Solid catalyst component for olefin polymerization, and method for preparing and using same - Patent Application 20070122997

Abstract

The present invention relates to the field of olefin polymerization catalysts and discloses a solid catalyst component for olefin polymerization, which comprises magnesium element, titanium element, a halogen, a poly-α-olefin, and an internal electron donor, and the Ti2p spectrogram obtained by XPS analysis of the solid catalyst component is subjected to peak splitting by Gauss-Lorentz peak splitting fitting, and the result of the peak splitting is Ti2p 3 / 2 The orbital spectrum peak has at least three characteristic peaks at electron binding energies of 459.9 eV to 454.9 eV. When the solid catalyst component is used in olefin polymerization, the activity decay slows with increasing storage time, and the content of the resulting polymer fine powder is low.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of Chinese patent applications 202211320920.2, 202211321506.3, 202211321006.X, 202211321023.3, and 202211321504.4, filed on October 26, 2022, the contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of olefin polymerization catalysts, in particular to solid catalyst components for olefin polymerization, as well as methods for preparing and using the same. [Background technology]

[0003] Ziegler-Natta spherical catalysts are widely used in loop polypropylene processes for the preparation of propylene homopolymer, propylene / ethylene (or butene) random copolymers, and impact copolymers. They offer high polymerization activity, high stereospecificity, and highly regular polymer particles. Spherical catalysts are also used in gas-phase polypropylene and polyethylene processes equipped with prepolymerization units, such as the SHPERIZONE and SHPERILENE processes for the production of polypropylene and polyethylene. Although these processes are equipped with prepolymerization units, the destruction of catalyst and polymer particles during resin production still occurs, resulting in the inclusion of a certain amount of fines in the polymer. In particular, in the production of propylene homopolymer with a high melt flow index (MFR), the polymer contains a large amount of fines, which affects the stability and long-term operation of the equipment. Polypropylene equipment without prepolymerization units, such as the UNIPOL process, is not suitable for the use of Ziegler-Natta spherical catalysts because the catalyst or polymer particles are almost completely destroyed during the polymerization process, resulting in the generation of a large amount of fines.

[0004] US9453088B2 discloses a prepolymerization catalyst for olefin polymerization, which has an average particle size of less than 30 μm, a prepolymerization ratio of less than 50 g polymer / g catalyst, and contains two electron donors, a 1,3-diether and an aromatic ester. The preparation method involves first preparing a spherical catalyst containing two electron donors, a 1,3-diether and an aromatic ester, and then prepolymerizing the catalyst with an olefin having 2 to 10 carbon atoms to obtain the prepolymerization catalyst. CN1421468A discloses a method for propylene polymerization or copolymerization, which involves prepolymerizing a Ziegler-Natta catalyst with ethylene or an α-olefin at -10°C to 80°C, controlling the prepolymerization ratio to 6 to 50,000, followed by propylene polymerization. US7329714B2 discloses a method for preparing polypropylene, which comprises prepolymerizing propylene or 4-methyl-1-pentene with a Ziegler-Zatta type catalyst at 0-40°C, followed by propylene polymerization.

[0005] However, when the prepolymerization catalyst is prepared using ethylene as the prepolymerization monomer, the catalyst is inevitably destroyed, and the polymer produced during the olefin polymerization reaction has a relatively high fines content. Prepolymerization catalysts prepared using propylene or other α-olefins as the prepolymerization monomer exhibit a relatively rapid decline in activity over time, reducing their commercial value. Regardless of whether the prepolymerization catalyst is prepared by ethylene prepolymerization or propylene prepolymerization, the polymerization activity declines over time, resulting in an "unstable" polymerization activity that cannot meet the requirements for industrial use. Summary of the Invention [Problem to be solved by the invention]

[0006] In view of this, an object of the present invention is to provide a solid catalyst component for olefin polymerization, as well as a method for preparing and using the same, which addresses the problem of existing Ziegler-Zatta type prepolymerization catalysts that their polymerization activity rapidly declines with increasing storage time. [Means for solving the problem]

[0007] First, the present invention provides a solid catalyst component for olefin polymerization, which comprises magnesium element, titanium element, a halogen, a poly-α-olefin, and an internal electron donor, and the Ti2p spectrogram obtained by XPS analysis of the solid catalyst component is subjected to peak splitting by Gauss-Lorentz peak splitting fitting, and the result of the peak splitting is Ti2p 3 / 2 The orbital spectrum has at least three characteristic peaks at electron binding energies between 459.9 eV and 454.9 eV. The Gaussian-Lorentzian peak split fitting method uses a Lorentzian-to-Gaussian ratio of 30% and Ti2p 1 / 2 Electron binding energies of orbital spectral peaks and Ti2p 3 / 2 The difference between the electron binding energy of the orbital spectrum peak and the Ti2p 1 / 2 The half-width of the orbital spectrum peak is Ti2p 3 / 2 1.7 times the half-width of the orbital spectrum peak, Ti2p 1 / 2 The peak height of the orbital spectrum peak is defined as Ti2p 3 / 2 0.28 times the peak height of the orbital spectrum peak, Ti2p 3 / 2 The present invention provides a solid catalyst component for olefin polymerization, which is configured so that each characteristic peak of the spectral peaks of the orbital has the same half-width.

[0008] Secondly, the present invention provides a method for preparing a solid catalyst component for olefin polymerization, the method comprising: Step (1) of contacting and reacting a catalyst component A, an alkylaluminum, and an external electron donor compound in the presence of an inert solvent, wherein the catalyst component A contains titanium element, magnesium element, a halogen, and an internal electron donor; Step (2) of mixing the reaction system obtained in step (1) with an α-olefin to carry out a polymerization reaction; and step (3) removing the unreacted α-olefin from step (2) and adding hydrogen gas to the resulting reaction system to react.

[0009] Third, the present invention provides a solid catalyst component prepared by the above method.

[0010] Fourth, the present invention provides a catalyst system for olefin polymerization, comprising the above-described solid catalyst component and / or the solid catalyst component prepared by the above-described method, an alkylaluminum, and an optional external electron donor compound, or a reaction product thereof.

[0011] Fifth, the present invention provides the use of the above solid catalyst component and / or the solid catalyst component prepared by the above method and / or the above catalyst system in olefin polymerization.

[0012] Sixth, the present invention provides a method for polymerizing olefins, the method comprising the step of polymerizing olefins in the presence of the above-mentioned solid catalyst component and / or the solid catalyst component prepared by the above-mentioned method and / or the above-mentioned catalyst system. [Effects of the Invention]

[0013] The present invention has the following advantages: The solid catalyst component according to the present invention belongs to the Ziegler-Zatta type prepolymerization catalyst, and has the advantages that the decay of polymerization activity is slow with increasing storage time, and the polymer obtained by using the solid catalyst component in polymerization has a low content of fine powder, and this solid catalyst component is not only suitable for olefin polymerization equipment equipped with a prepolymerization operation unit, but also for polyolefin equipment without a prepolymerization operation unit. [Brief explanation of the drawings]

[0014] [Figure 1] 1 shows XRD charts of catalyst E1 (top) of Example 1 and catalyst CE1 (bottom) of Comparative Example 1. [Figure 2] FIG. 1 is an XPS peak split fitting diagram of catalyst E1 (top) of Example 1 and catalyst CE1 (bottom) of Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will now be further described with reference to specific examples, which are not intended to limit the scope of the present invention.

[0016] According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization, comprising magnesium element, titanium element, a halogen, a poly-α-olefin, and an internal electron donor, the solid catalyst component being characterized in that a Ti2p spectrogram obtained by XPS analysis of the solid catalyst component is subjected to peak splitting by Gauss-Lorentz peak splitting fitting, and the result of the peak splitting is Ti2p 3 / 2 The orbital spectrum has at least three characteristic peaks at electron binding energies between 459.9 eV and 454.9 eV. Here, the Gaussian-Lorentzian peak split fitting method uses a Lorentzian-to-Gaussian ratio of 30% and Ti2p 1 / 2 Electron binding energies of orbital spectral peaks and Ti2p 3 / 2 The difference between the electron binding energy of the orbital spectrum peak and the Ti2p 1 / 2 The half-width of the orbital spectrum peak is Ti2p 3 / 2 1.7 times the half-width of the orbital spectrum peak, Ti2p 1 / 2 The peak height of the orbital spectrum peak is defined as Ti2p 3 / 2 0.28 times the peak height of the orbital spectrum peak, Ti2p 3 / 2 The present invention provides a solid catalyst component for olefin polymerization, which is configured so that each characteristic peak of the spectral peaks of the orbital has the same half-width.

[0017] As is well known in the art, the Ti2p spectrogram obtained by XPS analysis of the solid catalyst component was subjected to peak splitting by Gauss-Lorentzian peak splitting fitting, resulting in Ti2p 1 / 2 Orbital spectral peaks and Ti2p 3 / 2 A characteristic pair of peaks appears in the orbital spectrum. 1 / 2 Electron binding energies of orbital spectral peaks and Ti2p 3 / 2 The difference between the electron binding energy of the orbital spectrum peak is called "Ti2p 1 / 2 Orbital spectral peaks and Ti2p 3 / 2 It refers to the difference in electron binding energy between the characteristic peaks that appear as pairs in the orbital spectrum. 1 / 2 Half-width of the orbital spectral peak and Ti2p 3 / 2 The ratio of the half-width of the orbital spectrum peak to the 1 / 2 Orbital spectral peaks and Ti2p 3 / 2 It refers to the "ratio of half-widths between characteristic peaks that appear as pairs in the orbital spectrum." 1 / 2 Peak height of the orbital spectrum peak and Ti2p 3 / 2 The ratio of the peak height of the orbital spectrum peak to the peak height of the orbital spectrum peak is called "Ti2p 1 / 2 Orbital spectral peaks and Ti2p 3 / 2 For example, the ratio of the peak heights of the characteristic peaks appearing in pairs in the spectrum peaks of the Ti2p orbitals in the XPS spectrum of the solid catalyst component in descending order of electron binding energy is 3 / 2 The characteristic peaks of the orbital spectrum are named sequentially as the first characteristic peak, the second characteristic peak, the third characteristic peak, etc., in descending order of electron binding energy. 1 / 2 The characteristic peaks of the orbital spectrum are named sequentially as characteristic peak I, characteristic peak II, characteristic peak III, etc. 1 / 2 Electron binding energies of orbital spectral peaks and Ti2p 3 / 2The difference in electron binding energy between the orbital spectral peaks means that the difference in electron binding energy between the first characteristic peak and the first characteristic peak, the difference in electron binding energy between the second characteristic peak and the second characteristic peak, and the difference in electron binding energy between the third characteristic peak and the third characteristic peak are all 5.9 eV. 1 / 2 Half-width of the orbital spectral peak and Ti2p 3 / 2 Ratio of the spectral peak width at half maximum to the orbital width, and Ti2p 1 / 2 orbital spectral peak height and Ti2p 3 / 2 The ratio of the spectral peak of the orbit to the peak height is also the same.

[0018] According to the solid catalyst component of the present invention, the electron binding energy of Ti2p of titanium element and C1s of carbon element is measured by X-ray photoelectron spectroscopy (XPS). XPS uses a monochromated Al Kα radiation source and an electron neutralization gun to neutralize the charge on the sample surface until it is completely neutralized (charge neutralization). High-resolution spectrograms are acquired with a pass energy of 20 eV and a step size of 0.05 eV, and the analysis area is 500 μm 2 is.

[0019] XPS test sample preparation method: In a glove box, use an infrared press to press the sample onto non-conductive double-sided tape, then transfer the pressed sample to an air-sensitive sample protection table for sealed storage. Then, quickly transfer the air-sensitive sample protection table to the XPS sample preparation chamber and apply vacuum suction until the pressure in the preparation chamber reaches 10 -6 After the pressure drops below 10 mbar, open the sealing cover of the sensitive sample protection table and wait for the pressure in the preparation chamber to drop below 10 mbar again. -6 After the pressure drops below 100 mbar, the sample is transferred to the analysis chamber for XPS testing. The charge of the prepolymerized catalyst (i.e., the solid catalyst component described above) is calibrated based on the C1s peak top binding energy value of 284.80 eV of the polypropylene or polyethylene contained in the catalyst.

[0020] In some preferred embodiments, in the XPS spectrum of the solid catalyst component, Ti2p 3 / 2 The electron binding energy has 3 to 5 characteristic peaks within the range of 459.9 eV to 454.9 eV. For example, there are 3 characteristic peaks, 4 characteristic peaks, 5 characteristic peaks, etc. within the range of 459.9 eV to 454.9 eV. In the XPS spectrum of the solid catalyst component, Ti2p 3 / 2 The characteristic peaks of the orbitals are successively named as the first characteristic peak, the second characteristic peak, the third characteristic peak, the fourth characteristic peak, the fifth characteristic peak, etc. In a particularly preferred case, in the XPS spectrum of the solid catalyst component, Ti2p 3 / 2 The electron binding energy has three characteristic peaks in the range of 459.9 eV to 454.9 eV.

[0021] In some preferred embodiments, the Ti2p of the solid catalyst component 3 / 2 The orbital spectrum peak has three characteristic peaks at electron binding energies of 459.9 eV to 454.9 eV, which are named the first, second, and third characteristic peaks in descending order of electron binding energy. The electron binding energies of the first characteristic peak are 459.9 eV to 458.97 eV, the second characteristic peak are 458 eV to 457.45 eV, and the third characteristic peak are 456.2 eV to 454.9 eV. The naming of the three characteristic peaks does not limit the technical solution of the present invention, but is merely for distinguishing different characteristic peaks for better description.

[0022] In some embodiments, the Ti2p of the solid catalyst component 1 / 2 The electron binding energy of the orbital spectrum peak is 467 eV to 460 eV. The Ti2p spectrogram obtained by XPS analysis of the solid catalyst component was peak-split by Gauss-Lorentz peak split fitting. 1 / 2 orbital spectral peaks, and Ti2p3 / 2 The spectral peaks of the trajectories have the same number of characteristic peaks.

[0023] In some embodiments, the titanium element has a Ti2p 3 / 2 Electron binding energies, for example, 455.42 eV, 455.44 eV, 455.45 eV, 455.46 eV, 455.47 eV, 455.50 eV, 455.54 eV, 455.62 eV, 455.63 eV, 455.64 eV, 455.65 eV, 455.66 eV, 455.67 eV, 455.68 eV, 455.69 eV, 455.70 eV, 455.71 eV, 455.72 eV, 455.79 eV, 455.80 eV, 455.81 eV, 455.82 eV, or 455.83 eV for Ti2p 3 / 2 It has an electron binding energy.

[0024] In some embodiments, Ti2p between 456.20 eV and 454.90 eV, preferably between 455.40 eV and 455.85 eV 3 / 2 In addition to the electron binding energy, titanium element has Ti2p between 458.97 eV and 459.25 eV and / or 457.45 eV and 458.00 eV 3 / 2 For example, titanium has an electron binding energy of 459.09 eV to 459.19 eV and / or 457.60 to 457.75 eV, Ti2p 3 / 2 For example, titanium has an electron binding energy of 459.05 eV to 459.15 eV and / or 457.45 eV to 457.55 eV. 3 / 2 Further, for example, the titanium element has an electron binding energy of 458.97 eV to 459.25 eV and / or 457.53 to 458.00 eV, such as Ti2p 3 / 2 It has an electron binding energy.

[0025] In some preferred embodiments, the peak area of ​​the third characteristic peak accounts for 5 to 20%, preferably 5 to 15%, of the total peak area of ​​the first, second, and third characteristic peaks (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, and a range consisting of any two of the above points). Here, the peak area of ​​the first characteristic peak, the peak area of ​​the second characteristic peak, and the peak area of ​​the third characteristic peak are designated S1, S2, and S3, respectively.

[0026] In some preferred embodiments, the solid catalyst component does not contain detectable amounts of Group IVB elements other than Ti, for example, the solid catalyst component does not contain detectable amounts of Zr and / or Hf.

[0027] According to the solid catalyst component of the present invention, the poly-α-olefin is polyC2-C 10 The olefin is preferably selected from one or more of polyethylene, polypropylene, polybutene, polyoctene, and polyisopentene, more preferably polypropylene.

[0028] According to the solid catalyst component of the present invention, the internal electron donor comprises at least one of a diol ester compound, a 1,3-diether compound, and a carboxylate.

[0029] In some preferred embodiments, the diol ester compound has a chemical structure shown in formula (1). [ka] In formula (1), R1 to R6 are the same or different and each independently represent hydrogen, amino, C1 to C6 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10Alkylaryl and C7-C 10 aralkyl, wherein two or more groups among R1 to R6 are optionally bonded to each other to form one or more fused ring structures, and R7 and R8 are the same or different and each independently represent a C1 to C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkylaryl and C7-C 20 aralkyl.)

[0030] According to the solid catalyst component of the present invention, in formula (1), R1 to R6 are the same or different and each independently represent hydrogen, amino, C1 to C6 linear alkyl, C3 to C8 branched alkyl, C3 to C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkylaryl and C7-C 10 aralkyl, preferably two or more groups among R1 to R6 are optionally bonded to each other to form one or more fused ring structures.

[0031] According to the solid catalyst component of the present invention, in formula (1), R7 and R8 are the same or different, and each independently represent a C1-C6 linear alkyl, a C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkylaryl and C7-C 10 aralkyl.

[0032] According to the solid catalyst component of the present invention, the diol ester compound is 1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-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 dibenzoate, 1,3-diphenyl-2,2-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-butylbenzoate), 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl-1,3-butanediol dibenzoate, 2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di(p-methylbenzoate), 2,4-pentanediol di(p-tert-butylbenzoate), 2,4-pentanediol di(p-butylbenzoate), 2-methyl-1,3-pentanediol di(p-methylbenzoate), 2-butyl-1,3-pentanediol Di(p-methylbenzoate), 2-methyl-1,3-pentanediol di(p-tert-butylbenzoate), 2-methyl-1,3-pentanediol pivalate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-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, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3-propyl-3,5-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, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6 At least one selected from the group consisting of 4-methyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-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, and 4-methyl-4-ethyl-3,5-heptanediol dibenzoate.

[0033] In some preferred embodiments, the 1,3-diether compound has the chemical structure shown in formula (2). [ka] (In formula (2), R1 and R2 are the same or different and each independently represents hydrogen, C1 to C 20 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl and C7-C 20alkylaryl; R and R are the same or different and each independently represent a C to C 10 alkyl.

[0034] According to the solid catalyst component of the present invention, in formula (2), R1 and R2 are the same or different and each independently represent hydrogen, C1 to C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 20 Aralkyl and C7-C 10 alkylaryl, and / or R3 and R4 are each independently selected from C1-C6 alkyl.

[0035] According to the solid catalyst component of the present invention, the 1,3-diether compounds are 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-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-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,At least one selected from 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

[0036] According to the solid catalyst component of the present invention, in the formula (1) and formula (2), hydrogen on the benzene ring in the aryl, alkylaryl and / or aralkyl may be optionally substituted with a halogen atom.

[0037] According to the solid catalyst component of the present invention, the carboxylate is an aliphatic carboxylate and / or an aromatic carboxylate. In some embodiments, the carboxylate is at least one selected from monohydric aliphatic carboxylates, dihydric aliphatic carboxylates, monohydric aromatic carboxylates, and dihydric aromatic carboxylates. Among these, the aliphatic carboxylate refers to a carboxylate prepared from a monohydric (or dihydric) aliphatic carboxylic acid and an aliphatic monohydric alcohol or an aromatic monohydric alcohol, and the aromatic carboxylate refers to a carboxylate prepared from a monohydric (or dihydric) aromatic carboxylic acid and an aliphatic monohydric alcohol or an aromatic monohydric alcohol. Preferably, the carboxylate is one or more selected from benzoate-based compounds, phthalate-based compounds, and succinate-based compounds.

[0038] In the present invention, the benzoate-based compound may be one or more selected from methyl benzoate, ethyl benzoate, and n-butyl benzoate.

[0039] For example, the phthalate-based compound may be one or more selected from diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, and di-n-octyl phthalate.

[0040] For example, the succinate compound is one or more selected from diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, and diethyl 2-ethyl-2-methylsuccinate.

[0041] According to the solid catalyst component of the present invention, the internal electron donor comprises an internal electron donor a and an internal electron donor b, and the internal electron donor a and the internal electron donor b are as follows: Option I: the internal electron donor a is selected from the diol ester compounds, and the internal electron donor b is selected from 1,3-diether compounds, and any carboxylate; Option II: The internal electron donor a is selected from the 1,3-diether compounds, and the internal electron donor b is selected from the phosphate compounds represented by formula (3). [ka] (In formula (3), R5, R6 and R7 are the same or different and each independently represents a C1-C4 linear alkyl, a C3-C4 branched alkyl, a C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkylaryl and C7-C 20 aralkyl.)

[0042] According to the solid catalyst component of the present invention, in formula (3), R5, R6 and R7 are the same or different, and each independently represent C1 to C4 linear alkyl, C3 to C4 branched alkyl, C3 to C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkylaryl and C7-C 10 aralkyl.

[0043] According to the solid catalyst component of the present invention, the phosphate compound is at least one selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tritolyl phosphate, triisopropylphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl xylyl phosphate, phenyl diisopropylphenyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, and o-tolyl p-di-tert-butylphenyl phosphate.

[0044] According to the solid catalyst component of the present invention, the internal electron donor includes the internal electron donor a and the internal electron donor b, and the mass ratio of the internal electron donor a to the internal electron donor b may be 0.1:1 to 1000:1. For example, the mass ratio of the internal electron donor a to the internal electron donor b may be 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 2:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 80:1, 100:1, 200:1, 500:1, 800:1, 1000:1, and ranges thereof.

[0045] According to the solid catalyst component of the present invention, said solid catalyst component is a spherical solid particle.

[0046] In the preferred case, the average particle size D of the solid catalyst component50 For example, the average particle size D of the solid catalyst component is 5 to 150 μm. 50 Specifically, the average particle size D of the solid catalyst component may be 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 100 μm, 120 μm, 150 μm, or a range thereof. 50 The thickness may be 20 to 80 μm.

[0047] In the present invention, the average particle diameter D 50 is measured using a Master Sizer 2000 laser particle size analyzer (Malvern Instruments Ltd).

[0048] Preferably, the particle size distribution value (SPAN) of the solid catalyst component is 0.75 to 0.85.

[0049] In the present invention, the carrier was measured using a Masters Sizer 2000 particle size analyzer manufactured by Malvern Instruments, UK, to test the SPAN value, and n-hexane was used as the dispersion medium. The particle size distribution value Span = (D90 - D10) / D50.

[0050] In the solid catalyst component according to the present invention, the content of the poly-α-olefin is 0.1 to 89 wt %, preferably 1 to 50 wt %, more preferably 9 to 35 wt %, based on the total weight of the solid catalyst component; the content of titanium element is 0.1 to 3.5 wt %, preferably 0.5 to 2.5 wt %, more preferably 1.5 to 2.5 wt %; the content of magnesium element is 1 to 18 wt %, preferably 11 to 17 wt %; the content of halogen is 2 to 65 wt %, preferably 35 to 55 wt %; and the content of the internal electron donor is 0.6 to 15 wt %, preferably 1 to 10 wt %, more preferably 6 to 10 wt %, based on the total weight of the solid catalyst component.

[0051] In the present invention, the halogen is one or more selected from chlorine, chlorine, bromine, and iodine, preferably chlorine.

[0052] According to the solid catalyst component of the present invention, the magnesium element and / or halogen may be derived from a support, which is preferably an alkoxy magnesium support, a spherical magnesium chloride alcoholate support, or a spherical magnesium compound support, the type of which is as described in the second embodiment.

[0053] According to the solid catalyst component of the present invention, the titanium element and / or halogen may be derived from a titanium halide (e.g., titanium tetrachloride), wherein the type of said titanium halide is as described in the second embodiment.

[0054] The titanium content of the solid catalyst component of the present invention can be measured by colorimetry. Specifically, 0.2 to 0.5 g of sample is dissolved in 50 mL of 2N H2SO4, the upper suspension is filtered, and the clear solution is collected for colorimetric analysis. Using the 2N H2SO4 solution as a blank, a cuvette is set to a thickness of 1 cm and its absorbance E1 is measured at a wavelength of 410 μm. Next, one drop of 30% H2O2 is added, the mixture is shaken well, and its absorbance E2 is measured. The titanium content Ti (%) is calculated using the following formula: Ti%=[(E2-E1)×100) / (K·L·W·100)]×100 In the formula, W is the weight of the sample (g), L is the thickness of the cuvette (cm), K is the specific extinction coefficient, E1 is the absorbance of the blank, and E2 is the absorbance of the sample.

[0055] Magnesium content can be measured by EDTA titration. Specifically, 0.2–0.5 g of sample is placed in a 250 mL Erlenmeyer flask, 20–30 mL of 2N H2SO4 solution is added, 20 mL of triethanolamine (1+2) standard solution is added, and the pH is adjusted to 10 with 20% NaOH solution. Shake well, add 10 mL of pH 10 buffer, 6 drops of 30% H2O2, and 30–50 mL of distilled water. Add a small amount of chrome black T indicator, shake well, and titrate with 0.02 N EDTA solution until the color changes from reddish purple to blue (the purple light disappears). Calculate the magnesium content (Mg) (%) using the following formula: Mg(%)=[(VE·NE×24.31) / (G·1000)]×100 In the formula, G is the mass of the sample (g), VE is the amount of EDTA consumed (mL), NE is the number of equivalents of the EDTA solution, and 24.31 is the atomic weight of magnesium.

[0056] The chlorine content can be measured by silver nitrate titration. Specifically, 0.04–0.1 g of sample is weighed into an Erlenmeyer flask, 20 mL of 2N H2SO4 solution is added, and the flask is left to stand for 30 minutes. After rinsing with distilled water several times, 20–30 mL of 0.1N AgNO3 solution is added dropwise, followed by 3 mL of 1:1 HNO3 solution. Excess AgNO3 solution is titrated with 0.1N NH4CNS standard solution until the brick color does not disappear after 2 seconds. Calculate the chlorine content (Cl) (%) using the following formula: Cl(%)=[(V1-V2×D)×N1×35.45 / G·1000)]×100 In the formula, V1 is the volume of AgNO3 solution (mL), V2 is the volume of NH4CNS solution consumed (mL), D is the volume ratio of AgNO3 / NH4CNS solution, N1 is the equivalent concentration of AgNO3, G is the mass of the sample (g), and 35.45 is the atomic weight of chlorine.

[0057] The test method for the poly-α-olefin content in the solid catalyst component is to weigh a certain amount of sample (M1), dissolve it in ethanol and dilute hydrochloric acid, and dry the insoluble matter under vacuum at 80°C to obtain a solid (M2). 0.2 g of this solid is pressed and the poly-α-olefin content (C1) in the solid is measured using an infrared spectrometer, and the mass percentage of poly-α-olefin in the solid catalyst component is calculated using the following formula: C A =M2×C1 / M1 C A is the mass percentage of poly-α-olefin in the solid catalyst component, M1 and M2 are the masses (g) of the sample and dry solid, respectively, and C1 is the mass percentage of poly-α-olefin in the dry solid.

[0058] The test method for the content of internal electron donors in solid catalyst components is to dissolve the sample in ethyl acetate and hydrochloric acid solution (concentration 2 mol / L), extract the internal electron donors, and analyze their content using conventional liquid chromatography.

[0059] According to the solid catalyst component of the present invention, the solid catalyst component further contains an alkylaluminum and an external electron donor. The type and content of the alkylaluminum and external electron donor can be selected with reference to conventional olefin prepolymerization catalysts. In polymerization processes known in the art, small amounts of alkylaluminum and external electron donor remain in the polyolefin, and the content of the alkylaluminum and external electron donor is usually the residual amount in the polyolefin. The type of the alkylaluminum and external electron donor is as described in the second embodiment.

[0060] In addition to the above components, the solid catalyst component of the present invention may also contain other components, such as an inert solvent, for example, an inert solvent added in the preparation process of the solid catalyst component described in the second embodiment.

[0061] According to a second aspect of the present invention, there is provided a method for preparing a solid catalyst component for olefin polymerization, said method comprising the steps of: Step (1) of contacting and reacting catalyst component A, alkylaluminum, and an external electron donor in the presence of an inert solvent, wherein catalyst component A contains titanium element, magnesium element, a halogen, and an internal electron donor; Step (2) of mixing the reaction system obtained in step (1) with an α-olefin to carry out a polymerization reaction; and step (3) removing the unreacted α-olefin from step (2) and adding hydrogen gas to the resulting reaction system to react.

[0062] In the present invention, the catalyst component A represents a non-prepolymerized catalyst, and the solid catalyst component represents a prepolymerized catalyst.

[0063] In the preparation method according to the present invention, in step (1), both the alkylaluminum and the external electron donor compound may be selected with reference to conventional olefin prepolymerization catalysts, but are not particularly limited in the present invention. The alkylaluminum may have 1 to 3 alkyl groups, and the alkyl may have C1 to C8 carbon atoms. Typically, the alkylaluminum may be one or more selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and monochlorodiethylaluminum. The external electron donor compound may be at least one selected from silicon-containing compounds, and may be one or more selected from cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, and dicyclopentyldimethoxysilane.

[0064] Generally, the molar ratio of the alkyl aluminum, the external electron donor compound, and the catalyst component A in terms of elemental titanium may be 1 to 50:0.2 to 10:1. For example, the molar ratio of the alkyl aluminum, the external electron donor compound, and the catalyst component A in terms of elemental titanium may be 1:0.2:1, 5:0.2:1, 10:0.2:1, 15:0.2:1, 20:0.2:1, 30:0.2:1, 40:0.2:1, 50:0.2:1, 15:0.3:1, 15:0.5:1, 15:1:1, 15:2:1, 15:3:1, 15:4:1, 15:5:1, 15:20:1, or any range of values ​​between the alkyl aluminum and the external electron donor compound.

[0065] According to the preparation method of the present invention, in step (1), the amount of the alkyl aluminum used is 1 to 30 mmol, preferably 15 to 20 mmol, and the amount of the external electron donor compound used is 0.01 to 10 mmol, preferably 0.1 to 1 mmol, relative to 25 g of catalyst component A.

[0066] According to the preparation method of the present invention, the internal electron donor includes at least one of a diol ester compound, a 1,3-diether compound, and a carboxylate. The internal electron donor is the same as that in the first embodiment, and therefore will not be described in detail here.

[0067] According to the preparation method of the present invention, in step (1), the inert solvent may be selected with reference to the prior art. Generally, the inert solvent may be one or more selected from hexane, heptane, and decane. The amount of the inert solvent added is such that the mass concentration of the catalyst component A in the inert solvent can be 5 to 50 g / L.

[0068] According to the preparation method of the present invention, in step (1), the reaction conditions include that the temperature may be 0 to 30°C, preferably 15 to 25°C, and the reaction time may be 1 to 30 minutes, preferably 10 to 20 minutes.

[0069] According to the preparation method of the present invention, in step (2), the polymerization reaction conditions include that the temperature may be 0 to 50°C, preferably 15 to 25°C, and the time may be 5 to 30 minutes, preferably 10 to 20 minutes.

[0070] According to the preparation method of the present invention, in step (3), the reaction conditions include that the temperature may be 0 to 50°C, preferably 15 to 25°C, and the reaction time may be 5 to 30 minutes, preferably 10 to 20 minutes.

[0071] In the preparation method according to the present invention, the method for removing the unreacted α-olefin in step (2) may be a method commonly used in the art, for example, first releasing all the unreacted α-olefin and then replacing the remaining α-olefin with an inert gas. That is, step (3) comprises first releasing all the unreacted α-olefin in step (2), then replacing the remaining α-olefin with an inert gas, and then adding hydrogen gas to the resulting reaction system to cause a reaction.

[0072] In the present invention, unless otherwise specified, prior to carrying out the prepolymerization reaction in the second embodiment or the olefin polymerization reaction described in the sixth embodiment, the reactor is purged with an inert gas, the reactor is placed in an inert atmosphere, and then the raw materials are added to the reactor, as is known in the art.

[0073] In the present invention, the inert gas may be at least one of nitrogen gas, neon gas, argon gas, and krypton gas. The number of times of replacement with the inert gas is not particularly limited, and may be a common number of times in the art, for example, 1 to 5 times.

[0074] According to the preparation method of the present invention, the amount of hydrogen gas added is controlled so as to maintain the reaction pressure at 0.01 to 1 MPa, preferably 0.1 to 0.5 MPa, more preferably 0.2 to 0.3 MPa. In the present invention, the pressure is usually a gauge pressure unless otherwise specified.

[0075] According to the preparation method of the present invention, hydrogen gas may be added in the form of pure hydrogen gas or a mixed gas containing hydrogen gas. The mixed gas containing hydrogen gas may be composed of hydrogen gas and an inert gas, and the inert gas may be at least one selected from nitrogen gas, helium gas, neon gas, and argon gas. In the present invention, the concentration of hydrogen gas in the mixed gas containing hydrogen gas is not particularly limited as long as a predetermined reaction pressure can be achieved. Typically, the concentration of hydrogen gas in the mixed gas containing hydrogen gas may be 0.1 to 100% by volume, for example, 20 to 100% by volume.

[0076] According to the preparation method of the present invention, step (3) further includes a post-treatment step of subjecting the system obtained in step (3) to solid-liquid separation and drying to obtain the solid catalyst component. The post-treatment step generally includes the steps of removing unreacted hydrogen gas, filtering off the liquid, or optionally washing with hexane once or twice to obtain a solid product, and then drying the solid product under vacuum at 10 to 80°C to obtain the solid catalyst component. In the present invention, the vacuum drying may be performed using a conventional vacuum pump, but is not particularly limited in the present invention.

[0077] According to the preparation method of the present invention, the α-olefin is a C2-C 10 The α-olefin is selected from olefins, preferably one or more selected from ethylene, propylene, butene, octene, and isopentene, more preferably said α-olefin is propylene.

[0078] According to the preparation method of the present invention, the mass ratio of the α-olefin to the amount of catalyst component A used may be 0.04 to 10:1. For example, the mass ratio of the α-olefin to the amount of catalyst component A used may be 0.04:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or a range thereof.

[0079] According to the preparation method of the present invention, the catalyst component A may be prepared according to a conventional method for preparing a main catalyst in olefin polymerization catalysts in the art, and is not particularly limited in the present invention. For example, the catalyst component A may be prepared by referring to the methods disclosed in patent applications WO2012034357A1, WO2012097680A1 and patents ZL03153152.0, ZL200410062291.3, ZL201310491641.7, ZL201310491393.6, and ZL201310491648.9.

[0080] In the present invention, the catalyst component A may comprise, be, or be a reaction product of a titanium halide (e.g., titanium tetrachloride), a support, and an internal electron donor, and the support may preferably be an alkoxy magnesium support, a spherical magnesium chloride alcoholate support, or a spherical magnesium compound support.

[0081] In the present invention, the average particle size of the carrier is 5 to 150 μm, more preferably 20 to 80 μm, and more preferably 30 to 60 μm.

[0082] In some embodiments, the catalyst component A may be prepared with reference to the methods disclosed in patents WO2012034357A1 and WO2012097680A1. More specifically, the support is an alkoxymagnesium support, and the catalyst component A is a reaction product of titanium halide (e.g., titanium tetrachloride), the alkoxymagnesium support, and the internal electron donor in an inert solvent. The general formula of the alkoxymagnesium support is Mg(OEt) 2-k-l (OEH) k (OiPr) l where Et is ethyl, EH is 2-ethylhexyl, iPr is isopropyl, and k and l each independently represent 0 to 0.5.

[0083] The catalyst component A may be prepared by the following steps: alkoxymagnesium is reacted with titanium halide (e.g., titanium tetrachloride) and the internal electron donor, such as a carboxylate, in the presence of an inert solvent. The reaction temperature is usually -40 to 200°C, preferably -20 to 150°C, and the reaction time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours. The solid obtained above is washed with an inert solvent to obtain a solid catalyst component, and the inert solvent here is preferably toluene. The washing is usually carried out for 1 to 24 hours, preferably 6 to 10 hours.

[0084] The solid catalyst component may be stored dry or in an inert solvent.

[0085] In some other embodiments, the catalyst component A may be prepared by referring to the methods disclosed in Patents ZL03153152.0 and ZL200410062291.3. More specifically, the support is a spherical support of magnesium chloride alcoholate, and the catalyst component A is a reaction product of titanium halide (e.g., titanium tetrachloride), spherical magnesium chloride alcoholate, and the internal electron donor, such as a carboxylate.

[0086] The general formula of the spherical magnesium chloride alcoholate is Mg(R'OH) i (H2O) j wherein R' is methyl, ethyl, n-propyl, or isopropyl, i is 1.5 to 3.5, and j is 0 to 0.1.

[0087] The catalyst component A is prepared by a method comprising the following steps: 1) A titanium halide (for example, titanium tetrachloride) and the spherical carrier of magnesium chloride alcoholate are reacted at −20° C. to 0° C. for 20 to 120 minutes to obtain a mixture I. 2) The mixture I is heated to 100 to 120°C, and the internal electron donor, for example, a carboxylate, is added during the temperature increase, followed by reaction at 100 to 120°C for 20 to 200 minutes to obtain a solid product II. 3) The solid product II is washed with titanium halide (for example, titanium tetrachloride) and hexane, and then dried under vacuum.

[0088] In still other embodiments, the catalyst component A may be prepared with reference to the methods disclosed in Patents ZL201310491641.7, ZL201310491393.6, and ZL201310491648.9. More specifically, the support is a spherical magnesium compound support, and the catalyst component A is a reaction product of titanium halide (e.g., titanium tetrachloride), the spherical magnesium compound support, and the internal electron donor, such as a carboxylate.

[0089] The spherical magnesium compound support is represented by formula (4). [ka] (In formula (4), R1 is C1 to C 12R2 and R3 are the same or different and are hydrogen or a C1-C5 linear or branched alkyl, where the hydrogen in the alkyl may be optionally substituted with a halogen atom, X is a halogen, m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2.

[0090] The catalyst component A is prepared by a method comprising the following steps: 1) A titanium halide (for example, titanium tetrachloride) and the spherical magnesium compound support are reacted at −20° C. to 0° C. for 20 to 120 minutes to obtain a mixture I. 2) The mixture I is heated to 100 to 120°C, and the internal electron donor, for example, a carboxylate, is added during the temperature increase, followed by reaction at 100 to 120°C for 20 to 200 minutes to obtain a solid product II. 3) The solid product II is washed with titanium halide (for example, titanium tetrachloride) and hexane, and then dried under vacuum.

[0091] According to the preparation method of the present invention, the conditions for vacuum drying in the above operation include a temperature of 40 to 50°C and a time of 30 to 60 minutes. In the present invention, the vacuum drying may be performed using a normal vacuum pump, and is not particularly limited in the present invention.

[0092] According to a third aspect of the present invention, there is provided a solid catalyst component prepared by the method according to the second aspect of the present invention.

[0093] According to a fourth aspect of the present invention, there is provided a catalyst system for the polymerization of olefins comprising a solid catalyst component according to the present invention, an alkylaluminum, and optionally an external electron donor compound, or a reaction product thereof.

[0094] According to the catalyst system of the present invention, the alkyl aluminum, the external electron donor compound, and the content of each may be selected according to the prior art. In the present invention, the type of alkyl aluminum and the external electron donor compound used in the catalyst system may be the same as or different from the alkyl aluminum and the external electron donor compound used in the process for preparing the solid catalyst component. For example, the type of alkyl aluminum and the external electron donor compound described in the second aspect of the present invention may be used.

[0095] Generally, the alkyl aluminum may be one or more selected from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and monochlorodiethyl aluminum.

[0096] The ratio of the molar amount of the alkyl aluminum in terms of elemental aluminum to the molar amount of the solid catalyst component in terms of elemental titanium may be 1 to 1000: 1. For example, the ratio of the molar amount of the alkyl aluminum in terms of elemental aluminum to the molar amount of the solid catalyst component in terms of elemental titanium may be 1:1, 2:1, 5:1, 10:1, 20:1, 50:1, 100:1, 200:1, 500:1, 1000:1, or a range thereof.

[0097] In the catalyst system according to the present invention, the content of the alkyl aluminum is 0.01 to 100 mmol, preferably 0.1 to 10 mmol, more preferably 1 to 5 mmol, per 15 mg of the solid catalyst component.

[0098] Generally, the external electron donor compound may be at least one selected from cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and t-hexyltrimethoxysilane.

[0099] The ratio of the molar amount of the alkyl aluminum in terms of aluminum element to the molar amount of the external electron donor compound in terms of silicon element may be 2 to 1000: 1. For example, the ratio of the molar amount of the alkyl aluminum in terms of aluminum element to the molar amount of the external electron donor compound in terms of silicon element may be 2:1, 5:1, 10:1, 20:1, 50:1, 100:1, 200:1, 500:1, 1000:1, or a range thereof.

[0100] Fifth, the present invention provides the use of the above solid catalyst component and / or the solid catalyst component prepared by the above process and / or the above catalyst system in olefin polymerization.

[0101] Sixth, the present invention provides a method for polymerizing olefins, comprising the step of polymerizing an olefin in the presence of the above-mentioned solid catalyst component and / or the solid catalyst component prepared by the above-mentioned method and / or the above-mentioned catalyst system.

[0102] According to the method of the present invention, the general formula of the olefin is CH═CHR, where R is hydrogen, C₁-C₆ alkyl, or C₆-C₆ alkyl. 10 Preferably, the olefin is one or more selected from ethylene, propylene, butene, pentene, and hexene.

[0103] According to the method of the present invention, the polymerization reaction conditions may be selected according to the conventional methods in the art. For example, the reaction temperature is 0 to 150°C, preferably 60 to 90°C, and the reaction pressure is atmospheric pressure or higher.

[0104] Seventh, the present invention provides the use of the above solid catalyst component and / or the solid catalyst component prepared by the above method in reducing olefin polymerization activity.

[0105] The advantages of the technical solution of the present invention will be described in detail below through specific examples.

[0106] In the following examples and comparative examples, The isotactic index of a polymer (polypropylene) refers to the mass percentage of the polymer that is insoluble in boiling n-heptane under specific conditions, and is measured by the heptane extraction method (boiling with heptane for 6 hours). That is, 2 g of a dry polymer sample is taken, placed in an extractor, and extracted with boiling heptane for 6 hours. The residue is then dried to a constant weight, and the ratio of the resulting polymer mass (g) to 2 is the isotactic index. The melt index of a polymer is measured according to the method of ASTM D1238-99. The particle size distribution of a polymer refers to the mass percentage of the fractions calculated by screening with standard sieves. Measurement methods for specific surface area, pore size, pore volume, etc.: The carrier is tested using a fully automatic chemical adsorption apparatus AutoChem 2920 manufactured by MICROMERITICS, USA, and the specific surface area is tested using the BET method and the pore volume is tested using the BJH method. XRD spectrogram test method: The carrier is tested using a Bruker AXS, D8 Advance X-ray diffractometer manufactured by Bruker, Switzerland. The test conditions for this instrument are CuK α (λ=1.5406), tube voltage 40KV, tube current 40mA, slit system DS=SS=1°, receiving slit 0.3mm, graphite monochromator as monochromator, scintillation counter for counting, scanning speed 2θ=3° / min, scanning range 2θ=5°~75°.

[0107] In the following embodiments, unless otherwise specified, the "vacuum" refers to the degree of vacuum achieved by a normal vacuum pump.

[0108] The following preparation example is used to illustrate the preparation method of catalyst component A.

[0109] In the following preparation examples, the structural formula of the spherical magnesium compound carrier is as follows: [ka] Preparation Example 1

[0110] In a 3 L glass reaction flask equipped with a stirrer, 1.2 L of titanium tetrachloride was added, and after cooling to -20°C, 100 g of magnesium chloride alcoholate spherical carrier [Mg(C2H5OH) 2.6 ] (average particle size D50 = 45 μm) was added and the mixture was reacted at -20°C for 0.5 hours, then the temperature was slowly raised to 120°C, and 15 g of 2,4-pentanediol dibenzoate was added during the temperature increase, followed by a reaction at 120°C for 0.5 hours, the liquid was removed by filtration, 1 L of titanium tetrachloride was added, the mixture was maintained at 120°C for 2 hours, and the liquid was removed by filtration to obtain a solid product. The obtained solid product was washed five times with hexane and finally dried under vacuum at 45°C to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.79), which was designated A-1. Preparation Example 2

[0111] In a 3 L glass reaction flask equipped with a stirrer, 1.2 L of titanium tetrachloride was added, and after cooling to -20°C, magnesium chloride alcoholate spherical carrier [Mg(C2H5OH) 2.6 100 g of 2,4-pentanediol dibenzoate (average particle size D50 = 45 μm) was added and the mixture was reacted at -20°C for 0.5 hours, then the temperature was slowly raised to 120°C, and while the temperature was rising, 15 g of 2,4-pentanediol dibenzoate and 15 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added, followed by a reaction at 120°C for 0.5 hours. The liquid was removed by filtration, 1 L of titanium tetrachloride was added, and the mixture was maintained at 120°C for 1 hour. The liquid was then removed by filtration to obtain a solid product. The obtained solid product was washed five times with hexane and finally dried under vacuum at 45°C to obtain catalyst component A (average particle size D50 = 41 μm, SPAN value 0.78), which was designated A-2. Preparation Example 3

[0112] A suspension was prepared using 100 g of diethoxymagnesium support (average particle size D50 = 47 μm), 500 ml of toluene, and 20.0 ml of 4-ethyl-3,5-heptanediol dibenzoate. A 3000 ml reactor, which had been repeatedly purged with high-purity nitrogen gas, was charged with 100 ml of toluene and 900 ml of titanium tetrachloride, and the temperature was raised to 80°C. The suspension was then added to the reactor and maintained at this temperature for 1 hour. The temperature was then raised to 115°C and maintained for 2 hours, after which the liquid was thoroughly removed by pressure filtration. A mixture of 1200 ml of toluene and 300 ml of titanium tetrachloride was then added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This process was repeated three times, the liquid was removed by filtration, and the resulting solid was washed four times with 1500 ml of hexane, the liquid was removed by filtration, and the solid was dried to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82), designated A-3. Preparation Example 4

[0113] A suspension was prepared using 100 g of diethoxymagnesium support (average particle size D50 = 47 μm), 500 ml of toluene, 20.0 ml of 4-ethyl-3,5-heptanediol dibenzoate, and 20.0 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. 100 ml of toluene and 900 ml of titanium tetrachloride were added to a 3000 ml reactor that had been repeatedly purged with high-purity nitrogen gas. The mixture was heated to 80°C, and the suspension was added to the reactor. After maintaining the temperature for 1 hour, the temperature was further increased to 115°C and maintained for 2 hours. The liquid was then thoroughly removed by pressure filtration. Thereafter, a mixture of 1200 ml of toluene and 300 ml of titanium tetrachloride was added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This treatment was repeated three times, the liquid was removed by filtration, and the resulting solid was washed four times with 1500 ml of hexane, the liquid was removed by filtration, and the solid was dried to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82), designated A-4. Preparation Example 5

[0114] A 3-L glass reaction flask equipped with a stirrer was charged with 1.2 L of titanium tetrachloride, and the temperature was lowered to -20°C. While stirring, 100 g of a spherical magnesium compound support (average particle size D50 = 45 μm) was added, and the reaction was carried out at -20°C for 0.5 hours. The temperature was then slowly raised to 120°C, and 15 g of 2,4-pentanediol dibenzoate was added during the temperature increase. The reaction was then carried out at 120°C for 0.5 hours. The liquid was removed by filtration, and 1 L of titanium tetrachloride was added. The mixture was maintained at 120°C for 2 hours, after which the liquid was removed by filtration to obtain a solid product. The resulting solid product was washed five times with hexane and finally dried under vacuum to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.76), designated A-5. Preparation Example 6

[0115] A 3-L glass reaction flask equipped with a stirrer was charged with 1.2 L of titanium tetrachloride, and the temperature was lowered to -20°C. While stirring, 100 g of a spherical magnesium compound support (average particle size D50 = 45 μm) was added, and the reaction was carried out at -20°C for 0.5 hours. The temperature was then slowly raised to 120°C. While the temperature was rising, 15 g of 2,4-pentanediol dibenzoate and 15 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added, and the reaction was carried out at 120°C for 0.5 hours. The liquid was then filtered off, 1 L of titanium tetrachloride was added, and the mixture was maintained at 120°C for 1 hour. The liquid was then filtered off to obtain a solid product. The resulting solid product was washed five times with hexane, and finally, vacuum dried at 45°C to obtain catalyst component A (average particle size D50 = 41 μm, SPAN value 0.76), designated A-6. Preparation Example 7

[0116] In a 3 L glass reaction flask equipped with a stirrer, 1.2 L of titanium tetrachloride was added, and after cooling to -20°C, magnesium chloride alcoholate spherical carrier [Mg(C2H5OH) 2.6] (average particle size D50 = 45 μm) was added and the mixture was allowed to react at -20°C for 0.5 hours, then the temperature was slowly raised to 120°C, and 15 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added during the temperature increase, followed by a reaction at 120°C for 0.5 hours, after which the liquid was filtered off, 1 L of titanium tetrachloride was added, the mixture was maintained at 120°C for 2 hours, and the liquid was filtered off to obtain a solid product. The obtained solid product was washed five times with hexane and finally dried under vacuum at 45°C to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.79), designated A-7. Preparation Example 8

[0117] 1.1 L of titanium tetrachloride was added to a 3 L glass reaction flask equipped with a stirrer, and after cooling to -20°C, magnesium chloride alcoholate spherical carrier [Mg(C2H5OH) 2.6 100 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 0.6 g of tributyl phosphate were added during the temperature increase, and the mixture was then reacted at 120°C for 0.5 hours. The liquid was removed by filtration, and 1 L of titanium tetrachloride was added. The mixture was maintained at 120°C for 2 hours, and the liquid was removed by filtration to obtain a solid product. The resulting solid product was washed five times with hexane and finally dried under vacuum at 45°C to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.79), designated A-8. Preparation Example 9

[0118] A suspension was prepared using 100 g of diethoxymagnesium support (average particle size D50 = 47 μm), 500 ml of toluene, and 20.0 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. 100 ml of toluene and 900 ml of titanium tetrachloride were added to a 3000 ml reaction vessel, which had been repeatedly purged with high-purity nitrogen gas. The mixture was heated to 80°C, and the suspension was added to the vessel. After maintaining the temperature for 1 hour, the temperature was further increased to 115°C and maintained for 2 hours. The liquid was then thoroughly removed by pressure filtration. Thereafter, a mixture of 1200 ml of toluene and 300 ml of titanium tetrachloride was added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This treatment was repeated three times, the liquid was removed by filtration, and the resulting solid was washed four times with 1500 ml of hexane, the liquid was removed by filtration, and the solid was dried to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82), which was designated as A-9. Preparation Example 10

[0119] A suspension was prepared using 100 g of diethoxymagnesium support (average particle size D50 = 47 μm), 500 ml of toluene, and 20.0 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. 100 ml of toluene and 900 ml of titanium tetrachloride were added to a 3000 ml reactor that had been repeatedly purged with high-purity nitrogen gas. The mixture was heated to 80°C, and the suspension was added to the reactor. After maintaining the temperature for 1 hour, the temperature was further increased to 115°C and maintained for 2 hours. The liquid was then thoroughly removed by pressure filtration. Thereafter, a mixture of 1200 ml of toluene and 300 ml of titanium tetrachloride was added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This treatment was repeated three times, the liquid was removed by filtration, and the resulting solid was washed four times with 1500 ml of hexane, the liquid was removed by filtration, and the solid was dried to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82), which was designated A-10. Preparation Example 11

[0120] A 3-L glass reaction flask equipped with a stirrer was charged with 1.2 L of titanium tetrachloride, and the temperature was lowered to -20°C. 100 g of a spherical magnesium compound support (average particle size D50 = 45 μm) was added with stirring, and the mixture was allowed to react at -20°C for 0.5 hours. The temperature was then slowly raised to 120°C. 15 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added during the temperature increase, and the mixture was allowed to react at 120°C for 0.5 hours. The liquid was then filtered off, 1 L of titanium tetrachloride was added, and the mixture was maintained at 120°C for 2 hours. The liquid was then filtered off to obtain a solid product. The resulting solid product was washed five times with hexane and finally dried under vacuum at 45°C to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.76), designated A-11. Preparation Example 12

[0121] A 3-L glass reaction flask equipped with a stirrer was charged with 1.1 L of titanium tetrachloride, and the temperature was lowered to -20°C. 100 g of a spherical magnesium compound support (average particle size D50 = 45 μm) was added while stirring, and the mixture was allowed to react at -20°C for 0.5 hours. The temperature was then slowly raised to 120°C. 15 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 0.6 g of tributyl phosphate were added during the temperature increase, and the mixture was allowed to react at 120°C for 0.5 hours. The liquid was then filtered off, 1 L of titanium tetrachloride was added, and the mixture was maintained at 120°C for 2 hours. The liquid was then filtered off to obtain a solid product. The resulting solid product was washed five times with hexane and finally dried under vacuum at 45°C to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.76), designated A-12. Preparation Example 13

[0122] In a 3 L glass reaction flask equipped with a stirrer, 1.2 L of titanium tetrachloride was added, and after cooling to -20°C, magnesium chloride alcoholate spherical carrier [Mg(C2H5OH) 2.6] (average particle size D50 = 45 μm) was added and the mixture was allowed to react at -20°C for 0.5 hours, then the temperature was slowly raised to 120°C, and 15 g of diisobutyl phthalate was added during the temperature increase, followed by a reaction at 120°C for 0.5 hours, the liquid was removed by filtration, 1 L of titanium tetrachloride was added, the mixture was maintained at 120°C for 2 hours, and the liquid was removed by filtration to obtain a solid product. The obtained solid product was washed five times with hexane and finally dried under vacuum to obtain catalyst component A (average particle size D50 = 40 μm, SPAN value 0.79), designated A-13. Preparation Example 14

[0123] In a 3 L glass reaction flask equipped with a stirrer, 1.2 L of titanium tetrachloride was added, and after cooling to -20°C, magnesium chloride alcoholate spherical carrier [Mg(C2H5OH) 2.6 ] (average particle size D50 = 45 μm) 100 g was added and reacted at -20°C for 0.5 hours, then the temperature was slowly raised to 120°C, and 15 g of 2,3-diisopropyl diethyl succinate was added during the temperature increase, followed by a reaction at 120°C for 0.5 hours, the liquid was removed by filtration, 1 L of titanium tetrachloride was added, and the mixture was maintained at 120°C for 2 hours, after which the liquid was removed by filtration to obtain a solid product. The obtained solid product was washed five times with hexane and finally dried under vacuum to obtain catalyst component A (average particle size D50 = 41 μm, SPAN value 0.80), designated A-14. Preparation Example 15

[0124] A suspension was prepared using 650 g of diethoxymagnesium support (average particle size D50 = 47 μm), 3250 mL of toluene, and 65 mL of di-n-butyl phthalate (DNBP). 2600 mL of toluene and 3900 mL of titanium tetrachloride were added to a 16 L pressure-resistant reactor that had been repeatedly purged with high-purity nitrogen gas. The temperature was then lowered to -5°C. The suspension was then added to the reactor and kept at this temperature for 1 hour. After that, the temperature was slowly raised to 110°C. Once the temperature reached 80°C, 65 mL of DNBP was added and the mixture was kept at this temperature for 2 hours. The liquid was then thoroughly removed by pressure filtration. Thereafter, a mixed liquid of 5070 mL of toluene and 3380 mL of titanium tetrachloride was added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This treatment was repeated three times, and the liquid was removed by filtration. The resulting solid was washed four times with 150 mL of hexane, the liquid was removed by filtration, and the solid was dried to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82), which was designated A-15. Preparation Example 16

[0125] A suspension was prepared using 650 g of diethoxymagnesium support (average particle size D50 = 47 μm), 3250 mL of toluene, and 65 mL of 2,3-diisopropyldiethyl succinate. 2600 mL of toluene and 3900 mL of titanium tetrachloride were added to a 16 L pressure-resistant reactor that had been repeatedly purged with high-purity nitrogen gas. The temperature was then lowered to -5°C. The suspension was then added to the reactor and kept at this temperature for 1 hour. The temperature was then slowly raised to 110°C. Once the temperature reached 80°C, 65 mL of 2,3-diisopropyldiethyl succinate was added and kept at this temperature for 2 hours. The liquid was then thoroughly removed by pressure filtration. Thereafter, a mixed liquid of 5070 mL of toluene and 3380 mL of titanium tetrachloride was added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour. This treatment was repeated three times, the liquid was removed by filtration, and the resulting solid was washed four times with 150 mL of hexane, the liquid was removed by filtration, and the solid was dried to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82), which was designated as A-16. Preparation Example 17

[0126] A 3-L glass reaction flask equipped with a stirrer was charged with 1.2 L of titanium tetrachloride, and the temperature was lowered to -20°C. While stirring, 100 g of a spherical magnesium compound support (average particle size D50 = 46 μm) was added, and the mixture was allowed to react at -20°C for 0.5 hours. The temperature was then slowly raised to 120°C, and 15 g of diisobutyl phthalate was added during the temperature increase. The mixture was then allowed to react at 120°C for 0.5 hours. The liquid was then filtered off, and 1 L of titanium tetrachloride was added. The mixture was maintained at 120°C for 2 hours, and the liquid was then filtered off to obtain a solid product. The resulting solid product was washed five times with hexane and finally dried under vacuum to obtain catalyst component A (average particle size D50 = 41 μm, SPAN value 0.76), designated A-17. Preparation Example 18

[0127] A 3-L glass reaction flask equipped with a stirrer was charged with 1.2 L of titanium tetrachloride, and the temperature was lowered to -20°C. While stirring, 100 g of a spherical magnesium compound carrier (average particle size D50 = 46 μm) was added, and the mixture was allowed to react at -20°C for 0.5 hours. The temperature was then slowly raised to 120°C, and 15 g of 2,3-diisopropyldiethyl succinate was added during the temperature increase. The mixture was then allowed to react at 120°C for 0.5 hours. The liquid was then filtered off, and 1 L of titanium tetrachloride was added. The mixture was maintained at 120°C for 2 hours, after which the liquid was filtered off to obtain a solid product. The resulting solid product was washed five times with hexane and finally dried under vacuum to obtain catalyst component A (average particle size D50 = 42 μm, SPAN value 0.78), designated A-18.

[0128] The following examples illustrate the solid catalyst component of the present invention, as well as methods for its preparation and for olefin polymerization. Example 1

[0129] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.1L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-1, and the mixture was reacted at 22°C for 10 minutes. Then, 10g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off, and the mixture was dried under vacuum (at 45°C for 40 minutes) to obtain a solid catalyst component (average particle size D50 = 41μm, SPAN value 0.80), designated E-1. The composition of catalyst component E-1 was 2.2 wt % titanium, 15.3 wt % magnesium, 54.1 wt % chlorine, 9.0 wt % 2,4-pentanediol dibenzoate, and 9.5 wt % polyolefin. (2) Propylene Polymerization A A 5L autoclave was charged with 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane, and 15mg of solid catalyst component E-1. 1.5NL of hydrogen gas was introduced, followed by 2.0kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and unpolymerized propylene monomer was removed to obtain polypropylene, designated P-1A. Propylene Polymerization B The solid catalyst component E-1 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-1B. Example 2

[0130] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-2, and the mixture was reacted at 15°C for 10 minutes. Then, 12g of propylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42μm, SPAN value 0.79), designated E-2. The composition of catalyst component E-2 was 2.1 wt % titanium, 14.2 wt % magnesium, 50.2 wt % chlorine, 4.6 wt % 2,4-pentanediol dibenzoate, 5.1 wt % 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 17.1 wt % polyolefin. (2) Propylene Polymerization A Polymerization was carried out according to the method of propylene polymerization A in Example 1, except that E-2 was used instead of E-1, to obtain polypropylene, which was designated P-2A. Propylene Polymerization B The solid catalyst component E-2 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-2B. Example 3

[0131] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-2, and the mixture was reacted at 15°C for 10 minutes. Then, 12g of ethylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42μm, SPAN value 0.80), designated E-3. The composition of catalyst component E-3 was 2.1 wt % titanium, 14.4 wt % magnesium, 50.6 wt % chlorine, 4.7 wt % 2,4-pentanediol dibenzoate, 5.0 wt % 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 17.3 wt % polyolefin. (2) Propylene Polymerization A Polymerization was carried out according to the method of propylene polymerization A in Example 1, except that E-3 was used instead of E-1, to obtain polypropylene, designated P-3A. Propylene Polymerization B The solid catalyst component E-3 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-3B. Example 4

[0132] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-2, and the mixture was reacted at 15°C for 10 minutes. Then, 15g of propylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and a 20% by volume mixture of hydrogen and nitrogen gas was added up to a reaction pressure of 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 43μm, SPAN value 0.81), designated E-4. The composition of catalyst component E-4 was 1.7 wt % titanium, 11.6 wt % magnesium, 40.3 wt % chlorine, 3.9 wt % 2,4-pentanediol dibenzoate, 4.2 wt % 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 33.2 wt % polyolefin. (2) Propylene Polymerization A Polymerization was carried out according to the method of propylene polymerization A in Example 1, except that E-4 was used instead of E-1, to obtain polypropylene, designated P-4A. Propylene Polymerization B The solid catalyst component E-4 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-4B. Example 5

[0133] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.1L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-3, and the mixture was reacted at 22°C for 10 minutes. Then, 10g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 43μm, SPAN value 0.83), designated E-5. (2) Propylene Polymerization A A 5L autoclave was charged with 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane, and 15mg of solid catalyst component E-5. 1.5NL of hydrogen gas was introduced, followed by 2.0kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and unpolymerized propylene monomer was removed to obtain polypropylene, designated P-5A. Propylene Polymerization B The solid catalyst component E-5 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-5B. Example 6

[0134] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-4, and the mixture was reacted at 15°C for 10 minutes. Then, 10g of propylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 43μm, SPAN value 0.83), designated E-6. (2) Propylene Polymerization A Polymerization was carried out according to the method of propylene polymerization A in Example 5, except that E-6 was used instead of E-5, to obtain polypropylene, which was designated P-6A. Propylene Polymerization B The solid catalyst component E-6 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-6B. Example 7

[0135] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-4, and the mixture was reacted at 15°C for 10 minutes. Then, 10g of ethylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42μm, SPAN value 0.82), designated E-7. (2) Propylene Polymerization A Polymerization was carried out according to the method of Propylene Polymerization A in Example 5, except that E-7 was used instead of E-5, to obtain polypropylene, designated P-7A. Propylene Polymerization B The solid catalyst component E-7 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-7B. Example 8

[0136] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.1L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-5, and the mixture was reacted at 22°C for 10 minutes. Then, 10g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 41μm, SPAN value 0.77), designated E-8. (2) Propylene Polymerization A A 5L autoclave was charged with 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane, and 15mg of solid catalyst component E-5. 1.5NL of hydrogen gas was introduced, followed by 2.0kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and unpolymerized propylene monomer was removed to obtain polypropylene, designated P-8A. Propylene Polymerization B Solid catalyst component E-8 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A to obtain P-8B. Example 9

[0137] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-6, and the mixture was reacted at 15°C for 10 minutes. Then, 10g of propylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42μm, SPAN value 0.77), designated E-9. (2) Propylene Polymerization A Polymerization was carried out according to the method of Propylene Polymerization A in Example 8, except that E-9 was used instead of E-8, to obtain polypropylene, designated P-9A. Propylene Polymerization B Solid catalyst component E-9 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A to obtain P-9B. Example 10

[0138] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-6, and the mixture was reacted at 15°C for 10 minutes. Then, 10g of ethylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reaction pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42μm, SPAN value 0.77), designated E-10. (2) Propylene Polymerization A Polymerization was carried out according to the method of Propylene Polymerization A in Example 8, except that E-10 was used instead of E-8, to obtain polypropylene, designated P-10A. Propylene Polymerization B Solid catalyst component E-10 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A to obtain P-10B. Example 11

[0139] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 20mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-7, and the mixture was reacted at 22°C for 10 minutes. Then, 6g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reactor pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 41μm, SPAN value 0.80), designated E-11. The composition of catalyst component E-11 was 2.2% by weight of titanium, 16.3% by weight of magnesium, 53.1% by weight of chlorine, 9.1% by weight of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 13.0% by weight of polyolefin. (2) Propylene Polymerization A A 5L autoclave was charged with 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane, and 15mg of solid catalyst component E-11. 1.5NL of hydrogen gas was introduced, followed by 2.0kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and unpolymerized propylene monomer was removed to obtain polypropylene, designated P-11A. Propylene Polymerization B After storing the solid catalyst component E-11 for one year, propylene polymerization was carried out in the same manner as in Propylene Polymerization A. The obtained polypropylene was designated P-11B. Example 12

[0140] (1) Preparation of solid catalyst component The solid catalyst component was prepared in the same manner as in Example 11, except that A-8 was used instead of A-7. A solid catalyst component (average particle size D50 = 41 μm, SPAN value 0.80) was obtained and designated E-12. The composition of catalyst component E-12 was 2.3 wt% titanium, 16.1 wt% magnesium, 52.8 wt% chlorine, 8.9 wt% 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 13.2 wt% polyolefin. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 11, except that E-12 was used instead of E-11, and designated as P-12A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 11, except that E-12 was used instead of E-11, and designated as P-12B. Example 13

[0141] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 11, except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size D50 = 41 μm, SPAN value 0.80) designated E-13. The composition of catalyst component E-13 was 2.2 wt% titanium, 16.2 wt% magnesium, 52.9 wt% chlorine, 9.0 wt% 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 13.5 wt% polyolefin. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 11, except that E-13 was used instead of E-11, and designated as P-13A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 11, except that E-13 was used instead of E-11, and designated as P-13B. Example 14

[0142] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 11, except that 5 g of propylene and 0.2 g of ethylene were used instead of 6 g of propylene, thereby obtaining a solid catalyst component (average particle size D50 = 41 μm, SPAN value 0.80) designated E-14. The composition of catalyst component E-14 was 2.2 wt% titanium, 16.6 wt% magnesium, 53.8 wt% chlorine, 9.0 wt% 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 13.1 wt% polyolefin. (2) Propylene Polymerization A Polypropylene was obtained and designated as P-14A according to the method of propylene polymerization A in Example 11, except that E-11 was changed to E-14 as the solid catalyst component. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 11, except that E-14 was used instead of E-11, and designated as P-14B. Example 15

[0143] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 20mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-7, and the mixture was reacted at 22°C for 10 minutes. Then, 15g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reactor pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 41μm, SPAN value 0.81), designated E-15. The composition of catalyst component E-15 was 1.7% by weight of titanium, 12.6% by weight of magnesium, 40.2% by weight of chlorine, 7.0% by weight of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 33.8% by weight of polyolefin. (2) Propylene Polymerization A Polymerization was carried out according to the method of Propylene Polymerization A in Example 11, except that E-15 was used instead of E-11, to obtain polypropylene, which was designated as P-5A. Propylene Polymerization B The solid catalyst component E-15 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-15B. Example 16

[0144] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 20mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-9, and the mixture was reacted at 22°C for 10 minutes. Then, 6g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reactor pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 43μm, SPAN value 0.83), designated E-16. (2) Propylene Polymerization A A 5L autoclave was charged with 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane, and 15mg of the solid catalyst component E-16. 1.5NL of hydrogen gas was introduced, followed by 2.0kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. The stirring was stopped, and the unpolymerized propylene monomer was removed to obtain polypropylene, designated P-16A. Propylene Polymerization B After storing the solid catalyst component E-16 for one year, propylene polymerization was carried out in the same manner as in Propylene Polymerization A. The obtained polypropylene was designated P-16B. Example 17

[0145] (1) Preparation of solid catalyst component Except for using A10 instead of A9, the solid catalyst component was prepared in the same manner as in Example 16. A solid catalyst component (average particle size D50=43 μm, SPAN value 0.83) was obtained and designated E-17. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 16, except that E-17 was used instead of E-16, and designated as P-17A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 16, except that E-17 was used instead of E-16, and designated as P-17B. Example 18

[0146] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 16, except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size D50=43 μm, SPAN value 0.83), designated as E-18. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 16, except that E-18 was used instead of E-16, and designated as P-18A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 16, except that E-18 was used instead of E-16, and designated as P-18B. Example 19

[0147] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 16, except that 5g of propylene and 0.2g of ethylene were used instead of 6g of propylene, thereby obtaining a solid catalyst component (average particle size D50=43μm, SPAN value 0.83), designated as E-19. (2) Propylene Polymerization A Polypropylene was obtained and designated as P-19A according to the method of propylene polymerization A in Example 16, except that E-16 was changed to E-19 as the solid catalyst component. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 16, except that E-19 was used instead of E-16, and designated as P-19B. Example 20

[0148] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 20mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-11, and the mixture was reacted at 22°C for 10 minutes. Then, 6g of propylene was added, and the mixture was reacted at 23°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reactor pressure reached 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 41μm, SPAN value 0.77), designated E-20. (2) Propylene Polymerization A A 5L autoclave was charged with 1.3mmol of triethylaluminum, 0.05mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane, and 15mg of solid catalyst component E-20. 1.5NL of hydrogen gas was introduced, followed by 2.0kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and unpolymerized propylene monomer was removed to obtain polypropylene, designated P-20A. Propylene Polymerization B After storing the solid catalyst component E-20 for one year, propylene polymerization was carried out in the same manner as in Propylene Polymerization A. The obtained polypropylene was designated P-20B. Example 21

[0149] (1) Preparation of solid catalyst component Except for using A12 instead of A11, the solid catalyst component was prepared in the same manner as in Example 20. A solid catalyst component (average particle size D50=41 μm, SPAN value 0.77) was obtained and designated E-21. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 20, except that E-21 was used instead of E-20, and designated as P-21A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 20, except that E-21 was used instead of E-20, and designated as P-21B. Example 22

[0150] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 20, except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size D50=41 μm, SPAN value 0.77), designated as E-22. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 20, except that E-22 was used instead of E-20, and designated as P-22A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 20, except that E-22 was used instead of E-20, and designated as P-22B. Example 23

[0151] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 20, except that 5 g of propylene and 0.2 g of ethylene were used instead of 6 g of propylene, thereby obtaining a solid catalyst component (average particle size D50=41 μm, SPAN value 0.77), designated as E-23. (2) Propylene Polymerization A Polypropylene was obtained and designated as P-23A according to the method of propylene polymerization A in Example 20, except that E-23 was changed to E-20 as the solid catalyst component. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 20, except that E-23 was used instead of E-20, and designated as P-23B. Example 24

[0152] (1) Preparation of solid catalyst component A 5-L autoclave was charged with 1.0 L of hexane, 16 mmol of triethylaluminum, 0.3 mmol of cyclohexylmethyldimethoxysilane, and 25.0 g of catalyst component A-13, and the mixture was reacted at 22°C for 10 minutes. Subsequently, 10 g of propylene was added, and the mixture was reacted at 15°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the reactor pressure reached 0.3 MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 41 μm, SPAN value 0.80), designated E-24. The composition of catalyst component E-24 was 2.3 wt% titanium, 15.5 wt% magnesium, 54.3 wt% chlorine, 8.7 wt% diisobutyl phthalate, and 9.5% polyolefin. (2) Propylene Polymerization A A 5-liter autoclave was charged with 5.0 mmol of triethylaluminum, 0.2 mmol of cyclohexylmethyldimethoxysilane, 10 mL of hexane, and 15 mg of the solid catalyst component E-24. 1.5 mL of hydrogen gas was introduced, followed by 2.0 kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and the unpolymerized propylene monomer was removed to obtain polypropylene, designated P-24A. Propylene Polymerization B Solid catalyst component E-24 was stored under nitrogen gas for one year, and then propylene polymerization was carried out according to the method of propylene polymerization A to obtain P-24B. Example 25

[0153] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 24, except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.82) designated E-25. The composition of catalyst component E-25 was 2.3 wt% titanium, 15.1 wt% magnesium, 54.9 wt% chlorine, 8.5 wt% diisobutyl phthalate, and 9.4 wt% polyolefin. (2) Propylene Polymerization A Propylene polymerization was carried out according to the method of Propylene Polymerization A in Example 24, except that E-24 was changed to E-25 as the solid catalyst component, thereby obtaining polypropylene, designated as P-25A. Propylene Polymerization B The solid catalyst component E-25 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A in Example 24 to obtain P-25B. Example 26

[0154] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 24, except that A14 was used instead of A13 as the catalyst component, thereby obtaining a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.81) designated as E-26. The composition of catalyst component E-26 was 2.2 wt% titanium, 15.2 wt% magnesium, 55.0 wt% chlorine, 9.0 wt% diethyl 2,3-diisopropylsuccinate, and 9.1 wt% polyolefin. (2) Propylene Polymerization A Propylene polymerization was carried out in the same manner as in Propylene Polymerization A of Example 24, except that E-24 was changed to E-26 as the solid catalyst component, to obtain polypropylene, designated P-26A. Propylene Polymerization B Solid catalyst component E-26 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A in Example 24 to obtain P-26B. Example 27

[0155] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-14, and the mixture was reacted at 15°C for 10 minutes. Then, 15g of propylene was added, and the mixture was reacted at 22°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and a 20% hydrogen gas mixture was added up to a reaction pressure of 0.2MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42μm, SPAN value 0.82), designated E-27. The composition of catalyst component E-27 was 1.6% by weight of titanium, 11.9% by weight of magnesium, 39.3% by weight of chlorine, 6.0% by weight of diethyl 2,3-diisopropylsuccinate, and 32.5% by weight of polyolefin. (2) Propylene Polymerization A Polymerization was carried out according to the method of Example 24 Propylene Polymerization A, except that E-27 was used instead of E-24, to obtain polypropylene, designated P-27A. Propylene Polymerization B The solid catalyst component E-27 was stored in nitrogen for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-27B. Example 28

[0156] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-15, and the mixture was reacted at 22°C for 10 minutes. Then, 10g of propylene was added, and the mixture was reacted at 15°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the pressure in the reactor reached 0.3MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 43μm, SPAN value 0.83), designated E-28. (2) Propylene Polymerization A A 5-liter autoclave was charged with 5.0 mmol of triethylaluminum, 0.2 mmol of cyclohexylmethyldimethoxysilane, 10 mL of hexane, and 15 mg of the solid catalyst component E-28. After introducing 1.5 mL of hydrogen gas, 2.0 kg of liquid propylene was added. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. The stirring was stopped, and the unpolymerized propylene monomer was removed to obtain polypropylene, designated P-28A. Propylene Polymerization B Solid catalyst component E-28 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A to obtain P-28B. Example 29

[0157] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 28, except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size D50=43 μm, SPAN value 0.83), designated as E-29. (2) Propylene Polymerization A Propylene polymerization was carried out according to the method of Propylene Polymerization A in Example 28, except that E-28 was changed to E-29 as the solid catalyst component, thereby obtaining polypropylene, which was designated as P-29A. Propylene Polymerization B The solid catalyst component E-29 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A in Example 28 to obtain P-29B. Example 30

[0158] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 28, except that catalyst component A16 was used instead of A15, thereby obtaining a solid catalyst component (average particle size D50=43 μm, SPAN value 0.83) designated as E-30. (2) Propylene Polymerization A Propylene polymerization was carried out in the same manner as in Propylene Polymerization A of Example 28, except that E-28 was changed to E-30 as the solid catalyst component, to obtain polypropylene, designated P-30A. Propylene Polymerization B The solid catalyst component E-30 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A in Example 28 to obtain P-30B. Example 31

[0159] (1) Preparation of solid catalyst component A 5-L autoclave was charged with 1.0 L of hexane, 16 mmol of triethylaluminum, 0.3 mmol of cyclohexylmethyldimethoxysilane, and 25.0 g of catalyst component A-17, and the mixture was reacted at 22°C for 10 minutes. Subsequently, 10 g of propylene was added, and the mixture was reacted at 15°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and hydrogen gas was added until the pressure in the reactor reached 0.3 MPa. The mixture was reacted at 15°C for 10 minutes, after which all unreacted hydrogen gas was released. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component (average particle size D50 = 42 μm, SPAN value 0.77), designated E-31. (2) Propylene Polymerization A A 5-liter autoclave was charged with 5.0 mmol of triethylaluminum, 0.2 mmol of cyclohexylmethyldimethoxysilane, 10 mL of hexane, and 15 mg of solid catalyst component E-31. 1.5 mL of hydrogen gas was introduced, followed by 2.0 kg of liquid propylene. The temperature was raised to 70°C with stirring, and the polymerization reaction was carried out at 70°C for 1 hour. Stirring was stopped, and unpolymerized propylene monomer was removed to obtain polypropylene, designated P-31A. Propylene Polymerization B The solid catalyst component E-31 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A to obtain P-31B. Example 32

[0160] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 31, except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size D50=42 μm, SPAN value 0.77), designated as E-32. (2) Propylene Polymerization A Propylene polymerization was carried out according to the method of Propylene Polymerization A in Example 31, except that E-31 was changed to E-32 as the solid catalyst component, thereby obtaining polypropylene, which was designated as P-32A. Propylene Polymerization B The solid catalyst component E-32 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of Propylene Polymerization A in Example 31 to obtain P-32B. Example 33

[0161] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Example 31, except that catalyst component A-18 was used instead of A-17, thereby obtaining a solid catalyst component (average particle size D50=43 μm, SPAN value 0.79) designated as E-33. (2) Propylene Polymerization A Propylene polymerization was carried out in the same manner as in Propylene Polymerization A of Example 31, except that E-31 was changed to E-33 as the solid catalyst component, to obtain polypropylene, designated P-33A. Propylene Polymerization B The solid catalyst component E-33 was stored under nitrogen gas for one year, and then propylene polymerization was carried out in accordance with the method of propylene polymerization A in Example 31 to obtain P-33B. Comparative Example 1

[0162] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-1, and the mixture was allowed to react at 22°C for 10 minutes. Then, 10g of propylene and 2g of hydrogen gas were added, and the mixture was allowed to react at 23°C for 10 minutes, releasing any unreacted propylene. The reactor was then purged with nitrogen gas. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-1. (2) Propylene Polymerization A Propylene polymerization was carried out according to the method of Propylene Polymerization A in Example 1, except that the solid catalyst component E-1 was changed to CE-1, thereby obtaining polypropylene, which was designated as CP-1A. Propylene Polymerization B Propylene polymerization was carried out according to the method of Propylene Polymerization B in Example 1, except that E-1 was changed to CE-1 as the solid catalyst component, thereby obtaining polypropylene, which was designated as CP-1B. Comparative Example 2

[0163] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-4, and the mixture was reacted at 15°C for 10 minutes. 10g of ethylene was then added, and the mixture was reacted at 22°C for 10 minutes. All unreacted ethylene was then released, and the reactor was purged with nitrogen gas. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-2. (2) Propylene Polymerization A Propylene polymerization was carried out according to the method of Propylene Polymerization A in Example 6, except that the solid catalyst component E-6 was changed to CE-2, thereby obtaining polypropylene, which was designated as CP-2A. Propylene Polymerization B Propylene polymerization was carried out according to the method of Propylene Polymerization B in Example 6, except that E-6 was changed to CE-2 as the solid catalyst component, thereby obtaining polypropylene, which was designated as CP-2B. Comparative Example 3

[0164] (1) Preparation of solid catalyst component A 5-L autoclave was charged with 1.0 L of hexane, 20 mmol of triethylaluminum, 0.3 mmol of cyclohexylmethyldimethoxysilane, and 25.0 g of catalyst component A-7, and the mixture was reacted at 22°C for 10 minutes. 6 g of propylene was then added, and the mixture was reacted at 23°C for 10 minutes to release any unreacted propylene. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-3. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 10, except that CE-3 was used instead of E-10, and designated as CP-3A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 10, except that CE-3 was used instead of E-10, and designated as CP-3B. Comparative Example 4

[0165] (1) Preparation of solid catalyst component A solid catalyst component was prepared according to the method of Comparative Example 3, except that 6 g of ethylene was used instead of 6 g of propylene, thereby obtaining a solid catalyst component designated as CE-4. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 10, except that CE-4 was used instead of E-10, and designated as CP-4A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 10, except that CE-4 was used instead of E-10, and designated as CP-4B. Comparative Example 5

[0166] (1) Preparation of solid catalyst component A 5-L autoclave was charged with 1.0 L of hexane, 20 mmol of triethylaluminum, 0.3 mmol of cyclohexylmethyldimethoxysilane, and 25.0 g of catalyst component A-7, and the mixture was reacted at 22°C for 10 minutes. Then, 6 g of ethylene and 2 g of hydrogen gas were added, and the mixture was reacted at 23°C for 10 minutes, releasing any unreacted gas. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-5. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 10, except that CE-5 was used instead of E-10, and designated as CP-5A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 10, except that CE-5 was used instead of E-10, and designated as CP-5B. Comparative Example 6

[0167] (1) Preparation of solid catalyst component A 5L autoclave was charged with 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane, and 25.0g of catalyst component A-13, and the mixture was reacted at 22°C for 10 minutes. 10g of propylene was then added, and the mixture was reacted at 15°C for 10 minutes, after which all unreacted propylene was released. The reactor was purged with nitrogen gas, and the liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-6. (2) Propylene Polymerization A Propylene polymerization was carried out according to the method of Propylene Polymerization A in Example 24, except that E-24 was changed to CE-6 as the solid catalyst component, thereby obtaining polypropylene, which was designated as CP-6A. Propylene Polymerization B Propylene polymerization was carried out according to the method of Propylene Polymerization B in Example 24, except that E-24 was changed to CE-6 as the solid catalyst component, thereby obtaining polypropylene, which was designated as CP-6B. Comparative Example 7

[0168] (1) Preparation of solid catalyst component A 5-L autoclave was charged with 1.0 L of hexane, 16 mmol of triethylaluminum, 0.3 mmol of cyclohexylmethyldimethoxysilane, and 25.0 g of catalyst component A-13, and the mixture was reacted at 22°C for 10 minutes. Then, 10 g of ethylene and 2 g of hydrogen gas were added, and the mixture was reacted at 15°C for 10 minutes, releasing any unreacted gas. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-7. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 24, except that CE-7 was used instead of E-24, and designated as CP-7A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 24, except that CE-7 was used instead of E-24, and designated as CP-7B. Comparative Example 8

[0169] (1) Preparation of solid catalyst component A 5-L autoclave was charged with 1.0 L of hexane, 16 mmol of triethylaluminum, 0.3 mmol of cyclohexylmethyldimethoxysilane, and 25.0 g of catalyst component A-13, and the mixture was reacted at 22°C for 10 minutes. Subsequently, 10 g of propylene and 2 g of hydrogen gas were added, and the mixture was reacted at 15°C for 10 minutes, releasing any unreacted gas. The liquid in the reaction product was filtered off and then dried under vacuum to obtain a solid catalyst component designated CE-8. (2) Propylene Polymerization A Polypropylene was obtained in the same manner as in Propylene Polymerization A of Example 24, except that CE-8 was used instead of E-24, and designated as CP-8A. Propylene Polymerization B Polypropylene was obtained in the same manner as in Propylene Polymerization B of Example 24, except that CE-8 was used instead of E-24, and designated as CP-8B.

[0170] [Table 1]

[0171] [Table 2]

[0172] [Table 3]

[0173] [Table 4]

[0174] [Table 5] JPEG2025535479000012.jpg28169

[0175] [Table 6]

[0176] As can be seen from Tables 1 to 3, the solid catalyst component prepared by the preparation method of the present invention has a titanium component Ti2p 3 / 2 It was found that the electron binding energy changed and had a characteristic peak, which led to changes in olefin polymerization performance.

[0177] Tables 4 to 6 show that the solid catalyst component of the present invention has a relatively high polymerization activity when used in olefin polymerization, meeting the requirements for industrial application. Compared with conventional prepolymerization catalyst technology, for example, Comparative Examples 1 to 8, the decay of polymerization activity after one year of catalyst storage is significantly slower, providing a prepolymerization catalyst with stable polymerization activity for industrial polypropylene production. The solid catalyst component of the present invention has the advantage of a low polymer fines content when used in olefin polymerization.

[0178] Catalyst E1 in Example 1 has a specific surface area of ​​20.2 m 2 / g, pore volume 0.026 cm 3 / g, pore diameter of 5.1 nm, and the catalyst CE1 of Comparative Example 1 had a specific surface area of ​​24.3 m 2 / g, pore volume 0.022 cm 3 / g, and the pore diameter is 5.5 nm.

[0179] Catalyst E11 of Example 11 has a specific surface area of ​​31.5 m 2 / g, pore volume 0.035 cm 3 / g, pore diameter of 4.4 nm, and the catalyst CE3 of Comparative Example 3 had a specific surface area of ​​32.1 m 2 / g, pore volume 0.034 cm 3 / g, and the pore diameter is 4.9 nm.

[0180] By comparison, it was found that the specific surface area, pore volume, and pore diameter of the catalysts of the above two sets of Examples and Comparative Examples were not significantly different and could be considered to be almost the same. There was also no significant difference in the specific surface area, pore volume, and pore diameter between the catalyst prepared according to the method of the Examples of the present invention using catalyst component A in the Preparation Examples of the present invention and the catalyst prepared according to the method of the Comparative Examples. Therefore, the slow decay of the activity of the catalyst of the present invention had little correlation with the specific surface area, pore volume, and pore diameter of the catalyst.

[0181] The XRD charts of the solid catalyst component E-1 (top) of Example 1 and the solid catalyst component CE-1 (bottom) of Comparative Example 1 are shown in Figure 1. It can be seen from the figure that the XRD spectrograms of the catalysts are almost identical, and that the XRD charts of the catalysts prepared according to the methods of the Examples of the present invention and the Comparative Examples using the catalyst component A in the Preparation Examples of the present invention are almost identical. Therefore, the slow decay of the activity of the catalysts of the present invention had little correlation with the characteristic peaks in the XRD of the catalysts.

[0182] On the other hand, when the composition of the solid catalyst component of the example was tested, no detectable amounts of Group IVB elements other than Ti were detected.

[0183] The XPS peak split fitting diagrams of the solid catalyst component E-1 (top) of Example 1 and the solid catalyst component CE-1 (bottom) of Comparative Example 1 are shown in Figure 2. Here, the dotted line indicates the fitted peak shape. From the figure, it can be seen that the catalyst CE-1 of Comparative Example 1 has Ti2p 3 / 2 The solid catalyst component E-1 of Example 1 has two fitting peaks at Ti2p 3 / 2 Furthermore, it was found that the solid catalyst components of the examples of the present invention all have three characteristic peaks. 3 / 2 The solid catalyst components of the comparative examples all have three characteristic peaks. 3 / 2 (See Tables 1 to 3.) Therefore, the slow decay of activity of the catalyst of the present invention correlates with the three characteristic peaks in the XPS spectrogram of the catalyst.

[0184] It should be noted that the above-described examples are intended to illustrate the present invention and are not intended to limit the present invention in any way. While the present invention has been described with reference to exemplary embodiments, it should be understood that the terms used herein are descriptive and explanatory, rather than limiting. The present invention can be modified and altered without departing from the scope and spirit of the present invention, as defined by the appended claims. While the present invention described herein relates to specific methods, materials, and examples, it is not intended that the present invention be limited to the specific embodiments disclosed herein; rather, the present invention can extend to all other methods and uses having the same functions.

Claims

1. A solid catalyst component for olefin polymerization, comprising elemental magnesium, elemental titanium, a halogen, a poly-α-olefin, and an internal electron donor, The Ti2p spectrogram obtained by XPS analysis of the solid catalyst component was subjected to peak division by Gauss-Lorentz peak division fitting. As a result of the peak division, Ti2p ３／２ The orbital spectrum peak has at least three characteristic peaks at electron binding energies of 459.9 eV to 454.9 eV; Here, the Gaussian-Lorentzian peak split fitting method uses a Lorentzian-to-Gaussian ratio of 30% and Ti2p １／２ Electron binding energy of the orbital spectrum peak and Ti2p ３／２ The difference between the electron binding energy of the orbital spectrum peak is 5.9 eV, Ti2p １／２ The half-width of the orbital spectrum peak is Ti2p ３／２ 1.7 times the half-width of the orbital spectrum peak, Ti2p １／２ The peak height of the orbital spectrum peak is Ti2p ３／２ 0.28 times the peak height of the spectral peak of the orbital, and Ti2p ３／２ 1. A solid catalyst component for olefin polymerization, characterized in that each characteristic peak of the spectral peaks of the orbital is set to have the same half-width.

2. Ti2p of the solid catalyst component ３／２ The orbital spectrum peak has three characteristic peaks at electron binding energies of 459.9 eV to 454.9 eV, and the three characteristic peaks are named the first characteristic peak, the second characteristic peak, and the third characteristic peak in descending order of electron binding energy. The electron binding energy of the first characteristic peak is 459.9 eV to 458.97 eV, the electron binding energy of the second characteristic peak is 458 eV to 457.45 eV, and the electron binding energy of the third characteristic peak is 456.2 eV to 454.9 eV. and / or Ti2p of the solid catalyst component １／２ 2. The solid catalyst component according to claim 1, wherein the electron binding energy of the spectral peak of the orbital is between 467 eV and 462 eV.

3. 3. The solid catalyst component according to claim 2, wherein the peak area of ​​the third characteristic peak accounts for 5 to 20%, preferably 5 to 15%, of the total peak area of ​​the first characteristic peak, the second characteristic peak, and the third characteristic peak.

4. 4. The solid catalyst component according to claim 1, wherein the solid catalyst component does not contain detectable amounts of Group IVB elements other than Ti.

5. The polyα-olefin is polyC ２ ~C １０ The solid catalyst component according to any one of claims 1 to 4, which is an olefin, preferably one or more selected from polyethylene, polypropylene, polybutene, polyoctene and polyisopentene, more preferably polypropylene.

6. the internal electron donor is at least one of a diol ester compound, a 1,3-diether compound, and a carboxylate; Preferably, the diol ester compound has a chemical structure represented by formula (1): The solid catalyst component according to any one of claims 1 to 4, wherein the 1,3-diether compound preferably has a chemical structure represented by formula (2). 【Chemical 1】 (In formula (1), R １ ~R ６ are the same or different and each independently represent hydrogen, amino, C １ ~C １０ Straight chain alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C １０ Cycloalkyl, C ６ ~C １０ Aryl, C ７ ~C １０ alkylaryl, and C ７ ~C １０ aralkyl; R １ ~R ６ two or more groups of R are optionally joined together to form one or more fused ring structures; ７ and R ８ are the same or different, and each independently represents C １ ~C １０ Straight chain alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C ２０ Cycloalkyl, C ６ ~C ２０ Aryl, C ７ ~C ２０ alkylaryl, and C ７ ~C ２０ aralkyl.) 【Chemistry 2】 (In formula (2), R １ and R ２ are the same or different and each independently represent hydrogen, C １ ~C ２０ Straight chain alkyl, C ３ ~C １０ Branched alkyl, C ３ ~C ２０ Cycloalkyl, C ６ ~C ２０ Aryl, C ７ ~C ２０ Aralkyl, and C ７ ~C ２０ alkylaryl; R １ and R ２ are optionally bonded to each other to form a fused ring structure, and R ３ and R ４ are the same or different, and each independently represents C １ ~C １０ alkyl.)

7. The diol ester compounds include 1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-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 di acetate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-2,2-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-butylbenzoate), 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl-1,3-butanedio dibenzoate, 2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di(p-methylbenzoate), 2,4-pentanediol di(p-tert-butylbenzoate), 2,4-pentanediol di(p-butylbenzoate), 2-methyl-1,3-pentanediol di(p-methylbenzoate), 2-butyl-1,3-pentanediol di(p-methylbenzoate), 2-methyl-1,3 -pentanediol di(p-tert-butylbenzoate), 2-methyl-1,3-pentanediol pivalate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-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, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3-propyl-3,5-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, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptane at least one selected from diol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-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, and 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, And / or the 1,3-diether compound is 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-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-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,The solid catalyst component according to claim 6, which is at least one selected from the group consisting of 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

8. the carboxylate is an aliphatic carboxylate and / or an aromatic carboxylate; Preferably, the carboxylate is one or more of a benzoate-based compound, a phthalate-based compound, and a succinate-based compound; Preferably, the benzoate compound is one or more selected from methyl benzoate, ethyl benzoate, and n-butyl benzoate; Preferably, the phthalate compound is one or more selected from diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, and di-n-octyl phthalate; The solid catalyst component according to claim 6, wherein the succinate compound is preferably one or more selected from the group consisting of diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, and diethyl 2-ethyl-2-methylsuccinate.

9. The internal electron donor includes an internal electron donor a and an internal electron donor b, and the internal electron donor a and the internal electron donor b are as follows: Option I: the internal electron donor a is selected from the diol ester compounds, and the internal electron donor b is selected from 1,3-diether compounds, and any carboxylate; Option II: the internal electron donor a is selected from the 1,3-diether compounds, and the internal electron donor b is selected from the phosphate compounds represented by formula (3), The solid catalyst component according to any one of claims 1 to 8, wherein the phosphate compound is preferably at least one selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tritolyl phosphate, triisopropylphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl xylyl phosphate, phenyl diisopropylphenyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, and o-tolyl p-di-tert-butylphenyl phosphate. 【Chemistry 3】 (In formula (3), R ５ , R ６ , and R ７ are the same or different, and each independently represents C １ ~C ４ Straight chain alkyl, C ３ ~C ４ Branched alkyl, C ３ ~C ２０ Cycloalkyl, C ６ ~C ２０ Aryl, C ７ ~C ２０ alkylaryl, and C ７ ~C ２０ aralkyl.)

10. 10. The solid catalyst component according to claim 9, wherein the mass ratio of the internal electron donor a to the internal electron donor b is 0.1:1 to 1000:

1.

11. 11. The solid catalyst component according to claim 1, wherein the content of magnesium element in the solid catalyst component is 1 to 18 wt %, the content of titanium element is 0.1 to 3.5 wt %, the content of halogen is 2 to 65 wt %, the content of poly-α-olefin is 0.1 to 89 wt %, and the content of internal electron donor is 0.6 to 15 wt %, based on the total weight of the solid catalyst component.

12. 1. A process for preparing a solid catalyst component for olefin polymerization, the process comprising the steps of: Step (1) of contacting and reacting catalyst component A, alkylaluminum, and an external electron donor in the presence of an inert solvent, wherein the catalyst component A contains titanium element, magnesium element, a halogen, and an internal electron donor; Step (2) of mixing the reaction system obtained in step (1) with an α-olefin to carry out a polymerization reaction; and step (3) of removing the unreacted α-olefin in step (2) and adding hydrogen gas to the resulting reaction system to cause a reaction.

13. the molar ratio of the alkyl aluminum, the external electron donor compound, and the catalyst component A in terms of elemental titanium is 1 to 50:0.2 to 10:1; And / or, the number of alkyls in the alkyl aluminum is 1 to 3, and the number of carbon atoms in the alkyl is C １ ~C ８ and more preferably, the alkyl aluminum is one or more selected from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and monochlorodiethyl aluminum; and / or the external electron donor compound is at least one selected from silicon-containing compounds, preferably one or more selected from cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyltert-butyldimethoxysilane, and dicyclopentyldimethoxysilane; and / or the internal electron donor includes at least one of a diol ester compound, a 1,3-diether compound, and a carboxylate; and / or the α-olefin is C ２ ~C １０ 13. The process according to claim 12, wherein the olefin is preferably one or more selected from ethylene, propylene, butene, octene, and isopentene, more preferably propylene.

14. In step (1), the reaction conditions include a temperature of 0 to 30°C, preferably 15 to 25°C, and a reaction time of 1 to 30 min, preferably 10 to 20 min; and / or in step (2), the polymerization conditions include a temperature of 0 to 50°C, preferably 15 to 25°C, and a time of 5 to 30 minutes, preferably 10 to 20 minutes; and / or in step (3), the reaction conditions include a temperature of 0 to 50°C, preferably 15 to 25°C, and a time of 5 to 30 minutes, preferably 10 to 20 minutes; and / or, in step (3), the amount of hydrogen gas added is controlled so as to maintain the reaction pressure at 0.01 to 1 MPa; And / or the method according to claim 12 or 13, wherein in step (2), the mass ratio of the α-olefin to catalyst component A is 0.04 to 10:

1.

15. A solid catalyst component prepared by the method according to any one of claims 12 to 14.

16. 1. A catalyst system for olefin polymerization comprising: A catalyst system for olefin polymerization, characterized in that the catalyst system comprises the solid catalyst component according to any one of claims 1 to 11 and / or the solid catalyst component prepared by the method according to any one of claims 12 to 14, an alkylaluminum, an optional external electron donor compound, or a reaction product thereof.

17. Use of the solid catalyst component according to any one of claims 1 to 11 and / or the solid catalyst component prepared by the method according to any one of claims 12 to 14 and / or the catalyst system according to claim 16 in olefin polymerization.

18. 1. A process for olefin polymerization comprising: The method comprises the step of polymerizing an olefin in the presence of a solid catalyst component according to any one of claims 1 to 11 and / or a solid catalyst component prepared by a method according to any one of claims 12 to 14 and / or a catalyst system according to claim 16, Preferably, the general formula of the olefin is CH ２ =CHR, where R is hydrogen or C １ ~C ６ Alkyl or C ６ ~C １０ is aryl, Preferably, the temperature of the polymerization reaction is 0 to 150°C, more preferably 60 to 90°C.

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