Catalyst component containing furoate compound and preparation method thereof, olefin polymerization catalyst, olefin polymerization method and olefin polymer

Abstract

The invention belongs to the technical field of petrochemical engineering, and provides a furoate compound-containing catalyst component and a preparation method thereof, an olefin polymerization catalyst, an olefin polymerization method and an olefin polymer. The catalyst component comprises a magnesium element, a titanium element, halogen, an internal electron donor compound and a furoate compound, and the furoate compound has a structure as shown in a formula (I). According to the catalyst disclosed by the invention, the furoate compound is introduced in the preparation process of the catalyst, so that the isotactic index of the polymer can be improved and the generation of small-molecular-weight polymers can be inhibited on the premise of keeping the high flowability of the polymer.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemical industry, and relates to a catalyst component containing a furoate ester compound and a preparation method thereof, an olefin polymerization catalyst, an olefin polymerization method and an olefin polymer. Background Art

[0002] In recent years, with the continuous expansion of polypropylene production capacity, general-purpose polypropylene resin has been seriously oversupplied, but the market prospects of high-value-added polyolefin resins are still broad. Among them, high-flow, high-rigidity and impact-resistant polypropylene has a good balance of rigidity and toughness and is easy to process, and its market demand has increased year by year. The improvement of the fluidity of resin products can reduce the processing temperature and injection pressure of injection molded products, which is conducive to the thin-walled products. With the large-scale, complex, and energy-saving injection molded products, the requirements for the fluidity of polypropylene raw materials are getting higher and higher. With the continuous advancement of catalyst preparation technology, more and more methods to improve the fluidity of polypropylene resins are using hydrogen adjustment methods, using the chain transfer agent effect of hydrogen to adjust the molecular weight of polypropylene resin products, and then adjust the fluidity of the resin. However, when using the hydrogen adjustment method to adjust the molecular weight, it is inevitable that the isotactic index of the resin will change. Usually, the isotactic index of the polymer will decrease with the increase of hydrogen dosage. The reduction of the isotactic index will lead to a decrease in the crystallinity of the polymer, and the fracture strength, tensile strength and flexural modulus will all decrease to varying degrees, affecting the mechanical properties of the resin.

[0003] In order to resolve the contradiction between high fluidity and high rigidity, it is usually necessary to improve the comprehensive performance of the catalyst so that it can maintain a high stereo-orientation ability and the ability to inhibit the production of ultra-low molecular weight products under the premise of maintaining a high hydrogen adjustment sensitivity under high hydrogen concentration. Only in this way can the polymer have a higher melt flow rate (MFR), a higher molecular weight and a higher isotactic index, and the resin product can have both high mechanical properties and high processability. At the same time, a higher molecular weight and a higher isotactic index can also reduce the odor and dissolution rate of the resin, which is more conducive to expanding the application of the product in automotive interiors, household appliances, food packaging, medical and health products, etc. Summary of the invention

[0004] In view of the above-mentioned needs, the present invention designs and prepares a polyolefin catalyst, which has a high stereospecificity and a high molecular weight at different hydrogen concentrations. In particular, at high hydrogen concentrations, the propylene homopolymer product has a high isotactic index and a high weight-average molecular weight, and has the characteristics of a low content of small molecular weight polymers and a high content of high molecular weight polymers, which can meet the preparation requirements of low odor, low dissolution, high fluidity and high rigidity polyolefin resins.

[0005] In order to solve the above problems in the prior art, the present invention provides a solid catalyst component for olefin polymerization, a catalyst preparation method, an olefin polymerization catalyst, and application of the catalyst in olefin polymerization reactions.

[0006] In one aspect, the present invention provides a catalyst component, comprising magnesium, titanium, halogen, an internal electron donor compound and a furoate compound, wherein the furoate compound has a structure shown in formula (I);

[0007]

[0008] In formula (I), R1, R2, and R3 are each independently selected from hydrogen, halogen, C 1-10 Straight or branched alkanes, C 2-20 Mono- or poly-aliphatic ethers, C 2-10 Fatty acid esters or C 6-20 Aromatic acid esters, C 6-20 Cycloalkane or aromatic hydrocarbon or aromatic hydrocarbon with a substituent; said C 1-10 The straight or branched alkane has a halogen substituent or an N substituent;

[0009] R4 is C 1-20 Straight or branched chain alkanes, C 2-20 Mono- or poly-aliphatic ethers, C 2-10 Fatty acid esters or C 6-20 Aromatic acid esters, C 6-20 Cycloalkanes or aromatic hydrocarbons and aromatic hydrocarbons with substituents.

[0010] As a specific embodiment of the present invention, the magnesium element and the halogen element are from magnesium halide; the general formula of the magnesium halide is MgY2, Y is preferably bromine, chlorine or iodine, and more preferably, the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, preferably magnesium dichloride.

[0011] As a specific embodiment of the present invention, the titanium element comes from a titanium-containing compound, and the general formula of the titanium compound is TiX m (OR) 4-m , wherein X is halogen, preferably chlorine, bromine or iodine, and R is C 1-20 A hydrocarbon group, m is an integer of 1 to 4; more preferably, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium monochloride, preferably titanium tetrachloride.

[0012] As a specific embodiment of the present invention, the internal electron donor may be various internal electron donors commonly used in the art, for example, one or more alkyl esters selected from aliphatic or aromatic carboxylic acids. For example, it may be selected from C1-4 Saturated fatty acid C 1-4 Alkyl esters, C 7-8 Aromatic carboxylic acid C 1-4 Alkyl esters. Specifically, for example, it can be one or more of diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, phthalic acid, 1,3-dipentyl phthalate, methyl formate, ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, and butyl butyrate; preferably, di-n-butyl phthalate or diisobutyl phthalate is used.

[0013] As a specific embodiment of the present invention, based on each mole of magnesium halide, the titanium element is 0.5 to 25 moles, preferably 1 to 20 moles; the internal electron donor compound is 0.01 to 1 mole, preferably 0.04 to 0.5 mole; and the furoate compound is 0.005 to 1 mole, preferably 0.01 to 0.05 mole.

[0014] As a specific embodiment of the present invention, the above-mentioned furoate ester compounds include but are not limited to: methyl furoate, ethyl furoate, propyl furoate, isopropyl furoate, butyl furoate, isobutyl furoate, tert-butyl furoate, pentyl furoate, methyl 2-furoate isopentyl furoate, n-hexyl furoate, isohexyl furoate, octyl furoate, dodecyl furoate, octadecyl furoate, benzyl furoate, allyl furoate, ethyl 5-bromo-2-furoate, 2-furoyl acetic acid Methyl ester, 5-formylfuran-2-carboxylic acid methyl ester, 3-methyl-2-furancarboxylic acid methyl ester, 4-bromofuran-2-carboxylic acid methyl ester, 5-nitro-2-furancarboxylic acid methyl ester, 5-chloromethyl-2-furancarboxylic acid ethyl ester, 5-benzoyl-2-furancarboxylic acid methyl ester, 5-(chloromethyl)-2-furancarboxylic acid methyl ester, 4,5-dimethyl-2-furancarboxylic acid ethyl ester, 2,5-dihydro-2,5-dimethoxy-2-furancarboxylic acid methyl ester.

[0015] Among the above-mentioned furoate ester compounds, preferred are methyl furoate, ethyl 4,5-dimethyl-2-furoate, and methyl 2,5-dihydro-2,5-dimethoxy-2-furoate.

[0016] In another aspect, the present invention provides a method for preparing any one of the above catalyst components, comprising the steps of:

[0017] Step A, contacting a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound, and an emulsifier in a solvent I to form a solution;

[0018] Step B, contacting the solution with a titanium compound in the presence of a precipitation aid to obtain a mixture;

[0019] Step C, contacting the mixture obtained in step B with an internal electron donor compound III, changing the temperature, precipitating a solid, and filtering;

[0020] Step D, dispersing the solid in solvent II and contacting it with a furoate compound IV, filtering, washing and drying the solid to obtain the olefin polymerization catalyst component.

[0021] As a specific embodiment of the present invention, the amount of the organic epoxy compound is 0.1 to 10 moles, preferably 0.4 to 4 moles, per mole of magnesium halide; the amount of the organic phosphorus compound is 0.1 to 10 moles, preferably 0.4 to 5 moles.

[0022] As a specific embodiment of the present invention, the conditions for contacting I in step A include: a temperature of 10 to 100° C., preferably 30 to 80° C.; a time of 0.05 to 6 hours, preferably 0.1 to 4 hours;

[0023] The conditions of contacting II in step B include: temperature of -30°C to 60°C, preferably -20°C to 30°C; time of 0.1 to 5 hours, preferably 0.2 to 4 hours;

[0024] The conditions of contacting III in step C include: temperature of 0 to 120°C, preferably 20 to 80°C; time of 0.1 to 5 hours, preferably 0.2 to 2 hours;

[0025] The conditions for contacting IV in step D include: a temperature of 0 to 120° C., preferably 10 to 80° C.; a time of 0.1 to 5 hours, preferably 0.2 to 2 hours;

[0026] The stirring speed of the above steps can be 50-1000 rpm, preferably 200-800 rpm. The present invention has no special requirements on the filtering, washing and drying methods and conditions, which can be carried out with reference to the prior art and will not be described in detail here.

[0027] As a specific embodiment of the present invention, the organophosphorus compound can be various organophosphorus compounds commonly used in the art, and can be one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite, among which tributyl phosphate or tripentyl phosphate is preferred.

[0028] As a specific embodiment of the present invention, the organic epoxy compound is C 2-8 Aliphatic olefins (2-8 carbon atoms), C 2-8One or more of the oxidation products of halogenated aliphatic olefins (with 2-8 carbon atoms), specifically, preferably, one or more of ethylene oxide, propylene oxide, ethylene chloride, epichlorohydrin, butylene oxide, butadiene oxide, butadiene dioxide, methyl glycidyl ether and diglycidyl ether, preferably epichlorohydrin.

[0029] As a specific embodiment of the present invention, the precipitation aid of the present invention can be various precipitation aids commonly used in the art, for example, it can be preferably one or more of organic acids, organic anhydrides, organic ethers and organic ketones, specifically, for example, it can be acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether, preferably phthalic anhydride.

[0030] As a specific embodiment of the present invention, the amount of the titanium-containing compound is 0.5 to 25 moles, preferably 1 to 20 moles, per mole of magnesium halide.

[0031] As a specific embodiment of the present invention, the amount of the internal electron donor compound used is 0.01 to 1 mole, preferably 0.04 to 0.5 mole, calculated as magnesium halide.

[0032] As a specific embodiment of the present invention, the furoate compound is used in an amount of 0.005 to 1 mole, preferably 0.01 to 0.5 mole, per mole of magnesium halide.

[0033] As a specific embodiment of the present invention, the amount of the organic epoxy compound used is 0.1 to 10 moles, preferably 0.4 to 4 moles, per mole of magnesium halide.

[0034] As a specific embodiment of the present invention, the amount of the organic phosphorus compound used is 0.1 to 10 moles, preferably 0.4 to 5 moles, per mole of magnesium halide.

[0035] As a specific embodiment of the present invention, the emulsifier is 0.1 g to 1 g per gram of magnesium halide compound.

[0036] The emulsifier in the catalyst component preparation method of the present invention is a poly (meth) acrylate polymer, which can be a pour point depressant product with the trademark T602 purchased from an additive company.

[0037] The solvent I of the present invention can be any commonly used solvent in the art that can dissolve a mixture of magnesium compounds, organic epoxy compounds, organic phosphorus compounds and internal electron donor compounds, specifically a mixed reagent of aromatic hydrocarbons and saturated alkanes, and can be a mixture of toluene, ethylbenzene, benzene, xylene, chlorobenzene and hexane, heptane, octane and decane, or white oil, wherein a mixture of toluene and hexane, toluene and white oil, or toluene and decane is preferred. In the solvent, the mass ratio of aromatic hydrocarbons to saturated alkanes is 1:1000 to 1000:1, preferably 1:100 to 100:1.

[0038] The solvent II of the present invention can be any one of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane.

[0039] In another aspect, the present invention provides any of the olefin polymerization catalysts comprising:

[0040] Catalyst components;

[0041] Organoaluminum compounds;

[0042] Optionally, an external electron donor compound.

[0043] The molar ratio of the aluminum element in the organic aluminum to the titanium element in the catalyst component is 1 to 1500:1, preferably 10 to 1000:1.

[0044] As a specific embodiment of the present invention, the molar ratio of the external electron donor compound to the titanium element in the catalyst component is 0 to 500:1, more preferably 0 to 200:1.

[0045] As a specific embodiment of the present invention, the organoaluminum compound is an alkylaluminum compound; the chemical formula of the alkylaluminum compound is AlR' n’ X' 3-n’ , where R' is C 1-8 The alkyl or halogenated alkyl group is selected from the group consisting of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogenate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al(n-C6H 13 )3 and Al(n-C8H 17 )3; the alkyl aluminum compound is triethylaluminum and / or triisobutylaluminum.

[0046] As some embodiments of the present invention, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is 1 to 1500:1, preferably 10 to 1000:1.

[0047] As a specific embodiment of the present invention, the external electron donor compound is selected from one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds and organosilicon compounds.

[0048] As a specific embodiment of the present invention, the external electron donor compound is an organosilicon compound, the chemical formula of which is (R 13 )m'(R 14 )p'Si(OR 15 )q', where R 13 , R 14 and R 15 Each independently is C 1-18 Hydrocarbyl, preferably C 1-18 An alkane optionally containing a heteroatom, wherein the heteroatom is one or more of F, Cl, Br, N and I; m' and p' are each independently an integer of 0-2, q' is an integer of 1-3, and the sum of m', p' and q' is 4; R 13 and R 14 Each independently is C 3-10 Alkyl, C 3-10 Alkenyl, C 3-10 Alkylene, C 3-10 Substituted or unsubstituted cycloalkyl and C 6-10 R is one of substituted or unsubstituted aryl groups, optionally containing heteroatoms, wherein the heteroatoms are one or more of F, Cl, Br, N and I; 15 C 1-10 Alkyl, more preferably C 1-6 Alkyl, more preferably C 1-4 The alkyl group is more preferably a methyl group.

[0049] As a specific embodiment of the present invention, the external electron donor compound is cyclohexylmethyldimethoxysilane and / or dicyclopentyldimethoxysilane.

[0050] As a specific embodiment of the present invention, the organosilicon compound is selected from one or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, tert-hexyltrimethoxysilane and 2-ethylpiperidinyl-2-tert-butyldimethoxysilane; more preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane and / or dicyclopentyldimethoxysilane.

[0051] In another aspect, the present invention provides a method for olefin polymerization, comprising: subjecting an olefin to a homopolymerization reaction or a copolymerization reaction in the presence of the olefin polymerization catalyst according to any one of claims 6 to 8.

[0052] As a specific embodiment of the present invention, the olefin is selected from at least one of the compounds represented by formula (II);

[0053] CH2=CHR” Formula (II)

[0054] R" is hydrogen or C 1-6 of alkyl.

[0055] As a specific embodiment of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene;

[0056] As a specific embodiment of the present invention, the polymerization reaction conditions include: temperature of 50-100° C., time of 0.5-5 hours; molar ratio of hydrogen to propylene of 0-0.1, preferably 0-0.02.

[0057] In another aspect, the present invention provides an olefin polymer prepared by any of the above methods

[0058] As a specific embodiment of the present invention, when the molar ratio of propylene to hydrogen is ≤0.008, the isotactic index of the olefin polymer is ≥97.2%, the weight average molecular weight of the polymer is ≥248,000, and the content of small molecule polymer is low.

[0059] The above raw materials in the present invention can be prepared in-house or commercially available, and the present invention is not particularly limited thereto.

[0060] In the process of preparing the catalyst of the present invention, furoate compounds are introduced. The catalyst prepared by the method and the olefin polymerization method can further improve the isotactic index of the polymer and inhibit the generation of small molecular weight polymers while maintaining the high fluidity of the polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 The component distribution of propylene polymers prepared in Application Example 1 of the present invention and Comparative Application Example 1. DETAILED DESCRIPTION

[0062] The present invention is described in detail below through specific examples. These examples are only for illustration and are not intended to limit the application scope of the present invention.

[0063] The experimental method involved in the present invention is as follows:

[0064] (1) Propylene polymerization method

[0065] In a 5-liter autoclave, after nitrogen is fully replaced, 5 mL of triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol / mL), 1 mL of cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (the concentration of CHMMS is 0.1 mmol / mL), 10 mL of anhydrous hexane and 10 mg of catalyst components are added at room temperature. The autoclave is closed, and 4.5 L of hydrogen and 2.3 L of liquid propylene are added. The temperature is raised to 70°C, and the polymerization reaction is carried out at 70°C for 1 hour. After the reaction is completed, the reactor is cooled and stirring is stopped to discharge the reaction product to obtain an olefin polymer.

[0066] (2) Method for determining the content of each component in the catalyst

[0067] The titanium content was determined colorimetrically using a UV-visible spectrophotometer Model 722;

[0068] The magnesium content was measured by complexometric titration of magnesium ions and EDTA;

[0069] The halogen content was measured by AgNO3-NH4CNS back titration method;

[0070] Determination of internal electron donor content: using chromatography, decomposing the catalyst powder with dilute acid, extracting the internal electron donor compound with an extractant, and determining it with a liquid chromatograph;

[0071] Determination of furoate ester compound content: Agilent high-performance GC-MS was used for determination.

[0072] The isotacticity index (II) of propylene polymer is determined by the heptane extraction method: 2 grams of dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours, and the residue is dried to constant weight. The ratio of the obtained polymer weight (g) to 2 (g) is the isotactic index.

[0073] The melt flow index (MFR) of the polymer was measured using a 6932 melt flow index tester from CEAST, Italy, in accordance with GB / T3682-2000 standard;

[0074] Catalyst activity AC = (polymer weight) / (catalyst weight).

[0075] In the present invention, the organic raw materials involved were purchased from Bailingwei Chemical Reagent Co., Ltd., and the polymethacrylate compound used in some embodiments was pour point depressant T602, which was purchased from Liyang Wandefu Chemical Company.

[0076] Example 1

[0077] In a reactor that has been repeatedly replaced with high-purity nitrogen, 7.2g of anhydrous magnesium chloride, 40mL of toluene and 55mL of white oil, 6.0mL of epichlorohydrin, 30mL of tributyl phosphate and 3.5g of T602 are added in sequence, and stirred at 60°C for 2 hours. Then 2.0g of phthalic anhydride is added, and stirring is continued at 60°C for 1 hour. The solution is cooled to 10°C and 70mL of titanium tetrachloride is added. After the addition is completed, continue to maintain for 1 hour, gradually increase the temperature to 85°C, add 2.0mL of di-n-butyl phthalate during the heating process, and maintain at 85°C for 1 hour. After filtering the clear liquid, the solid is washed with 200mL of toluene at 80°C for 0.5 hour. After filtering, the solid is dispersed in 200mL of toluene, 0.4mL of methyl furoate is added at 40°C, and the temperature is kept constant at 40°C for 0.5 hour, and the temperature is increased to 100°C and kept constant for 0.5 hour. After filtration, the solid was added with 120 mL toluene and 80 mL titanium tetrachloride, treated at 110°C for 0.5 hour, and the filtrate was removed. 120 mL toluene and 80 mL titanium tetrachloride were added, treated at 110°C for 0.5 hour, and the filtrate was removed. After repeated washing with 200 mL hexane for 4 times, a solid olefin polymerization catalyst component was obtained.

[0078] Application Example 1

[0079] Propylene polymerization: After nitrogen is fully replaced in a 5-liter stainless steel autoclave, 5 ml of a 0.5 mol / L hexane solution of triethylaluminum and 1 ml of a 1 mol / L hexane solution of methylcyclohexyldimethoxysilane (CMMS, external electron donor) and 10 mg of the catalyst component prepared in Example 1 are added, and then 10 ml of hexane is added to flush the feed line, and then 4.5 liters of hydrogen under standard conditions and 2 liters of refined propylene are added, and the temperature is raised to 70° C., and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and stirring is stopped to discharge the reaction product to obtain a propylene polymer.

[0080] Example 2

[0081] Preparation of catalyst components: The method is the same as in Example 1, except that the amount of methyl furoate used is increased to 0.7 mL.

[0082] Application Example 2

[0083] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 2.

[0084] Example 3

[0085] Preparation of catalyst components: The method is the same as Example 1, except that the amount of methyl furoate used is increased to 1.0 mL.

[0086] Application Example 3

[0087] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 3.

[0088] Example 4

[0089] Preparation of catalyst components: The method is the same as that of Example 1, except that 0.6 g of ethyl 4,5-dimethyl-2-furancarboxylate is used instead of methyl furoate.

[0090] Application Example 4

[0091] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 4.

[0092] Example 5

[0093] Preparation of catalyst components: The method is the same as that of Example 1, except that 0.5 g of methyl 2,5-dihydro-2,5-dimethoxy-2-furancarboxylate is used instead of methyl furoate.

[0094] Application Example 5

[0095] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 5.

[0096] Application Example 6

[0097] Using the catalyst prepared in Example 1, propylene polymerization was carried out in the same manner as in Example 1, except that 1 liter of hydrogen was used.

[0098] Application Example 7

[0099] Using the catalyst prepared in Example 1, propylene polymerization was carried out in the same manner as in Example 1, except that 6 liters of hydrogen were used.

[0100] Comparative Example 1

[0101] Preparation of catalyst components: The method is the same as in Example 1, except that no furoate compound is used.

[0102] Comparative application example 1

[0103] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Comparative Example 1.

[0104] Comparative Application Example 2

[0105] Using the catalyst prepared in Comparative Example 1, propylene polymerization was carried out in the same manner as in Example 1, except that 1 liter of hydrogen was used.

[0106] Comparative Application Example 3

[0107] Using the catalyst prepared in Comparative Example 1, propylene polymerization was carried out in the same manner as in Example 1, except that 6 liters of hydrogen were used.

[0108] The test data of the catalysts prepared in Examples 1-5 and Comparative Example 1 and the corresponding polymerization application example data are shown in Table 1.

[0109] Table 1 Test results

[0110]

[0111] According to the test results in Table 1, in Examples 1-3, with the addition of furoate compounds, the catalysts prepared were polymerized under 4.5 liters of hydrogen to obtain homopolymer products. Compared with Comparative Example 1 without the addition of furoate compounds, the isotactic index and weight-average molecular weight of the polymers were significantly higher than those of Comparative Example 1 at similar melt flow indexes. In Examples 4-5, with the addition of furoate compounds, compared with Comparative Example 1, at higher melt flow indexes, the weight-average molecular weight of the polymers was higher, the content of dissolved matter was reduced, and the isotactic index was higher. It can be seen from Application Examples 1, 6, and 7 and Comparative Application Examples 1-3 that, at different hydrogen concentrations, the propylene polymerization products of the catalysts prepared by adding furoate compounds all had higher molecular weights and isotactic indexes. As the hydrogen concentration increases, the advantages of the polymers having higher isotactic indexes and higher molecular weights become more obvious. Figure 1 As shown, from the molecular weight distribution diagram of the propylene polymer of Application Example 1 and Comparative Application Example 1, it can be seen that under high hydrogen concentration, the addition of furoate compounds reduces the production of low molecular weight polymers, while increasing the content of high molecular weight polymers, inhibiting the production of oligomers, and reducing the odor of the polymer product.

[0112] Any numerical value mentioned in the present invention, if there is only an interval of two units between any minimum value and any maximum value, includes all values ​​from the minimum value to the maximum value each time increasing by one unit. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0113] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A catalyst component comprising magnesium, titanium, halogen, an internal electron donor compound and a furoate compound, wherein the furoate compound has a structure shown in formula (I); In formula (I), R1, R2, and R3 are each independently selected from hydrogen, halogen, C 1-10 Straight or branched alkanes, C 2-20 Mono- or poly-aliphatic ethers, C 2-10 Fatty acid esters or C 6-20 Aromatic acid esters, C 6-20 Cycloalkane or aromatic hydrocarbon or aromatic hydrocarbon with a substituent; said C 1-10 The straight or branched alkane has a halogen substituent or an N substituent; R4 is C 1-20 Straight or branched chain alkanes, C 2-20 Mono- or poly-aliphatic ethers, C 2-10 Fatty acid esters or C 6-20 Aromatic acid esters, C 6-20 Cycloalkanes or aromatic hydrocarbons and aromatic hydrocarbons with substituents.

2. The catalyst component according to claim 1, characterized in that The magnesium element and the halogen element are from magnesium halide; the general formula of the magnesium halide is MgY2, Y is a halogen, preferably bromine, chlorine or iodine, and more preferably, the magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide; And / or, the titanium element comes from a titanium-containing compound, the general formula of the titanium compound is TiX m (OR) 4-m , wherein X is halogen, preferably chlorine, bromine or iodine, and R is C 1-20 A hydrocarbon group, m is an integer of 1 to 4; more preferably, the titanium-containing compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium monochloride; And / or, the internal electron donor is selected from at least one of the alkyl esters of aliphatic or aromatic carboxylic acids, preferably selected from C 1-4 Saturated fatty acid C 1-4 Alkyl esters, C 7-8 Aromatic carboxylic acid C 1-4 The alkyl ester is more preferably at least one of diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 1,3-dipentyl phthalate, methyl formate, ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate and butyl butyrate; and / or, the furoate ester compound is selected from methyl furoate, ethyl furoate, propyl furoate, isopropyl furoate, butyl furoate, isobutyl furoate, tert-butyl furoate, pentyl furoate, isopentyl 2-furoate, n-hexyl furoate, isohexyl furoate, octyl furoate, dodecyl furoate, octadecyl furoate, benzylic furoate, allyl furoate, ethyl 5-bromo-2-furoate, methyl 2-furoyl acetate, 5-formyl furan at least one of methyl-2-formate, methyl-3-methyl-2-furancarboxylate, methyl-4-bromofuran-2-carboxylate, methyl-5-nitro-2-furancarboxylate, ethyl-5-chloromethyl-2-furancarboxylate, methyl-5-benzoyl-2-furancarboxylate, methyl-5-(chloromethyl)-2-furancarboxylate, ethyl-4,5-dimethyl-2-furancarboxylate, and methyl-2,5-dihydro-2,5-dimethoxy-2-furancarboxylate; and / or, Calculated per mole of magnesium halide, The titanium element is 0.5 to 25 moles, preferably 1 to 20 moles; The internal electron donor compound is 0.01 to 1 mole, preferably 0.04 to 0.5 mole; The furoate compound is 0.005 to 1 mol, preferably 0.01 to 0.05 mol.

3. The method for preparing the catalyst component according to claim 1 or 2, comprising the steps of: Step A, contacting a magnesium halide compound, an organic phosphorus compound, an organic epoxy compound, and an emulsifier in a solvent I to form a solution; Step B, contacting the solution with a titanium compound in the presence of a precipitation aid to obtain a mixture; Step C, contacting the mixture obtained in step B with an internal electron donor compound III, changing the temperature, precipitating a solid, and filtering; Step D, dispersing the solid in solvent II and contacting it with a furoate compound IV, filtering, washing and drying the solid to obtain the olefin polymerization catalyst component.

4. The preparation method according to claim 3, characterized in that: The organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite; And / or, the organic epoxy compound is C 2-8 Aliphatic olefins, C 2-8 One or more of the oxidation products of halogenated aliphatic olefins, preferably at least one of ethylene oxide, propylene oxide, ethylene oxide, epichlorohydrin, butylene oxide, butadiene oxide, butadiene dioxide, methyl glycidyl ether and diglycidyl ether; and / or, the precipitation aid is selected from one or more of organic acids, organic anhydrides, organic ethers and organic ketones, and specifically, for example, may be at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether; and / or, per mole of magnesium halide, the amount of the organic epoxy compound is 0.1 to 10 moles, preferably 0.4 to 4 moles; the amount of the organic phosphorus compound is 0.1 to 10 moles, preferably 0.4 to 5 moles; and / or, the emulsifier is 0.1 g to 1 g per gram of magnesium halide compound; And / or, the conditions of contacting I in step A include: temperature of 10 to 100° C., preferably 30 to 80° C.; time of 0.05 to 6 hours, preferably 0.1 to 4 hours; And / or, the conditions of contacting II in step B include: temperature of -30°C to 60°C, preferably -20°C to 30°C; time of 0.1 to 5 hours, preferably 0.2 to 4 hours; And / or, the conditions of contacting III in step C include: temperature of 0 to 120°C, preferably 20 to 80°C; time of 0.1 to 5 hours, preferably 0.2 to 2 hours; And / or, the conditions for contacting IV in step D include: temperature of 0 to 120° C., preferably 10 to 80° C.; time of 0.1 to 5 hours, preferably 0.2 to 2 hours.

5. An olefin polymerization catalyst comprising the catalyst component according to claim 1 or 2 or the catalyst component prepared by the method according to claim 3 or 4.

6. The olefin polymerization catalyst according to claim 5, characterized in that The olefin polymerization catalyst comprises: The catalyst component; Organoaluminum compounds; Optionally, an external electron donor compound; and / or, the molar ratio of the aluminum element in the organic aluminum to the titanium element in the catalyst component is 1 to 1500:1, preferably 10 to 1000:1; and / or, the molar ratio of the external electron donor compound to the titanium element in the catalyst component is 0 to 500:1, more preferably 0 to 200:1; And / or, the organoaluminum compound is an alkylaluminum compound; the chemical formula of the alkylaluminum compound is AlR' n’ X' 3-n’ , where R' is C 1-8 The alkyl or halogenated alkyl group is selected from the group consisting of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogenate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al(n-C6H 13 )3 and Al(n-C8H 17 ) 3 or more; the alkyl aluminum compound is triethyl aluminum and / or triisobutyl aluminum; And / or, the external electron donor compound is selected from at least one of carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, ketone, ether, alcohol, lactone, organophosphorus compound and organosilicon compound, and the external electron donor compound is an organosilicon compound with the chemical formula (R 13 )m'(R 14 )p'Si(OR 15 )q', where R 13 , R 14 and R 15 Each independently is C 1-18 Hydrocarbyl, preferably C 1-18 An alkane optionally containing a heteroatom, wherein the heteroatom is one or more of F, Cl, Br, N and I; m' and p' are each independently an integer of 0-2, q' is an integer of 1-3, and the sum of m', p' and q' is 4; R 13 and R 14 Each independently is C 3-10 Alkyl, C 3-10 Alkenyl, C 3-10 Alkylene, C 3-10 Substituted or unsubstituted cycloalkyl and C 6-10 R is one of substituted or unsubstituted aryl groups, optionally containing heteroatoms, wherein the heteroatoms are one or more of F, Cl, Br, N and I; 15 C 1-10 Alkyl, more preferably C 1-6 Alkyl, more preferably C 1-4 Alkyl, more preferably methyl; Preferably, the organosilicon compound is selected from one or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, tert-hexyltrimethoxysilane and 2-ethylpiperidinyl-2-tert-butyldimethoxysilane.

7. A method for the polymerization of olefins, characterized in that The method comprises: subjecting olefin to homopolymerization or copolymerization in the presence of the olefin polymerization catalyst according to claim 5 or 6.

8. The method for olefin polymerization according to claim 7, characterized in that The olefin is selected from at least one of the compounds represented by formula (II); CH2=CHR” Formula (II) R" is hydrogen or C 1-6 The alkyl group; Preferably, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene; And / or, the polymerization reaction conditions include: temperature of 50-100° C., time of 0.5-5 hours; molar ratio of hydrogen to propylene of 0-0.1, preferably 0-0.

02.

9. The olefin polymer prepared by the method for olefin polymerization according to claim 7 or 8.

10. The olefin polymer according to claim 9, characterized in that When the molar ratio of hydrogen to propylene is ≤0.008, the isotactic index of the olefin polymer is ≥97.2%, and the weight average molecular weight of the polymer is ≥248,000.

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