Catalyst components for the polymerization of olefins and their use

Abstract

The application provides a catalyst component for olefin polymerization and application thereof. The catalyst component comprises a reaction product of the following components: A) alkoxy magnesium particles, B) an internal electron donor compound: a) a carboxylic acid ester electron donor compound, b) a polyhydric alcohol ester compound, and c) a silicon-hydrogen functional group-containing organosilicon compound; and C) a titanium-containing halide, wherein the alkoxy magnesium particles comprise a reaction product of the following components: 1) magnesium powder, 2) mixed alcohol, 3) a halogenating agent, and 4) a crosslinking agent, wherein the crosslinking agent is a titanate compound. The catalyst component of the application has high polymerization activity and high polymer isotacticity in the polymerization process of alpha-olefins.

Description

TECHNICAL FIELD

[0001] The present application relates to a catalyst component for olefin polymerization and a preparation method thereof, and belongs to the field of olefin polymerization. BACKGROUND

[0002] The stereoregularity of the catalyst determines the isotacticity of the polymer, and the isotacticity is an important performance indicator of the polymer. The higher the isotacticity of the polypropylene is, the higher the regularity and crystallinity of the polypropylene are, and the mechanical properties such as hardness, stiffness, modulus, breaking and yield strength of the product are increased, and the melting point, thermal stability, aging resistance and radiation resistance are also improved accordingly. Therefore, in order to improve the stereoregularity of the catalyst, researchers have been conducting a large amount of research work. In some researches, catalysts containing two (or more than two) internal electron donors in combination are used to make up for the insufficient performance of catalysts containing a single internal electron donor, so as to improve the performance of the catalyst. However, the effect of combination is not a simple superposition of the performance of several electron donors. For example, the isotacticity of the polypropylene obtained by the catalyst with monocarboxylic acid ester as the internal electron donor is low, and the product needs to be de-ran. WO03002617 discloses a catalyst component for olefin polymerization and a catalyst obtained by using monocarboxylic acid ester and dicarboxylic acid ester in combination, but the stereoregularity and polymerization activity of the catalyst are still not very high. CN101643519A discloses a preparation method of a catalyst component for olefin polymerization. The titanium-containing catalyst component is prepared by dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a uniform solution, mixing the solution with titanium tetrahalide or its derivative, precipitating a solid in the presence of a multi-ester compound, loading at least one surface modifier, at least one transition metal titanium halide or its derivative, and an electron donor compound on the precipitated solid, and washing with a diluent to obtain the catalyst. The preparation process of the catalyst is relatively complex, the types of raw materials used are various, the reaction process is long, and the amount of diol ester is relatively large. The polymerization activity and stereoregularity of propylene need to be improved.

[0003] Isotactic polybutene-1 has good mechanical properties, outstanding creep resistance, low-temperature flow resistance and environmental stress cracking resistance, and also has wear resistance, flexibility and high filler filling property. Compared with other polyolefins, the stress cracking resistance of polybutene-1 is the best, and the creep resistance is significantly higher than that of polyethylene or polypropylene. In particular, under the action of stress not exceeding the yield point, the outstanding creep resistance of isotactic polybutene-1 remains unchanged up to 110℃. Moreover, isotactic polybutene-1 still shows good mechanical properties under heat conditions. Its heat resistance allows it to be used at 80-90℃ for a long time, and the upper limit of the use temperature in hot water is up to 110℃, and the wear resistance can be compared with that of ultra-high molecular weight polyethylene. Therefore, it has a unique advantage in the application of hot water pipe materials.

[0004] However, due to the limitations of catalyst level and polymerization process, the polymerization activity of polybutene-1 is low, and the stereoregularity is not high enough, and it is often necessary to treat the product by removing ash or removing random substances, and the polymerization process is complex, resulting in high price of polybutene-1 polymer product, which limits its wide application and development. SUMMARY

[0005] In view of the defects of the catalysts in the prior art, the present application provides a titanium-containing solid catalyst component for high-activity and high-stereoregularity polyolefin. The first step of the present application is to use magnesium metal and mixed alcohol, halogenating agent and crosslinking agent to react to produce spherical alkoxymagnesium solid particles as a carrier, and then use carboxylate compound a, polyol ester compound b and organosilicon compound c containing Si-H functional group as internal electron donor to prepare the catalyst component. In the polymerization process of α-olefin, the prepared catalyst component has high polymerization activity, high polymer isotacticity and does not need to remove ash.

[0006] The olefin polymerization catalyst component of the present application comprises the reaction product of the following components:

[0007] A) Alkoxymagnesium particles;

[0008] B) Internal electron donor compound, the internal electron donor compound comprising a) carboxylate compound, b) polyol ester compound and c) organosilicon compound containing Si-H functional group; and

[0009] C) Titanium-containing halide.

[0010] According to an embodiment of the present application, the alkoxymagnesium particles comprise the reaction product of the following components: 1) magnesium powder, 2) mixed alcohol, 3) halogenating agent and 4) crosslinking agent, wherein the crosslinking agent is a titanate compound.

[0011] According to an embodiment of the present application, the structure of the titanate compound is shown in Formula I:

[0012] (R 1 O) a Ti(OR 2 ) b (OR 3 ) c X d Formula I

[0013] In Formula I, R 1 , R 2 and R 3which can be the same or different, are selected from the group consisting of H and alkyl, especially C1-C10 alkyl, X is selected from the group consisting of alkoxy, preferably C1-C10 alkoxy, carboxyl, preferably C1-C10 carboxyl, chloro, sulfonic acid group, phosphoric acid group and sulfuric acid group, a, b, c and d are independently an integer from 0 to 4, and a+b+c+d = 4. Preferably, the titanate is selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetraisonyl titanate, tetradecyl titanate and isomers thereof. Preferably, one or more of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate.

[0014] According to an embodiment of the present application, the weight ratio of the titanate compound to the magnesium powder is (0.01-5): 1, preferably (0.05-2): 1.

[0015] The magnesium powder used in the present application can be in any shape, such as granular, ribbon or powder, as long as it has good reactivity. To ensure good reactivity, the magnesium powder is preferably in the form of spherical particles with an average particle size of 360 μm or less. The surface of the magnesium powder is not particularly limited, but the formation of a coating of hydroxide or the like on the surface of the magnesium powder can slow down the reaction, so it is desirable that the coating on the surface of the magnesium powder be as thin as possible. According to the requirements of the present application, the thickness of the coating on the surface of the magnesium powder is 0.5 μm or less.

[0016] The mixed alcohol used in the present application is a linear or branched mono- or polyhydric alcohol, preferably a mixture of C1-C10 alcohols. Specific examples of C1-C10 alcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-ethylbutanol, 2-ethylhexanol, 4-methyl-2-pentanol, 3,3,5-trimethylpentanol, 4-methyl-3-heptanol, benzyl alcohol, 2-phenylethanol, 1-phenyl-1-propanol, ethylene glycol, glycerol and the like. 10 10

[0017] According to an embodiment of the present application, the mixed alcohol is a mixture of ethanol and isooctanol. According to some preferred embodiments, the mixed alcohol contains 80-99 wt% of ethanol and 1-20 wt% of isooctanol. The water content of the alcohol is not particularly limited in the present application, but it is desirable that the water content be as low as possible in order to obtain good performance of the magnesium alkoxide. The water content of the alcohol is generally controlled to be 1000 ppm or less, preferably 200 ppm or less.

[0018] According to an embodiment of the present application, the molar ratio of the mixed alcohol to magnesium is (2-50): 1, preferably (2.5-18): 1.​​

[0019] According to an embodiment of the present application, the halogenating agent is a halogen element and / or an inorganic halide, preferably at least one selected from the group consisting of iodine element, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide and alkoxymagnesium halide; more preferably at least one selected from the group consisting of iodine element, magnesium iodide, magnesium chloride and alkoxymagnesium halide, and particularly preferably a mixture of iodine element and magnesium chloride. The iodine element or magnesium chloride can be applied to the reaction in a pure state or in a solution. The iodine element and magnesium chloride can be added to the reaction system separately or partially or wholly mixed together.

[0020] According to an embodiment of the present application, the molar ratio of the halogenating agent to magnesium powder is (0.0002-0.2): 1, preferably (0.0025-0.05): 1, based on the halogen atoms. The inventors have found that the amount of halogen atoms added affects the particle morphology and particle size of the final alkoxymagnesium. When the amount of halogen atoms used is too small, the particle morphology of the resulting alkoxymagnesium is very poor; if the amount of halogen atoms used is too large, not only will the cost of preparing the alkoxymagnesium increase, but also the particle size of the alkoxymagnesium will be very uneven and the reaction will be difficult to control.

[0021] The order of addition of the reaction materials can be determined as required. Specifically, there is no particular limitation on the method of adding the titanate compound and the halogenating agent, which can be added dissolved in ethanol, added directly in solid or liquid form to the magnesium powder and alcohol, or prepared by dropping an alcohol solution of the halogenating agent into the magnesium powder and alcohol solution during heating.

[0022] All of the reactions of the present application are carried out under an inert gas atmosphere, for example, an argon or nitrogen atmosphere, and the present application preferably uses nitrogen.

[0023] In addition, in the present application, for the addition of the magnesium powder, mixed alcohol, halogen-containing substance and inert solvent in the preparation of the alkoxymagnesium particles, the reaction materials can be initially added all at once or can be added in portions. Adding the raw materials in portions prevents the instantaneous generation of a large amount of hydrogen gas and the splashing of alcohol or halogen due to the instantaneous generation of a large amount of hydrogen gas, and this method of adding is preferred from the viewpoint of safety. The number of portions can be determined according to the scale of the reactor and the amounts of the various materials.

[0024] The reaction temperature for preparing the magnesium alkoxide particles in the present application can be in the range of 0°C to the reflux temperature of the reaction system. The reflux temperature can be changed by a slight change in the reaction pressure. The higher the reaction temperature, the faster the reaction. The reaction temperature can also be changed during the reaction. The particle size and the particle morphology can be changed by selecting the reaction temperature. The preferred reaction temperature is the reflux temperature of the reaction system. The reaction degree can be determined by observing the amount of hydrogen gas produced during the reaction. The reaction time is usually in the range of 2 to 30 hours. According to the embodiments of the present application, the product is dried or suspended in a dispersing agent. After the reaction, the product can be washed with the alcohol used to prepare the magnesium alkoxide and / or a mixture of alcohols; the product can also be washed with the organic solvent used in the reaction; or the product can be washed according to the specific conditions. The washing method and the number of washing are not particularly limited.

[0025] According to the embodiments of the present application, the a) carboxylic acid ester compound in B) is selected from benzoic acid monoesters or phthalic acid ester compounds as shown in Formula II,

[0026]

[0027] In Formula II, R1and R2are independently selected from substituted or unsubstituted C1-C8alkyl, C3-C10cycloalkyl or C6-C10aromatic group; and R3-R6are independently selected from hydrogen, halogen, C1-C4alkyl or C1-C4alkoxy. Preferably, at least three of R3-R6are hydrogen. More preferably, the carboxylic acid ester electron donor compound is selected from at least one of ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, and pentyl hexyl phthalate, and isomers thereof. 10 20 10 20

[0028] According to the embodiments of the present application, the molar ratio of the a) carboxylic acid ester compound to magnesium in the magnesium alkoxide particles is in the range of (0.01-5):1, preferably in the range of (0.02-2):1.

[0029] According to an embodiment of the present application, the b) polyol ester compound in B) is selected from the group consisting of dihydric alcohol ester compounds represented by Formula III,

[0030]

[0031] In Formula III, R1-R2 are the same or different, each independently a substituted or unsubstituted straight-chain C1-C 20 alkyl, substituted or unsubstituted branched C3-C 20 alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 alkylaryl, substituted or unsubstituted C7-C 20 aralkyl, substituted or unsubstituted C2-C 10 alkenyl or substituted or unsubstituted C 10 -C 20 fused ring aryl; R3-R8 are the same or different, each independently hydrogen, halogen, substituted or unsubstituted straight-chain C1-C 20 alkyl, substituted or unsubstituted branched C3-C 20 alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 alkylaryl, substituted or unsubstituted C7-C 20 aralkyl, substituted or unsubstituted C2-C 10 alkenyl or substituted or unsubstituted C 10 -C 20 fused ring aryl; or at least one of R3-R6 forms a ring with at least one of R7-R8.

[0032] The b) polyol ester compound in B) can be at least one of 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethylbenzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dineopentanoate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoate cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2-methyl-3,5-heptanediol dibenzoate, and the like, preferably at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 2,4-pentanediol dibenzoate.

[0033] According to the embodiment of the present application, the molar ratio of the electron-donating compound of the polyol ester compound in B) b) to magnesium in the magnesium alkoxide particles is (0.01-5): 1, preferably (0.02-2): 1.

[0034] According to the embodiment of the present application, the Si-H functional group-containing organosilicon compound in B) c) is selected from c1 an organosilicon compound as shown in Formula IV and c2 an organosilicon compound as shown in Formula V,

[0035]

[0036] In Formula IV, R 1 -R 7 are the same or different, each independently selected from one of an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, an alkylaryl group having 6-20 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6-20 carbon atoms; and n is an integer of 2-100.

[0037]

[0038] In Formula V, R 8 are the same or different, each independently selected from one of an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, an alkylaryl group having 6-20 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6-20 carbon atoms; and n is an integer of 3-20.

[0039] According to the olefin polymerization catalyst component of the present application, the Si-H functional group-containing organosilicon compound can be a polymer c1 as shown in Formula IV. Preferably, R 1 are the same or different, each independently selected from one of an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, an alkylaryl group having 6-20 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6-20 carbon atoms; and n is an integer of 3-20. 2 -R 7 are the same or different, each independently selected from one of an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, an alkylaryl group having 6-20 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 6-20 carbon atoms; and n is an integer of 3-20.

[0040] The organosilicon compound having a Si-H functional group in the olefin polymerization catalyst component according to the present application can be a compound c2 represented by Formula V, which is not particularly limited. In Formula V, R 8 is preferably an alkyl group having 1 to 12 carbon atoms; and n is preferably an integer of 3 to 8. In a preferred case, examples of the compound represented by Formula V can be selected from tetraethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, and the like.

[0041] The above-mentioned compound cl or c2 can be used alone or in combination. The compound represented by Formula IV or Formula V used in the present application can be commercially available or can be prepared by chemical reactions such as alkylation, condensation, and the like from corresponding precursor compounds.

[0042] According to an embodiment of the present application, the molar ratio of the organosilicon compound having a Si-H functional group in c) of B) to magnesium in the magnesium alkoxide particles is (0.01 to 5): 1, and preferably (0.02 to 2): 1.

[0043] According to an embodiment of the present application, the contact temperature in a), b), and c) of B) is -40 to 200°C, and preferably -20 to 150°C, and the reaction time is 1 minute to 20 hours, and preferably 5 minutes to 8 hours.

[0044] According to an embodiment of the present application, the titanium-containing halide is represented by Formula VI:

[0045] TiX n (OR7) 4-n Formula VI

[0046] In Formula VI, X is halogen, preferably chlorine, R7 is a hydrocarbon group having 1 to 4 carbon atoms, and n is an integer of 0 to 4. 20 The hydrocarbon group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms.

[0047] According to an embodiment of the present application, the molar ratio of the titanium-containing halide to the magnesium alkoxide particles is (0.5 to 100): 1, and preferably (1 to 50): 1.

[0048] The contact temperature is -40 to 200°C, and preferably -20 to 150°C, and the reaction time is 1 minute to 20 hours, and preferably 5 minutes to 8 hours.

[0049] The inert diluent used for the formation of the mother liquor in the above-mentioned method can be at least one of hexane, heptane, octane, decane, benzene, toluene, and xylene. The amount of each component used for the formation of the mother liquor is usually 0.5 to 100 moles, and preferably 1 to 50 moles. The contact temperature is usually -40 to 200°C, and preferably -20 to 150°C; and the contact time is usually 1 minute to 20 hours, and preferably 5 minutes to 8 hours.

[0050] In the titanium treatment process, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene can be optionally added to the titanium tetrachloride-containing solution. In this case, the amount of each component in the titanium tetrachloride-containing solution used is, per mole of magnesium, 0.5 to 100 moles, preferably 1 to 50 moles, of the titanium compound; and the amount of the inert diluent used is usually 0 to 100 moles, preferably 0 to 50 moles. The number of times of the titanium treatment is 0 to 10, preferably 1 to 5.

[0051] In the titanium treatment process, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene can be optionally added to the titanium tetrachloride-containing solution. In this case, the amount of each component in the titanium tetrachloride-containing solution used is, per mole of magnesium, 0.5 to 100 moles, preferably 1 to 50 moles, of the titanium compound; and the amount of the inert diluent used is usually 0 to 100 moles, preferably 0 to 50 moles. The number of times of the titanium treatment is 0 to 10, preferably 1 to 5.

[0052] According to an embodiment of the present application, the content of titanium atoms in the catalyst component is 1.0 to 8.0 wt%, preferably 1.6 to 6.0 wt%; the content of magnesium atoms is preferably 10 to 70 wt%, preferably 15 to 40 wt%; the content of halogen atoms is 20 to 86 wt%, preferably 36 to 80 wt%; and the total content of internal electron donor compounds is 2 to 30 wt%, preferably 3 to 20 wt%.

[0053] It is another object of the present application to provide a catalyst for the polymerization of olefins, said catalyst comprising the reaction product of:

[0054] (1) the aforementioned catalyst component;

[0055] (2) an organoaluminum compound;

[0056] (3) optionally, an external electron donor compound.

[0057] According to an embodiment of the present application, the organoaluminum compound is an organoaluminum compound of the formula AlR' m X' 3-m wherein R' is selected from any one of hydrogen, a C1-C 20 alkyl group and a C6-C 20 aryl group; and X' is a halogen and m is an integer of 1 to 3.

[0058] According to an embodiment of the present application, the external electron donor compound is an organosilicon compound of the formula R 4 p R 5 q Si(OR 6 ) 4-p-q wherein R4 and R 5 is independently selected from any one of halogen, hydrogen atom, C1-C 20 alkyl group, C3-C 20 cycloalkyl group, C6-C 20 aryl group and C1-C 20 haloalkyl group, R 6 is selected from any one of C1-C 20 alkyl group, C3-C 20 cycloalkyl group, C6-C 20 aryl group and C1-C 20 haloalkyl group; p and q are independently integers from 0 to 3, and p+q<4.

[0059] According to the embodiments of the present application, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is (5-5000):1, preferably (20-1000):1, more preferably (50-500):1; the molar ratio of aluminum in the organoaluminum compound to the external electron donor compound is (0.1-500):1, preferably (1-300):1, more preferably (3-100):1.

[0060] The present application also provides an olefin polymerization method, which comprises contacting an olefin with the catalyst under olefin polymerization conditions. Preferably, at least one of the olefins is represented by the general formula CH2=CHR, wherein R is any one of hydrogen and C1-C6 alkyl group.

[0061] The olefin polymerization method of the present application can be used for homopolymerization of olefins, or for copolymerization of multiple olefins. Specific examples of the α-olefin represented by the general formula CH2=CHR include ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene, more preferably, the olefin represented by the general formula CH2=CHR is selected from at least one of ethylene, propylene and 1-butene.

[0062] According to the embodiments of the present application, the olefin polymerization conditions are: temperature 0-150°C, preferably 60-130°C; time 0.1-5h, preferably 0.5-4h; pressure 0.01-10MPa, preferably 0.5-5MPa.

[0063] The present application has the following advantages:

[0064] The present application selects a mixture containing a small amount of halogenated substance as the halogenating agent, and when titanium ester compounds and / or inert organic solvents are added during the reaction, the reaction is easier to control, and the particle morphology is better maintained.

[0065] The alkoxymagnesium particles of the present application are used as a carrier, and then a carboxylate compound a, a polyhydric alcohol ester compound b, and a silicone compound c having a Si-H functional group are used as internal electron donors, and the catalyst component thus prepared has high polymerization activity and high isotacticity in the polymerization of an α-olefin. The catalyst thus obtained has high activity and high isotacticity. It is particularly suitable for developing a high-rigidity low-ash grade polyolefin resin. DETAILED DESCRIPTION

[0066] The present application is described in detail below in conjunction with examples, but the present application is not limited by the following examples.

[0067] It should be noted that the evaluation of the alkoxymagnesium particles and the polyolefin prepared in the examples of the present application is performed by the following methods.

[0068] 1. The particle size and the particle size distribution of the dialkoxymagnesium and the catalyst are measured by a Malvern Mastersizer TM 2000 n-hexane dispersant laser diffraction method, wherein SPAN = (D90 - D10) / D50.

[0069] 2. The internal electron donor content in the olefin polymerization catalyst component is measured by gas chromatography.

[0070] 3. The activity of the polymer is calculated by dividing the weight of the finally prepared polymer by the weight of the initially added catalyst component.

[0071] 4. The test method for the isotacticity (II) of the polypropylene is as follows: 2 g of a dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours, and then the remaining material is dried to a constant weight, and the isotacticity is calculated by the following formula:

[0072] Isotacticity II = the mass of the polymer after extraction / 2 x 100%.

[0073] 5. The test method for the isotacticity (II) of the polybutene-1 is as follows: 3 g of a polybutene-1 sample dried in a vacuum oven at 75 ± 5°C for 60 minutes is placed in an extractor and wetted with diethyl ether, and then extracted with diethyl ether for 12 hours, and then the remaining material is dried to a constant weight, and the isotacticity is calculated by the following formula:

[0074] Isotacticity II = the mass of the polybutene-1 after extraction / 3 x 100%.

[0075] 6. Propylene polymerization: A 5 liter autoclave was purged with nitrogen at 70°C for 1 hour. Then, 5 mL of triethylaluminum in hexane (0.5 mmol / mL), 1 mL of cyclohexylmethyldimethoxysilane (CHMMS) in hexane (0.10 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of the solid catalyst component were introduced into the reactor under a nitrogen stream at room temperature. The autoclave was closed, and 1.0 L (standard state) of hydrogen and 2.0 L of liquid propylene were introduced. The temperature was increased to 70°C over 10 minutes with stirring. After 2 hours of polymerization at 70°C, the stirring was stopped, the unreacted propylene monomer was removed, and the polymer was collected for testing.

[0076] 7. Butene-1 polymerization: A 5 liter autoclave was pressurized, leak tested, and checked for air tightness. The reactor was started with stirring at 100 rpm. The reactor was heated to 70-75°C, and then evacuated for at least 2 minutes with a vacuum pump. The reactor was then purged with nitrogen for at least 5 times, and then pressurized to 0.05-0.10 MPa with nitrogen.

[0077] The prepared triisobutylaluminum solution and dicyclopentyl dimethoxysilane solution were introduced into the feed injector under nitrogen. The catalyst sample (mass m0) was introduced into the feed injector using a syringe. The mixture was introduced into the reactor, and the syringe was flushed with 5 mL of hexane and introduced into the reactor. The feed valve and the vent valve were closed. The hydrogen valve was opened, and 0.85 L (standard state) of hydrogen was introduced. The hydrogen valve was closed. The butene-1 valve was opened, and 2.3 L of liquid butene-1 was introduced. The stirring speed was adjusted to 300 rpm, and the reactor was heated using a temperature control water system. The reaction was started when the reactor temperature reached 70°C, and the reaction was continued for 1 hour. The reactor temperature was controlled at 70°C ± 1°C using the temperature control water system.

[0078] Preparation Examples 1-9

[0079] Preparation of the Alkoxymagnesium Particles: A reactor equipped with a stirrer, reflux condenser, thermometer, and burette was used. After purging with nitrogen, ethanol with a water content of less than 200 ppm and a small amount of isooctanol with a water content of less than 200 ppm were introduced into the reactor, and iodine and magnesium chloride were introduced to dissolve them. Then, 32 g of magnesium powder (less than 360 μm) was introduced. A certain amount of titanate compound was introduced into the reaction solution, and the reaction was performed. After the stirring was started, the temperature was increased until the reflux temperature of the reaction system was reached, and the reaction was continued until the hydrogen gas was no longer discharged. Then, the reaction solution was washed, separated, and dried. The amounts of the raw materials introduced and the results are shown in Table 1.

[0080] Comparative Examples 1-3

[0081] Preparation of alkoxymagnesium support: In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a burette were installed. After thorough purging with nitrogen, ethanol and a small amount of isooctanol were added to the reactor, followed by the addition of elemental iodine and magnesium chloride to dissolve them. Then, magnesium powder and toluene were added. A titanate compound with a specific structure was added to the reaction solution to initiate the reaction. After stirring, the temperature was increased until the reflux temperature of the reaction system was reached, and the reaction was continued until completion, i.e., no more hydrogen gas was emitted. Then, washing, separation, and drying were performed. The specific amounts of each raw material added and the results are shown in Table 1.

[0082] Table 1 Test data of the preparation example

[0083]

[0084]

[0085] Example 1

[0086] In a 100 mL reactor that has been fully purged with high-purity nitrogen, 10 g of magnesium alkoxy particles from Preparation Example 1, 50 mL of toluene, 3 mL of polymethylhydrosiloxane (n≈35), 2.8 mL of di-n-butyl phthalate (DNBP), and 1.2 mL of diethyl phthalate are added. The mixture is heated to 80 °C and held at that temperature for 2 hours to obtain suspension X1. Simultaneously, in a 300 mL reactor that has been fully purged with high-purity nitrogen, 10 mL of toluene and 90 mL of titanium tetrachloride are added. The mixture is heated to 80 °C, and then suspension X1 is added. The mixture is slowly heated to 115 °C, and during the heating process, 1.0 mL of 3,5-heptanediol dibenzoate is added. The mixture is held at that temperature for 2 hours, and then the liquid is filtered clean. Then, a mixture of 30 ml titanium tetrachloride and 120 ml toluene was added, heated to 110°C, and held at that temperature for 1 hour. The liquid was then filtered clean. Next, a mixture of 120 ml titanium tetrachloride and 30 ml toluene was added, heated to 110°C, and stirred for 1 hour. This process was repeated twice. The liquid was then filtered off, and the resulting solid was washed four times with 150 ml of hexane at 60°C. The liquid was then filtered off and the solid powder was dried, yielding the solid catalyst component. Test data are shown in Table 2.

[0087] Example 2

[0088] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Preparation Example 2 were added. Test data are shown in Table 2.

[0089] Example 3

[0090] The solid catalyst component was prepared according to the method of Example 1, except that alkoxymagnesium particles from Preparation Example 3 were added. Test data are shown in Table 2.

[0091] Example 4

[0092] The solid catalyst component was prepared according to the method of Example 1, except that the alkoxy magnesium granules of Preparation Example 4 were added. The test data are reported in Table 2.

[0093] Example 5

[0094] The solid catalyst component was prepared according to the method of Example 1, except that the alkoxy magnesium granules of Preparation Example 7 were added. The test data are reported in Table 2.

[0095] Example 6

[0096] The solid catalyst component was prepared according to the method of Example 1, except that 2,4-pentanediol dibenzoate 1.0 ml was added instead of 3,5- heptanediol dibenzoate 1.0 ml. The test data are reported in Table 2.

[0097] Example 7

[0098] The solid catalyst component was prepared according to the method of Example 1, except that di-n-butyl phthalate (DNBP) 4.0 ml was added instead of di-n-butyl phthalate (DNBP) 2.8 ml and no diethyl phthalate was added. The test data are reported in Table 2.

[0099] Example 8

[0100] The solid catalyst component was prepared according to the method of Example 1, except that diisobutyl phthalate (DIBP) 2.8 ml was added instead of di-n-butyl phthalate (DNBP) 2.8 ml. The test data are reported in Table 2.

[0101] Example 9

[0102] The solid catalyst component was prepared according to the method of Example 1, except that polymethylhydrosiloxane (n ~ 6) 3.0 ml was added instead of polymethylhydrosiloxane (n ~ 35) 3.0 ml. The test data are reported in Table 2.

[0103] Example 10

[0104] The solid catalyst component was prepared according to the method of Example 1, except that tetramethylcyclotetrasiloxane 3.0 ml was added instead of polymethylhydrosiloxane (n ~ 35) 3.0 ml. The test data are reported in Table 2.

[0105] Comparative Example 1

[0106] The solid catalyst component was prepared according to the method of Example 1, except that the alkoxy magnesium granules of Comparative Preparation Example 1 were added. The test data are reported in Table 2.

[0107] Comparative Example 2

[0108] The solid catalyst component was prepared according to the procedure of Example 1 except that the alkoxy magnesium particles of Comparative Preparation 2 were added. The test data are shown in Table 2.

[0109] Comparative Example 3

[0110] The solid catalyst component was prepared according to the procedure of Example 1 except that di-n-butyl phthalate (DNBP) 4.0 ml was added instead of di-n-butyl phthalate (DNBP) 2.8 ml, no diethyl phthalate was added, no polymethylhydrosiloxane (n ~ 35) was added, and di-n-butyl phthalate (DNBP) 1.0 ml was added instead of 3,5-heptanediol dibenzoate 1.0 ml during the temperature increase. The test data are shown in Table 2.

[0111] Table 2 Test data of Examples

[0112]

[0113]

[0114] As can be seen from the data of the 9 preparation examples and 2 comparative preparation examples in Table 1, the spherical alkoxymagnesium solid particles prepared by the present application using magnesium metal and mixed alcohols, halogenating agents, and crosslinking agents for reaction are uniform in particle size, stable in performance, and suitable for use as a carrier for preparing polyolefin catalyst components.

[0115] As can be seen from the data of the 10 examples and 3 comparative examples in Table 2, the catalyst components prepared by the present application using carboxylic acid ester compound a, polyhydric alcohol ester compound b, and organosilicon compound c containing Si-H functional groups as internal electron donors have high polymerization activity and high isotacticity when used for propylene polymerization and butene-1 polymerization, are suitable for development of high-performance polyolefin grades, and have broad application prospects.

[0116] Although the present application has been described with reference to some embodiments above, various modifications can be made thereto without departing from the scope of the present application, and equivalent substitutions can be made thereto. The features of each of the embodiments disclosed in the present application can be used in any combination, and the combinations thereof are not exhaustively described in the present specification only for the purpose of omitting the length and saving resources. Therefore, the present application is not limited to the specific embodiments disclosed herein, but falls within the scope of all technical solutions of the claims.

Claims

1. An olefin polymerization catalyst component comprising the reaction product of the following components: A) Alkoxy magnesium particles; B) Internal electron-donating compounds, said internal electron-donating compounds including a) carboxylic acid ester electron-donating compounds, b) polyol ester compounds and c) organosilicon compounds containing Si-H functional groups; and C) Titanium-containing halides, The alkoxymagnesium particles comprise a reaction product of the following components: 1) magnesium powder, 2) a mixed alcohol, 3) a halogenating agent, and 4) a crosslinking agent, wherein, The crosslinking agent is a titanate compound; The weight ratio of the titanate compound to magnesium powder is (0.05-2):1, the molar ratio of the mixed alcohol to magnesium powder is (2.5-18):1, and the molar ratio of the halogenating agent to magnesium powder is (0.0025-0.05):

1. The carboxylic acid ester electron-donating compound is selected from benzoic acid monoesters or phthalic acid esters as shown in Formula II. Formula II In Formula II, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups and C3-C4 alkyl groups. 10 cycloalkyl or C6-C 20 The aromatic group; R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy; The polyol ester compound is selected from diol ester compounds as shown in Formula III. Formula III In Formula III, R1-R2 may be the same or different, and each represents a substituted or unsubstituted linear C1-C1 bond. 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkyl, substituted or unsubstituted C7-C 20 Aryl, substituted or unsubstituted C2-C 10 olefinic or substituted or unsubstituted C 10 -C 20 Fused ring aryl group; R3-R8 may be the same or different, each being hydrogen, halogen, substituted or unsubstituted, straight-chain C1-C. 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C7-C 20 Alkyl, substituted or unsubstituted C7-C 20 Aryl, substituted or unsubstituted C2-C 10 olefinic or substituted or unsubstituted C 10 -C 20 Fused ring aryl group; or at least one of R3-R6 forms a ring with at least one of R7-R8; The organosilicon compounds containing Si-H functional groups are selected from formula IV and organosilicon compounds as shown in formula V. Formula IV In Equation IV, R 1 -R 7 Same or different, is one of the following: alkyl with 1-12 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkylaryl with 6-20 carbon atoms, or substituted or unsubstituted aromatic group with 6-20 carbon atoms; degree of polymerization n is an integer from 2 to 100; and / or Formula V In Equation V, R 8 It is one of the following: alkyl with 1-12 carbon atoms, cycloalkyl with 3-10 carbon atoms, alkylaryl with 6-20 carbon atoms, or substituted or unsubstituted aromatic group with 6-20 carbon atoms; the degree of polymerization n is an integer from 3 to 20.

2. The olefin polymerization catalyst component according to claim 1, characterized in that, The structure of the titanate compound is shown in Formula I: (R 1 O) a Ti(OR 2 ) b (OR 3 ) c X d Formula I In Equation I, R 1 R 2 and R 3 The same or different, selected from H and alkyl, X selected from alkoxy, carboxyl, chlorine, sulfonic acid, phosphoric acid and sulfate, a, b, c and d are independent integers from 0 to 4, and a+b+c+d=4.

3. The olefin polymerization catalyst component according to claim 2, characterized in that, In Equation I, R 1 R 2 and R 3 Same or different, selected from H and C1-C 10 Alkyl group, X is selected from C1-C 10 Alkoxy, C1-C 10 Carboxyl, chlorine, sulfonic acid, phosphate, and sulfate groups.

4. The olefin polymerization catalyst component according to claim 2, characterized in that, The titanate compounds are selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetranonyl titanate, tetradecyl titanate, and their isomers.

5. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, The mixed alcohol is a mixture of straight-chain or branched monohydric alcohols or polyhydric alcohols.

6. The olefin polymerization catalyst component according to claim 5, characterized in that, The mixed alcohol is C1-C 10 A mixture of alcohols.

7. The olefin polymerization catalyst component according to claim 6, characterized in that, The mixed alcohol is a mixture of ethanol and isooctyl alcohol.

8. The olefin polymerization catalyst component according to claim 7, characterized in that, In the mixed alcohol, ethanol accounts for 80-99 wt% and isooctyl alcohol accounts for 1-20 wt%.

9. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, The halogenating agent is an elemental halogen and / or an inorganic halide.

10. The olefin polymerization catalyst component according to claim 9, characterized in that, The halogenating agent is selected from at least one of elemental iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, and alkoxymagnesium halide.

11. The olefin polymerization catalyst component according to claim 10, characterized in that, The halogenating agent is selected from at least one of elemental iodine, magnesium iodide, magnesium chloride, and magnesium alkoxyhalides.

12. The olefin polymerization catalyst component according to claim 11, characterized in that, The halogenating agent is a mixture of elemental iodine and magnesium chloride.

13. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, In Formula II, at least three of R3-R6 are hydrogen atoms.

14. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, The electron-donating compounds of the carboxylic acid esters are selected from ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, and phthalic acid esters. Dinonyl formate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, pentyl hexyl phthalate, and at least one of the isomers of the above substances.

15. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, The molar ratio of magnesium in polyol ester compounds to magnesium in alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of magnesium in carboxylic acid ester electron donor compounds to magnesium in alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of magnesium in organosilicon compounds containing Si-H functional groups to magnesium in alkoxy magnesium particles is (0.01-5):

1.

16. The olefin polymerization catalyst component according to claim 15, characterized in that, The molar ratio of magnesium in polyol ester compounds to magnesium in alkoxy magnesium particles is (0.02-2):1; and / or the molar ratio of magnesium in carboxylic acid ester electron donor compounds to magnesium in alkoxy magnesium particles is (0.02-2):1; and / or the molar ratio of magnesium in organosilicon compounds containing Si-H functional groups to magnesium in alkoxy magnesium particles is (0.02-2):

1.

17. The olefin polymerization catalyst component according to any one of claims 1-4, characterized in that, The titanium-containing halide is shown in Formula VI: TiX n (OR7) 4-n Formula VI In formula VI, X is a halogen, and R7 is a C1-C halogen. 20 The hydrocarbon group, where n is an integer from 0 to 4.

18. The olefin polymerization catalyst component according to claim 17, characterized in that, X is chlorine, and R7 is a C1-C5 alkyl group.

19. A catalyst for olefin polymerization, comprising the reaction product of the following components: (1) The catalyst component according to any one of claims 1-18; (2) Organoaluminum compounds; (3)Optionally, external electron donor compounds.

20. An olefin polymerization method comprising contacting an olefin with the catalyst of claim 19 under olefin polymerization conditions.

21. The olefin polymerization method according to claim 20, characterized in that, At least one of the olefins is represented by the general formula CH2=CHR, where R is hydrogen or a C1-C6 alkyl group.

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