Titanium-containing solid catalyst components and olefin polymerization catalysts

Abstract

This invention provides a titanium-containing solid catalyst component and its application. The titanium-containing solid catalyst component provided by this invention comprises the reaction products of the following components: A) alkoxymagnesium particles; B) particle protectants, including a) titanate compounds and b) polysiloxanes; C) electron donor compounds, including c) carboxylic acid ester compounds and d) polyol ester compounds; and D) titanium-containing halides. The catalyst component of this invention exhibits high polymerization activity and a high isotactic index in the polymerization of α-olefins.

Description

Technical Field

[0001] This invention relates to a titanium-containing solid catalyst component and an olefin polymerization catalyst, belonging to the field of olefin polymerization. Background Technology

[0002] As the demand for polyolefins increases, the requirements for olefin polymerization catalysts are also becoming more stringent. Currently, the most widely used catalyst is the Ziegler-Natta catalyst supported on magnesium chloride. Chinese patents CN85100997A and CN1453298A disclose catalyst preparation methods that generally consist of a solid catalyst component composed of magnesium, titanium, halogens, and electron-donating organic compounds. However, meeting various performance requirements, such as high stereoregularity, high catalyst activity, and low ash content, makes the preparation of such a catalyst component very difficult.

[0003] Isotactic polybutene-1 possesses excellent mechanical properties, outstanding creep resistance, low-temperature fluidity, and resistance to environmental stress cracking, as well as abrasion resistance, flexibility, and high filler capacity. Compared to other polyolefins, polybutene-1 exhibits the best resistance to stress cracking, and its creep resistance is significantly higher than that of polyethylene or polypropylene. Particularly under stress not exceeding the yield point, its outstanding creep resistance remains unchanged up to 110°C. Furthermore, isotactic polybutene-1 maintains excellent mechanical properties under heated conditions; its heat resistance allows for long-term use at 80–90°C, with an upper limit of 110°C for use in hot water. Its abrasion resistance is comparable to that of ultra-high molecular weight polyethylene, thus giving it a unique advantage in hot water pipe applications.

[0004] However, due to limitations in catalyst level and polymerization process, polybutene-1 has always had low polymerization activity and insufficient stereoregularity, often requiring deashing or removal of atactic substances. Furthermore, the complex polymerization process has resulted in excessively high prices for polybutene-1 polymer products, limiting its widespread application and development.

[0005] Methods for preparing isotactic polybutene-1 generally include gas-phase methods and liquid-phase methods using hydrocarbons or butene-1 monomers as solvents. In liquid-phase polymerization, currently disclosed processes typically use butene-1 monomer itself as the solvent or reaction medium to address the separation of the product after polymerization. Polymerization is carried out under the combined action of the main catalyst titanium trichloride and the co-catalyst diethylaluminum chloride (DEAC). In some cases, a mixture of diethylaluminum iodide and DEAC is also used, as disclosed in European Patent EP187034. However, this process system has low polymerization activity, and the stereoregularity of the resulting polybutene-1 is not high enough, often requiring deashing or removal of atactic compounds. The post-polymerization processing is complex, and the properties of the resulting polymer are not ideal. The polybutene-1 prepared using patent US6306996 has improved isotacticity to 95% and activity to 14000 g / gcat.4h. However, due to the high ash content of the obtained polymer, the isotacticity and polymerization activity are not ideal, and the performance of the obtained polymer is not satisfactory. Summary of the Invention

[0006] To address the shortcomings of existing catalysts, this invention provides a titanium-containing solid catalyst component for highly active high isotactic polyolefins. This invention uses alkoxymagnesium particles as a support, and then pretreats the alkoxymagnesium particles using titanate compound a and polysiloxane substance b as protective agents; then, it uses two or more carboxylic acid ester compounds c and polyol ester compounds d as internal electron donors. The prepared catalyst component exhibits high polymerization activity and a high isotactic index during the polymerization of α-olefins, without the need for deashing.

[0007] The titanium-containing solid catalyst component provided by this invention includes the reaction products of the following components:

[0008] A) Alkoxy magnesium particles;

[0009] B) Particulate protectant, said particulate protectant comprising a) titanate compounds and b) polysiloxane substances;

[0010] C) Electron-donating compounds, said electron-donating compounds comprising c) carboxylic acid esters and d) polyol esters; and

[0011] D) Titanium-containing halides.

[0012] According to some embodiments of the present invention, the alkoxymagnesium in A) is a solid substance as shown in Formula I.

[0013] Mg(OR9) 2-p (OR 10 ) p Formula I

[0014] In Equation I, R9 and R 10 Whether identical or different, each is an alkyl group with 1-8 carbon atoms, 0≤p≤2. According to the present invention, the alkoxymagnesium represented by Formula I only indicates the composition and content of each alkoxy group in the alkoxymagnesium, and does not represent the specific structure of the alkoxymagnesium. Specifically, Mg(OEt)(OiPr) only indicates that the molar ratio of ethoxy to isopropoxy in the alkoxymagnesium compound is 1. It can be a mixture of magnesium diethoxy and magnesium diisopropoxy with a molar ratio of 1, or an ethoxyisopropoxymagnesium compound, or a mixture of all three; it can be a mixture of alkoxymagnesium compounds with various structures where the total molar ratio of ethoxy to isopropoxy is 1. Wherein Et represents ethyl, and iPr represents isopropyl. Preferably R 9 and R 10 The derivatives are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-hexyl, and (2-ethyl)hexyl, respectively; more preferably, R9 and R... 10 The same applies, meaning that the alkoxymagnesium represented by general formula (II) is specifically selected from one or more of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, dihexyloxymagnesium, and di(2-ethyl)hexyloxymagnesium. More preferably, it is diethoxymagnesium or a mixture of diethoxymagnesium and other alkoxymagnesiums.

[0015] According to an embodiment of the present invention, the structure of the titanate compound in the B) particulate protectant is as shown in Formula II:

[0016] (R 1 O) a Ti(OR 2 ) b (OR 3 ) c X d Formula II

[0017] In Equation II, R 1 R 2 and R 3 They can be the same or different, selected from H and alkyl groups, especially C1-C. 10 The alkyl group, X, is selected from alkoxy groups preferably having 1-10 carbon atoms, carboxyl groups preferably having 1-10 carbon atoms, chlorine, sulfonic acid, phosphoric acid, and sulfate groups, and a, b, c, and d are independent integers from 0 to 4, and a+b+c+d=4. Preferably, the titanate ester is 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, more preferably one or more of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.

[0018] According to an embodiment of the present invention, the molar ratio of the titanate compound to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0019] According to an embodiment of the present invention, the structure of the polysiloxane-based substance in B) of the particulate protectant is as shown in Formula III:

[0020] (R1R2R3)SiO[(R7R8)SiO] n ···[(R p R q )SiO] m Si(R4R5R6) Formula III

[0021] In Formula III, R1, R2, R3, R4, R5, R6, R7, R8, R p and R q Whether the groups are the same or different, each group is independently selected from alkyl groups with 1-12 carbon atoms, alkenyl groups with 1-12 carbon atoms, cycloalkyl groups with 3-10 carbon atoms, aryl groups with 6-20 carbon atoms, substituted or unsubstituted aromatic groups, hydrogen, hydroxyl groups, alkoxy groups with 1-12 carbon atoms, acetoxy groups, chlorine, carbon functional groups, and polyether chains; the degree of polymerization n+m is an integer from 2 to 100. According to embodiments of the present invention, the polysiloxane material is selected from polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethylhydrosiloxane, polyhydroxyhydrosiloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyethersiloxane, polycarboxylic acidsiloxane, polyol hydroxysiloxane, polyphenol hydroxysiloxane, polythiol siloxane, and other modified polysiloxanes, preferably one or more of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, polyether-modified siloxane, and nitrile-containing siloxane. There are no particular limitations on the number-average molecular weight and viscosity of the polysiloxane; as long as the effects and functions described in the present invention can be achieved, they are within the scope of the present invention.

[0022] The aforementioned polymethylsiloxanes, also known as methyl silicone oils, have different number-average molecular weights and viscosities due to differences in their average degree of polymerization (n value), but all possess the functions and effects described in this invention and are preferred polysiloxanes b in this invention. For example, polymethylhydrosiloxanes with number-average molecular weights Mn = 1700-3200 (n = 29-55, viscosity 12-45 cSt) and Mn ≈ 390 (n ≈ 6) are preferred polysiloxanes in this invention.

[0023] According to an embodiment of the present invention, in B), the molar ratio of the polysiloxane substance in b) to the magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0024] According to embodiments of the present invention, in C), the carboxylic acid ester compound c) is selected from benzoic acid monoesters or phthalic acid esters as shown in Formula IV.

[0025]

[0026] In Formula IV, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 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 groups, preferably, at least three of R3-R6 are hydrogens, more preferably, the carboxylic acid ester compound is 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, phthalic acid ester, etc. 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, pentyl hexyl phthalate, and at least two of the isomers of the above substances.

[0027] According to an embodiment of the present invention, the molar ratio of the carboxylic acid ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0028] According to an embodiment of the present invention, in C), d) the polyol ester compound is selected from diol ester compounds as shown in Formula V.

[0029]

[0030] In formula V, R1-R2 may be the same or different, and each represents a substituted or unsubstituted linear chain C1-C1. 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 20aryl, 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 A fused-ring aryl group; or at least one of R3-R6 forming a ring with at least one of R7-R8.

[0031] According to embodiments of the present invention, the polyol ester compound in d) of C) can be 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 dinepentate, or 2,4-pentanediol dibenzoate. At least one of the following: formate, 2-methyl-1,3-pentanediol benzoate, 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, preferably at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2,4-pentanediol dibenzoate.

[0032] According to an embodiment of the present invention, the molar ratio of the polyol ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0033] According to an embodiment of the present invention, the titanium-containing halide in D) is as shown in Formula VI:

[0034] TiX n (OR7) 4-n Formula VI

[0035] 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.

[0036] According to embodiments of the present invention, in formula VI, X is chlorine, R7 is a C1-C5 alkyl group, and n is an integer from 0 to 4. According to a preferred embodiment of the present invention, the titanium-containing halide is titanium tetrachloride.

[0037] According to an embodiment of the present invention, the molar ratio of the titanium-containing halide to the alkoxymagnesium particles is (0.5-100):1, preferably (1-50):1.

[0038] In this invention, the catalyst component can be prepared using conventional methods for preparing olefin catalyst components in the art; preferably, the solid catalyst component of this invention is prepared using the following method. Alkoxymagnesium particles are suspended in an inert diluent to form a suspension, a protective agent is added for specific treatment, and then the suspension is contacted with a titanium-containing halide and two or more compounded internal electron donors to obtain a solid dispersion system, commonly referred to as the mother liquor. The mother liquor is filtered, and the resulting solid material is suspended in a solution containing titanium tetrachloride for contact treatment, commonly referred to as titanium treatment; then, after filtration, washing, and drying, the solid component of this invention is obtained.

[0039] According to an embodiment of the present invention, in step C), the contact temperature of c) and d) is -40-200℃, preferably -20-150℃, and the reaction time is 1min-20h, preferably 5min-8h.

[0040] The inert diluent used in the formation of the mother liquor in the above method can be at least one selected from hexane, heptane, octane, decane, benzene, toluene, and xylene. The amount of each component used in the formation of the mother liquor, particularly the amount of the inert diluent, is typically 0.5-100 mol, preferably 1-50 mol. The contact temperature is typically -40 to 200°C, preferably -20 to 150°C; the contact time is typically 1 minute to 20 hours, preferably 5 minutes to 8 hours.

[0041] In the titanium treatment process described above, an inert diluent, such as at least one selected from hexane, heptane, octane, decane, benzene, toluene, and xylene, may be selectively added to the titanium tetrachloride-containing solution. The amount of each component in the titanium tetrachloride-containing solution, calculated per mole of magnesium, is 0.5-100 moles of titanium compound, preferably 1-50 moles; the amount of inert diluent is typically 0-100 moles, preferably 0-50 moles. The number of titanium treatments is 0-10 times, preferably 1-5 times.

[0042] Furthermore, during the titanium treatment process, the aforementioned electron donor compound may be selectively added, wherein the amount of internal electron donor is typically 0.005-10 mol, preferably 0.01-1 mol. The titanium treatment temperature is typically 0-200°C, preferably 30-150°C; the contact time is typically 1 minute-20 hours, preferably 5 minutes-6 hours.

[0043] According to the solid catalyst composition of the present invention, the content of titanium atoms is 1.0-8.0 wt%, preferably 1.6-6.0 wt%; the content of magnesium atoms is preferably 10-70 wt%, preferably 15-40 wt%; the content of halogen atoms is 20-86 wt%, preferably 36-80 wt%; and the total content of internal electron donor compounds is 2-30 wt%, preferably 3-20 wt%.

[0044] Another object of the present invention is to provide a catalyst for olefin polymerization, said catalyst comprising the reaction product of the following components:

[0045] (1) The aforementioned catalyst components;

[0046] (2) Organoaluminum compounds;

[0047] (3)Optionally, external electron-donating compounds.

[0048] According to an embodiment of the present invention, the organoaluminum compound is of formula AlR' m X' 3-m The organoaluminum compound shown, wherein R' is selected from hydrogen, C1-C 20 Alkyl and C6-C 20 Any of the aryl groups; X' is a halogen, and m is an integer from 1 to 3.

[0049] According to an embodiment of the present invention, the external electron donor compound is of formula R. 4 p R 5 q Si(OR 6 ) 4-p-q The organosilicon compound shown, wherein R 4 and R 5 Independently selected from halogens, hydrogen atoms, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl and C1-C 20 Any one of the haloalkyl groups, R 6 Selected from C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl and C1-C 20Any one of the haloalkyl groups; p and q are integers from 0 to 3, and p + q < 4.

[0050] According to an embodiment of the present invention, 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.

[0051] The present invention also provides an olefin polymerization method, comprising contacting an olefin with the catalyst under olefin polymerization conditions, wherein 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 groups.

[0052] The olefin polymerization method of the present invention can be used for homopolymerization of olefins, and can also be used for copolymerization of multiple olefins. Specific examples of α-olefins 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.

[0053] According to an embodiment of the present invention, the olefin polymerization conditions are: temperature 0-150℃, preferably 60-130℃; time 0.1-5h, preferably 0.5-4h; pressure 0.01-10MPa, preferably 0.5-5MPa.

[0054] The beneficial effects of this invention are:

[0055] This invention uses a small amount of a mixture of halogenated substances as a halogenating agent. When titanate compounds and / or inert organic solvents are added during the reaction, the reaction is easier to control and the particle morphology is better maintained.

[0056] This invention uses alkoxymagnesium particles as a support, and then employs carboxylic acid ester compound a, polyol ester compound b, and polysiloxane compound c as internal electron donors. The prepared catalyst component exhibits high polymerization activity and a high polymer isotactic index during the polymerization of α-olefins. The resulting catalyst has high activity and a high isotactic index, making it particularly suitable for developing high-rigidity, low-ash polyolefin resins. Detailed Implementation

[0057] The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the following embodiments.

[0058] It should be noted that the evaluation of the alkoxymagnesium particles and polyolefins prepared in the embodiments of the present invention was carried out using the following methods:

[0059] 1. The particle size and particle size distribution of alkoxy magnesium compounds and catalysts were measured using the Malvern Mastersizer™ 2000 hexane dispersant laser diffraction method, where SPAN = (D90-D10) / D50.

[0060] 2. The content of internal electron donors in the olefin polymerization catalyst components was determined by gas chromatography.

[0061] 3. The activity of the polymer is calculated by dividing the weight of the final polymer by the weight of the initially added catalyst components.

[0062] 4. The isotactic index (II) of polypropylene is tested as follows: 2 grams of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to constant weight, and the isotacticity is calculated using the following formula:

[0063] Isotacticity II = Mass of extracted polymer / 2 × 100%.

[0064] 5. The isotactic index (II) of polybutene-1 is tested as follows: 3 grams of the sample is dried in a vacuum oven at 75±5℃ for 60 minutes. The polybutene-1 sample is then moistened with ether in an extractor and extracted with ether by boiling for 12 hours. The residue is then dried to constant weight, and the isotacticity is calculated using the following formula:

[0065] Isotacticity II = mass of polybutene-1 after extraction / 3 × 100%.

[0066] 6. Propylene Polymerization: In a 5-liter high-pressure reactor, nitrogen gas was used to purge at 70°C for 1 hour. Then, at room temperature, 5 mL of a triethylaluminum solution in hexane (0.5 mmol / mL), 1 mL of a cyclohexylmethyldimethoxysilane (CHMMS) solution in hexane (0.10 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst were introduced into the nitrogen gas stream. The high-pressure reactor was closed, and 1.0 L (under standard conditions) of hydrogen and 2.0 L of liquid propylene were introduced. The temperature was raised to 70°C within 10 minutes with stirring. After polymerization at 70°C for 2 hours, stirring was stopped, unpolymerized propylene monomers were removed, and the polymer was collected for testing.

[0067] 7. Butene-1 Polymerization: Use a 5L high-pressure polymerization reactor. After pressurizing and leak testing, and verifying that the reactor is airtight, start the reactor agitator and adjust the speed to 100rpm. Heat the polymerization reactor to 70℃~75℃, use a vacuum pump to statically evacuate for at least 2 minutes, and fully purge the reactor with nitrogen at least 5 times. Then, purge the reactor with nitrogen to 0.05MPa~0.10MPa.

[0068] Under nitrogen protection, the prepared triisobutylaluminum solution and dicyclopentyldimethoxysilane solution were added to the feeder. Using a syringe containing a catalyst sample (mass m0), the mixture in the feeder was drawn up and added to the mixture. The feed valve between the polymerization reactor and the feeder was opened, and the mixture containing the catalyst was added to the reactor. The syringe was rinsed with 5 mL of hexane and added to the polymerization reactor. The feed valve and vent valve were then closed. The hydrogen valve was opened, and 0.85 L (under standard conditions) of hydrogen was added. The hydrogen valve was then closed. The liquid butene-1 feed valve was opened, and 2.3 L of liquid butene-1 was added. The feed valve was then closed. The stirring speed was adjusted to 300 rpm, and the reactor was heated using the temperature-regulating water system. Timing was started when the reactor temperature reached 70°C, and the reaction was carried out for 1 hour. The reactor temperature was maintained at 70°C ± 1°C using the temperature-regulating water system.

[0069] Preparation Example 1

[0070] Alkoxymagnesium particles were prepared according to Example 6 of patent CN102453150B: After fully purging a 16L pressure reactor equipped with a stirrer with nitrogen, 10200mL of ethanol, 300mL of 2-ethylhexanol, 6g of iodine, and 4g of magnesium chloride were added to the reactor and dissolved. The mixture was stirred and heated until the reflux temperature of the reaction system was reached. Then, 640g of magnesium powder was added sequentially. The reaction was continued until completion, i.e., no more hydrogen was emitted. The mixture was then washed, separated, and dried. The resulting diekoxymagnesium support had an average particle size (D50) of 47.0μm, a particle size distribution index of 0.82, and a magnesium isooctoxy content of 1.7wt%.

[0071] Example 1

[0072] 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, 3.0 mL of polymethylsiloxane with a kinematic viscosity of 100 cSt, and 2.0 mL of tetraethyl titanate were added. The mixture was heated to 60 °C and held at that temperature for 8 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 were added. The mixture was heated to 80 °C, and then suspension X1 was added. The mixture was slowly heated to 115 °C. During the heating process, 3.0 mL of di-n-butyl phthalate (DNBP), 1.0 mL of diethyl phthalate, and 1.0 mL of 3,5-heptanediol dibenzoate were added. The mixture was held at that temperature for 2 hours, and then the liquid was 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 1.

[0073] Example 2

[0074] The solid catalyst component was prepared according to the method in Example 1, except that 1.0 ml of polymethylsiloxane and 1.0 ml of tetraethyl titanate with a kinematic viscosity of 100 cSt were added instead of 3.0 ml of polymethylsiloxane and 2.0 ml of tetraethyl titanate with a kinematic viscosity of 100 cSt. Test data are shown in Table 1.

[0075] Example 3

[0076] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of polymethylsiloxane and 2.0 ml of tetrabutyl titanate with a kinematic viscosity of 10 cSt were added instead of 3.0 ml of polymethylsiloxane and 2.0 ml of tetraethyl titanate with a kinematic viscosity of 100 cSt. Test data are shown in Table 1.

[0077] Example 4

[0078] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of epoxy-modified polymethylsiloxane and 2.0 ml of tetraisopropyl titanate with a kinematic viscosity of 100 cSt were added instead of 3.0 ml of polymethylsiloxane and 2.0 ml of tetraethyl titanate with a kinematic viscosity of 100 cSt. The test data are shown in Table 1.

[0079] Example 5

[0080] The solid catalyst component was prepared according to the method in Example 1, except that 6.0 ml of polymethylphenylsiloxane and 6.0 ml of tetraethyl titanate with a kinematic viscosity of 100 cSt were added instead of 3.0 ml of polymethylsiloxane and 2.0 ml of tetraethyl titanate with a kinematic viscosity of 100 cSt. Test data are shown in Table 1.

[0081] Example 6

[0082] The solid catalyst component was prepared according to the method in Example 1, except that 1.0 ml of 2,4-pentanediol dibenzoate was added instead of 1.0 ml of 3,5-heptanediol dibenzoate. The test data are shown in Table 1.

[0083] Example 7

[0084] The solid catalyst component was prepared according to the method in Example 1, except that 3.8 ml of di-n-butyl phthalate and 0.2 ml of diethyl phthalate were added instead of 3.0 ml of di-n-butyl phthalate and 1.0 ml of diethyl phthalate. The test data are shown in Table 1.

[0085] Example 8

[0086] The solid catalyst component was prepared according to the method in Example 1, except that 0.5 ml of di-n-butyl phthalate and 3.5 ml of diethyl phthalate were added instead of 3.0 ml of di-n-butyl phthalate and 1.0 ml of diethyl phthalate. The test data are shown in Table 1.

[0087] Example 9

[0088] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of diisobutyl phthalate and 1.0 ml of diisopropyl phthalate were added instead of 3.0 ml of di-n-butyl phthalate and 1.0 ml of diethyl phthalate. The test data are shown in Table 1.

[0089] Example 10

[0090] The solid catalyst component was prepared according to the method in Example 1, except that 0.2 ml of 3,5-heptanediol dibenzoate was added instead of 1.0 ml of 3,5-heptanediol dibenzoate. The test data are shown in Table 1.

[0091] Comparative Example 1

[0092] The solid catalyst component was prepared according to the method in Example 1, except that 3.0 ml of polymethylsiloxane with a kinematic viscosity of 100 cSt and 2.0 ml of tetraethyl titanate were not added. The test data are shown in Table 1.

[0093] Comparative Example 2

[0094] The solid catalyst components were prepared according to the method in Example 1, except that 5.0 ml of di-n-butyl phthalate was added instead of 3.0 ml of di-n-butyl phthalate, 1.0 ml of diethyl phthalate, and 1.0 ml of 3,5-heptanediol dibenzoate. The test data are shown in Table 1.

[0095] Table 1 Test data from the embodiments

[0096]

[0097] As can be seen from the data of the 10 examples and 2 comparative examples in Table 1, the present invention uses alkoxymagnesium particles with a specific composition as a support, and then pretreats the alkoxymagnesium using titanate compound a and polysiloxane substance b as protective agents; then, it uses two or more carboxylic acid ester compounds c and polyol ester compounds d as internal electron donors. The prepared catalyst component exhibits high polymerization activity and a high polymer isotactic index during the polymerization of α-olefins, and does not require deashing. It is suitable for the development of higher performance polyolefin grades, and the catalyst has broad application prospects.

[0098] Although the present invention has been described above with reference to some embodiments, various modifications can be made thereto without departing from the scope of the invention, and equivalent substitutions can be made for the substances therein. The features in the various embodiments disclosed herein can be combined with each other in any manner; the lack of an exhaustive description of these combinations in this specification is merely for the purpose of saving space and resources. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but rather to all technical solutions falling within the scope of the claims.

Claims

1. A titanium-containing solid catalyst component, comprising the reaction product of the following components: A) Alkoxy magnesium particles; B) Particulate protectant, said particulate protectant comprising a) titanate compounds and b) polysiloxane substances; C) an electron-donating compound, said electron-donating compound comprising c) two or more carboxylic acid ester compounds, d) a polyol ester compound; and D) Titanium-containing halides; The alkoxymagnesium is as shown in Formula I. Mg(OR9) 2-p (OR 10 ) p Formula I In Equation I, R9 and R 10 They are the same, each being an alkyl group with 1-8 carbon atoms, and 0≤p≤2; The carboxylic acid ester compounds are selected from benzoic acid monoesters or phthalic acid esters as shown in Formula IV. In Formula IV, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 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 compounds are selected from diol ester compounds as shown in Formula V. In formula V, R1-R2 may be the same or different, and each represents a substituted or unsubstituted linear chain C1-C1. 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 A fused-ring aryl group; or at least one of R3-R6 forming a ring with at least one of R7-R8.

2. The titanium-containing solid catalyst component according to claim 1, characterized in that, In Equation I, R9 and R 10 Same, R 9 and R 10 The compounds are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-hexyl, and (2-ethyl)hexyl, respectively.

3. The titanium-containing solid catalyst component according to claim 1, characterized in that, The alkoxy magnesium is selected from one or more of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, diisobutoxy magnesium, dipentoxy magnesium, dihexoxy magnesium, and di(2-ethyl)hexoxy magnesium.

4. The titanium-containing solid catalyst component according to any one of claims 1-3, characterized in that, The structures of titanate compounds are shown in Formula II: (R 1 O) a Ti(OR 2 ) b (OR 3 ) c X d Formula II In Equation II, R 1 R 2 and R 3 They may be the same or different, each independently selected from H and alkyl, X is 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.

5. The titanium-containing solid catalyst component according to claim 4, characterized in that, In Equation II, R 1 R 2 and R 3 Whether the two are the same or different, they are each independently selected from H and C1-C. 10 Alkyl group, X is selected from alkoxy group with 1-10 carbon atoms, carboxyl group with 1-10 carbon atoms, chlorine group, sulfonic acid group, phosphoric acid group and sulfate group, a, b, c and d are independent integers from 0 to 4, and a+b+c+d=4.

6. The titanium-containing solid catalyst component according to claim 4, 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.

7. The titanium-containing solid catalyst component according to any one of claims 1-3, characterized in that, The molar ratio of magnesium in the titanate compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of magnesium in the polysiloxane compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of magnesium in the carboxylic acid ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of magnesium in the polyol ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; and / or the molar ratio of magnesium in the titanium-containing halide compound to magnesium in the alkoxy magnesium particles is (0.5-100):

1.

8. The titanium-containing solid catalyst component according to claim 7, characterized in that, The molar ratio of magnesium in the titanate compound to magnesium in the alkoxymagnesium particles is (0.02-2):1; and / or the molar ratio of magnesium in the polysiloxane compound to magnesium in the alkoxymagnesium particles is (0.02-2):1; and / or the molar ratio of magnesium in the carboxylic acid ester compound to magnesium in the alkoxymagnesium particles is (0.02-2):1; and / or the molar ratio of magnesium in the polyol ester compound to magnesium in the alkoxymagnesium particles is (0.02-2):1; and / or the molar ratio of magnesium in the titanium-containing halide to magnesium in the alkoxymagnesium particles is (1-50):

1.

9. The titanium-containing solid catalyst component according to any one of claims 1-3, characterized in that, The polysiloxanes are selected from one or more of the following: polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethylhydrosiloxane, polyhydroxyhydrosiloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyethersiloxane, polycarboxylic acid siloxane, polyol hydroxysiloxane, polyphenol hydroxysiloxane, polythiol siloxane, and other modified polysiloxanes.

10. The titanium-containing solid catalyst component according to claim 9, characterized in that, The polysiloxane material is selected from one or more of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, and polyether-modified siloxane.

11. The titanium-containing solid catalyst component according to any one of claims 1-3, characterized in that, In Formula IV, at least three of R3-R6 are hydrogen atoms.

12. The titanium-containing solid catalyst component according to claim 11, characterized in that, The carboxylic acid ester compounds 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. 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, pentyl hexyl phthalate, and at least two isomers of the above substances.

13. The titanium-containing solid catalyst component according to any one of claims 1-3, 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.

14. The titanium-containing solid catalyst component according to claim 13, characterized in that, In formula VI, X is chlorine and R7 is a C1-C5 alkyl group.

15. A catalyst for olefin polymerization, comprising the reaction product of the following components: (1) The catalyst component according to any one of claims 1-14; (2) Organoaluminum compounds; (3)Optionally, external electron-donating compounds.

16. An olefin polymerization method comprising contacting an olefin with the catalyst of claim 15 under olefin polymerization conditions.

17. The olefin polymerization method according to claim 16, 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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