organic phosphorus compound, and an organic alcohol compound is added in the process of forming the solution or after the solution is formed and reacts for a certain time to obtain a reaction solution; the solvent system referred to herein includes the use or absence of an inert diluent.
The magnesium halide to be used preferably has a particle size dissolved under stirring at a temperature of-10 to 150 ℃ and preferably 20 to 130 ℃. The dissolution may be carried out with or without inert diluents such as: benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbons. Among them, benzene, toluene and xylene are preferable, and toluene and xylene are more preferable.
The invention also aims to provide the application of the catalyst for olefin polymerization in ethylene homopolymerization or copolymerization.
The catalyst of the invention is suitable for homopolymerization of ethylene or copolymerization of ethylene and other alpha-olefin, wherein the alpha-olefin adopts one of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methylpentene-1. Slurry polymerization or gas phase polymerization can be adopted during polymerization, and the polymerization temperature can be 0-150 ℃, and preferably 60-90 ℃.
The slurry polymerization medium comprises: and inert solvents such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, e.g., isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.
In order to adjust the molecular weight of the final polymer, hydrogen is used as a molecular weight regulator.
Magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound to form a uniform solution, an organic alcohol compound is added in the process of forming the solution or after the solution is formed, halide of transition metal titanium or a derivative thereof is added under the condition of low temperature for reaction, an electron donor is added in the process of carrying titanium or after the process of carrying titanium is finished, a catalyst is gradually separated out slowly in a system, and a certain temperature rising trend is controlled, so that the catalyst is obtained. When the catalyst is used for ethylene polymerization, the catalyst shows higher catalytic activity, better hydrogen regulation sensitivity and good copolymerization performance.
Due to the addition of the internal electron donor aromatic ester compound and the halogenated hydrocarbon compound, the olefin polymerization catalyst prepared by the invention not only can show good activity and copolymerization performance, but also can show high polymerization activity and high polymer melt index under the polymerization condition of high hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure is more than or equal to 1.5). The catalyst has simple preparation process, and is very suitable for slurry polymerization process of ethylene and combined polymerization process of catalyst with high copolymerization performance and high hydrogen regulation sensitivity.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples. Experimental test method
1. The relative weight percentage of titanium element in the solid catalyst component is as follows: adopting a spectrophotometry method;
2. polymer Melt Index (MI): determined according to ASTM D1238-99, load 2.16kg, 190 ℃;
3. density of polymer: according to ASTM GB/T1033.1-2008;
4. content of copolymerized units in the polymer powder: using liquid nuclear magnetism13C-NMR measurement.
Example 1
(1) Preparation of solid catalyst component A
4.0g of magnesium dichloride, 50mL of toluene, 3mL of epichlorohydrin, 8mL of tributyl phosphate and 4mL of ethanol are sequentially added into a reactor which is fully replaced by high-purity nitrogen, the reaction mixture is heated to 70 ℃ under stirring, and the reaction is carried out for 2 hours at 70 ℃ after the solid is completely dissolved to form a uniform solution. The system was cooled to-20 ℃ and 40mL of titanium tetrachloride was added dropwise, 3.0mL of ethyl benzoate was added during or after the titanium loading. After keeping the temperature for 30 minutes, 3mL of 1, 2-dichloroethane was slowly added dropwise, the temperature was raised to 80 ℃ and the reaction was carried out for 2 hours. Stirring was stopped, the suspension was allowed to settle, the suspension was quickly separated, the supernatant was removed and washed four times with hexane. Drying the mixture by high-purity nitrogen to obtain the solid catalyst component with good fluidity.
(2) Homopolymerization reaction
Polymerization with low hydrogen/ethylene ratio
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of 1M triethyl aluminum are added, then the solid catalyst component (containing 0.4mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa, and the polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 1.
② polymerization with high hydrogen/ethylene ratio
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of triethyl aluminum with the concentration of 1M are added, then the solid catalyst component (containing 0.4mg of titanium) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.58MPa, then ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa, and the polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 2.
(3) Copolymerization reaction
A stainless steel reaction vessel having a volume of 2L was fully purged with high-purity nitrogen, 1L of hexane and 1.0mL of triethylaluminum having a concentration of 1M were added, the solid catalyst component (containing 0.4mg of titanium) prepared by the above method was added, 20mL of hexene solution was added, the temperature was raised to 70 ℃ and hydrogen was introduced to make the pressure in the vessel 0.28MPa, and ethylene was introduced to make the total pressure in the vessel 0.73MPa, and polymerization was carried out at 80 ℃ for 2 hours, the polymerization results being shown in Table 3.
Example 2
(1) As in example 1, only 1, 2-dichloroethane was replaced by 1,1, 1-trichloroethane.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 3
(1) As in example 1, only 1, 2-dichloroethane was replaced by 1,2, 3-trichloropropane.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 4
(1) Just 1, 2-dichloroethane was changed to 1,1,2, 2-tetrachloroethane as in example 1.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 5
(1) As in example 1, the amount of 1, 2-dichloroethane added was adjusted to 2mL only.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2, similar to example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 6
(1) As in example 1, the amount of 1, 2-dichloroethane added was adjusted to 4mL only.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 7
(1) As in example 2, the amount of 1,1, 1-trichloroethane alone was adjusted to 2 mL.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 8
(1) As in example 2, the amount of 1,1, 1-trichloroethane alone was adjusted to 4 mL.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 9
(1) As in example 3, the amount of 1,2, 3-trichloropropane added was adjusted to 2mL only.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 10
(1) As in example 3, the amount of 1,2, 3-trichloropropane added was adjusted to 4mL only.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2, similar to example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 11
(1) As in example 4, the amount of 1,1,2, 2-tetrachloroethane alone was adjusted to 2 mL.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Example 12
(1) As in example 4, the amount of 1,1,2, 2-tetrachloroethane alone was adjusted to 4 mL.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization reaction
The polymerization results are shown in Table 3, as in example 1.
Comparative example 1
(1) Preparation of solid catalyst component
4.0g of magnesium dichloride, 50mL of toluene, 3mL of epichlorohydrin, 8mL of tributyl phosphate and 4mL of ethanol are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 70 ℃ under stirring, and the reaction is carried out for 2 hours at 70 ℃ after the solid is completely dissolved to form a uniform solution. The system was cooled to-20 deg.C, 40mL of titanium tetrachloride was slowly added dropwise, followed by 3.0mL of tetraethoxysilane. The temperature was slowly raised to 80 ℃ and the reaction was carried out for 2 hours. Stirring was stopped, the suspension was allowed to settle, the suspension was quickly separated, the supernatant was removed and washed four times with hexane. Drying the mixture by high-purity nitrogen to obtain the solid catalyst component with good fluidity.
(2) Homopolymerization reaction
The polymerization results are shown in tables 1 and 2 in the same manner as in example 1.
(3) Copolymerization of ethylene with propylene
The polymerization results are shown in Table 3, as in example 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst of the present invention has better activity and hydrogen response under low hydrogen polymerization conditions after the addition of the internal electron donors of ethyl benzoate and halogenated hydrocarbon.
TABLE 2
As can be seen from the data in Table 2, after the internal electron donor benzoate and the halogenated hydrocarbon are added, the activity and the hydrogen response sensitivity of the catalyst of the invention under the high hydrogen polymerization condition are obviously superior to those of the comparative example. This feature facilitates the production of bimodal products in slurry polymerization processes, and high melt index products in gas phase polymerization processes. It can be seen that the combined action of the benzoate compound and the halogenated hydrocarbon can improve the activity and hydrogen response of the catalyst.
TABLE 3
As can be seen from Table 3, the polymer powder obtained by using the catalyst of the present invention had a higher content of copolymerized units and a significant decrease in density as compared with the comparative example. It is understood that the polymer powder obtained in the examples of the present invention has a large amount of the comonomer in the molecular chain. Therefore, the combined action of the benzoate and the halogenated hydrocarbon compound as the internal electron donor can improve the copolymerization performance of the catalyst, and the method is favorable for reducing the addition of the comonomer, the long-period stable operation of a production device and the improvement of the comprehensive performance of the product when the product with the double-peak mark is produced.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (13)
1. A catalyst for the polymerization of olefins, characterized in that it comprises the following components:
(A) solid catalyst component:
the solid catalyst component is prepared by a method comprising the following steps: reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound to form a uniform solution, and then mixing the uniform solution with an aromatic ester compound, a halide of transition metal titanium or a derivative thereof and a halogenated hydrocarbon compound to obtain a solid catalyst component;
(B) the cocatalyst component:
the cocatalyst component is selected from an organic aluminum compound with the general formula of AlR1 aX1 bHcIn the formula, R1Is hydrogen or Cl～C20Hydrocarbyl radical, X1A, b and c are integers of 0-3, and a + b + c is 3;
the ratio of the cocatalyst component to the solid catalyst component is (5-500): 1 in terms of the molar ratio of aluminum in the cocatalyst component to titanium in the solid catalyst component;
wherein the general formula of the aromatic ester compound is R1 nR2 mC6H6-n-m-x[(CH2)yCOOR3]xWherein R is1，R2Selected from alkyl, aryl, alicyclic group or alkoxy with 1-20 carbon atoms, R3Selected from alkyl, aryl and alicyclic groups with 1-20 carbon atoms, n is more than or equal to 0 and less than 5, m is more than or equal to 0 and less than 5, 0<x is less than 5, y is more than or equal to 0 and less than or equal to 9, n, m, x and y are integers, and n + m + x is less than 5;
the halogenated hydrocarbon compound is selected from at least one of trichloromethane, dichloromethane, methyl bromide, monochloroethane, monochloropropane, chlorobutane, chloropentane, monochlorohexane, bromoethane, 1, 2-dichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, 1, 3-dichloropropane, 1,2, 3-trichloropropane, 1, 4-dichlorobutane, 1, 5-dichloropentane, 1, 6-dichlorohexane, chlorocyclopentane, chlorocyclohexane, monochlorobenzene, dichlorobenzene and bromobenzene;
wherein the charging ratio of the magnesium halide, the organic epoxy compound, the organic phosphorus compound, the organic alcohol compound, the aromatic ester compound, the halide of the transition metal titanium or the derivative thereof and the halogenated hydrocarbon compound is 0.2-10 mol of the organic epoxy compound, 0.1-10 mol of the organic phosphorus compound, 0-6 mol of the organic alcohol compound, 0.1-1 mol of the aromatic ester compound, 1-20 mol of the halide of the transition metal titanium or the derivative thereof and 0.2-1.2 mol of the halogenated hydrocarbon compound, not including 0.2 mol, per mol of the magnesium halide.
2. The catalyst for olefin polymerization according to claim 1, characterized in that:
in the general formula of the organoaluminum compound, X is1Selected from fluorine, chlorine or bromine.
3. The catalyst for olefin polymerization according to claim 1, characterized in that:
the ratio of the cocatalyst component to the solid catalyst component is (20-200): 1 in terms of the molar ratio of aluminum in the cocatalyst component to titanium in the solid catalyst component.
4. The catalyst for olefin polymerization according to claim 1, characterized in that:
the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide.
5. The catalyst for olefin polymerization according to claim 1, characterized in that:
the aromatic ester compound is selected from one of ethyl benzoate, propyl benzoate, ethyl phenylacetate and propyl phenylacetate.
6. The catalyst for olefin polymerization according to claim 1, characterized in that:
the organic epoxy compound is selected from at least one of oxides and glycidyl ethers of aliphatic olefin with 2-8 carbon atoms, diolefin or halogenated aliphatic olefin or diolefin;
the organophosphorus compound is selected from a hydrocarbyl ester of orthophosphoric acid or a hydrocarbyl ester of phosphorous acid or a halogenated hydrocarbyl ester of phosphorous acid.
7. The catalyst for olefin polymerization according to claim 1, characterized in that:
the organic alcohol compound is selected from straight chain, branched chain or naphthenic alcohol with 1-10 carbon atoms or alcohol with 6-20 carbon atoms and containing aryl.
8. The catalyst for olefin polymerization according to claim 7, characterized in that:
the organic alcohol compound is an aliphatic alcohol compound containing 1-10 carbon atoms.
9. The catalyst for olefin polymerization according to claim 1, characterized in that:
the halide of the transition metal titanium or the derivative thereof has the general formula of Ti (OR)aXbWherein R is C1～C14A hydrocarbon group of (a); x is a halogen atom, a, b are integers of 1 to 4, and a + b is 3 or 4.
10. The catalyst for olefin polymerization according to claim 9, characterized in that:
in the general formula of the halide or the derivative of the halide, R is C1～C8An alkyl group.
11. The catalyst for olefin polymerization according to claim 1, characterized in that:
the halide of the transition metal titanium or the derivative thereof is selected from TiCl3、TiCl4、TiBr4、Ti(OC2H5)Cl3、Ti(OC2H5)2Cl2And Ti (OC)2H5)3At least one of Cl.
12. The method for preparing a catalyst for olefin polymerization according to any one of claims 1 to 11, characterized in that:
the preparation method of the solid catalyst component of the catalyst for olefin polymerization comprises the following steps:
dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound under stirring to form a uniform transparent solution, wherein the dissolving temperature is 50-90 ℃, adding an organic alcohol compound during the solution forming process or after the solution is formed, and reacting to obtain a reaction solution; mixing the reaction solution with an aromatic ester compound, a halide of transition metal titanium or a derivative thereof, and a halogenated hydrocarbon compound at-30-0 ℃; and slowly heating the mixture to 50-120 ℃, separating out solids, filtering, removing mother liquor, and washing the solids to obtain the solid catalyst component.
13. Use of the catalyst for olefin polymerization according to any one of claims 1 to 11 or a catalyst comprising the solid catalyst component prepared by the preparation method of claim 12 in ethylene homopolymerization or copolymerization.
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