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    • 专利摘要:
    CATALYST COMPONENT FOR OLEFINES POLYMERIZATION, METHOD FOR PREPARING A CATALYST COMPONENT, CATALYST FOR OLEFINES POLYMERIZATION, USE OF THE CATALYST AND METHOD FOR POLYMERIZING OLEFINS. The present invention provides a catalyst component for polymerization of olefins and a method of preparing the same, and a catalyst for polymerization of olefins and an application thereof. The catalyst component for olefin polymerization comprises reaction products of the following components: (1) a solid component; (2) at least one titanium compound; and (3) at least two internal electron donors, the solid component comprising a magnesium compound represented by formula (1) and an epoxide represented by formula (2), in which R1 is a linear C1-C12 alkyl group or branched; R2 and R3 are identical or different, and are independently hydrogen or straight or branched C1-C5 alkyl unsubstituted or substituted with halogen; X is halogen; m is in the range of 0.1 to 1.9; n is in the range of 0.1 to 1.9; and (m + n) = 2.
    公开号:BR112016008602B1
    申请号:R112016008602-3
    申请日:2014-10-17
    公开日:2021-01-19
    发明作者:Xianzhi Xia；Jin Zhao；Weili Li；Yuexiang Liu；Yongtai Ling；Ping Gao；Yang Tan；Futang GAO；Renqi Peng；Jigui Zhang
    申请人:China Petroleum & Chemical Corporation；Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation；
    IPC主号:
    专利说明:

    Field of invention
    [0001] The present invention relates to a catalyst component for polymerization of olefins, to a method for preparing a catalyst component, to a catalyst component for polymerization of olefins prepared by the method, to a catalyst for polymerization of olefins comprising the catalyst component, and the use of the catalyst for polymerization of olefins in polymerization of olefins. Technique history
    [0002] Most catalysts for olefin polymerization are prepared by supporting a titanium halide over an active magnesium chloride. A common method used to prepare the active magnesium chlorides is to react MgCl2 with an alcohol to form a magnesium chloride-alcohol adduct of the general formula: MgCl2 ^ mROH ^ nH2O. Then, a titanium halide is supported in such an adduct to provide a solid catalyst component for polymerization of olefins. Such alcohol adducts can be prepared by known processes, such as spray drying process, spray cooling process, high pressure extrusion process or high speed stirring process. See, for example, U.S. 4,421,674. U.S. 4,469,648, WO 8707620, WO 9311166, U.S. 5,100,849, U.S. 6,020,279, U.S. 4,399,054, EP 0395383, U.S. 6,127,304 and U.S. 6,323,152.
    [0003] Other magnesium-containing complex carriers useful in the preparation of catalysts for polymerization of olefins are also known in the art. For example, CN102040681A discloses a compound that can be used as a catalyst carrier for polymerization of olefins having a structure:
    in which R1 is a straight or branched C1-C12 alkyl group; R2 and R3 are identical or different, and are, independently, straight or branched hydrogen or C1-C5 alkyl, substituted with halogen; X is chlorine or bromine, and one of X may be C1-C14 alkyl, C1-C14 alkoxy, C6-C14 aryl or C6-C14 aroxy; m is in a range of 0.1 to 1.9, n is in a range of 0.1 to 1.9, and (p + m + n) = 2. The said compound is prepared as follows: MgX2 reacts with an alcohol of the general formula R1OH in the presence of an inert dispersion medium at a temperature of 30 to 160 ° C to form a magnesium halide-alcohol adduct solution; then, the solution reacts with an oxirane at a temperature of 30 to 160 ° C to form the magnesium compound useful as a carrier, where X is chlorine or bromine, R1 is a straight or branched C1-C12 alkyl group. CN102040680A also discloses an olefin polymerization catalyst, which is prepared using said compound useful as an olefin polymerization catalyst carrier disclosed in the patent application mentioned above.
    [0004] There is still a need for a catalyst component for polymerization of olefins that exhibits desired properties, such as high activity and high capacity for stereo targeting, and a method by which such a catalyst component can be prepared simply and effectively and that is low cost. Summary of the invention
    [0005] An object of the invention is to provide a new catalyst component for polymerization of olefins.
    [0006] An additional object of the invention is to provide a method for preparing the catalyst component for polymerization of olefins.
    [0007] Another objective of the invention is to provide for the use of the catalyst in polymerization of olefins. In some embodiments, the present invention provides a catalyst component for polymerization of olefins comprising reaction products of the following components: (1) a solid component; (2) at least one titanium compound; and (3) at least two internal electron donors; the solid component comprising a magnesium compound represented by formula (1) and an epoxide represented by formula (2),
    in which, R1 is a straight or branched C1-C12 alkyl group; RII and RIII are identical or different, and are, independently, straight or branched hydrogen or C1-C5 alkyl unsubstituted or substituted with halogen; X is halogen; m is in the range of 0.1 to 1.9; n is in the range of 0.1 to 1.9; and (m + n) = 2; and the epoxide content represented by formula (2) is in the range of 0.01 to 0.8 mol per mol of the magnesium compound represented by formula (1). In some embodiments, the present invention provides a method for preparing the catalyst component comprising the steps of: (1) preparing a solid component by a process comprising: (a) reacting a magnesium halide of formula MgX2 with an alcohol of formula RIOH in the presence of at least one polymeric dispersion stabilizer at a temperature of 30 to 160 ° C in a closed vessel to form a magnesium-alcohol halide adduct solution; and (b) reacting the magnesium-alcohol halide adduct solution with an epoxide represented by formula (2):
    at a temperature of 30 to 160 ° C to form a solid component, where X is halogen; RI is straight or branched C1-C12 alkyl; RII and RIII are identical or different, and are, independently, straight or branched C1-C5 alkyl substituted with halogen, and with respect to one mole of magnesium halide, the amount of alcohol used ranges from 3 to 30 moles and the amount used of the epoxide represented by formula (2) varies from 1 to 10 moles, and the polymeric dispersion stabilizer is used in an amount of 0.1 to 10% by weight, based on the total weight of the magnesium halide and the alcohol; and (2) contacting and reacting the solid component of step (1) with a titanium compound in the presence or absence of an inert solvent, and adding at least two internal electron donors in one or more stages before, during and / or after the reaction.
    [0008] In some embodiments, the present invention provides a catalyst component for polymerization of olefins prepared by the method described above.
    [0009] In some embodiments, the present invention provides a catalyst for polymerizing olefins comprising: (I) the catalyst component for polymerizing olefins according to the present invention; (II) at least one alkyl aluminum compound; and (III) optionally, at least one external electron donor.
    [0010] In some embodiments, the present invention provides for the use of the olefin polymerization catalyst in the olefin polymerization reaction.
    [0011] By means of these technical solutions, the present invention achieves the following virtues: (1) in the preparation of the solid component, solid particles having good particle morphology and narrow particle size distribution can be obtained without adding an inert dispersion medium , thereby improving the production of a solid component of a reactor unit volume; (2) compared to the inert dispersion media used in the prior art, the polymeric dispersion stabilizer used in the preparation of the solid component can be recovered more easily, thereby reducing the costs associated with recovery; (3) when the catalysts for polymerization of olefins according to the invention are used in polymerization of olefins (especially in polymerization or copolymerization of propylene), the resulting polymers have relatively high isotacticities; and (4) the olefin polymerization catalysts according to the invention exhibit high activities.
    [0012] These and other characteristics and virtues of the invention will become evident from the following detailed description. Brief description of the figures
    [0013] The drawings are provided to further illustrate the invention and form a part of this specification. The drawings and the following description together explain the invention, but do not limit the invention. In the drawings:
    [0014] Figure 1 shows a 1H NMR spectrum of the solid component prepared in Preparation Example 1;
    [0015] Figure 2 shows a 1H NMR spectrum of the solid component prepared in Preparation Example 2;
    [0016] Figure 3 shows a 1H NMR spectrum of the solid component prepared in Preparation Example 13;
    [0017] Figure 4 shows a 1H NMR spectrum of the solid component prepared in Preparation Example 15;
    [0018] Figure 5 is an optical microphotograph of the solid component prepared in Preparation Example 1; and
    [0019] Figure 6 is an optical microphotograph of the solid component prepared in Comparative Example 2. Detailed description of the preferred embodiments In a first aspect, the present invention provides a catalyst component for polymerization of olefins comprising reaction products of the following components: (1 ) a solid component; (2) at least one titanium compound; and (3) at least two internal electron donors; the solid component comprising a magnesium compound represented by formula (1) and an epoxide represented by formula (2),
    in which, R1 is a straight or branched C1-C12 alkyl group; RII and RIII are identical or different, and are, independently, straight or branched hydrogen or C1-C5 alkyl unsubstituted or substituted with halogen; X is halogen; m is in the range of 0.1 to 1.9; n is in the range of 0.1 to 1.9; and (m + n) = 2; and the epoxide content represented by formula (2) is in the range of 0.01 to 0.8 mol per mol of the magnesium compound represented by formula (1).
    [0020] In the solid component, RI is preferably straight or branched C1-C8 alkyl, such as ethyl, propyl, butyl or pentyl.
    [0021] In the solid component, preferably RII and RIII are independently hydrogen or straight or branched C1-C3 alkyl unsubstituted or substituted with halogen, and more preferably hydrogen, methyl, ethyl, propyl, chloromethyl, chloroethyl, bromomethyl, bromoethyl or bromopropyl .
    [0022] In the solid component, X is preferably bromine, chlorine or iodine, and more preferably chlorine.
    [0023] Preferably, in the solid component, m is in the range of 0.5 to 1.5, n is in the range of 0.5 to 1.5 and (m + n) = 2. Most preferably, m is 1 and n is 1.
    [0024] In the solid component, the epoxide represented by formula (2) is preferably at least one of epoxy ethane, epoxy propane, epoxy butane, epoxy chloro-propane, epoxy chloro-butane, epoxy bromo-propane and epoxy bromo-butane.
    [0025] In the solid component, the epoxide content represented by formula (2) is preferably in the range of 0.02 to 0.5 mol, more preferably from 0.02 to 0.3 mol and even more preferably from 0.02 at 0.1 mol per mol of the magnesium compound represented by formula (1).
    [0026] Preferably, the solid component is present in the form of spherical particles and has an average particle size (D50) of 30 to 125 μm, and more preferably 40 to 85 μm. Preferably, the solid component has a particle size distribution value (SPAN = (D90-D10) / D50) from 0.6 to 2.5, and more preferably from 0.6 to 0.85. The average particle size and particle size distribution value of the solid component particles can be measured on a Model 2000 Masters Sizer (manufactured by Malvern Instruments Co., Ltd.).
    [0027] In the reaction to form the catalyst component, with respect to one mole of the magnesium compound represented by formula (1) in the solid component, the titanium compound can be used in an amount of 5 to 200 moles, preferably 10 to 50 mol; and the internal electron donor can be used in an amount of 0.04 to 0.6 mol, preferably from 0.07 to 0.5 mol, and more preferably from 0.1 to 0.4 mol.
    [0028] According to the present invention, the titanium compound can be any titanium compound commonly used in the art. For example, the titanium compound can be chosen from those represented by the formula Ti (ORIV) 4-aXa, in which RIV can be a C1-C14 aliphatic hydrocarbyl group, preferably C1-C8 alkyl, such as methyl, ethyl, propyl , butyl, pentyl, hexyl, heptyl or the like; X can be halogen, such as F, Cl, Br, I or a combination thereof; and a is an integer ranging from 1 to 4. Preferably, the titanium compound is chosen from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium tetrabutoxy chloride, titanium dibutoxy dichloride , titanium butoxy trichloride, titanium triethoxy chloride, titanium diethoxy dichloride and titanium ethoxy trichloride.
    [0029] According to the present invention, internal electron donors can be a combination of any two conventional internal electron donors. Preferably, in order that the olefin polymerization catalyst using said catalyst component exhibits improved catalytic activity in the olefin polymerization and gives olefinic polymer having improved isotacticity, the internal electron donors are a combination of a first internal electron donor and a second internal electron donor, the first internal electron donor being at least one diol ester, and the second internal electron donor is at least one diether. More preferably, the molar ratio of the first internal electron donor to the second internal electron donor is in the range of 0.55: 1 to 50: 1, preferably 0.6: 1 to 30: 1, and more preferably 0 , 65: 1 to 10: 1.
    [0030] The diol ester can be any diol ester used conventionally as an internal electron donor. Preferably, the diol ester is chosen from those represented by formula (3):
    in which R1 and R2 are identical or different, and are, independently, straight or branched C1-C10 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl, with the hydrogen atoms in the phenyl ring in the aryl, the alkylaryl and the arylalkyl are optionally substituted by halogen atoms; R3-R6 and R1-R2n are identical or different, and are independently hydrogen, halogen, straight or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20, C2-C10 alkenyl or C10-C20 fused ring aryl, with carbon atoms and / or hydrogen atoms in R3-R6 and R1-R2n being optionally substituted by heteroatoms chosen from nitrogen, oxygen, sulfur, silicon, phosphorus and halogen, and two or more of R3 to R6 and R1 to R2n are optionally linked to form a saturated or unsaturated ring; and n is an integer ranging from 0 to 10.
    [0031] More preferably, the diol ester is chosen from those represented by formula (4):
    independently, chosen from hydrogen and straight or branched C1- C20 alkyl.
    [0032] Even more preferably, the diol ester is chosen from 1,3-propylene glycol dibenzoate, 2-methyl-1,3-propylene glycol dibenzoate, 2-ethyl-1,3-propylene glycol dibenzoate, dibenzoate 2-propyl-1,3-propylene glycol, 2-butyl-1,3-propylene glycol dibenzoate, 2,2-dimethyl-1,3-propylene glycol dibenzoate, 2-ethyl-2-butyl dibenzoate 1,3-propylene glycol, 2,2-diethyl-1,3-propylene glycol dibenzoate, 2-methyl-2-propyl-1,3-propylene glycol dibenzoate, 2-isopropyl-2-isopentyl-dibenzoate , 3-propylene glycol, 2,4-pentylene glycol dibenzoate, 3-methyl-2,4-pentylene glycol dibenzoate, 3-ethyl-2,4-pentylene glycol dibenzoate, 3-propyl-2,4 dibenzoate - pentylene glycol, 3-butyl-2,4-pentylene glycol dibenzoate, 3,3-dimethyl-2,4-pentylene glycol dibenzoate, 2-methyl-1,3-pentylene glycol dibenzoate, 2,2 dibenzoate -dimethyl-1,3-pentylene glycol, 2-ethyl-1,3-pentylene glycol dibenzoate, 2-butyl-1,3-pentylene glycol dibenzoate, 2-dibenzoate - methyl-1,3-pentylene glycol, 2-ethyl-1,3-pentylene glycol dibenzoate, 2-propyl-1,3-pentylene glycol dibenzoate, 2-butyl-1,3-pentylene glycol dibenzoate, dibenzoate 2,2,4-trimethyl-1,3-pentylene glycol, 3-methyl-3-butyl-2,4-pentylene glycol dibenzoate, 2,2-dimethyl-1,5-pentylene glycol dibenzoate, dibenzoate 1,6-hexylene glycol, 6-ene-2,4-heptylene glycol dibenzoate, 2-methyl-6-ene-2,4-heptylene glycol dibenzoate, 3-methyl-6-ene-2,4 dibenzoate -heptylene glycol, 4-methyl-6-ene-2,4-heptylene glycol, 5-methyl-6-ene-2,4-heptylene glycol dibenzoate, 6-methyl-6-ene-2 dibenzoate, 4-heptylene glycol, 3-ethyl-6-ene-2,4-heptylene glycol, 4-ethyl-6-ene-2,4-heptylene dibenzoate, 5-ethyl-6-ene-2 dibenzoate , 4-heptylene glycol, 6-ethyl-6-ene-2,4-heptylene glycol, 3-propyl-6-ene-2,4-heptylene glycol, 4-propyl-6-eno- dibenzoate 2,4-heptylene glycol, 5-propyl-6-ene-2,4-heptylene glycol dibenzoate, diben 6-propyl-6-ene-2,4-heptylene glycol zoate, 3-butyl-6-ene-2,4-heptylene glycol dibenzoate, 4-butyl-6-glycol dibenzoate, 5-butyl dibenzoate 6-butyl-6-ene-2,4-heptylene 3,5-heptylene glycol 6-ene-2,4-dibenzoate, 3-methyl-3,5-heptylene glycol dibenzoate, 4-methyl-3 dibenzoate , 5-heptylene glycol, 5-methyl-3,5-heptylene glycol dibenzoate, 6-methyl-3,5-heptylene glycol dibenzoate, 3-ethyl-3,5-heptylene glycol dibenzoate, 4-ethyl dibenzoate -3,5-heptylene glycol, 5-ethyl-3,5-heptylene glycol dibenzoate, 3-propyl-3,5-heptylene glycol dibenzoate, 4-propyl-3,5-heptylene glycol dibenzoate, 3-dibenzoate -butyl-3,5-heptylene glycol, 2,3-dimethyl-3,5-heptylene glycol dibenzoate, 2,4-dimethyl-3,5-heptylene glycol dibenzoate, 2,5-dimethyl-3 dibenzoate, 5-heptylene glycol, 2,6-dimethyl-3,5-heptylene glycol dibenzoate, 3,3-dimethyl-3,5-heptylene glycol dibenzoate, 4,4-dimethyl-3,5-heptylene glycol dibenzoate, 6,6-dimethyl-3,5-heptylene dibenzoate g lycol, 2,6-dimethyl-3,5-heptylene glycol dibenzoate, 3,4-dimethyl-3,5-heptylene glycol dibenzoate, 3,5-dimethyl-3,5-heptylene glycol dibenzoate, 3-dibenzoate , 6-dimethyl-3,5-heptylene glycol, 4,5-dimethyl-3,5-heptylene glycol dibenzoate, 4,6-dimethyl-3,5-heptylene glycol dibenzoate, 4,4-dimethyl dibenzoate 3,5-heptylene glycol, 6,6-dimethyl-3,5-heptylene glycol dibenzoate, 2-methyl-3-ethyl-3,5-heptylene glycol dibenzoate, 2-methyl-4-ethyl-3 dibenzoate , 5-heptylene glycol, 2-methyl-5-ethyl-3,5-heptylene glycol dibenzoate, 3-methyl-3-ethyl-3,5-heptylene glycol dibenzoate, 3-methyl-4-ethyl- dibenzoate 3,5-heptylene glycol, 3-methyl-5-ethyl-3,5-heptylene glycol, 4-methyl-3-ethyl-3,5-heptylene dibenzoate, 4-methyl-4-ethyl dibenzoate -3,5-heptylene glycol, 4-methyl-5-ethyl-3,5-heptylene glycol dibenzoate, 2-methyl-3-propyl-3,5-heptylene glycol dibenzoate, 2-methyl-4- dibenzoate propyl-3,5-heptylene glycol, 2-methyl-5-propyl-3,5-h dibenzoate eptilene glycol, 3-methyl-3-propyl-3,5-heptylene glycol, 3-methyl-4-propyl-3, 5-heptylene glycol, 3-methyl-5-propyl-3 dibenzoate, 5 - heptylene glycol, 4-methyl-3-propyl-3 dibenzoate, 5-heptylene glycol, 4-methyl-4-propyl-3 dibenzoate, 5-heptylene glycol and 4-methyl-5-propyl-3 dibenzoate, 5- heptylene glycol.
    [0033] Most preferably, the diol ester is chosen from the pentylene glycol esters mentioned above and from the heptylene glycol esters mentioned above.
    [0034] The diether can be any diester conventionally used in the art as an internal electron donor. Preferably, the diether is chosen from those represented by formula (5):
    in which RI, RII, RIII, RIV, RV and RVI are identical or different, and are chosen independently from hydrogen, halogen, linear or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, arylalkyl C7-C20 and C7-C20 alkylaryl; RVII and RVIII are identical or different, and are chosen independently from straight or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 arylalkyl and C7-C20 alkylaryl; and two more of the RI-RVI groups optionally bond to form a ring.
    [0035] More preferably, the diether is chosen from those represented by the general formula: R1R2C (CH2OR3) (CH2OR4), in which R1 and R2 are identical or different, and are chosen independently of linear or branched C1-C18 alkyl, cycloalkyl of C3-C18, C6-C18 aryl and C7-C18 arylalkyl, and optionally bond to form a ring; and R3 and R4 are identical or different, and are, independently, straight or branched C1-C10 alkyl.
    [0036] Even more preferably, the diether is chosen from 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2- secbutyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2- (2-cyclohexyl-ethyl) -1,3-dimethoxypropane, 2- (2-phenyl-ethyl) -1,3-dimethoxypropane, 2- (p-chloro-phenyl) -1,3-dimethoxypropane, 2- (diphenyl-methyl) -1,3-dimethoxypropane, 2,2-dicyclo- hexyl-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-cyclohexyl-ethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethyl- hexyl) -1,3-dime toxipropane, 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-methyl-butyl) -2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1 , 3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-secbutyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl -2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-secbutyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-secbutyl -1,3-dimethoxypropane, 2-isopropyl-2-secbutyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexyl-methyl-1,3-dimethoxypropane and 9,9-dimethoxy-methyl-fluorene . In a second aspect, the present invention provides a method for preparing a catalyst component for polymerization of olefins, comprising the steps of: (1) preparing a solid component by a process comprising: (a) reacting a magnesium halide of formula MgX2 with an alcohol of formula RIOH in the presence of at least one polymeric dispersion stabilizer at a temperature of 30 to 160 ° C in a closed container to form a magnesium-alcohol halide adduct solution; and (b) reacting the magnesium-alcohol halide adduct solution with an epoxide represented by formula (2):
    at a temperature of 30 to 160 ° C to directly precipitate a solid component, where X is halogen; RI is straight or branched C1-C12 alkyl; RII and RIII are identical or different, and are, independently, straight or branched C1-C5 alkyl substituted with halogen, and with respect to one mole of magnesium halide, the amount of alcohol used ranges from 3 to 30 moles and the amount used of the epoxide represented by formula (2) varies from 1 to 10 moles, and the polymeric dispersion stabilizer is used in an amount of 0.1 to 10% by weight, based on the total weight of the magnesium halide and the alcohol; and (2) contacting and reacting the solid component of step (1) with a titanium compound in the presence or absence of an inert solvent, and adding at least two internal electron donors in one or more stages before, during and / or after the reaction.
    [0037] When used here, the expression “directly precipitate a solid component” has the following meanings: (1) the solid component precipitates through the chemical reaction, that is, in preparation, the solid component precipitates directly through the chemical reaction, from original system, and there is no need to use other means such as vaporizing a solvent or changing the temperature of the system (such as reducing the temperature of the spray drying system) to precipitate solid particles from the reagents; and (2) obtaining the shape (typically spherical shape) of the solid component can be achieved without the need to introduce an inert carrier material having good particle morphology (for example, SiO2, metal oxides or the like) in the precipitation.
    [0038] In step (1), preferably, in relation to one mole of magnesium halide, the amount of alcohol used varies from 4 to 20 moles and the amount used of the epoxide represented by formula (2) varies from 2 to 6 moles , and the polymeric dispersion stabilizer is used in an amount of 0.2 to 5% by weight, based on the total weight of the magnesium halide and alcohol.
    [0039] In the magnesium halide MgX2, X is preferably bromine, chlorine or iodine. More preferably, the magnesium halide is at least one chosen from magnesium dichloride, magnesium dibromide and magnesium diiodide, and most preferably magnesium dichloride.
    [0040] In RIOH alcohol, RI is preferably a straight or branched C1-C8 alkyl group, more preferably a straight or branched C2-C5 alkyl group such as ethyl, propyl, butyl or pentyl. In particular, the alcohol can be at least one chosen from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentane, n-hexanol, n-octanol and 2-ethylhexanol.
    [0041] In the epoxide represented by formula (2), preferably RII and RIII are, independently, straight or branched hydrogen or C1-C3 alkyl, unsubstituted or substituted with halogen, and more preferably hydrogen, methyl, ethyl, propyl, chloromethyl , chloroethyl, chloropropyl, bromomethyl, bromoethyl or bromopropyl. In particular, the epoxide may be at least one chosen from epoxy ethane, epoxy propane, epoxy butane, epoxy chloropropane, epoxy chloro-butane, epoxy bromo-propane and epoxy bromo-butane.
    [0042] According to the invention, there is no specific limitation regarding the molecular weight of the polymeric dispersion stabilizer. However, it is preferred that the polymeric dispersion stabilizer has a weight average molecular weight greater than 1,000, more preferably greater than 3,000, even more preferably 6,000 to 2,000,000. Particularly the polymeric dispersion stabilizer can be at least one chosen from polyacrylates, styrene / maleic anhydride copolymers, polystyrene sulfonates, naphthalene sulfonic acid / formaldehyde condensation products, condensed alkyl phenyl ether sulfates, polyoxyethylene ether alkyl phosphates condensates, polyethyleneimines modified with oxyalkyl acrylate copolymer, salts of poly (vinyl benzyl trimethyl ammonium), poly (vinyl alcohols), polyacrylamides, block copolymers of ethylene oxide / propylene oxide, polyvinylpyrrolidone (PVPs), poly (acetates from PVPs) vinyl-pyrrolidone-co-vinyl), poly (ethylene glycols) (PEGs), alkyl phenyl polyoxyethylene ethers and poly (alkyl methacrylates), preferably at least one of polyvinylpyrrolidone, poly (vinyl-pyrrolidone-co-vinyl acetates) and poly (ethylene glycols).
    [0043] In step (a) of the process to prepare the solid component, the magnesium halide, the alcohol and the polymeric dispersion stabilizer can participate, in a form comprising a minimum amount of water, in the formation of the halide adduct solution. magnesium-alcohol. The so-called “minimum amount of water” means water introduced inevitably during industrial production or storage or transportation, but not added on purpose.
    [0044] In step (a) of the process to prepare the solid component, the magnesium halide, the alcohol and the polymeric dispersion stabilizer can be added in any order of addition.
    [0045] In step (a) of the process to prepare the solid component, the reaction time can be in the range of 0.1 to 5 hours, and preferably 0.5 to 2 hours.
    [0046] In step (b) of the process for preparing the solid component, the reaction time can be in the range of 0.1 to 5 hours, and preferably 0.3 to 1 hours.
    [0047] Steps (a) and (b) of the process for preparing the solid component optionally use an inert dispersion medium. The inert dispersion medium is any one commonly used in the art. For example, the inert dispersion medium can be at least one chosen from liquid aliphatic, aromatic or alicyclic hydrocarbons and silicone oils. In particular, the inert dispersion medium can be at least one of linear or branched liquid alkanes having a carbon chain length greater than 6 carbons, kerosenes, paraffinic oils, petroleum jelly oils, white oils and methyl silicone oils. Preferably, no inert dispersion medium is used in both steps (a) and (b).
    [0048] In a preferred embodiment, the process for preparing the solid component comprises: (I) heating the mixture of the magnesium halide, alcohol and at least one polymeric dispersion stabilizer in a closed vessel with stirring at a temperature of 30 to 160 ° C , and preferably from 40 to 120 ° C, and allow the mixture to react for 0.1 to 5 hours, and preferably for 0.5 to 2 hours, to form a magnesium-alcohol halide adduct solution, in which the amount of alcohol used varies from 3 to 30 moles, and preferably from 4 to 25 moles, per mole of magnesium halide, and the amount used of the polymeric dispersion stabilizer is 0.1 to 10% by weight, and preferably 0 , 2 to 5% by weight, based on the total weight of magnesium halide and alcohol; and (II) add the epoxide represented by formula (2) to the magnesium alcohol halide adduct solution with stirring, and allow the mixture to react at a temperature of 30 to 160 ° C, and preferably from 40 to 120 ° C, for 0.1 to 5 hours, and preferably for 0.3 to 1 hour, to form the particulate solid component, in which the amount of epoxide used varies from 1 to 10 moles, and preferably from 2 to 6 moles, per mole of magnesium halide.
    [0049] Preferably, the particulate solid component obtained by the process described above to prepare the solid component is washed with an inert hydrocarbon solvent, for example, hexane, heptane, octane, decane, toluene or the like, and then dried to be quickly used in the subsequent step (2) to prepare the catalyst component for polymerization of olefins.
    [0050] Preferably, step (2) of the inventive method is carried out as follows: the solid component is suspended in a feed of titanium compound at a temperature of -30 ° C to 0 ° C, and then the suspension is heated until a temperature of 40 to 130 ° C and allowed to react for 0.1 to 5 hours. More preferably, step (2) of the inventive method is carried out as follows: the solid component is suspended in a feed of titanium compound at a temperature of -20 ° C to -10 ° C, and then the suspension is heated to a 80 to 130 ° C and allowed to react for 0.5 to 2 hours. The titanium compound feed can be the pure titanium compound or a mixture of the titanium compound and an inert solvent. The inert solvent can be chosen from aliphatic hydrocarbons and aromatic hydrocarbons, for example, hexanes, heptanes, octanes, decanes, toluene and the like.
    [0051] In step (2), the internal electron donors can be added in one or more stages before, during and / or after the reaction of the solid component with the titanium compound, and the at least two internal electron donors can be added be introduced together or separately at different stages. Preferably, the at least two internal electron donors are introduced during the heating of the mixture of the solid component and the titanium compound.
    [0052] Preferably, the method for preparing the catalyst component further comprises: after reacting the solid component with the titanium compound, the liquid is filtered and the solids are recovered. Then, the recovered solids are washed with a liquid titanium compound (for example, liquid tetrachloride) one or more times, and preferably 2 to 4 times, and then with an inert solvent multiple times, to produce the solid catalyst component. . The inert solvent can be chosen from aliphatic hydrocarbons and aromatic hydrocarbons, for example, hexanes, heptanes, octanes, decanes, toluene and the like.
    [0053] In step (2), in relation to one mole of magnesium, the amount used of the titanium compound can vary from 5 to 200 moles, and preferably from 10 to 50 moles, and the amount used from the internal electron donors can be from 0.04 to 0.6 mol, preferably from 0.07 to 0.5 mol, and more preferably from 0.1 to 0.4 mol.
    [0054] In the above method, the titanium compound and the internal electron donors are as described above.
    [0055] In a third aspect, the present invention provides a catalyst component for polymerization of olefins by the method described above.
    [0056] In a fourth aspect, the present invention provides a catalyst for polymerization of olefins comprising: (I) the catalyst component for polymerization of olefins according to the present invention; (II) at least one alkyl aluminum compound; and (III) optionally, at least one external electron donor.
    [0057] The alkyl aluminum compound can be any of the alkyl aluminum compounds commonly used in the art. For example, alkyl aluminum may be of the general formula AlR'3, in which the R 'are independently halogen or C1-C8 alkyl unsubstituted or substituted with halogen with the proviso that at least one R' is not halogen. Examples of C1-C8 alkyl include, but are not limited to, methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl and n-octyl. Halogen can be fluorine, chlorine, bromine or iodine. Particularly the alkyl aluminum compound can be, for example, one or more chosen from triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, di chloride -n-butyl aluminum, ethyl aluminum dichloride, isobutyl aluminum dichloride and n-hexyl aluminum dichloride.
    [0058] The external electron donor can be chosen from carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, lactones, organic phosphorus compounds and organic silicon compounds. Preferably, the external electron donor is a silicon compound of the general formula (R17) x (R18) ySi (OR19) z, in which R17, R18 and R19 are independently a C1C18 hydrocarbyl group optionally comprising a heteroatom, x and y they are independently an integer from 0 to 2, z is an integer 1 to 3, and the sum of x, y and z is 4. Preferably, R17 and R18 are independently C3-C10 alkyl or cycloalkyl comprising a heteroatom; R19 is C1-C10 alkyl optionally comprising a heteroatom. In particular, the external electron donor may be chosen, for example, from cyclohexyl methyl dimethoxy silane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, diisobutyl dimethoxy silane, diphenyl dimethoxy silane, methyl terciobutyl dimethoxy silane, dicyclopentyl dimethoxy silane, 2-ethyl-piperidine tert-butyl dimethoxy silane, 1,1,1-trifluor-2-propyl 2-ethyl-piperidine dimethoxy silane and 1,1,1-trifluor-2-propyl methyl dimethoxy silane.
    [0059] In general, in the catalyst for polymerization of olefins, a molar ratio of the catalyst component for polymerization of olefins in terms of titanium to alkyl aluminum in terms of aluminum can vary from 1: 1 to 1: 1,000, preferably from 1 : 20 to 1: 500, and a molar ratio of the external electron donor to alkyl aluminum in terms of aluminum can vary from 1: 2 to 1: 200, preferably from 1: 2.5 to 1: 100.
    [0060] According to the present invention, in the preparation of the catalyst for polymerization of olefins, the alkyl aluminum and the optional external electron donor compound can be mixed separately with the catalyst component for polymerization of olefins and then allowed to react, or the alkyl aluminum and the optional external electron donor compound can be mixed first, and then combined and reacted with the catalyst component for olefin polymerization.
    [0061] According to the present invention, when the catalyst for polymerization of olefins is used in an polymerization of olefins, the catalyst component for polymerization of olefins, alkyl aluminum and the optional external electron donor can be added in a polymerization reactor , either separately or after they have been mixed. Alternatively, the olefin polymerization catalyst can be subjected to olefin polymerization through a polymerization process well known in the art and then added to a polymerization reactor.
    [0062] In a fifth aspect, the invention provides the use of the catalyst of the invention in an olefin polymerization.
    [0063] The improvement of the invention is characterized by the fact that a new catalyst is used for the polymerization of olefins, although the specific types of the olefin to be polymerized as well as the processes and conditions of the olefinic polymerization are the same known in the prior art.
    [0064] According to the present invention, the catalyst described above is especially suitable for the homopolymerization and copolymerization of olefins of the general formula CH2 = CHR, in which R is hydrogen, C1-C6 alkyl or C6-C12 aryl.
    [0065] According to the present invention, the polymerization of olefins can be carried out according to known processes. Specifically, the polymerization of olefins can be carried out in liquid monomer phase or in an inert solvent containing monomer, or in gas phase, or in a combination of gas phase and liquid phase, in an inert atmosphere. In general, the polymerization temperature is in a range of 0 ° C to 150 ° C, and preferably 60 ° C to 90 ° C, and the polymerization pressure can be greater than or equal to normal pressure, for example, in a range from 0.01 to 10 MPa (gauge), preferably from 0.01 to 2 MPa (gauge), and more preferably from 0.1 to 2 MPa (gauge). In polymerization, hydrogen can be added as a regulator of the molecular weight of the polymer to the reaction system to adjust the molecular weight and melt index of a polymer. In addition, the inert solvent and gas used in the polymerization of olefins as well as their amounts are well known to a person skilled in the art, and consequently, are not described herein.
    Therefore, in accordance with this aspect of the invention, the present invention further provides a method for polymerizing olefins, comprising contacting an olefin of formula CH2 = CR, in which R is hydrogen, C1-C6 alkyl or C6 aryl -C12, and optionally a comonomer with the catalyst of the invention under polymerization conditions, to form an olefinic polymer; and recovering the resulting olefinic polymer.
    [0067] In a preferred embodiment, the polymerization of olefins is homopolymerization of propylene or copolymerization of propylene and a comonomer. Examples of the copolymer copolymer with propylene include ethylene, C4-12 α-olefins and C4-20 diolefins. EXAMPLES
    [0068] The following examples are provided to further illustrate the present invention and with no intention of limiting its scope. Test methods:
    [0069] 1. Solid component composition: the solid component was dissolved in tri-n-butyl phosphate phosphate and deuterotoluene, and a 1H NMR spectrum was acquired on a nuclear magnetic resonance spectrometer.
    [0070] 2. Polymer melting index: measured according to ASTM D1238-99.
    [0071] 3. Polymer isotacticity: measured by heptane extraction method performed as follows: 2 g of dry polymer sample with boiling heptane was extracted in an extractor for 6 hours, then the residual substance was dried to weight constant, and the weight ratio of the residual polymer (in g) to 2 g was considered to be isotactic.
    [0072] Particle size distribution: the average particle size and particle size distribution of the solid component particles were measured on the Masters Sizer Model 2000 (manufactured by Malvern Instruments Co., Ltd.), with the value of particle size distribution being defined as SPAN = (D90-D10) / D50. Preparation Examples 1 to 17
    [0073] A 500 ml reactor with magnesium chloride, an alcohol (R1OH) and a polymeric dispersion stabilizer were successively charged. Then the contents were heated to the reaction temperature (T) with stirring and allowed to react at that temperature for 1 hour. Then, an epoxide (E) was added to the contents, and the reaction continued at that temperature for 0.5 h. The liquid was filtered and the residual solids were washed 5 times with hexane and then vacuum dried to provide a particulate solid component. Spherical solid components A1 to A17 were prepared using the preparation conditions shown in Table 1 below, respectively, and Table 1 also shows their average particle sizes (D50) and the particle size distribution values (SPAN). Figure 1 shows a 1H NMR spectrum of solid component A1, Figure 2 shows a 1H NMR spectrum of solid component A2, Figure 3 shows a 1H NMR spectrum of solid component A13, and Figure 4 shows a 1H NMR spectrum of solid component A15 and Figure 5 shows an optical microphotograph of solid component A1. Table 1

    [0074] It can be seen from Table 1 and Figure 5 that the particles of the solid components prepared by the inventive method are spherical in shape and have a narrow particle size distribution.
    [0075] The designation and integral area of each peak in the 1H NMR spectrum of solid component A1 are Table 2
    Notation: The peak in Figure 1 that is not assigned to a group is the solvent peak.
    [0076] Therefore, it can be known that the solid component A1 consists mainly of the compound of formula (V) and the compound of formula (VI), with the molar ratio of the compound of

    [0077] The designation and integral area of each peak in the 1H NMR spectrum of solid component A2 is shown in Table 3 below. Table 3
    Notation: The peak in Figure 2 that is not assigned to a group is the solvent peak.
    [0078] Therefore, it can be known that the solid component A2 consists mainly of the compound of formula (V) and the compound of formula (VI), with the molar ratio of the compound of formula (V) to the compound of formula (VI ) being 1: 0.07.
    [0079] The designation and integral area of each peak in the 1H NMR spectrum of solid component A13 are shown in Table 4 below. Table 4
    Notation: The peak in Figure 3 that is not assigned to a group is the solvent peak.
    [0080] Therefore, it can be known that the solid component A13 consists mainly of the compound of formula (VII) and the compound of formula (VI), with the molar ratio of the compound of formula (VII) to the compound of formula (VI ) being 1: 0.02.

    [0081] The designation and integral area of each peak in the 1H NMR spectrum of solid component A15 are shown in Table 5 below. Table 5
    Notation: The peak in Figure 4 that is not assigned to a group is the solvent peak
    [0082] Therefore, it can be known that the solid component A15 consists mainly of the compound of formula (V), the compound of formula (VI) and the compound of formula (VII), with the molar ratio of the compound of formula (VI ) for the sum of the compound of formula (V) and the compound of formula (VII) is 0.24: 1 and the molar ratio of the compound of formula (VI) to the compound of formula (VII) is 1: 1.74 . Comparative Example 1
    [0083] A solid component was prepared according to the procedure described in Preparation Example 1, except that the PVP (polyvinylpyrrolidone) used in Preparation Example 1 was replaced by 180 ml of white oil, thereby producing the spherical solid component. D1. Comparative Example 2
    [0084] A solid component was prepared according to the procedure described in Preparation Example 1, except that the PVP used in Preparation Example 1 was replaced by the same weight of non-ionic surfactant Span 80, thus producing the D2 agglomerated solid component . Figure 6 shows an optical microphotograph of this solid component. Comparative Example 3
    [0085] A solid component was prepared according to the procedure described in Preparation Example 1, except that the polymeric dispersion stabilizer PVP was omitted, thus producing the agglomerated solid component D3. Example 1
    [0086] This example is used to illustrate the inventive catalyst component for polymerization of olefins, the preparation thereof, catalyst for polymerization of olefins and their use. (1) Preparation of the catalyst component
    [0087] 100 ml of titanium tetrachloride was added in a 300 ml glass reactor and cooled to -20 ° C. Then, 8 g of solid component A1 of Preparation Example 1 was added to the reactor, and the contents were heated to 110 ° C, with 4.4 mmol of 2,4-pentylene glycol dibenzoate and 5, 2 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. After the contents were kept at 110 ° C for 0.5 hour, the liquid was removed by vacuum filtration, and the residues were washed twice with titanium tetrachloride and three times with hexane, and vacuum dried to give a solid Cat-1 catalyst component. (2) Mass polymerization in liquid propylene phase
    [0088] Mass polymerization in liquid propylene phase in a 5 L stainless steel autoclave was carried out as follows: in a nitrogen atmosphere, the autoclave was successively charged with 1 ml of solution of triethyl aluminum in hexane (having a concentration of 0.5 mmol / mL), 0.1 mL of a solution of cyclohexyl methyl dimethoxy silane (CHMMS) in hexane (having a concentration of 0.1 mmol / mL) and 4 mg of the solid Cat-1 catalyst prepared above. The autoclave was closed, and then a certain amount (standard volume) of hydrogen gas and 2.3 L of liquid propylene was introduced. The contents were heated to 70 ° C and the polymerization continued at 70 ° C for 1 hour. The autoclave was cooled, ventilated and discharged. The propylene homopolymer obtained was dried and then weighed. Table 6 below shows the results. Example 2
    [0089] This example is used to illustrate the inventive catalyst component for polymerization of olefins, the preparation thereof, catalyst for polymerization of olefins and their use.
    [0090] According to the procedure described in Example 1, a catalyst component was prepared and bulk polymerization was carried out in liquid propylene phase, except that in the preparation of the catalyst component, the solid component used is the solid component A2 prepared in Preparation Example 2, and internal electron donors were added as follows: 2.1 mmol of 2,4-pentylene glycol dibenzoate and 2.5 mmol of 2-isopropyl-2-isopentyl-1,3- dimethoxypropane was added at the beginning of the heating, and 2.3 mmol of 2,4-pentylene glycol dibenzoate and 2.8 mmol of 9,9-dimethoxy-methyl-fluorene were added when the temperature reached a value close to the target temperature ( i.e., 110 ° C). Table 6 below shows the results. Example 3
    [0091] This example is used to illustrate the inventive catalyst component for polymerization of olefins, the preparation thereof, catalyst for polymerization of olefins and their use.
    [0092] According to the procedure described in Example 1, a catalyst component was prepared and bulk polymerization was carried out in liquid propylene phase, except that in the preparation of the catalyst component, the solid component used is the solid component A13 prepared in Preparation Example 13, and internal electron donors were added as follows: 5 mmol of 3-butyl-3,5-heptylene glycol dibenzoate were added at the start of the heating, and 5.2 mmol of 9, 9-dimethoxy-methyl-fluorene was added when the temperature reached a value close to the target temperature (i.e., 110 ° C). Table 6 below shows the results. Comparative Example 4
    [0093] According to the procedure described in Example 1, a catalyst component was prepared and mass polymerization was carried out in liquid propylene phase, except that in the preparation of the catalyst component, the solid component used is the solid component D1 prepared in Comparative Example 1. Table 6 below shows the results. Table 6 Example No. Solid component Al / Si (mol / mol) Amount of hydrogen gas (NL) Polymerization activity (kg PP / g Cat) Isotactic polymer index (% by weight) Melting index of polymer (g / 10min)
    Notation: “-“ indicates that no external electron donor was used.
    [0094] From the data in Table 6, it can be seen that, when using the catalyst of the invention in the propylene polymerization, a high polymerization activity and a high capacity of stereo targeting can be obtained and, at the same time, the olefin polymerization catalyst of the invention has a good hydrogen response. Particularly, when using the catalyst of the invention to perform propylene polymerization, the resulting polymer has a high isotactic index, even when it has a high melt index.
    权利要求:
    Claims (30)
    [0001]
    1. Catalyst component for polymerization of olefins, characterized by the fact that it comprises reaction products of the following components: (1) a solid component; (2) at least one titanium compound; and (3) at least two internal electron donors; the solid component comprising a magnesium compound represented by formula (1) and an epoxide represented by formula (2),
    [0002]
    2. Catalyst component, according to claim 1, characterized in that RI is a linear or branched C1-C8 alkyl group; RII and RIII are, independently, hydrogen or straight or branched C1-C3 alkyl unsubstituted or substituted with halogen; X is chlorine; m be in a range of 0.5 to 1.5; n be in a range of 0.5 to 1.5; and (m + n) = 2.
    [0003]
    3. Catalyst component according to either of Claims 1 or 2, characterized in that, in the solid component, the content of the epoxide represented by formula (2) is in the range of 0.02 to 0.5 mol, by mol of the magnesium compound represented by formula (1).
    [0004]
    4. Catalyst component, according to claim 1, characterized in that in the solid component, the amount of epoxide represented by formula (2) is in a range of 0.02 to 0.1 mol, per mol of the compound of magnesium represented by the formula (1).
    [0005]
    5. Catalyst component, according to claim 1, characterized in that the ratio for one mole of the magnesium compound represented by formula (1) in the solid component, the amount of the titanium compound is from 5 to 200 moles, and the number of internal electron donors is 0.04 to 0.6 mol.
    [0006]
    6. Catalyst component, according to claim 1, characterized by the fact that the ratio for one mole of the magnesium compound represented by formula (1) in the solid component, the amount of the titanium compound is 10 to 50 moles; and the number of internal electron donors is 0.1 to 0.4 mol.
    [0007]
    Catalyst component according to any one of claims 1, 5 or 6, characterized in that the titanium compound is chosen from those of the formula Ti (ORIV) 4-aXa, in which RIV is a C1 aliphatic hydrocarbyl group -C14, X is halogen, and a is an integer ranging from 1 to 4.
    [0008]
    8. Catalyst component according to claim 7, characterized in that the titanium compound is chosen from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium tetrabutoxy chloride , titanium dibutoxy dichloride, titanium butoxy trichloride, titanium triethoxy chloride, titanium diethoxy dichloride and titanium ethoxy trichloride.
    [0009]
    Catalyst component according to any one of claims 1, 5 or 6, characterized in that the internal electron donors are a combination of a first internal electron donor and a second internal electron donor, the the first internal electron donor is at least one diol ester, and the second internal electron donor is at least one diether compound, and the molar ratio of the first internal electron donor to the second internal electron donor is in a range of 0.55: 1 to 50: 1.
    [0010]
    10. Catalyst compound according to claim 9, characterized in that the molar ratio of the first internal electron donor to the second internal electron donor is in the range of 0.6: 1 to 30: 1.
    [0011]
    11. Catalyst compound according to claim 9, characterized in that the molar ratio of the first internal electron donor to the second internal electron donor is in the range of 0.65: 1 to 10: 1.
    [0012]
    12. Catalyst component according to any one of claims 9 to 11, characterized in that the diol ester is chosen from those represented by formula (3): (3), <DRAW-CODE>> in which, R1 and R2 are identical or different, and are, independently, straight or branched C1-C10 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl or C7-C20 arylalkyl, with the hydrogen atoms in the phenyl ring in the aryl, in the alkylaryl and in the arylalkyl they are optionally substituted by halogen atoms; R3-R6 and R1-R2n are identical or different, and are independently hydrogen, halogen, straight or branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, arylalkyl C7-C20, C2-C10 alkenyl or C10-C20 fused ring aryl, with carbon atoms and / or hydrogen atoms in R3-R6 and R1-R2n being optionally substituted by heteroatoms chosen from nitrogen, oxygen, sulfur, silicon, phosphorus and halogen, and two or more of R3 to R6 and R1 to R2n are optionally linked to form a saturated or unsaturated ring; and n is an integer ranging from 0 to 10.
    [0013]
    13. Catalyst component according to claim 12, characterized in that the diol ester is chosen from those represented by formula (4): (4),
    [0014]
    14. Catalyst component according to claim 12, characterized in that the diol ester is chosen from 1,3-propylene glycol dibenzoate, 2-methyl-1,3-propylene glycol dibenzoate, 2- ethyl-1,3-propylene glycol, 2-propyl-1,3-propylene glycol dibenzoate, 2-butyl-1,3-propylene glycol dibenzoate, 2,2-dimethyl-1,3-propylene glycol dibenzoate, 2-ethyl-2-butyl-1,3-propylene glycol dibenzoate, 2,2-diethyl-1,3-propylene glycol dibenzoate, 2-methyl-2-propyl-1,3-propylene glycol dibenzoate, dibenzoate 2-isopropyl-2-isopentyl-1,3-propylene glycol, 2,4-pentylene glycol dibenzoate, 3-methyl-2,4-pentylene glycol dibenzoate, 3-ethyl-2,4-pentylene glycol dibenzoate , 3-propyl-2,4-pentylene glycol dibenzoate, 3-butyl-2,4-pentylene glycol dibenzoate, 3,3-dimethyl-2,4-pentylene glycol dibenzoate, 2-methyl-1 dibenzoate, 3-pentylene glycol, 2,2-dimethyl-1,3-pentylene glycol dibenzoate, 2-ethyl-1,3-pentylene glycol dibenzoate, d 2-butyl-1,3-pentylene glycol ibenzoate, 2-methyl-1,3-pentylene glycol dibenzoate, 2-ethyl-1,3-pentylene glycol dibenzoate, 2-propyl-1,3-pentylene dibenzoate glycol, 2-butyl-1,3-pentylene glycol dibenzoate, 2,2,4-trimethyl-1,3-pentylene glycol dibenzoate, 3-methyl-3-butyl-2,4-pentylene glycol dibenzoate, dibenzoate 2,2-dimethyl-1,5-pentylene glycol, 1,6-hexylene glycol dibenzoate, 6-ene-2,4-heptylene glycol dibenzoate, 2-methyl-6-ene-2,4- dibenzoate heptylene glycol, 3-methyl-6-ene-2,4-heptylene glycol, 4-methyl-6-ene-2,4-heptylene dibenzoate, 5-methyl-6-ene-2,4 dibenzoate -heptilene glycol, 6-methyl-6-ene-2,4-heptylene glycol dibenzoate, 3-ethyl-6-ene-2,4-heptylene glycol dibenzoate, 4-ethyl-6-ene-2 dibenzoate, 4-heptylene glycol, 5-ethyl-6-ene-2,4-heptylene glycol, 6-ethyl-6-ene-2,4-heptylene glycol dibenzoate, 3-propyl-6-ene-2 dibenzoate , 4-heptylene glycol, 4-propyl-6-ene-2,4-heptylene glycol dibenzoate , 5-propyl-6-ene-2,4-heptylene glycol dibenzoate, 6-propyl-6-ene-2,4-heptylene glycol dibenzoate, 3-butyl-6-ene-2,4-heptylene dibenzoate glycol, 4-butyl-6-ene-2,4-heptylene dibenzoate glycol, 5-butyl-6-ene-2,4-heptylene dibenzoate, 6-butyl-6-ene-2,4- dibenzoate heptylene glycol, 3,5-dimethyl-6-ene-2,4-heptylene glycol, 3,5-diethyl-6-ene-2,4-heptylene glycol dibenzoate, 3,5-dipropyl-6 dibenzoate -eno-2,4-heptylene glycol, 3,5-dibutyl-6-ene-2,4-heptylene glycol dibenzoate, 3,3-dimethyl-6-ene-2,4-heptylene glycol dibenzoate, dibenzoate 3,3-diethyl-6-ene-2,4-heptylene glycol, 3,3-dipropyl-6-ene-2,4-heptylene glycol dibenzoate, 3,3-dibutyl-6-ene-2 dibenzoate, 4-heptylene glycol, 3,5-heptylene glycol dibenzoate, 2-methyl-3,5-heptylene glycol dibenzoate, 3-methyl-3,5-heptylene glycol dibenzoate, 4-methyl-3,5- dibenzoate heptylene glycol, 5-methyl-3,5-heptylene glycol dibenzoate, 6-methyl-3,5-heptylene glycol dibenzoate, dib 3-ethyl-3,5-heptylene glycol enzoate, 4-ethyl-3,5-heptylene glycol dibenzoate, 5-ethyl-3,5-heptylene glycol dibenzoate, 3-propyl-3,5-heptylene dibenzoate glycol, 4-propyl-3,5-heptylene dibenzoate, 3-butyl-3,5-heptylene glycol dibenzoate, 2,3-dimethyl-3,5-heptylene glycol dibenzoate, 2,4-dimethyl dibenzoate -3,5-heptylene glycol, 2,5-dimethyl-dibenzoate-3,5-heptylene glycol, 2,6-dimethyl-3,5-heptylene glycol dibenzoate, 3,3-dimethyl-3,5- dibenzoate heptylene glycol, 4,4-dimethyl-3,5-heptylene glycol dibenzoate, 6,6-dimethyl-3,5-heptylene glycol dibenzoate, 2,6-dimethyl-3,5-heptylene glycol dibenzoate, dibenzoate 3,4-dimethyl-3,5-heptylene glycol, 3,5-dimethyl-3,5-heptylene glycol dibenzoate, 3,6-dimethyl-3,5-heptylene glycol dibenzoate, 4,5-dimethyl dibenzoate -3,5-heptylene glycol, 4,6-dimethyl-dibenzoate-3,5-heptylene glycol, 4,4-dimethyl-3,5-heptylene glycol dibenzoate, 6,6-dimethyl-3,5- dibenzoate heptylene glycol, dibenzoate of 2-methyl-3-ethyl-3,5-heptylene glycol, 2-methyl-4-ethyl-3,5-heptylene glycol dibenzoate, 2-methyl-5-ethyl-3,5-heptylene glycol dibenzoate, dibenzoate 3-methyl-3-ethyl-3,5-heptylene glycol, 3-methyl-4-ethyl-3,5-heptylene glycol dibenzoate, 3-methyl-5-ethyl-3,5-heptylene glycol dibenzoate, 4-methyl-3-ethyl-3,5-heptylene glycol dibenzoate, 4-methyl-4-ethyl-3,5-heptylene glycol dibenzoate, 4-methyl-5-ethyl-3,5-heptylene glycol dibenzoate , 2-methyl-3-propyl-3,5-heptylene glycol dibenzoate, 2-methyl-4-propyl-3,5-heptylene glycol dibenzoate, 2-methyl-5-propyl-3,5-heptylene dibenzoate glycol, 3-methyl-3-propyl-3,5-heptylene dibenzoate glycol, 3-methyl-4-propyl-3, 5-heptylene glycol, 3-methyl-5-propyl-3 dibenzoate, 5- heptylene glycol, 4-methyl-3-propyl-3 dibenzoate, 5-heptylene glycol, 4-methyl-4-propyl-3 dibenzoate, 5-heptylene glycol and 4-methyl-5-propyl-3 dibenzoate, 5 - heptylene glycol.
    [0015]
    15. Catalyst component according to any one of claims 9 to 11, characterized in that the diether is chosen from those represented by formula (5):
    [0016]
    16. Catalyst component, according to claim 15, characterized in that the diether is chosen from those represented by the general formula: R1R2C (CH2OR3) (CH2OR4), in which R1 and R2 are identical or different, and are chosen independently of linear or branched C1-C18 alkyl, C3-C18 cycloalkyl, C6-C18 aryl and C7-C18 arylalkyl, and optionally bond to form a ring; and R3 and R4 are identical or different, and are, independently, straight or branched C1-C10 alkyl.
    [0017]
    17. Catalyst component according to claim 15, characterized in that the diether component is chosen from 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2 -butyl-1,3-dimethoxypropane, 2-secbutyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2- (2-cyclohexyl- ethyl) -1,3-dimethoxypropane, 2- (2-phenyl-ethyl) -1,3-dimethoxypropane, 2- (p-chloro-phenyl) -1,3-dimethoxypropane, 2- (diphenyl-methyl) -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-cyclohexyl-ethyl) -1,3-dimethoxypropane, 2-methyl l-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-methyl-butyl) -2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2 -phenyl-2-secbutyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-secbutyl-1 , 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-secbutyl-1,3-dimethoxypropane, 2-isopropyl-2-secbutyl-1,3-dimethoxypropane , 2-cyclohexyl-2-cyclohexyl-methyl-1,3-dimethoxypropane and 9,9-dimethoxy-methyl-fluorene.
    [0018]
    18. Method for preparing a catalyst component, characterized by the fact that it comprises the steps of: (1) preparing a solid component by a process comprising: (a) reacting a magnesium halide of formula MgX2 with an alcohol of formula RIOH in the presence at least one polymeric dispersion stabilizer at a temperature of 30 to 160 ° C in a closed container to form a magnesium-alcohol halide adduct solution; and (b) reacting the magnesium-alcohol halide adduct solution with an epoxide represented by formula (2):
    [0019]
    19. Method, according to claim 18, characterized in that in relation to one mole of magnesium halide, the amount of alcohol used varies from 4 to 20 moles and the amount of epoxide used by formula (2) varies from 2 to 6 moles, and using the polymeric dispersion stabilizer in an amount of 0.2 to 5% by weight, based on the total weight of the magnesium halide and alcohol.
    [0020]
    20. Method according to either of claims 18 or 19, characterized in that the magnesium halide is at least one chosen from magnesium dichloride, magnesium dibromide and magnesium diiodide, and the alcohol is at least one chosen from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentane, n-hexanol, n-octanol and 2-ethylhexanol, and the epoxide is at least one chosen from epoxy ethane, epoxy propane, epoxy butane, chloro-propane epoxy, chloro-butane epoxy, bromo-propane epoxy and bromo-butane epoxy.
    [0021]
    21. Method according to either of claims 18 or 19, characterized in that the polymeric dispersion stabilizer is at least one chosen from polyvinylpyrrolidone, poly (vinyl pyrrolidone-co-vinyl acetate) and poly (ethylene glycol).
    [0022]
    22. Method according to either of claims 18 or 19, characterized in that the weight average molecular weight of the polymeric dispersion stabilizer is greater than 3000.
    [0023]
    23. The method of claim 18 or 19, characterized in that the average molecular weight of the polymeric dispersion stabilizer is 6,000 to 2,000,000.
    [0024]
    24. Method according to claim 18, characterized in that steps (a) and (b) are optionally performed in the presence of an inert dispersion medium, and the inert dispersion medium is at least one chosen from aliphatic hydrocarbons , aromatic or alicyclic liquids and silicone oils.
    [0025]
    25. Method according to either of claims 18 or 19, characterized in that no inert dispersion medium is used in both steps (a) and (b).
    [0026]
    26. Method according to claim 18, characterized in that step (2) is performed as follows: the solid component is suspended in a feed of titanium compound at a temperature of -30 ° C to 0 ° C, and then the suspension is heated to a temperature of 40 to 130 ° C and allowed to react for 0.1 to 5 hours, the titanium compound feed being a pure titanium compound or a mixture of the titanium compound and an inert solvent .
    [0027]
    27. Catalyst component for polymerization of olefins, characterized by the fact that it is prepared by the method, as defined in any one of claims 18 to 26.
    [0028]
    28. Catalyst for polymerization of olefins, characterized by the fact that it comprises: (I) the catalyst component for polymerization of olefins, as defined in any of claims 1 to 17 and 27; (II) at least one alkyl aluminum compound; and (III) optionally, at least one external electron donor.
    [0029]
    29. Use of the catalyst, as defined by claim 28, characterized by the fact that it is in an olefin polymerization.
    [0030]
    30. Method for polymerizing olefins, characterized by the fact that it comprises contacting an olefin of formula CH2 = CHR, in which R is hydrogen, C1-C6 alkyl or C6-C12 aryl, and optionally a comonomer with the catalyst, as defined by claim 28, under polymerization conditions, to form an olefinic polymer; and recovering the resulting olefinic polymer.
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    同族专利:
    公开号 | 公开日
    TWI650336B|2019-02-11|
    SA516370960B1|2021-02-24|
    KR20160073978A|2016-06-27|
    EP3059264B1|2018-12-26|
    AU2014336758B2|2018-07-05|
    SG11201602999WA|2016-05-30|
    WO2015055137A1|2015-04-23|
    JP2016537455A|2016-12-01|
    KR101973078B1|2019-04-26|
    ES2722413T3|2019-08-09|
    CN104558282B|2017-02-15|
    US9809663B2|2017-11-07|
    EP3059264A4|2017-05-24|
    EP3059264A1|2016-08-24|
    MY178722A|2020-10-20|
    JP6523271B2|2019-05-29|
    RU2674026C2|2018-12-04|
    US20160264694A1|2016-09-15|
    CN104558282A|2015-04-29|
    RU2016118998A|2017-11-23|
    TW201527340A|2015-07-16|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-03-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/10/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201310491626.2|2013-10-18|
    CN201310491626.2A|CN104558282B|2013-10-18|2013-10-18|Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application|
    PCT/CN2014/088808|WO2015055137A1|2013-10-18|2014-10-17|Catalyst component for olefin polymerization, preparation method thereof, and catalyst comprising same|
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