An olefin polymerization catalyst support and a method for preparing the same, a catalyst component, a catalyst and an olefin polymerization method

Abstract

本发明涉及催化剂技术领域，提供了一种烯烃聚合催化剂载体及其制备方法、催化剂组分、催化剂及烯烃聚合方法。所述催化剂载体包括如下式所示的镁化合物和磷化合物，其中，R1为C1～C12的直链烷基或C3～C12的支链烷基；R2和R3各自独立选自氢、C1～C5的直链烷基或C3～C5的支链烷基，被卤原子取代的C1～C5的直链烷基或C3～C5的支链烷基；X选自卤素；m为0.1～1.9；n为0.1～1.9；m+n＝2；磷化合物来源于通式为LK+2PKO3K+1所示的聚磷酸盐，式中L为金属元素，K为3‑5的整数；催化剂载体中磷化合物的含量以磷元素重量计0<p<3wt％。本发明通过加入聚磷酸盐可以在不加入高分子分散稳定剂的情况下得到良好颗粒形态的催化剂载体，制备的催化剂在用于烯烃聚合时具有较高的聚合活性。

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and more specifically, to an olefin polymerization catalyst support and its preparation method, catalyst components, catalyst, and olefin polymerization method. Background Technology

[0002] Most catalysts used in olefin polymerization are prepared by supporting titanium halide on active anhydrous magnesium chloride. Further research has revealed that a method of first preparing a magnesium compound support with good particle morphology, and then loading the active component, can yield a catalyst solid component with controllable particle morphology. The particle morphology and size of the support determine the particle morphology and size of the catalyst. Currently, the most commonly used magnesium compound supports are magnesium chloride alcohol supports (such as those disclosed in US4421674A, US4469648A, WO8707620A1, WO9311166A1, US5100849A, US6020279A, US4399054A, US6127304A, US6323152B1, CN1463990A, CN1580136A, etc.) and alkoxy magnesium supports (such as those disclosed in patents CN101134789A, US4727051A, CN101190953A, etc.).

[0003] To further simplify the support preparation process and improve the polymerization performance of catalysts, researchers have developed a new process for preparing spherical magnesium compound supports using a reaction precipitation method. Patent CN200910235565.7 discloses a compound that can be used as a catalyst support for olefin polymerization and its preparation method. This method involves heating magnesium halide, an alcohol compound, and an inert dispersion medium to form a magnesium halide alcohol solution, followed by reaction of this solution with an ethylene oxide compound to generate a spherical support. Patent CN201310491393.6, by adding a polymeric dispersion stabilizer during the above support preparation process, achieves solid particles with good morphology and narrow particle size distribution without the need for an inert dispersion medium, thereby improving single-batch yield and reducing solvent recovery costs. However, the addition of the polymeric dispersion stabilizer not only increases the production cost of the support but also adversely affects the recovery and treatment of by-products, increasing the difficulty of solvent recovery.

[0004] Therefore, it is of great significance to develop a new catalyst support for olefin polymerization that can overcome the above-mentioned defects of the existing technology. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this invention proposes an olefin polymerization catalyst support and its preparation method, catalyst components, catalyst, and olefin polymerization method.

[0006] The technical solution adopted by the present invention comprises:

[0007] In a first aspect, the present invention provides an olefin polymerization catalyst support, comprising a magnesium compound represented by formula (I) and a phosphorus compound,

[0008]

[0009] wherein R1 is C1~C 12 linear alkyl or C3~C 12 branched alkyl; R2 and R3 are the same or different, each independently selected from hydrogen, C1-C5 linear alkyl or C3-C5 branched alkyl, and the hydrogen on the C1-C5 linear alkyl or C3-C5 branched alkyl is optionally substituted by a halogen atom; X is selected from halogen; m is 0.1 to 1.9, preferably 0.8 to 1.2; n is 0.1 to 1.9, preferably 0.8 to 1.2; m+n=2;

[0010] The phosphorus compound is derived from a polyphosphate represented by the general formula L K+2 P K O 3K+1 wherein L is a metal element, and K is an integer of 3 to 5;

[0011] The content of the phosphorus compound in the catalyst support is 0<p<3wt%, preferably 0.01wt%<p<1wt%, for example, 0.02wt%, 0.05wt%, 0.08wt%, 0.10wt%, 0.15wt%, 0.20wt%, 0.25wt%, 0.35wt%, 0.40wt%, 0.50wt%, 0.60wt%, 0.70wt%, 0.80wt%, 0.90wt%, etc., by weight of phosphorus element.

[0012] In a large number of experiments, the inventors of the present invention have surprisingly found that by introducing the polyphosphate represented by the general formula L K+2 P K O 3K+1 into the system for preparing the olefin polymerization catalyst support, a support with good morphology can be obtained without using a polymer dispersion stabilizer, and the prepared catalyst has high catalytic activity.

[0013] It should be noted that the "support" in the present invention refers to a substance having no olefin polymerization activity, that is, the support does not contain an active component capable of forming olefin polymerization activity, such as a titanium compound.

[0014] According to some embodiments of the present invention, the polyphosphate includes at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate and hydrates thereof.

[0015] According to some embodiments of the present invention, R1 is a straight-chain alkyl group of C1 to C8 or a branched alkyl group of C3 to C8; preferably, R1 is selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl and 2-ethylhexyl.

[0016] According to some embodiments of the present invention, R2 and R3 may be the same or different, and each is independently selected from hydrogen, C1-C3 straight-chain alkyl or isopropyl or halogen-substituted C1-C3 straight-chain alkyl or isopropyl; preferably, R2 and R3 are each independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, bromoethyl.

[0017] According to some embodiments of the present invention, the halogen is selected from chlorine, bromine and iodine, preferably chlorine.

[0018] According to some embodiments of the present invention, the catalyst support is a spherical particle.

[0019] According to some embodiments of the present invention, the catalyst support has an average diameter of 10-100 μm, preferably 30-70 μm, and a particle size distribution of less than 1.2, preferably 0.6-0.9.

[0020] Secondly, the present invention provides a method for preparing an olefin polymerization catalyst support, comprising:

[0021] (a) Magnesium halides represented by the general formula MgX2, alcohols represented by the general formula R1OH, and compounds represented by the general formula L K+ 2P K O 3K+1 The polyphosphate reaction shown forms a suspension, where X is a halogen and R1 is a C1-C1 halogen. 12 Straight-chain alkyl or C3-C 12 Branched alkyl groups, where L is a metallic element and K is an integer between 3 and 5;

[0022] (b) The suspension formed in step (a) is reacted with an epoxy compound to generate an olefin polymerization catalyst support;

[0023] Preferably, the epoxy compound is shown in general formula (II).

[0024]

[0025] R2 and R3 may be the same or different, and each is independently selected from hydrogen, a straight-chain alkyl group of C1 to C5 or a branched alkyl group of C3 to C5, wherein the hydrogen on the straight-chain alkyl group of C1 to C5 or the branched alkyl group of C3 to C5 may optionally be replaced by a halogen atom.

[0026] In the preparation method provided by the present invention, the order of adding magnesium halide, alcohol compound and polyphosphate in step (a) is not important.

[0027] According to some embodiments of the present invention, the polyphosphate includes at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, and their hydrates.

[0028] According to some embodiments of the present invention, R1 is a C1-C8 straight-chain alkyl group or a C3-C8 branched-chain alkyl group.

[0029] According to some embodiments of the present invention, the alcohol compound represented by the general formula R1OH includes at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethyl-1-hexanol.

[0030] According to some embodiments of the present invention, R2 and R3 may be the same or different, and each is independently selected from hydrogen, C1-C3 straight-chain alkyl or isopropyl or halogen-substituted C1-C3 straight-chain alkyl or isopropyl.

[0031] According to some embodiments of the present invention, R2 and R3 are each independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl.

[0032] According to some embodiments of the present invention, the epoxy compound includes at least one of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, chlorobutane, bromopropane, and bromobutane.

[0033] According to some embodiments of the present invention, the magnesium halide represented by the general formula MgX2 includes at least one of magnesium dichloride, magnesium dibromide, and magnesium diiodide, preferably magnesium dichloride.

[0034] According to some embodiments of the present invention, the molar ratio of the alcohol compound to the magnesium halide is (3-30):1, preferably (4-25):1, for example, it can be 5:1, 8:1, 10:1, 12:1, 14:1, 17:1, 20:1, 23:1, etc.; the molar ratio of the polyphosphate to the magnesium halide is 1:(10-300), for example, it can be 1:12, 1:20, 1:40, 1:60, 1:88, 1:100, 1:122, 1:150, 1:179, 1:180, 1:182, 1:190, 1:220, 1:250, 1:270, 1:290, etc., preferably 1:(20-200).

[0035] According to some embodiments of the present invention, the reaction temperature in step (a) is 30 to 160°C, preferably 40 to 120°C, such as 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, etc., and the reaction time is 0.1 to 5 hours, preferably 0.5 to 2 hours, such as 1 hour.

[0036] According to some embodiments of the present invention, step (a) is performed in a closed container.

[0037] According to some embodiments of the present invention, the polyphosphate in step (a) is prepared into an aqueous solution of polyphosphate and then participates in the reaction.

[0038] According to some embodiments of the present invention, the concentration of the polyphosphate aqueous solution is 10-60 wt%, preferably 30-60 wt%.

[0039] According to some embodiments of the present invention, the molar ratio of the epoxy compound to magnesium halide is (1-10):1, preferably (2-6):1, for example, it can be 3:1, 4:1, 5:1, etc.

[0040] According to some embodiments of the present invention, the reaction temperature in step (b) is 30 to 160°C, preferably 40 to 120°C, for example 60°C, and the reaction time is 0.1 to 5 hours, preferably 0.2 to 1 hour, for example 0.5 hours.

[0041] According to some embodiments of the present invention, an inert dispersion medium may or may not be added during the preparation of the suspension in step (a). The inert dispersion medium may be selected from at least one of liquid aliphatic, aromatic, cycloaliphatic hydrocarbons, or silicone oil. The volume ratio of the inert dispersion medium to the alcohol compound is (0-5):1, preferably (0-2):1.

[0042] According to some embodiments of the present invention, the trace amounts of water in each of the raw materials added in step (a) can participate in the reaction to form a suspension.

[0043] According to some embodiments of the present invention, the preparation method further includes step (c) recovering the obtained catalyst support.

[0044] In this invention, the recovery mentioned in step (c) refers to obtaining a solid particulate catalyst support using solid-liquid separation techniques known in the art, such as filtration, decanting, and centrifugation. It also includes washing and drying the obtained catalyst support with an inert hydrocarbon solvent. The inert hydrocarbon solvent is preferably a straight-chain or branched liquid alkane or aromatic hydrocarbon with a carbon chain length greater than four carbons, such as hexane, heptane, octane, decane, and toluene.

[0045] According to a preferred embodiment of the present invention, the method for preparing the catalyst support includes:

[0046] (1) In a sealed container, magnesium halide MgX2, alcohol compound R1OH, and a compound with the structure L K+2 P K O 3K+1 An aqueous solution of polyphosphate is reacted at 30-160°C (preferably 40-120°C) for 0.1-5 hours (preferably 0.5-2 hours) to form a suspension;

[0047] (2) The suspension is reacted with the epoxy compound shown in formula (II) above at 30-160°C (preferably 40-120°C) for 0.1-5 hours (preferably 0.2-1 hours) to precipitate solid particles;

[0048] (3) The solid particles are recovered by solid-liquid separation technology to obtain a catalyst support.

[0049] According to a more preferred embodiment of the present invention, the method for preparing the catalyst support includes:

[0050] (1) In a sealed container, magnesium halide MgX2, alcohol compound R1OH, and L are stirred together. K+2 P K O 3K+1 An aqueous solution of polyphosphate is heated to 30-160°C (preferably 40-120°C) and reacted for 0.1-5 hours (preferably 0.5-2 hours) to form a mixed suspension; wherein, based on each mole of magnesium, the amount of the alcohol compound is 3-30 moles, preferably 4-25 moles; and the amount of the polyphosphate is 0.002-0.1 moles, preferably 0.004-0.05 moles.

[0051] (2) Under stirring, the epoxy compound shown in formula (II) above is added to the above mixture suspension and reacted at 30-160°C (preferably 40-120°C) for 0.1-5 hours (preferably 0.2-1 hours) to form solid particles, wherein the amount of the epoxy compound used per mole of magnesium is 1-10 moles, preferably 2-6 moles;

[0052] (3) The solid particles are recovered by solid-liquid separation technology to obtain a catalyst support.

[0053] Thirdly, the present invention provides an olefin polymerization catalyst support, which is prepared by the preparation method described in the second aspect.

[0054] According to some embodiments of the present invention, the catalyst support is a spherical particle.

[0055] According to some embodiments of the present invention, the catalyst support has an average diameter of 10-100 μm, preferably 30-70 μm, and a particle size distribution of less than 1.2, preferably 0.6-0.9.

[0056] Fourthly, the present invention provides an olefin polymerization catalyst component comprising the reaction product of the catalyst support described in the first aspect or the catalyst support described in the third aspect with a titanium compound and optionally an internal electron donor compound.

[0057] According to some embodiments of the present invention, the amount of titanium compound used is 5-200 moles, preferably 10-100 moles, relative to each mole of magnesium compound of formula (I) in the catalyst support; the amount of internal electron donor used is 0-0.5 moles, preferably 0.08-0.4 moles.

[0058] According to some embodiments of the present invention, the titanium compound is selected from those with the general formula Ti(OR4). 4-a X a Titanium compounds, wherein R4 is C1-C 14 The aliphatic hydrocarbon group, where X is a halogen and a is an integer from 0 to 4.

[0059] According to some embodiments of the present invention, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichlorobutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy.

[0060] According to some embodiments of the present invention, the internal electron donor is selected from esters, ethers, ketones, amines and silanes.

[0061] According to some embodiments of the present invention, the internal electron donor is selected from mono- or poly-aliphatic carboxylic acid esters or aromatic carboxylic acid esters, diol esters, and diethers.

[0062] According to some embodiments of the present invention, the mono- or poly-aliphatic carboxylic acid ester or aromatic carboxylic acid ester is selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, and di-2,3-diisopropylsuccinate. Dimethyl succinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl biphenyltrioxide, tributyl biphenyltrioxide, tetraethyl pyromellitic acid, and tetrabutyl pyromellitic acid.

[0063] According to some embodiments of the present invention, the glycol ester compound is selected from 1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, (R)-1-phenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol di-n-propionate, 1,3-diphenyl-2-methyl-1,3-propanediol dipropionate, 1,3-diphenyl-2-methyl-1,3-propanediol diacetate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol diacetate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dibenzo ... 2-Dimethyl-1,3-propanediol dipropionate, 1,3-di-tert-butyl-2-ethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol diacetate, 1,3-diisopropyl-1,3-propanol di(4-butylbenzoic acid) ester, 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl-1,3-butanediol dibenzoate, phenyl-2-methyl-1,3-butanediol dinepentyl ester, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, (2S,4S)-(+)-2,4-pentanediol dibenzoate, (2R,4R)-(+)-2,4-pentanediol dibenzoate, 2 4-Pentanediol di(p-chlorobenzoic acid) ester, 2,4-Pentanediol di(m-chlorobenzoic acid) ester, 2,4-Pentanediol di(p-bromobenzoic acid) ester, 2,4-Pentanediol di(o-bromobenzoic acid) ester, 2,4-Pentanediol di(p-methylbenzoic acid) ester, 2,4-Pentanediol di(p-tert-butylbenzoic acid) ester, 2,4-Pentanediol di(p-butylbenzoic acid) ester, 2-Methyl-1,3-Pentanediol di(p-chlorobenzoic acid) ester, 2-Methyl-1,3-Pentanediol di(p-methylbenzoic acid) ester, 2-Butyl-1,3-Pentanediol di(p-methylbenzoic acid) ester, 2-Methyl-1,3-Pentanediol di(p-tert-butylbenzoic acid) ester, 2-Methyl-1,3-Pentanediol neopentyl ester, 2-Methyl-1,3-Pentanediol benzoic acid cinnamon Ester, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol cinnamic acid ester, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-allyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 1,3-pentanediol di(p-chlorobenzoate), 1,3-pentanediol di(m-chlorobenzoate), 1,3-pentanediol di(p-bromobenzoate), 1,3-Pentanediol di(o-bromobenzoic acid) ester, 1,3-Pentanediol di(p-methylbenzoic acid) ester, 1,3-Pentanediol di(p-tert-butylbenzoic acid) ester, 1,3-Pentanediol di(p-butylbenzoic acid) ester, 1,3-Pentanediol benzoic acid cinnamate, 1,3-Pentanediol dicinnamate, 1,3-Pentanediol dipropionate, 2-Methyl-1,3-Pentanediol benzoic acid cinnamate, 2,2-Dimethyl-1,3-Pentanediol dibenzoic acid cinnamate, 2,2-Dimethyl-1,3-Pentanediol dibenzoic acid cinnamate, 2-Ethyl-1,3-Pentanediol dibenzoic acid ester, 2-Butyl-1,3-Pentanediol dibenzoic acid ester, 2-Allyl-1,3-Pentanediol dibenzoic acid cinnamate 2,2,4-Trimethyl-1,3-pentanediol diisopropylcarboxylate, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-fluoromethylbenzoate, 2,4-pentanediol di(2-furanoic acid) ester, 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5 6-Ethyl-6-hepten-2,4-heptanediol dibenzoate, 3-propyl-6-hepten-2,4-heptanediol dibenzoate, 4-propyl-6-hepten-2,4-heptanediol dibenzoate, 5-propyl-6-hepten-2,4-heptanediol dibenzoate, 6-propyl-6-hepten-2,4-heptanediol dibenzoate, 3-butyl-6-hepten-2,4-heptanediol dibenzoate, 4-butyl-6-hepten-2,4-heptanediol dibenzoate, 5-butyl-6-hepten-2,4-heptanediol dibenzoate, 6-butyl-6-hepten-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-hepten-2,4-heptanediol Benzoic acid esters, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoic acid esters, 3-ethyl-3,5-heptanediol dibenzoic acid esters, 4-ethyl-3,5-heptanediol dibenzoic acid esters, 5-ethyl-3,5-heptanediol dibenzoic acid esters, 3-propyl-3,5-heptanediol dibenzoic acid esters5-Heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,3-dimethyl-3,5-heptanediol dibenzoate 4,4-Dimethyl-3,5-heptanediol benzoate, 4,5-Dimethyl-3,5-heptanediol benzoate, 4,6-Dimethyl-3,5-heptanediol benzoate, 4,4-Dimethyl-3,5-heptanediol benzoate, 6,6-Dimethyl-3,5-heptanediol benzoate, 2-Methyl-3-ethyl-3,5-heptanediol benzoate, 2-Methyl-4-ethyl-3,5-heptanediol benzoate Benzoate esters, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-3-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptanediol dibenzoate, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 9,9-bis( Fluorene, 9,9-bis((m-methoxybenzylcarboxy)methyl)fluorene, 9,9-bis((m-chlorobenzylcarboxy)methyl)fluorene, 9,9-bis((p-chlorobenzylcarboxy)methyl)fluorene, 9,9-bis(cinnamon carboxymethyl)fluorene, 9-(benzylcarboxymethyl)-9-(propenylcarboxymethyl)fluorene, 9,9-bis(propenylcarboxymethyl)fluorene, 9,9-bis(propenylcarboxymethyl)fluorene, and 9,9-bis(neopentylcarboxymethyl)fluorene.

[0064] According to some embodiments of the present invention, the diether compound is selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1 3-Dimethoxypropane, 2,2-Dicyclopentyl-1,3-dimethoxypropane, 2,2-Diethyl-1,3-dimethoxypropane, 2,2-Dipropyl-1,3-dimethoxypropane, 2,2-Diisopropyl-1,3-dimethoxypropane, 2,2-Dibutyl-1,3-dimethoxypropane, 2-Methyl-2-propyl-1,3-dimethoxypropane, 2-Methyl-2-benzyl-1,3-dimethoxypropane, 2-Methyl-2-ethyl-1,3-dimethoxypropane, 2-Methyl-2-isopropyl-1,3-dimethoxypropane, 2-Methyl-2-phenyl-1,3-dimethoxypropane, 2-Methyl-2-cyclohexyl-1 3-Dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2 -Isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, and 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane.

[0065] Therefore, the present invention further provides the application of the catalyst support described in the first aspect or the catalyst support described in the third aspect in the preparation of olefin polymerization catalysts.

[0066] In this invention, the catalyst components can be synthesized using conventional methods in the art, such as those described in Chinese Patent CN1091748A, which involves directly reacting spherical magnesium-containing composition particles with titanium halide; or as described in Chinese Patent CN104558274A, which involves first reacting the spherical magnesium-containing composition with an alkoxytitanium compound having the structural formula Ti(OR)4 to obtain an intermediate product, and then reacting it with titanium halide for preparation. During the above catalyst preparation process, some internal electron-donating compounds known in the industry may be optionally added, depending on the needs of the actual application.

[0067] Fifthly, the present invention provides an olefin polymerization catalyst comprising the catalyst component described in the fourth aspect, an alkylaluminum compound, and optionally an external electron donor compound.

[0068] According to some embodiments of the present invention, in the catalyst for olefin polymerization, the molar ratio of the alkylaluminum compound (calculated as aluminum) to the catalyst component for olefin polymerization (calculated as titanium) is 1-2000:1, preferably 20-500:1; the molar ratio of the external electron donor compound to the alkylaluminum compound (calculated as aluminum) is 0.005-0.5:1, preferably 0.01-0.4:1.

[0069] In this invention, the alkylaluminum compound can be selected from various alkylaluminum compounds commonly used in the art.

[0070] According to some embodiments of the present invention, the alkylaluminum compound is at least one selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, di-n-hexylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, and di-n-hexylaluminum chloride.

[0071] In this invention, the external electron donor compound can be selected from various external electron donor compounds commonly used in the art.

[0072] According to some embodiments of the present invention, the external electron donor is selected from at least one of carboxylic acids, acid anhydrides, esters, ketones, ethers, alcohols, organophosphorus compounds, and silicon compounds.

[0073] According to some embodiments of the present invention, the external electron donor is of general formula R. a x R b y Si(OR c ) z The organosilicon compound shown, in the general formula, R a R b and R c Each is C1-C 18hydrocarbon groups or C1-C containing heteroatoms 18 The hydrocarbon group; x and y are each integers from 0 to 2, z is an integer from 1 to 4, and x + y + z = 4.

[0074] According to some embodiments of the present invention, in general formula R a x R b y Si(OR c ) z In the middle, R a and R b At least one of them is selected from C3-C 10 Branched alkyl groups with or without heteroatoms, C3-C 10 With or without heteroatoms, cycloalkyl groups and C6-C 10 Any of the aryl groups, R c For C1-C 10 Straight-chain alkyl and C3-C 10 Any one of the branched alkyl groups, preferably methyl or ethyl; x is 1, y is 1, z is 2; or, R b For C3-C 10 Branched alkyl or C3-C 10 cycloalkyl, and R c For methyl, x is 0, y is 1, and z is 3.

[0075] According to some embodiments of the present invention, examples of the organosilicon compound may be, but are not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0076] In a sixth aspect, the present invention provides an olefin polymerization method, comprising: contacting at least one olefin with the catalyst described in the fifth aspect under olefin polymerization conditions.

[0077] According to some embodiments of the present invention, the olefin has the general formula CH2=CHR, wherein R is hydrogen or C1-C7 alkyl.

[0078] According to some embodiments of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.

[0079] The beneficial effects of this invention are at least as follows:

[0080] (1) By adding polyphosphate, a catalyst support with good particle morphology can be obtained without adding a polymeric dispersion stabilizer.

[0081] (2) The catalyst prepared using the catalyst support prepared in this invention has high polymerization activity when used for olefin polymerization. Attached Figure Description

[0082] Figure 1 This is an optical microscope image of the catalyst support prepared in Example 1.

[0083] Figure 2 This is an optical microscope image of the catalyst support prepared in Comparative Example 1. Detailed Implementation

[0084] To make the technical problem to be solved, the technical solution, and the beneficial effects of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely for illustrating this patent and do not limit the scope of protection of this invention in any way.

[0085] Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art. Unless otherwise specified, the reagents used in the following embodiments are conventional biochemical reagents; the raw materials, instruments, and equipment used in the following embodiments can all be obtained commercially or by existing methods; unless otherwise specified, the reagent dosages are those used in routine experimental operations; unless otherwise specified, the experimental methods are conventional methods.

[0086] In the various embodiments and comparative examples of the present invention, the performance data were tested according to the following test methods:

[0087] 1. Polymer melt index: determined according to ASTM D1238-99.

[0088] 2. Polymer isotactic index: The isotactic index is determined by the heptane extraction method (boiling heptane extraction for 6 hours). 2g of dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotactic index.

[0089] 3. Particle size distribution test: The average particle size and particle size distribution of the carrier particles were determined using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd). The particle size distribution value SPAN = (D90 - D10) / D50.

[0090] 4. The morphology of the catalyst support for olefin polymerization was observed using an optical microscope, model Eclipse E200, purchased from Nikon.

[0091] 5. Phosphorus content in the carrier: determined by inductively coupled plasma mass spectrometry.

[0092] 6. Catalyst activity = weight of polymer obtained / weight of catalyst used.

[0093] Example 1

[0094] In a 1.0 L reactor, 2.8 mol of ethanol, 0.2 mol of magnesium chloride, and 1.6 g of a 25 wt% sodium tripolyphosphate aqueous solution were added. The mixture was heated to 60 °C with stirring (450 rpm). After reacting at a constant temperature for 1 hour, 0.6 mol of epichlorohydrin was added, and the reaction was maintained at the temperature for 0.5 hours. The liquid was filtered off, the solid was washed five times with hexane, and dried under vacuum to obtain solid particles.

[0095] The main structure of the carrier was analyzed using nuclear magnetic resonance (NMR) as follows:

[0096]

[0097] Inductively coupled plasma mass spectrometry determined that the carrier contained 0.25 wt% phosphorus.

[0098] The carrier particle size distribution is D50 = 51.6 μm, Span = 0.6, and the particle morphology is shown in [reference needed]. Figure 1 .

[0099] Example 2

[0100] In a 1.0 L reactor, 2.4 mol of ethanol, 0.2 mol of magnesium chloride, and 1.0 g of a 50 wt% potassium tripolyphosphate aqueous solution were added. The mixture was heated to 70 °C with stirring (450 rpm). After reacting at a constant temperature for 1 hour, 0.6 mol of epichlorohydrin was added, and the reaction was maintained at the temperature for 0.5 hours. The liquid was filtered off, the solid was washed five times with hexane, and dried under vacuum to obtain solid particles.

[0101] The main structure of the carrier was analyzed using nuclear magnetic resonance (NMR) as follows:

[0102]

[0103] Inductively coupled plasma mass spectrometry determined that the carrier contained 0.3 wt% phosphorus.

[0104] The carrier particle size distribution is D50 = 45.8 μm and Span = 0.6.

[0105] Example 3

[0106] The preparation method is the same as in Example 1, except that 1g of a 25wt% sodium tripolyphosphate aqueous solution is added.

[0107] Inductively coupled plasma mass spectrometry determined that the carrier contained 0.15 wt% phosphorus.

[0108] The carrier particle size distribution is D50 = 40 μm and Span = 0.65.

[0109] Example 4

[0110] The preparation method is the same as in Example 1, except that 2.4g of a 25wt% sodium tripolyphosphate aqueous solution is added.

[0111] Inductively coupled plasma mass spectrometry determined that the carrier contained 0.35 wt% phosphorus.

[0112] The carrier particle size distribution is D50 = 60 μm and Span = 0.8.

[0113] Example 5

[0114] (1) Preparation of catalyst components

[0115] Under an inert atmosphere, 100 mL of titanium tetrachloride was added to a 300 mL glass reaction flask, cooled to -20 °C, and 8 g of the catalyst support prepared in Example 1 was added. The temperature was then raised to 110 °C. During the heating process, 1.5 mL of diisobutyl phthalate was added, the liquid was filtered off, and the sample was washed twice with titanium tetrachloride, three times with hexane, and dried under vacuum to obtain the catalyst component.

[0116] (2) Propylene polymerization

[0117] Propylene liquid-phase bulk polymerization was carried out in a 5L stainless steel high-pressure reactor. Under nitrogen protection, 5 mL of a hexane solution of triethylaluminum (0.5 mmol / mL), 1 mL of a hexane solution of cyclohexylmethyldimethoxysilane (CHMMS) (0.1 mmol / mL), and 9 mg of the above catalyst components were added sequentially to the reactor. The high-pressure reactor was closed, and 1.5 L (standard volume) of hydrogen and 2.3 L of liquid propylene were added. The temperature was raised to 70°C, and the reaction was carried out for 1 hour. The reactor was then cooled, depressurized, and discharged. The resulting propylene homopolymer was dried and weighed.

[0118] The results showed that the catalyst had a propylene polymerization activity of 3.5 kgPP / gCat, a polymer isotactic index of 97.2 wt%, and a polymer melt index of 8.2 g / 10 min.

[0119] Comparative Example 1

[0120] The preparation method is the same as in Example 1, except that sodium tripolyphosphate is not added.

[0121] See the morphology of the carrier particles Figure 2 .from Figure 2 It can be seen that the carrier particles adhered together, forming irregularly shaped particles.

[0122] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on 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 terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst support for olefin polymerization, characterized in that, The catalyst support comprises a magnesium compound and a phosphorus compound as shown in formula (I), （I） Where R1 is C1~C 12 Straight-chain alkyl or C3-C 12 The branched alkyl group; R2 and R3 may be the same or different, each independently selected from hydrogen, a C1-C5 straight-chain alkyl group or a C3-C5 branched alkyl group, wherein the hydrogen on the C1-C5 straight-chain alkyl group or the C3-C5 branched alkyl group is optionally substituted with a halogen atom; X is selected from halogens; m is 0.1-1.9; n is 0.1-1.9; m+n=2; The phosphorus compound includes at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, and their hydrates; The phosphorus compound content in the catalyst support is 0 by weight of phosphorus element. <p<3wt%。 2. The catalyst support according to claim 1, characterized in that, The phosphorus compound content in the catalyst support is 0.01 wt% based on the elemental weight of phosphorus. <p<1wt%。 3. The catalyst support according to claim 1, characterized in that, R1 is a C1-C8 straight-chain alkyl group or a C3-C8 branched alkyl group; And / or, R2 and R3 may be the same or different, each independently selected from hydrogen, C1-C3 straight-chain alkyl or isopropyl or halogen-substituted C1-C3 straight-chain alkyl or isopropyl; And / or, the halogen is selected from chlorine, bromine and iodine.

4. The catalyst support according to claim 3, characterized in that, R1 is selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl, and 2-ethylhexyl; And / or, R2 and R3 are each independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl; And / or, the halogen is chlorine.

5. The catalyst support according to any one of claims 1-4, characterized in that, The catalyst support is a spherical particle.

6. The catalyst support according to claim 5, characterized in that, The catalyst support has an average diameter of 10-100 μm and a particle size distribution of less than 1.

2.

7. The catalyst support according to claim 6, characterized in that, The catalyst support has an average diameter of 30-70 μm and / or a particle size distribution of 0.6-0.

9.

8. A method for preparing an olefin polymerization catalyst support, characterized in that, include: (a) A suspension is formed by reacting magnesium halide of general formula MgX2, an alcohol compound of general formula R1OH and a polyphosphate, wherein the polyphosphate includes at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate and their hydrates; (b) The suspension formed in step (a) is reacted with an epoxy compound to generate an olefin polymerization catalyst support; The epoxy compound is shown in general formula (II). (II) R2 and R3 may be the same or different, and each is independently selected from hydrogen, a straight-chain alkyl group of C1 to C5 or a branched alkyl group of C3 to C5, wherein the hydrogen on the straight-chain alkyl group of C1 to C5 or the branched alkyl group of C3 to C5 may optionally be replaced by a halogen atom.

9. The preparation method according to claim 8, characterized in that, R1 is a C1-C8 straight-chain alkyl group or a C3-C8 branched alkyl group; And / or, R2 and R3 may be the same or different, each independently selected from hydrogen, C1-C3 straight-chain alkyl or isopropyl or halogen-substituted C1-C3 straight-chain alkyl or isopropyl; And / or, the magnesium halide represented by the general formula MgX2 includes at least one of magnesium dichloride, magnesium dibromide, and magnesium diiodide.

10. The preparation method according to claim 9, characterized in that, The alcohols represented by the general formula R1OH include at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethyl-1-hexanol; And / or, R2 and R3 are each independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, and bromoethyl; And / or, the epoxy compound includes at least one of ethylene oxide, propylene oxide, epibutylene oxide, epichlorohydrin, epichlorohydrin, epibromopropane, and epibromobutane; And / or, the magnesium halides represented by the general formula MgX2 include magnesium dichloride.

11. The preparation method according to any one of claims 8-10, characterized in that, The molar ratio of the alcohol compound to magnesium halide is (3-30):1; the molar ratio of the polyphosphate to magnesium halide is 1:(10-300). And / or, the reaction temperature in step (a) is 30–160°C, and the reaction time is 0.1–5 hours; And / or, step (a) is performed in a closed container; And / or, the polyphosphate in step (a) is prepared into an aqueous solution of polyphosphate and then participates in the reaction; And / or, the molar ratio of the epoxy compound to magnesium halide is (1-10):1; And / or, the reaction temperature in step (b) is 30–160°C and the reaction time is 0.1–5 hours.

12. The preparation method according to claim 11, characterized in that, The molar ratio of the alcohol compound to the magnesium halide is (4-25):1; And / or, the molar ratio of the polyphosphate to magnesium halide is 1:(20-200); And / or, the reaction temperature in step (a) is 40–120°C, and the reaction time is 0.5–2 hours; And / or, the concentration of the polyphosphate aqueous solution is 10–60 wt%; And / or, the molar ratio of the epoxy compound to magnesium halide is (2-6):1; And / or, the reaction temperature in step (b) is 40–120°C and the reaction time is 0.2–1 hour.

13. The preparation method according to claim 12, characterized in that, The concentration of the polyphosphate aqueous solution is 30–60 wt%.

14. An olefin polymerization catalyst support, prepared by any one of claims 8-13.

15. The catalyst support according to claim 14, characterized in that, The catalyst support is a spherical particle.

16. The catalyst support according to claim 15, characterized in that, The catalyst support has an average diameter of 10-100 μm and a particle size distribution of less than 1.

2.

17. The catalyst support according to claim 16, characterized in that, The catalyst support has an average diameter of 30-70 μm and a particle size distribution of 0.6-0.

9.

18. An olefin polymerization catalyst component comprising the reaction product of a catalyst support according to any one of claims 1-7 or a catalyst support according to any one of claims 14-17 with a titanium compound and optionally an internal electron donor compound.

19. An olefin polymerization catalyst comprising the catalyst component of claim 18, an alkylaluminum compound, and optionally an external electron donor compound.

20. A method for olefin polymerization, comprising: Under olefin polymerization conditions, at least one olefin is contacted and reacted with the catalyst of claim 19.

21. The olefin polymerization method according to claim 20, characterized in that, The olefin has the general formula CH2=CHR, where R is hydrogen or a C1-C7 alkyl group.

22. The olefin polymerization method according to claim 21, characterized in that, The olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.

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