Pyrroline compound-containing catalyst component and preparation method thereof, olefin polymerization catalyst, olefin polymerization method and olefin polymer

Abstract

The invention belongs to the field of petrochemical industry, and provides a pyrroline 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 pyrroline compound, and the pyrroline compound has a structure as shown in a formula (I). Compared with a propylene homopolymerization product obtained by polymerization under the same condition without using a catalyst prepared by using a pyrroline compound, the propylene homopolymerization product obtained by adding a pyrroline compound in the catalyst preparation process of # imgabs0 # has a higher isotactic index.

Description

Technical Field

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

[0002] As we all know, hydrogen is a chain transfer agent in the olefin polymerization process and plays a role in regulating molecular weight in the industrial production of polyolefins. With the increase in the amount of hydrogen used, the molecular weight of the polymer decreases and the isotactic index of the polymer decreases. As the market demand for high-strength impact polypropylene resins increases year by year, there is a higher demand for the stereospecificity of the catalyst under high hydrogen concentration. High-flow high-strength impact copolymer polypropylene has a high melt flow rate (MFR), high modulus and high impact strength, and can be directly used for injection molding of home appliance parts, office products, automotive modified materials, etc.

[0003] In order to achieve high fluidity of the product, industrial equipment needs to add a large amount of hydrogen in the homopolymerization reaction part. The addition of hydrogen will lead to a decrease in the iso-index of the homopolymerization part and a decrease in the rigidity of the product. In order to achieve high rigidity of the product, it is necessary to select a polyolefin catalyst with high stereospecificity under high hydrogen concentration, or select an appropriate external electron donor compound. Summary of the invention

[0004] In view of the above-mentioned needs, the present invention designs and prepares a polyolefin catalyst, which has high stereospecificity under high hydrogen concentration and can meet the preparation requirements of high-rigidity and high-fluidity 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 pyrroline compound, wherein the pyrroline compound has a structure shown in formula (I);

[0007]

[0008] In formula (I), R1, R2, R3, and R4 are each independently selected from hydrogen, oxygen, 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 Cycloalkanes or aromatic hydrocarbons or aromatic hydrocarbons with substituents;

[0009] R5 is C 1-20Straight 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, C 2-20 Mono- or poly-aliphatic ethers.

[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 MgX2, X 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 TiY m (OR) 4-m , wherein Y 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.

[0012] As a specific embodiment of the present invention, the internal electron donor may be various internal electron donors commonly used in the art, and may be one or more alkyl esters selected from aliphatic or aromatic carboxylic acids. For example, it may be selected from C 1-4 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, 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, in the catalyst component, 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 pyrroline compound is 0.005 to 2 moles, preferably 0.01 to 1 mole.

[0014] As a specific embodiment of the present invention, the pyrroline compounds include but are not limited to: 3-pyrroline-1-carboxylic acid methyl ester, 3-pyrroline-1-carboxylic acid ethyl ester, 3-pyrroline-1-carboxylic acid propyl ester, 3-pyrroline-1-carboxylic acid isopropyl ester, 3-pyrroline-1-carboxylic acid butyl ester, 3-pyrroline-1-carboxylic acid isobutyl ester, N-BOC-3-pyrroline, 3-pyrroline-1-carboxylic acid n-pentyl ester, 3-pyrroline-1-carboxylic acid isopentyl ester, 3-pyrroline-1-carboxylic acid hexyl ester, 3-pyrroline-1-carboxylic acid cyclohexyl ester, 3-pyrroline-1-carboxylic acid heptyl ester, 3-pyrroline-1-carboxylic acid octyl ester, 3-pyrroline-1-carboxylic acid methyl ... 3-pyrroline-1-carboxylic acid isooctyl ester, 3-pyrroline-1-carboxylic acid dodecyl ester, 3-pyrroline-1-carboxylic acid octadecyl ester, 3-pyrroline-1-carboxylic acid ethoxy-n-butyl ester, 3-pyrroline-1-carboxylic acid benzyl ester, 3-pyrroline-1-carboxylic acid-2-methylbenzyl ester, 3-pyrroline-1-carboxylic acid-3-methylbenzyl ester, 3-pyrroline-1-carboxylic acid-p-methylbenzyl ester, 2-methyl-3-pyrroline-1-carboxylic acid benzyl ester, 3-methyl-3-pyrroline-1-carboxylic acid benzyl ester, 3-n-butyl-3-pyrroline-1-carboxylic acid benzyl ester, N-Boc-2,5-dihydropyrrole-3-carboxylic acid ethyl ester, N-(methoxycarbonyl)maleimide.

[0015] Among the above-mentioned pyrroline compounds, preferred are N-(methoxycarbonyl)maleimide, 3-pyrroline-1-carboxylic acid benzyl ester, N-Boc-2,5-dihydropyrrole-3-carboxylic acid ethyl ester, and N-BOC-3-pyrroline. More preferred are N-(methoxycarbonyl)maleimide and 3-pyrroline-1-carboxylic acid benzyl ester.

[0016] On the other hand, the present invention provides a method for preparing any of the above catalyst components, 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;

[0017] Step B, contacting the solution with a titanium-containing compound in the presence of a precipitation aid to obtain a mixture;

[0018] Step C, contacting the mixture obtained in step B with an internal electron donor compound III, changing the temperature, precipitating a solid, and filtering;

[0019] Step D, dispersing the solid in solvent II and contacting it with a pyrroline compound IV, filtering, washing and drying the solid to obtain the olefin polymerization catalyst component.

[0020] 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.

[0021] 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;

[0022] 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;

[0023] 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;

[0024] 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;

[0025] 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.

[0026] 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.

[0027] As a specific embodiment of the present invention, the organic epoxy compound is C 2-8 Aliphatic olefins (2-8 carbon atoms), C 2-8 One 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] As a specific embodiment of the present invention, the pyrroline compound is used in an amount of 0.005 to 2 moles, preferably 0.01 to 1 mole, per mole of magnesium halide.

[0032] 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.

[0033] 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.

[0034] As a specific embodiment of the present invention, the emulsifier is 0.1 g to 10 g per gram of magnesium halide compound.

[0035] 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.

[0036] 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.

[0037] The solvent II of the present invention is a commonly used solvent in the art, and can be any one of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane.

[0038] In another aspect, the present invention provides any of the olefin polymerization catalysts comprising:

[0039] Catalyst components;

[0040] Organoaluminum compounds;

[0041] Optionally, an external electron donor compound.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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 C1-4 The alkyl group is more preferably a methyl group; the external electron donor compound is selected from one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organic phosphorus compounds and organic silicon compounds.

[0046] 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.

[0047] In another aspect, the present invention provides a method for olefin polymerization, the method comprising: subjecting an olefin to homopolymerization or copolymerization in the presence of the olefin polymerization catalyst according to any one of claims 6 to 8. As a specific embodiment of the present invention, the olefin is selected from at least one of the compounds represented by formula (II);

[0048] CH2=CHR” Formula (II)

[0049] R" is hydrogen or C 1-6 of alkyl.

[0050] As a specific embodiment of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene;

[0051] As a specific embodiment of the present invention, the polymerization reaction conditions include: temperature of 50-100° C., time of 0.5-5 hours; hydrogen to propylene molar ratio of 0-0.1, preferably 0-0.01.

[0052] In another aspect, the present invention provides an olefin polymer obtained by any one of the above olefin polymerization methods.

[0053] As a specific embodiment of the present invention, the isotactic index of the olefin polymer is ≥95%. The above raw materials in the present invention can be self-made or commercially available, and the present invention is not particularly limited thereto.

[0054] After adding the pyrroline compound during the catalyst preparation process, the propylene homopolymerization product of the obtained catalyst under 4.5 liters of hydrogen has a higher isotactic index than the propylene homopolymerization product obtained by polymerizing the catalyst under the same conditions without using the pyrroline compound, and can polymerize to obtain a polypropylene product with an isotactic index ≥96%. DETAILED DESCRIPTION

[0055] 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.

[0056] The experimental method involved in the present invention is as follows:

[0057] (1) Propylene polymerization method

[0058] 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 1.2 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 and 2 hours respectively. After the reaction is completed, the reactor is cooled and stirring is stopped to discharge the reaction product to obtain an olefin polymer.

[0059] (2) Method for determining the content of each component in the catalyst

[0060] The titanium content was determined colorimetrically using a UV-visible spectrophotometer Model 722;

[0061] The magnesium content was measured by complexometric titration of magnesium ions and EDTA;

[0062] The halogen content was measured by AgNO3-NH4CNS back titration method;

[0063] 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;

[0064] Determination of pyrroline compound content: Agilent high-performance GC-MS was used for determination.

[0065] 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.

[0066] 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;

[0067] Catalyst activity AC = (polymer weight) / (catalyst weight).

[0068] 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.

[0069] Example 1

[0070] In a reactor that has been repeatedly replaced with high-purity nitrogen, add 7.2g of anhydrous magnesium chloride, 48mL of toluene and 90mL of decane, 4.5mL of epichlorohydrin, 36mL of tributyl phosphate and 3.0g of T602 in sequence, and stir at 350rpm for 2 hours at 60°C. Then add 2.0g of phthalic anhydride and continue stirring at 60°C for 1 hour. Cool the solution to 0°C and add 73mL of titanium tetrachloride. After the addition is completed, continue to maintain for 1 hour, gradually raise 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 was washed with 200 mL toluene at 80°C for 0.5 hours. After filtering, the solid was dispersed in 200 mL toluene, 0.4 mL 3-pyrroline-1-carboxylic acid benzyl ester was added at 40°C, the temperature was kept constant at 40°C for 0.5 hours, and the temperature was raised to 100°C and kept constant for 0.5 hours. After filtering, the solid was added with 120 mL toluene and 80 mL titanium tetrachloride, treated at 110°C for 0.5 hours, and the filtrate was removed. 120 mL toluene and 80 mL titanium tetrachloride were added, treated at 110°C for 0.5 hours, and the filtrate was removed. After washing with 200 mL hexane for 4 times, a solid olefin polymerization catalyst component was obtained.

[0071] Application Example 1

[0072] 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 an olefin polymer. The specific results are shown in Table 1.

[0073] Example 2

[0074] Preparation of catalyst components: The method is the same as Example 1, except that the amount of 3-pyrroline-1-carboxylic acid benzyl ester used is increased to 0.6 mL.

[0075] Application Example 2

[0076] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 2.

[0077] Example 3

[0078] Preparation of catalyst components: The method is the same as Example 1, except that the amount of 3-pyrroline-1-carboxylic acid benzyl ester used is increased to 1.0 mL.

[0079] Application Example 3

[0080] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 3.

[0081] Example 4

[0082] Preparation of catalyst components: The method is the same as that of Example 1, except that 0.6 g of N-(methoxycarbonyl)maleimide is used instead of 3-pyrroline-1-carboxylic acid benzyl ester.

[0083] Application Example 4

[0084] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 4.

[0085] Example 5

[0086] Preparation of catalyst components: The method is the same as in Example 1, except that 0.5 g of ethyl N-Boc-2,5-dihydropyrrole-3-carboxylate is used instead of benzyl 3-pyrroline-1-carboxylate.

[0087] Application Example 5

[0088] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 5.

[0089] Example 6

[0090] Preparation of catalyst components: The method is the same as in Example 1, except that 0.4 g of N-BOC-3-pyrroline is used instead of 3-pyrroline-1-carboxylic acid benzyl ester.

[0091] Application Example 6

[0092] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 6.

[0093] Example 7

[0094] Preparation of catalyst components: The method is the same as in Example 1, except that 0.8 g of N-BOC-3-pyrroline is used instead of 3-pyrroline-1-carboxylic acid benzyl ester.

[0095] Application Example 7

[0096] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 7.

[0097] Example 8

[0098] Preparation of catalyst components: The method is the same as that of Example 1, except that 1.0 g of N-(methoxycarbonyl)maleimide is used instead of 3-pyrroline-1-carboxylic acid benzyl ester.

[0099] Application Example 8

[0100] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Example 8.

[0101] Application Example 9

[0102] Propylene polymerization: The catalyst prepared in Example 2 was used, and the method was the same as in Application Example 1, except that 1 liter of hydrogen was used.

[0103] Application Example 10

[0104] Propylene polymerization: The catalyst prepared in Example 2 was used, and the method was the same as in Application Example 1, except that 6 liters of hydrogen was used.

[0105] Comparative Example 1

[0106] Preparation of catalyst components: The method is the same as that of Example 1, except that no pyrroline compound is used.

[0107] Comparative application example 1

[0108] Propylene polymerization: The method is the same as that of Application Example 1, using the catalyst prepared in Comparative Example 1.

[0109] Comparative Application Example 2

[0110] Propylene polymerization: The catalyst prepared in Comparative Example 1 was used in the same manner as in Application Example 1, except that 1 liter of hydrogen was used.

[0111] Comparative Application Example 3

[0112] Propylene polymerization: The catalyst prepared in Comparative Example 1 was used in the same manner as in Application Example 1, except that 6 liters of hydrogen were used.

[0113] The various data of the catalysts prepared in Examples 1-8 and Comparative Example 1, and the polymer data of Application Examples 1-10 and Comparative Application Examples 1-3 are shown in Table 1.

[0114] Table 1 Catalyst test results

[0115]

[0116] According to the test results in Table 1, with the addition of the pyrroline compound, the catalysts prepared in Examples 1-8 polymerized under 4.5 liters of hydrogen to obtain homopolymer products. Compared with Comparative Example 1 without the addition of the pyrroline compound, under the condition of having the same melt flow index, the isotactic index of the polymers in Application Examples 1-8 is significantly higher than that in Comparative Example 1. It can be seen from Application Examples 2, 9, 10 and Comparative Application Examples 1-3 that, under different hydrogen concentrations, the addition of the pyrroline compound can improve the stereospecificity of the catalyst and the isotactic index of the polymer.

[0117] 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.

[0118] 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 pyrroline compound, wherein the pyrroline compound has a structure represented by formula (I); In formula (I), R1, R2, R3, R4 are each independently selected from hydrogen, oxygen, 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 Cycloalkanes or aromatic hydrocarbons or aromatic hydrocarbons with substituents; R5 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, C 2-20 Mono- or poly-aliphatic ethers.

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 MgX2, X 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 TiY m (OR) 4-m , wherein Y 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 pyrroline compound is selected from 3-pyrroline-1-carboxylic acid methyl ester, 3-pyrroline-1-carboxylic acid ethyl ester, 3-pyrroline-1-carboxylic acid propyl ester, 3-pyrroline-1-carboxylic acid isopropyl ester, 3-pyrroline-1-carboxylic acid butyl ester, 3-pyrroline-1-carboxylic acid isobutyl ester, N-BOC-3-pyrroline, 3-pyrroline-1-carboxylic acid n-pentyl ester, 3-pyrroline-1-carboxylic acid isopentyl ester, 3-pyrroline-1-carboxylic acid hexyl ester, 3-pyrroline-1-carboxylic acid cyclohexyl ester, 3-pyrroline-1-carboxylic acid heptyl ester, 3-pyrroline-1-carboxylic acid octyl ester, 3-pyrroline-1-carboxylic acid isooctyl ester, 3-pyrroline at least one of 1-dodecyl-1-carboxylate, 3-pyrroline-1-carboxylic acid octadecyl ester, 3-pyrroline-1-carboxylic acid ethoxy-n-butyl ester, 3-pyrroline-1-carboxylic acid benzyl ester, 3-pyrroline-1-carboxylic acid-2-methylbenzyl ester, 3-pyrroline-1-carboxylic acid-3-methylbenzyl ester, 3-pyrroline-1-carboxylic acid-p-methylbenzyl ester, 2-methyl-3-pyrroline-1-carboxylic acid benzyl ester, 3-methyl-3-pyrroline-1-carboxylic acid benzyl ester, 3-n-butyl-3-pyrroline-1-carboxylic acid benzyl ester, N-Boc-2,5-dihydropyrrole-3-carboxylic acid ethyl ester and N-(methoxycarbonyl)maleimide; And / or, in the catalyst component, 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 pyrroline compound is 0.005 to 2 moles, preferably 0.01 to 1 mole.

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-containing 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 pyrroline compound IV, filtering, washing and drying the solid to obtain the olefin polymerization catalyst component.

4. The preparation method according to claim 4, 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 (2-8 carbon atoms), C 2-8 One or more of the oxidation products of halogenated aliphatic olefins (with 2 to 8 carbon atoms), 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 10 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.

7. The olefin polymerization catalyst according to claim 6, characterized in that 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 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 Alkyl, more preferably methyl; the external electron donor compound is selected from one or more of carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, ketone, ether, alcohol, lactone, organophosphorus compound and organosilicon compound; 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; more preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane and / or dicyclopentyldimethoxysilane.

8. 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 any one of claims 5 to 7; Preferably, 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-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene; And / or, the polymerization reaction conditions include: temperature of 50-100° C., time of 0.1-5 hours; molar ratio of hydrogen to propylene of 0-0.1, preferably 0-0.

01.

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

10. The olefin polymer according to claim 9, characterized in that The isotactic index of the olefin polymer is ≥95%.

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