WO2022078492A1 - 具有多峰孔分布的镁基固体物和催化剂组分以及它们的制备方法 - Google Patents

具有多峰孔分布的镁基固体物和催化剂组分以及它们的制备方法 Download PDF

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WO2022078492A1
WO2022078492A1 PCT/CN2021/124050 CN2021124050W WO2022078492A1 WO 2022078492 A1 WO2022078492 A1 WO 2022078492A1 CN 2021124050 W CN2021124050 W CN 2021124050W WO 2022078492 A1 WO2022078492 A1 WO 2022078492A1
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magnesium
pore size
titanium
solid
pore
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PCT/CN2021/124050
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English (en)
French (fr)
Inventor
岑为
周俊领
付梅艳
严立安
施展
张晓帆
夏先知
郭正阳
张纪贵
林洁
齐琳
张天一
张军辉
赵惠
王宇
王迎
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority claimed from CN202011105894.2A external-priority patent/CN114426609B/zh
Priority claimed from CN202011104541.0A external-priority patent/CN114426598B/zh
Priority claimed from CN202011105648.7A external-priority patent/CN114426602B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to JP2023523092A priority Critical patent/JP2023547809A/ja
Priority to KR1020237016487A priority patent/KR20230088456A/ko
Priority to US18/249,096 priority patent/US20230391902A1/en
Priority to EP21879533.4A priority patent/EP4230662A1/en
Publication of WO2022078492A1 publication Critical patent/WO2022078492A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size

Definitions

  • the present invention relates to the technical field of olefin polymerization, in particular to a magnesium-based solid substance and a catalyst component for olefin polymerization, and a preparation method and application thereof.
  • Magnesium chloride-supported Ziegler-Natta catalysts are the main olefin polymerization catalysts currently on the market.
  • magnesium-containing compounds or complex solids can be prepared first as a carrier.
  • this carrier such as magnesium chloride alcohol complex.
  • titanium-containing compounds to form magnesium chloride-supported titanium catalyst solids, which are then supported with internal electron donor compounds to form catalyst components.
  • Testing of such catalyst components by nitrogen adsorption generally shows a unimodal pore distribution with a most probable pore size within 10 nm.
  • a solution of magnesium compound or complex can be obtained first, and then contacted with a titanium-containing compound to crystallize a magnesium chloride-supported titanium catalyst solid, which is further contacted with an internal electron donor compound to form a catalyst component.
  • a titanium-containing compound to crystallize a magnesium chloride-supported titanium catalyst solid, which is further contacted with an internal electron donor compound to form a catalyst component.
  • an internal electron donor compound to form a catalyst component.
  • polyolefin catalysts with a multimodal pore distribution structure are generally prepared by using molecular sieves with multimodal pore distribution or silica gel as a carrier. Titanium or single active site metal is used to prepare polyethylene catalyst, and polyethylene with bimodal or broad molecular weight distribution can be obtained.
  • titanium or single active site metal is used to prepare polyethylene catalyst, and polyethylene with bimodal or broad molecular weight distribution can be obtained.
  • the activity of olefin polymerization catalysts prepared with molecular sieve or silica gel supports is too low.
  • the magnesium chloride-supported catalyst component may also have a multimodal pore distribution structure.
  • the structure of the catalyst is cracked, and the internal microporous structure is destroyed and transformed into Mesopores and macropores, but at the same time the specific surface drops sharply, or even disappears; therefore, the catalyst component with this multimodal pore distribution structure has a very small specific surface, and the catalyst basically fails.
  • One of the objectives of the present invention is to provide a magnesium-based solid with multimodal pore distribution, which uses magnesium halide as a carrier and contains titanium element, and has multimodal pore size distribution and high specific surface area.
  • the second object of the present invention is to provide a method for preparing a magnesium-based solid substance corresponding to one of the objects.
  • the third object of the present invention is to provide a solid catalyst component for olefin polymerization prepared based on magnesium-based solid matter.
  • the fourth object of the present invention is to provide a method for preparing a solid catalyst component for olefin polymerization corresponding to the third object.
  • the fifth object of the present invention is to provide an olefin polymerization catalyst comprising the catalyst component.
  • the sixth object of the present invention is to provide the application of the catalyst in olefin polymerization.
  • the seventh object of the present invention is to provide an olefin polymerization method corresponding to the above object.
  • the olefin polymerization catalyst prepared by using the magnesium-based solid substance with multimodal pore distribution when used for propylene polymerization, it has higher polymerization activity and higher stereo-orientation ability; In the case of electrons, the polymer molecular weight distribution of the catalyst of the present invention used for the preparation of propylene polymerization is wider.
  • the present invention provides a magnesium-based solid with multimodal pore distribution, which uses magnesium halide as a carrier and contains titanium element, and the magnesium-based solid has a size of not less than 50 m 2 as determined by nitrogen adsorption method /g specific surface area, and the pore size distribution of the magnesium-based solid matter is in the range of 1 nm-300 nm, wherein there are at least one peak in the pore size range of less than 10 nm and the pore size range of not less than 10 nm, respectively.
  • the pore size distribution of the magnesium-based solids is obtained by testing with nitrogen adsorption method and calculating with NLDFT algorithm.
  • the specific surface area of the magnesium-based solids is obtained by testing with nitrogen adsorption method.
  • the magnesium-based solid object has a spherical or spherical-like structure.
  • the most probable pore size corresponding to the peak within the pore size range of less than 10 nm is 2 nm-8 nm, preferably 2 nm-6 nm; at the same time, the peak within the pore size range not less than 10 nm corresponds to
  • the most probable pore size is 15nm-200nm, preferably 20nm-100nm, more preferably 30nm-90nm.
  • the ratio of the pore volume of pores with a pore size of less than 10 nm to the pore volume of pores with a pore size of not less than 10 nm is (0.1-20):1, preferably (0.25-15): 1.
  • the pore volume of pores with a pore diameter of less than 5 nm accounts for 10%-90% of the total pore volume, preferably 15%-70%; the pore volume of pores with a pore diameter of not less than 30 nm accounts for the total pore volume 5%-70% by volume, preferably 10%-60%.
  • the specific surface area of the magnesium-based solid is 100 m 2 /g-500 m 2 /g.
  • the present invention provides a method for preparing the above-mentioned magnesium-based solid, comprising:
  • the Lewis base includes an organic phosphorus compound, and the amount of the organic phosphorus compound is 1.5-10 moles per mole of magnesium halide; in step S2, the Lewis acid includes a titanium compound.
  • the Lewis base includes an organic phosphorus compound, and the amount of the organic phosphorus compound is 2-5 moles per mole of magnesium halide.
  • the mixture comprises colloids, two-phase solutions, emulsions and other forms.
  • the mixture is formed in the form of a mixture comprising at least two liquid phases.
  • one or more methods such as vibration, stirring, atomization, shearing, etc., can be used to promote the mixture to form a uniform emulsion, so that spherical solids can be solidified and precipitated.
  • step S3 the mixture is heated to a target temperature, so that the magnesium-based solids are precipitated from the mixture, wherein the target temperature is 50°C-110°C °C.
  • step S3 after the temperature rise is completed, the target temperature is maintained for 0.1h-24h under stirring conditions.
  • the suspension can be stirred at a certain temperature for a certain period of time, such as 10 minutes to 24 hours, in order to make the crystal form more stable and improve the particle strength.
  • step S3 the heating process takes 0.01h-36h, preferably 0.1h-24h.
  • the heating process of the mixture is not specifically limited, and any known method can be used for heating, such as slow, step-by-step, rapid or programmed heating.
  • the specific heating method can be adjusted according to the specific formula, contact temperature, etc.
  • the inventors have found that, in the preparation method of the present invention, when other conditions are the same, different heating processes will affect the particle shape and particle size distribution of the final catalyst; To obtain better particle shape, on the contrary, too fast heating rate will lead to poor particle shape; therefore, the heating process of the mixture can be 1 minute to 36 hours, preferably 3 minutes to 24 hours.
  • step S1 the general formula of the magnesium halide is shown in formula (1):
  • X 1 is halogen, preferably chlorine, bromine or iodine.
  • the magnesium halide is one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide.
  • the magnesium halide is magnesium dichloride.
  • the organophosphorus compound is selected from one or more of the compounds represented by formula (2) or formula (3):
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from linear or branched chain alkyl, cycloalkane having 1 to 20 carbon atoms. or aromatic hydrocarbon groups and aromatic hydrocarbon groups with substituents such as alkyl groups.
  • the organophosphorus compound is trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripentyl phosphate, triphenyl phosphate, tris(o-, m- or p-toluene phosphate) ), one or more of trimethyl phosphite, triethyl phosphite, tributyl phosphite and trityl phosphite.
  • the organophosphorus compound is tributyl phosphate.
  • the organic solvent is selected from one or more of aromatic hydrocarbon compounds and halogenated hydrocarbon compounds.
  • the organic solvent is selected from one or more of toluene, ethylbenzene, benzene, xylene and chlorobenzene.
  • the organic solvent is toluene.
  • the organic solvent is used in an amount of 1-40 moles, preferably 2-30 moles per mole of magnesium halide.
  • the Lewis base further includes organic epoxy compounds and/or hydroxyl-containing compounds.
  • the organic epoxy compound is one or more of the oxidation products of aliphatic olefins with 2-8 carbon atoms and halogenated aliphatic olefins, specifically ethylene oxide, propylene oxide, One or more of epichlorohydrin, epichlorohydrin, butylene oxide, butadiene oxide, butadiene double oxide, methyl glycidyl ether and diglycidyl ether, preferably cyclic Oxychloropropane.
  • the general formula of the hydroxyl-containing compound is HOR, wherein R is a hydrocarbon group of 2-20 carbon atoms, which can be a saturated or unsaturated linear or branched alkane group, a cycloalkane group or an aromatic group Hydrocarbyl.
  • the hydroxyl-containing compound is preferably an alcohol compound, more preferably including one or more of ethanol, propanol, butanol, 2-ethylhexanol, benzyl alcohol and phenethyl alcohol.
  • the organic epoxy compound is used in an amount of 0.1-10 moles, preferably 0.4-4 moles per mole of magnesium halide.
  • the amount of the hydroxyl-containing compound is 0.1-10 moles, preferably 0.1-5 moles per mole of magnesium halide.
  • the magnesium-containing solution can be formed by contacting magnesium halide and organic phosphorus compound in an organic solvent; it can also be formed by contacting magnesium halide, organic epoxy compound and organic phosphorus compound in an organic solvent; or It can be formed by contacting magnesium halide, organic epoxy compound, organic phosphorus compound, and hydroxyl-containing compound in an organic solvent.
  • the contact method for forming the magnesium-containing solution described in the present invention is not particularly limited, the purpose of the contact is to form a uniform solution containing magnesium elements, and the contact conditions include: the contact temperature is 10-150°C, preferably 30-130°C, The time is 0.05-10 hours, preferably 0.1-6 hours.
  • the inert dispersion medium is selected from one of kerosene, paraffin oil, white oil, petrolatum oil, methyl silicone oil, aliphatic and cycloaliphatic hydrocarbons or variety.
  • the inert dispersion medium is selected from one or more of white oil, hexane and decane.
  • the amount of the inert dispersing medium is 0.1 g-300 g, preferably 1 g-150 g per gram of magnesium halide.
  • the Lewis acid includes a titanium-containing compound and optionally a silicon-containing compound, and the general formula of the titanium-containing compound is shown in formula (4):
  • X 2 is halogen, preferably chlorine, bromine or iodine
  • R 1 is a hydrocarbon group of 1-20 carbon atoms
  • m is an integer of 1-4.
  • the titanium-containing compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, and monochlorotriethoxide
  • titanium tetrachloride titanium tetrabromide
  • titanium tetraiodide titanium tetrabutoxide
  • titanium tetraethoxide titanium tetraethoxide
  • monochlorotriethoxide One or more of titanium-based titanium, titanium dichlorodiethoxide and titanium trichloromonoethoxide.
  • the titanium-containing compound is used in an amount of 0.5-25 moles, preferably 1-20 moles per mole of magnesium halide.
  • the general formula of the silicon-containing compound is shown in formula (5):
  • X 3 is halogen, preferably chlorine, bromine or iodine
  • R 2 is a hydrocarbon group of 1-20 carbon atoms
  • n is an integer of 1-4.
  • the silicon-containing compound is silicon tetrachloride.
  • the silicon-containing compound is used in an amount of 0.1-40 moles, preferably 0.1-20 moles per mole of magnesium halide.
  • the method of contacting the magnesium-containing solution, the inert dispersion medium and the Lewis acid to form a mixture can be any method.
  • the magnesium-containing solution may be contacted with the inert dispersion medium first, and then the Lewis acid may be added dropwise; the magnesium-containing solution may be contacted with the Lewis acid first, and then the inert dispersion medium may be added; or the inert dispersion medium and the Lewis acid may be added. After the contact, it is then contacted with the magnesium-containing solution.
  • the auxiliary precipitation agent is selected from one or more of organic acids, organic acid anhydrides, organic ethers and organic ketones.
  • the auxiliary precipitation agent is selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, One or more of propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether and amyl ether.
  • step S3 the amount of the auxiliary precipitation agent is 0.01-1 mole, preferably 0.04-0.4 mole per mole of magnesium halide.
  • the surfactant is selected from polymer surfactants.
  • the surfactant is selected from the group consisting of (meth)acrylic acid alkyl ester polymers and copolymers of (meth)acrylic acid alkyl esters, maleic anhydride One or more of the alcoholylate of the polymer and the alcoholylate of the maleic anhydride copolymer.
  • the surfactant specifically includes alcoholylate of polymaleic anhydride, alcoholylate of maleic anhydride-styrene copolymer, maleic anhydride-benzene At least one of the alcoholysate of ethylene-(meth)acrylic acid alkyl ester terpolymer and the alcoholysate of maleic anhydride-(meth)acrylic acid alkyl ester copolymer; wherein (meth)acrylic acid alkyl
  • the alkyl chain of the base ester is a straight-chain or branched alkane, cycloalkane or aromatic hydrocarbon with 1-30 carbon atoms, preferably those with 1-20 carbon atoms;
  • the maleic anhydride type copolymer refers to a copolymer comprising at least one The copolymer of maleic anhydride monomer;
  • the alcoholysis refers to the polymer product obtained by the reaction of this product with an organic alcohol compound, such as the structure of the
  • the surfactant of the present invention comprises at least one of (meth)acrylic acid alkyl ester-based polymers and (meth)acrylic acid alkyl ester-based copolymers, for example, it can be It is at least one of polyalkyl (meth)acrylate, alkyl (meth)acrylate-maleic anhydride copolymer, and alkyl (meth)acrylate-maleic anhydride-styrene copolymer; wherein
  • the ester side chains are straight or branched alkanes, cycloalkanes or aromatic hydrocarbons of 1 to 30 carbon atoms, preferably those of 1 to 20 carbon atoms.
  • the poly(meth)acrylate polymer surfactant can be purchased from Guangzhou Ruishengyan Chemical Technology Co., Ltd. as a pour point depressant product under the trade names of T602, T632 and the like.
  • the addition position of the surfactant may be any position in the preparation method, and may be added as a whole or dispersedly.
  • the location where the surfactant is added may be added in whole or in part during or after the formation of the magnesium-containing solution; may be added in the entirety to the inert dispersion medium; or may be added in part to the inert dispersion medium , and the other part is added to the magnesium-containing solution; or it can be added after the magnesium-containing solution, the inert dispersion medium and the Lewis acid are contacted.
  • step S3 if the surfactant, especially the above-mentioned surfactant, is not used, the magnesium-based solid obtained will be powdery, and the magnesium-based solid with spherical or quasi-spherical structure cannot be obtained.
  • the amount of the surfactant is 0.01g-5g, preferably 0.05g-1g per gram of magnesium halide.
  • the present invention provides a solid catalyst component for olefin polymerization with a multimodal pore distribution, which comprises the above-mentioned magnesium-based solid substance and at least one internal electron donor.
  • the solid catalyst component measured by the nitrogen adsorption method, has a pore size distribution of multiple peaks and a specific surface area of not less than 50 m 2 /g; wherein, the pore size distribution of the multiple peaks of the solid is as follows There is at least one peak in the pore size range of 1 nm-100 nm, and at least another peak in the pore size range of 5 nm-200 nm.
  • the solid catalyst component measured by nitrogen adsorption method, has a pore size distribution with multiple peaks and a specific surface area of not less than 50 m 2 /g; wherein, the pore size distribution of the multiple peaks of the solid catalyst component It is the case that there is at least a first peak in the pore size range of 1 nm-10 nm, while at least a second peak is in the pore size range of 10 nm-200 nm.
  • the pore size distribution is calculated by using the NLDFT algorithm on the data measured by the nitrogen adsorption method.
  • the pore size distribution of the multiple peaks of the solid catalyst component is such that the most probable pore size of at least one peak in the pore size range of 1 nm-100 nm is 1 nm-50 nm, preferably is 1nm-10nm, more preferably 2nm-8nm, further preferably 3nm-6nm; the most probable pore size of at least another peak in the pore size range of 5nm-200nm is 10nm-200nm, preferably 20nm-100nm, more preferably 30nm-90nm.
  • the pore size distribution of the plurality of peaks of the solid catalyst component is such that the most probable pore size of the peaks in the pore size range of 1 nm-10 nm is 2 nm-8 nm, more preferably 2 nm-6 nm; The most probable pore size of the peaks in the pore size range of 15nm-200nm, preferably 20nm-100nm, more preferably 30nm-90nm.
  • the pore volume of pores with a pore diameter of less than 5 nm accounts for 10%-90% of the total pore volume, preferably 15%-70%; meanwhile, the pore volume of pores with a pore diameter of not less than 30 nm accounts for 10%-90% of the total pore volume;
  • the total pore volume is from 5% to 70%, preferably from 10% to 60%.
  • the specific surface area of the solid matter is not less than 100 m 2 /g, preferably not less than 150 m 2 /g.
  • the internal electron donor can be various internal electron donors commonly used in the field, preferably one or more selected from esters, ethers, ketones, amines, and silanes, preferably mono- or polyvalent aliphatic carboxylic acids At least one of esters, aromatic carboxylic acid esters, glycol ester compounds and diether compounds, preferably including dibasic aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol esters and diether compounds at least one of them.
  • internal electron donor compounds suitable for use in the present invention include, but are not limited to: diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisophthalate Octyl ester, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl adipate, dibutyl adipate, diethyl sebacate, sebacic acid Dibutyl, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitate Tributyl acid, triethyl bimellitic acid, tributyl bimellitic acid, tetraethyl pyromellitic acid, tetrabutyl pyromellitic acid, 1,3-propylene glycol di
  • preferred internal electron donors are di-n-butyl phthalate, diisobutyl phthalate, 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate acid ester, diethyl 2,3-diisopropyl succinate, diisobutyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, 2,3 - Diisopropyl succinate, diisobutyl 2,2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate, 2-ethyl-2-methyl succinate At least one of diethyl succinate, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 9,9-dimethoxymethylfluorene, ethylene glycol dibutyl ether A sort of.
  • the addition amount of the internal electron donor has no special requirements, and can be the conventional addition amount in the field.
  • the molar ratio of the internal electron donor to the magnesium halide is 0.001-1:1, preferably 0.01-1:1.
  • the present invention provides a method for preparing a solid catalyst component for olefin polymerization, comprising:
  • Method 1 at least one internal electron donor is added in the preparation process of the above-mentioned magnesium-based solid to obtain the solid catalyst component for olefin polymerization;
  • At least one internal electron donor is added in the preparation process of the above-mentioned magnesium-based solid, and the separated solid continues to contact with at least one internal electron donor to obtain the solid catalyst component for olefin polymerization;
  • Or method 3 at least one internal electron donor is contacted with the above-mentioned magnesium-based solid to obtain the solid catalyst component for olefin polymerization.
  • the internal electron donor in the method 1 and the method 2, can be added at any position in the preparation process of the magnesium-based solid, and can be added as a whole or in batches.
  • the position where the internal electron donor is added in the method 1 and method 2 includes that the whole or part can be added to the homogeneous solution containing the magnesium element in step S1; it can be whole or part after the mixture in step S2 is formed. and added in the process of curing, heating, and precipitation in step S3.
  • the present invention provides a catalyst system for olefin polymerization, comprising:
  • the molar ratio of aluminum in the aluminum alkyl compound to titanium in the solid catalyst component is (5-5000):1, preferably (20-800):1 .
  • the molar ratio of the aluminum alkyl compound to the external electron donor compound is (0.1-500): 1, preferably (1-100): 1, more preferably (1-100): 1, calculated as aluminum. Preferably (3-100):1.
  • the general formula of the aluminum alkyl compound is a compound represented by AlR n X 3-n , wherein R is hydrogen, a hydrocarbon group with 1-20 carbon atoms, especially an alkyl group , aralkyl, aryl, etc.; X is halogen, n is an integer of 1-3.
  • it can be trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diethylaluminum monochloride, diethylaluminum monohydrogen At least one of isobutylaluminum, sesquiethylaluminum chloride and dichloroethylaluminum, preferably triethylaluminum and/or triisobutylaluminum.
  • the external electron donor compound is preferably an organosilicon compound.
  • the general formula of the organosilicon compound is R n Si(OR y ) 4-n , wherein n is an integer from 0 to 3, and R is an alkyl group, a cycloalkyl group, an aryl group, an alkyl halide one or more of radicals, halogens and hydrogen atoms, R y is one or more of alkyl, cycloalkyl, aryl and halogenated alkyl; preferably the organosilicon compound is trimethylmethoxy Silane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, diphenyl Dimethoxysilane, Diphenyldiethoxysilane, Bicyclohexyldimethoxysilane, Phenyl
  • the present invention provides an application of the above-mentioned solid catalyst component or the above-mentioned catalyst system in an olefin polymerization reaction.
  • the olefin polymerization catalyst of the present invention can be used for the homopolymerization of olefins, and can also be used for copolymerization of a plurality of olefins.
  • the present invention provides the use of the above-mentioned solid catalyst component or the above-mentioned catalyst system in the polymerization of propylene.
  • the present invention provides a method for olefin polymerization, comprising polymerizing olefin in the presence of the above-mentioned solid catalyst component or the above-mentioned catalyst system.
  • the polymerization of olefins is carried out according to known methods, in the liquid phase of liquid phase monomers or solutions of monomers in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas phase and liquid phase. .
  • the conditions of the polymerization reaction include: the temperature is 0°C-150°C, preferably 60°C-100°C; and the pressure is 0.1 MPa-10.0 MPa.
  • the beneficial effects of the present invention are at least as follows: the solid catalyst component has unique multimodal pore distribution characteristics, and the polymer prepared by using the catalyst of the present invention for propylene polymerization has a wider molecular weight distribution.
  • Fig. 1 shows the pore size distribution diagram of the magnesium-based solid prepared in Example 1, tested by nitrogen adsorption method and calculated by NLDFT algorithm.
  • Fig. 2 shows the pore size distribution diagram of the magnesium-based solid prepared in Example 2, tested by nitrogen adsorption method and calculated by NLDFT algorithm.
  • FIG. 3 shows the pore size distribution of the magnesium-based solid prepared in Example 3 by nitrogen adsorption method and calculated by NLDFT algorithm.
  • Figure 4 shows the pore size distribution of the magnesium-based solid prepared in Comparative Example 1, which was tested by nitrogen adsorption method and calculated by NLDFT algorithm.
  • FIG. 5 shows the pore size distribution diagram of the catalyst component prepared in Example 7 tested by nitrogen adsorption method and calculated by NLDFT algorithm.
  • FIG. 6 shows the pore size distribution diagram of the catalyst component prepared in Comparative Example 5, tested by nitrogen adsorption method and calculated by NLDFT algorithm.
  • FIG. 7 shows a microscope image of the magnesium-based solid prepared in Example 1.
  • the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer.
  • the reagents or instruments used without the manufacturer's indication are conventional products that can be obtained through commercial channels.
  • Particle size distribution of magnesium-containing carrier or catalyst measured according to laser diffraction method, using Malvern 2000 particle size analyzer, n-hexane dispersant;
  • Specific surface area and pore size distribution of magnesium-containing carrier or catalyst determined by nitrogen adsorption method with ASAP2460 specific surface area and porosity analyzer from Micromeritics, USA;
  • the isotactic index (II) of the propylene polymer was determined by the heptane extraction method: 2 g of the dried polymer sample was placed in an extractor and extracted with boiling heptane for 6 hours, and the residue was dried to constant weight, the ratio of the obtained polymer weight (g) to 2 (g) is the isotacticity;
  • the melt flow index (MI) of the polymer it is measured by the MI-4 melt flow index tester of the German GOTTFERT company, and is measured according to the GB/T 3682.1-2018 standard.
  • Example 1 is used to illustrate the preparation of magnesium-based solids.
  • the obtained solid had an average particle diameter D50 of 34.2 ⁇ m, a SPAN value (ie (D90-D10)/D50) of 0.60, a titanium content of 2.0% by weight, and a Mg content of 20.3% by weight. Micrographs of the solids are shown in FIG. 7 .
  • the pore size distribution of the solid was tested by nitrogen adsorption and the NLDFT algorithm was used as shown in Figure 1. It can be seen from FIG. 1 that the pore size distribution shows a multimodal pore size distribution, the pore size below 10 nm contains at least one peak pore size distribution, and at the same time the pore size above 10 nm also contains at least another peak pore size distribution.
  • Example 2 is used to illustrate the preparation of magnesium-based solids.
  • T632 continue stirring for 1 hour.
  • 136ml of titanium tetrachloride and 240ml of food-grade No. 100 white oil (kinematic viscosity (40°C) at 100mm2/s) were dropped at the same time.
  • the mixture was stirred at 400 rmp for 1 hour.
  • the temperature was then gradually increased to 80°C.
  • the mother liquor was filtered, and the solid was washed twice with hot toluene, then twice with hexane, and dried to obtain a titanium-containing magnesium-based solid.
  • the obtained solid had an average particle diameter D50 of 62.1 ⁇ m, a SPAN value of 0.63, a titanium content of 2.3% by weight, and a Mg content of 21.1% by weight.
  • the pore size distribution of the solid was tested by nitrogen adsorption and the NLDFT algorithm was used as shown in FIG. 2 . It can be seen from FIG. 2 that the pore size distribution shows a multimodal pore size distribution, the pore size below 10 nm contains at least one peak pore size distribution, and at the same time the pore size above 10 nm also contains at least another peak pore size distribution.
  • the magnesium-based solid was prepared by the method of Example 1, except that the amount of epichlorohydrin used was changed to 14.2g, the amount of tributyl phosphate was changed to 53.2g, the amount of toluene was changed to 197ml, and the amount of titanium tetrachloride was changed to 197ml. Change it to 133ml, add phthalic anhydride, and maintain the solution at 60°C for another 1 hour, then cool the solution to 8°C. The resulting solid had a titanium content of 2.1% by weight and a Mg content of 21.2% by weight.
  • the pore size distribution of the solid was tested by nitrogen adsorption and the NLDFT algorithm was used as shown in FIG. 3 . It can be seen from FIG. 3 that the pore size distribution shows a multimodal pore size distribution, the pore size below 10 nm contains at least one peak pore size distribution, and at the same time the pore size above 10 nm also contains at least another peak pore size distribution.
  • the magnesium-based solid was prepared by the method of Example 1, except that the amount of epichlorohydrin used was changed to 7.2g, the amount of tributyl phosphate was changed to 65.1g, and 2.2g was added after adding tributyl phosphate Ethanol, the amount of white oil was changed to 184ml, the amount of titanium tetrachloride was changed to 203ml, phthalic anhydride was added, and after maintaining at 60°C for another 1 hour, the solution was cooled to 0°C.
  • the obtained solid had a titanium content of 3.6% by weight and a Mg content of 20.2% by weight.
  • the pore size data of the solids measured by the nitrogen adsorption method are shown in Table 1, and the pore size distribution shows a multimodal pore size distribution.
  • Example 1 The method of Example 1 was used to prepare a titanium-containing magnesium-based solid. The difference was that the amount of epichlorohydrin used was 10.75g, the amount of tributyl phosphate was changed to 33.2g, the amount of toluene was changed to 72ml, and the amount of white oil was changed to 120ml, the amount of titanium tetrachloride was changed to 112ml, phthalic anhydride was added, and after maintaining at 60°C for another 1 hour, the solution was cooled to 0°C, the obtained solid content of titanium was 2.6% by weight, and the Mg content was 21.4 %(weight).
  • the pore size data of the solids measured by the nitrogen adsorption method are shown in Table 1, and the pore size distribution shows a unimodal pore size distribution.
  • the obtained solid had an average particle diameter D50 of 27.1 ⁇ m, a SPAN value of 1.24, a titanium content of 2.1% by weight, and a Mg content of 20.2% by weight.
  • FIG. 1 The pore size data of the solids measured by the nitrogen adsorption method are shown in Table 1, and the pore size distribution diagram is shown in Figure 4, which shows a unimodal pore size distribution.
  • Figure 4 is a diagram of the aperture distribution of the NLDFT algorithm.
  • Adopt the solid substance prepared by the preparation method of Example 1 in the patent CN1097597C the difference is that the electron donor diisobutyl phthalate is not added and the subsequent steps are changed, after the solid substance is separated out, the mother liquor is filtered, and the solid is heated with toluene After being washed twice, washed twice with hexane, and dried to obtain a titanium-containing magnesium-based solid.
  • the obtained solid had an average particle diameter D50 of 24.1 ⁇ m, a SPAN value of 1.14, a titanium content of 2.3% by weight, and a Mg content of 21.1% by weight.
  • the pore size data of the solids measured by the nitrogen adsorption method are shown in Table 1, and the pore size distribution is a unimodal pore size distribution.
  • the proportion of pore volume with pore diameter ⁇ 5nm under NLDFT algorithm refers to the ratio of pore volume with pore diameter ⁇ 5nm obtained by NLDFT algorithm to the total pore volume calculated under this algorithm, and the meanings of other representations are deduced accordingly.
  • the pore volume given in Table 1 is the BJH algorithm pore volume.
  • the pore size data of solids measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a multimodal pore size distribution.
  • 100 white oil ( Kinematic viscosity (40°C) at 100mm2/s) was mixed uniformly to form mixture 1.
  • 135mL of titanium tetrachloride and mixture 1 were added dropwise at the same time.
  • the mixture was stirred at 400 rmp for 2 hours.
  • the temperature was then gradually increased to 85°C over 3 hours.
  • 3 mL of 2,4-pentanediol dibenzoate electron donor was added, the temperature was raised to 85° C., and the temperature was kept constant for 1 hour. Filter and wash the solid twice with hot toluene.
  • the pore size distribution of the solid was tested by nitrogen adsorption and the NLDFT algorithm was used as shown in FIG. 5 . It can be seen from FIG. 5 that the pore size distribution shows a multimodal pore size distribution, the pore size below 10 nm contains at least one peak pore size distribution, and at the same time the pore size above 10 nm also contains at least another peak pore size distribution.
  • the pore size data of solids measured by nitrogen adsorption method are shown in Table 2.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the pore size data of solids measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a multimodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • Example 6 Basically the same as Example 6, the difference is only that the amount of epichlorohydrin is changed to 14.2g, the amount of tributyl phosphate is changed to 53.2g, the amount of toluene is changed to 197ml, and the amount of titanium tetrachloride is changed to 133ml. Phthalic anhydride, after maintaining at 60°C for an additional hour, the solution was cooled to 8°C. Catalyst component data are shown in Table 3.
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a multimodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • Example 6 Basically the same as Example 6, the difference is that the amount of epichlorohydrin used is changed to 7.2g, the amount of tributyl phosphate is changed to 65.1g, and 2.2g of ethanol is added after adding tributyl phosphate, white oil The amount was changed to 184ml, the amount of titanium tetrachloride was changed to 203ml, phthalic anhydride was added, and after maintaining at 60°C for another hour, the solution was cooled to 0°C. Catalyst component data are shown in Table 3.
  • the pore size data of the solids measured by the nitrogen adsorption method are shown in Table 2, and the pore size distribution shows a multimodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • Example 6 Basically the same as Example 6, the difference is that the amount of epichlorohydrin used is 10.75g, the amount of tributyl phosphate is changed to 33.2g, the amount of toluene is changed to 72ml, the amount of white oil is changed to 120ml, and the amount of titanium tetrachloride is changed to 120ml. The amount was changed to 112 ml, phthalic anhydride was added, and after maintaining at 60°C for another 1 hour, the solution was cooled to 0°C. Catalyst component data are shown in Table 3.
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a monomodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • Example 6 Basically the same as Example 6, except that the amount of tributyl phosphate used was changed to 38.8 g. Catalyst component data are shown in Table 3.
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a monomodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the solid was then thermostated at 85°C for 1 hour with 260 ml of a 20% titanium tetrachloride solution in toluene and 3 ml of di-n-butyl phthalate electron donor. Filter and wash the solid twice with toluene. Then, 100 ml of titanium tetrachloride and 150 ml of toluene were added at a constant temperature of 110° C. for 0.5 hours and filtered, and the operation was repeated. Then, the obtained solid was washed 5 times with hexane and then vacuum-dried to obtain a solid substance of an olefin polymerization catalyst component. Catalyst component data are shown in Table 3.
  • the pore size distribution of the solid was tested by nitrogen adsorption and the NLDFT algorithm was used as shown in FIG. 6 .
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a monomodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the solid product prepared by the preparation method of implementation 1 in patent CN1097597C is different in that diisobutyl phthalate is changed to 1.5 g of 9,9-dimethoxymethyl fluorene.
  • Catalyst component data are shown in Table 3.
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a monomodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • Catalyst component data are shown in Table 3.
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a monomodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the pore size data of catalyst measured by nitrogen adsorption method are shown in Table 2.
  • the pore size distribution of the catalyst is a monomodal pore size distribution.
  • the propylene polymerization method is the same as that in Example 6, and the catalyst polymerization data and polymer data are shown in Table 3.
  • the proportion of pore volume with pore diameter ⁇ 5nm under NLDFT algorithm refers to the ratio of pore volume with pore diameter ⁇ 5nm obtained by NLDFT algorithm to the total pore volume calculated under this algorithm.
  • the pore volume given in Table 2 is the BJH algorithm pore volume.
  • Example 11 The electron donating content in Example 11 is the content of 2-isopropyl-2-isoamyl-1,3-dimethoxypropane
  • the titanium-containing magnesium-based solids and the magnesium chloride-supported olefin polymerization catalyst components obtained by the present invention have multimodal pore size distribution characteristics and higher specific surface areas.
  • the magnesium chloride-supported olefin polymerization catalyst shown in the comparative example only has a monomodal pore size distribution characteristic.
  • the catalyst of the present invention is used for propylene polymerization, it has higher polymerization activity and higher stereo-orientation ability, and the prepared polymer has wider molecular weight distribution.

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Abstract

本发明提供一种镁基固体物以及烯烃聚合用固体催化剂组分，通过氮气吸附法测定，所述固体物具有多峰孔分布和不低于50m 2/g的比表面积，并且所述固体物的孔径分布在1nm-300nm的范围内，其中，在小于10nm的孔径范围内至少具有一个峰，同时在不小于10nm的孔径范围内至少具有另一个峰。采用该固体催化剂组分形成的催化剂用于丙烯聚合时，具有较高的聚合活性和较高立构定向能力，所制备的聚合物的分子量分布较宽。

Description

具有多峰孔分布的镁基固体物和催化剂组分以及它们的制备方法
相关申请的交叉引用
本申请要求2020年10月15日提交的CN202011104541.0、CN202011105894.2和CN202011105648.7的优先权和权益，通过引用并且为了所有的目的将所述文件整体结合在本申请中。
技术领域
本发明涉及烯烃聚合技术领域，具体涉及一种烯烃聚合用的镁基固体物和催化剂组分及它们的制备方法和应用。
背景技术
氯化镁负载型的Ziegler-Natta催化剂是目前市场上主要应用的烯烃聚合催化剂。生产这种催化剂可以先制备含镁化合物或者配合物固体物作为载体，例如众所周知的高速搅拌技术、高压挤出技术、喷雾技术、超重力技术等均是用来制备这种载体，如氯化镁醇合物载体，然后将它们与含钛化合物接触生成氯化镁负载钛的催化剂固体物，再负载上内给电子体化合物形成催化剂组分。采用氮气吸附法对这类催化剂组分进行测试，通常显示在10nm以内具有一个最可几孔径的单峰孔分布。
另外还可以是先获得镁化合物或配合物的溶液，然后与含钛化合物接触，结晶析出氯化镁负载钛的催化剂固体物，再进一步与内给电子体化合物接触形成催化剂组分。无论是早期所公开的专利如CN85100997A和CN1097597C制备的催化剂组分，或者是近年来进一步采用乳液技术来控制结晶过程所公开的专利如CN103619475B和CN107207657A等制备的催化剂组分，未见具有多峰孔分布结构氯化镁负载型催化剂组分的报道。
目前，具有多峰孔分布结构的聚烯烃催化剂一般是采用多峰孔分布的分子筛或者硅胶作为载体来制备的，如专利CN104650267A、CN105175586A、CN105330769A、US5231066的报道，它们通过在这种载体上负载上钛或者单活性中心金属来制备聚乙烯催化剂，可以得到双峰或宽峰分子量分布的聚乙烯。但众所周知，相比于氯化镁负载型催化剂，采用分子筛或者硅胶类载体制备的烯烃聚合催化剂活性太低。
另外，氯化镁负载型催化剂组分还有一种可能会出现多峰孔分布结构的情况，是催化剂组分在与空气接触的暴空状态下，催化剂的结构出现裂痕，内部微孔结构被破坏转化为介孔和大孔，但同时比表面急剧下降，甚至消失；因此，这种多峰孔分布的结构的催化剂 组分，比表面很小，催化剂基本失效。
仍然需要显示希望的性能的镁基催化剂载体、由其制备的聚烯烃催化剂组分和相应的催化剂体系。
发明内容
本发明的目的之一在于提供一种具有多峰孔分布的镁基固体物，其以卤化镁为载体且含有钛元素，并且在具有多峰孔径分布特征的同时还具有较高的比表面积。
本发明的目的之二在于提供一种与目的之一相对应的镁基固体物的制备方法。
本发明的目的之三在于提供一种基于镁基固体物制备的烯烃聚合用固体催化剂组分。
本发明的目的之四在于提供一种与目的之三相对应的烯烃聚合用固体催化剂组分的制备方法。
本发明的目的之五在于提供一种包含所述催化剂组分的烯烃聚合催化剂。
本发明的目的之六在于提供所述催化剂在烯烃聚合中的应用。
本发明的目的之七在于提供一种与上述目的相对应的烯烃聚合方法。
本发明发现，采用所述多峰孔分布的镁基固体物制备的烯烃聚合催化剂用于丙烯聚合时，具有较高的聚合活性和较高立构定向能力；与已知技术相比，在相同内给电子体情况下，本发明催化剂用于丙烯聚合制备的聚合分子量分布较宽。
优选实施方案的详细描述
在第一方面，本发明提供了一种具有多峰孔分布的镁基固体物，其以卤化镁为载体且含有钛元素，通过氮气吸附法测定所述镁基固体物具有不低于50m 2/g的比表面积，并且所述镁基固体物的孔径分布在1nm-300nm的范围内，其中在小于10nm的孔径范围内和在不小于10nm的孔径范围内，分别具有至少一个峰。
根据本发明，所述镁基固体物的孔径分布是通过采用氮气吸附法测试并运用NLDFT算法计算得到。
根据本发明，所述镁基固体物的比表面积是通过采用氮气吸附法测试得到。
根据本发明的一些实施方式，所述镁基固体物具有球型或类球型结构。
在本发明的一些优选的实施方式中，在小于10nm的孔径范围内的峰对应的最可几孔径为2nm-8nm，优选为2nm-6nm；同时，在不小于10nm的孔径范围内的峰对应的最可几孔径为15nm-200nm，优选为20nm-100nm，更优选为30nm-90nm。
在本发明的一些优选的实施方式中，所述镁基固体物中，孔径小于10nm的孔的孔体 积与孔径不小于10nm的孔的孔体积的比值为(0.1-20):1，优选为(0.25-15):1。
在本发明的一些优选的实施方式中，孔径小于5nm的孔的孔体积占总孔体积的10％-90％，优选为15％-70％；孔径不小于30nm的孔的孔体积占总孔体积的5％-70％，优选为10％-60％。
在本发明的一些优选的实施方式中，所述镁基固体物的比表面积为100m 2/g-500m 2/g。
在第二方面，本发明提供了一种上述的镁基固体物的制备方法，包括：
S1.使卤化镁与路易斯碱在有机溶剂中接触，形成含镁溶液；
S2.使所述含镁溶液、惰性分散介质和路易斯酸接触，形成混合物；
S3.在助析出剂和表面活性剂的存在下，使所述镁基固体物从所述混合物中析出，
其中，步骤S1中，所述路易斯碱包括有机磷化合物，且以每摩尔卤化镁计，所述有机磷化合物的用量为1.5-10摩尔；步骤S2中，所述路易斯酸包含钛化合物。
在本发明的一些优选的实施方式中，步骤S1中，所述路易斯碱包括有机磷化合物，且以每摩尔卤化镁计，所述有机磷化合物的用量为2-5摩尔。
根据本发明，步骤S2中，所述混合物包含胶体、两相溶液、乳液和其他形式。优选混合物形成至少包含两个液相的混合物形式。这样在表面活性剂存在下，采用振动、搅拌、雾化、剪切等一种或多种方法，可促使混合物形成均匀乳液，从而可固化析出球形固体物。
在本发明的一些优选的实施方式中，步骤S3中，将所述混合物升温至目标温度，从而使所述镁基固体物从所述混合物中析出，其中，所述目标温度为50℃-110℃。
在本发明的一些优选的实施方式中，步骤S3中，在升温结束后，在搅拌的条件下于目标温度保持0.1h-24h。
根据本发明，混合物析出固体物后，可以将悬浮液在一定温度下搅拌一定时间、例如10分钟到24小时，目的是为了让结晶形态更稳定，提高粒子强度。
在本发明的一些优选的实施方式中，步骤S3中，升温过程耗时0.01h-36h，优选0.1h-24h。
根据本发明，混合物升温过程没有具体限定，可以采用任何已知的方法进行升温，如缓慢、分步、快速或者程序升温，具体升温方式可根据具体的配方、接触温度等来调整。本发明人研究发现，本发明所述的制备方法中，其他条件均相同的情况下，不同的升温过程会影响到最终催化剂的粒子形态、粒径分布；具体地，采用较慢的升温过程可以获得较好的颗粒形态，反之，升温速度过快，会导致粒型变差；因此，混合物升温过程可以为1分钟到36小时，优选3分钟到24小时。
在本发明的一些优选的实施方式中，步骤S1中，所述卤化镁的通式如式(1)所示：
MgX 1 2       式(1)
式(1)中，X 1为卤素，优选为氯、溴或碘。
在本发明的一些优选的实施方式中，所述卤化镁为二氯化镁、二溴化镁和二碘化镁中的一种或多种。
在本发明的一些优选的实施方式中，所述卤化镁为二氯化镁。
在本发明的一些优选的实施方式中，所述有机磷化合物选自式(2)或式(3)所示的化合物中的一种或多种：
Figure PCTCN2021124050-appb-000001
式(2)和式(3)中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自1-20个碳原子的直链或支链烷基、环烷基或芳香烃基及带有取代基如烷基的芳香烃基。
在本发明的一些优选的实施方式中，所述有机磷化合物为磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三戊酯、磷酸三苯酯、磷酸三(邻、间或对甲苯)酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丁酯和亚磷酸三苯甲酯中的一种或多种。
根据本发明，所述有机磷化合物为磷酸三丁酯。
在本发明的一些优选的实施方式中，所述有机溶剂选自芳香族烃类化合物和卤代烃类化合物中的一种或多种。
在本发明的一些优选的实施方式中，所述有机溶剂选自甲苯、乙苯、苯、二甲苯和氯苯中的一种或多种。
根据本发明的一些优选的实施方式，所述有机溶剂为甲苯。
在本发明的一些优选的实施方式中，以每摩尔卤化镁计，所述有机溶剂的用量为1-40摩尔，优选2-30摩尔。
根据本发明的一些实施方式，所述路易斯碱还包括有机环氧化合物和/或含羟基类化合物。
根据本发明，所述有机环氧化合物为碳原子数2-8的脂肪族烯烃、卤代脂肪族烯烃的氧化产物中的一种或多种，具体可以为环氧乙烷、环氧丙烷、环氧氯乙烷、环氧氯丙烷、环氧丁烷、丁二烯氧化物、丁二烯双氧化物、甲基缩水甘油醚和二缩水甘油醚中的一种或 多种，优选为环氧氯丙烷。
根据本发明，所述含羟基类化合物的通式为HOR，式中R为2-20个碳原子的烃基，可以是饱和或不饱和的直链或支链的烷烃基、环烷烃基或芳香烃基。含羟基类化合物优选为醇类化合物，更优选为包括乙醇、丙醇、丁醇、2-乙基己醇、苯甲醇和苯乙醇中的一种或多种。
根据本发明，以每摩尔卤化镁计，所述有机环氧化合物的用量为0.1-10摩尔，优选为0.4-4摩尔。
根据本发明，以每摩尔卤化镁计，所述含羟基类化合物的用量为0.1-10摩尔，优选为0.1-5摩尔。
根据本发明，所述的含镁溶液，可以是将卤化镁、有机磷化合物在有机溶剂中接触形成；也可以是将卤化镁、有机环氧化合物、有机磷化合物在有机溶剂中接触形成；还可以是将卤化镁、有机环氧化合物、有机磷化合物、含羟基类化合物在有机溶剂中接触形成。
本发明所述形成含镁溶液的接触方式没有特别的限定，接触的目的是为了形成含镁元素均匀溶液，接触的条件包括：接触的温度为10-150℃，优选为30-130℃，接触时间为0.05-10小时，优选为0.1-6小时。
在本发明的一些优选的实施方式中，步骤S2中，所述惰性分散介质选自煤油、石蜡油、白油、凡士林油、甲基硅油、脂族和环脂族烃类中的一种或多种。
在本发明的一些优选的实施方式中，步骤S2中，所述惰性分散介质选自白油、己烷和癸烷中的一种或多种。
在本发明的一些优选的实施方式中，步骤S2中，以每克卤化镁计，所述惰性分散介质的用量为0.1g-300g，优选为1g-150g。
在本发明的一些优选的实施方式中，所述路易斯酸包括含钛化合物和任选地含硅化合物，所述含钛化合物的通式如式(4)所示：
TiX 2 m(OR 1) 4-m        式(4)
式(4)中，X 2为卤素，优选为氯、溴或碘，R 1为1-20个碳原子的烃基，m为1-4的整数。
在本发明的一些优选的实施方式中，所述含钛化合物选自四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、四乙氧基钛、一氯三乙氧基钛、二氯二乙氧基钛和三氯一乙氧基钛中的一种或多种。
在本发明的一些优选的实施方式中，以每摩尔卤化镁计，所述含钛化合物的用量为0.5-25摩尔，优选1-20摩尔。
在本发明的一些优选的实施方式中，所述含硅化合物的通式如式(5)所示：
SiX 3 nR 2 4-n        式(5)
式(5)中，X 3为卤素，优选为氯、溴或碘，R 2为1-20个碳原子的烃基，n为1-4的整数。
在本发明的一些优选的实施方式中，所述含硅化合物为四氯化硅。
在本发明的一些优选的实施方式中，以每摩尔卤化镁计，所述含硅化合物的用量为0.1-40摩尔，优选0.1-20摩尔。
根据本发明，步骤S2中，所述的使所述含镁溶液、惰性分散介质和路易斯酸接触形成混合物的接触的方式可以是任意方式。具体例如可以是先将含镁溶液与惰性分散介质接触后，然后滴加路易斯酸；也可是先将含镁溶液与路易斯酸接触后，再加入惰性分散介质；还可以是惰性分散介质和路易斯酸接触后，再与含镁溶液接触。
在本发明的一些优选的实施方式中，步骤S3中，所述助析出剂选自有机酸、有机酸酐、有机醚和有机酮中的一种或多种。
在本发明的一些优选的实施方式中，步骤S3中，所述助析出剂选自乙酸酐、邻苯二甲酸酐、丁二酸酐、顺丁烯二酸酐、均苯四甲酸二酐、醋酸、丙酸、丁酸、丙烯酸、甲基丙烯酸、丙酮、甲乙酮、二苯酮、甲醚、乙醚、丙醚、丁醚和戊醚中的一种或多种。
在本发明的一些优选的实施方式中，步骤S3中，以每摩尔卤化镁计，所述助析出剂的用量为0.01-1摩尔，优选0.04-0.4摩尔。
在本发明的一些优选的实施方式中，步骤S3中，所述表面活性剂选自高分子表面活性剂。
在本发明的一些优选的实施方式中，步骤S3中，所述表面活性剂选自(甲基)丙烯酸烷基酯类聚合物和(甲基)丙烯酸烷基酯类的共聚物、马来酸酐聚合物的醇解物和马来酸酐类共聚物的醇解物中的一种或多种。
在本发明的一些优选的实施方式中，步骤S3中，所述表面活性剂具体地包括聚马来酸酐的醇解物、马来酸酐-苯乙烯共聚物的醇解物、马来酸酐-苯乙烯-(甲基)丙烯酸烷基酯三元共聚物的醇解物、马来酸酐-(甲基)丙烯酸烷基酯共聚物的醇解物中的至少一种；其中(甲基)丙烯酸烷基酯的烷基链是1-30个碳原子的直链或支链烷烃、环烷烃或芳香烃，优选1-20的碳原子的那些；所述马来酸酐类共聚物是指包括至少一个马来酸酐单体的共聚物；所述醇解物是指该物与有机醇类化合物反应得到的聚合物产物，有机醇类化合物如结构是ROH，其中R是2-20的碳原子的直链或支链烷烃、环烷烃或芳香烃。
在本发明的一些优选的实施方式中，本发明的表面活性剂包含(甲基)丙烯酸烷基酯类 聚合物和(甲基)丙烯酸烷基酯类的共聚物中的至少一种，例如可以是聚(甲基)丙烯酸烷基酯、(甲基)丙烯酸烷基酯-马来酸酐共聚物、(甲基)丙烯酸烷基酯-马来酸酐-苯乙烯的共聚物的至少一种；其中酯侧链是1-30个碳原子的直链或支链烷烃、环烷烃或芳香烃，优选1-20的碳原子的那些。
可用于本发明的各种表面活性剂可商购得到。例如，所述的聚(甲基)丙烯酸酯类聚合物表面活性剂可以从广州锐圣研化工科技有限公司作为降凝剂产品购买获得，商品名为T602、T632等。
本发明所述制备方法中，表面活性剂的加入位置可以是所述制备方法中的任意位置，可以为整体或者分散加入。根据本发明，所述的表面活性剂加入的位置，可以是整体或者部分在形成含镁溶液之中或之后加入；可以为整体加入到惰性分散介质中；或者可以为部分加入到惰性分散介质中，另一部分加入到含镁溶液；或者可以在含镁溶液、惰性分散介质和路易斯酸接触后加入。
步骤S3中，若不采用表面活性剂、尤其是上述表面活性剂，将导致制得的镁基固体物为粉末状，而无法制得具有球形或类球形结构的镁基固体物。
在本发明的一些优选的实施方式中，步骤S3中，以每克卤化镁计，所述表面活性剂的用量为0.01g-5g，优选0.05g-1g。
在第三方面，本发明提供了一种具有多峰孔分布的烯烃聚合用固体催化剂组分，其包括上述的镁基固体物和至少一种内给电子体。
根据本发明，所述固体催化剂组分，采用氮气吸附法测定，具有多个峰的孔径分布以及不低于50m 2/g的比表面积；其中，所述固体的多个峰的孔径分布情况为在1nm-100nm的孔径范围内至少具有一个峰，同时在5nm-200nm的孔径范围内至少具有另一个峰。
优选地，所述固体催化剂组分，采用氮气吸附法测定，具有多个峰的孔径分布以及不低于50m 2/g的比表面积；其中，所述固体催化剂组分的多个峰的孔径分布情况为在1nm-10nm的孔径范围内具有至少第一个峰，同时在10nm-200nm的孔径范围内具有至少第二个峰。
根据本发明，所述孔径分布是通过利用NLDFT算法对氮气吸附法测得的数据进行计算得到的。
在本发明的一些优选的实施方式中，所述固体催化剂组分的多个峰的孔径分布情况为，在1nm-100nm的孔径范围内的至少一个峰的最可几孔径为1nm-50nm，优选为1nm-10nm，更优选为2nm-8nm，进一步优选为3nm-6nm；在5nm-200nm的孔径范围内的至少另一个峰的最可几孔径为10nm-200nm，优选为20nm-100nm，更优选为30nm-90nm。
优选地，所述固体催化剂组分的多个峰的孔径分布情况为，在1nm-10nm的孔径范围内的峰的最可几孔径为2nm-8nm，进一步优选为2nm-6nm；在10nm-200nm的孔径范围内的峰的最可几孔径为15nm-200nm，优选为20nm-100nm，更优选为30nm-90nm。
在本发明的一些优选的实施方式中，孔径小于5nm的孔的孔体积占总孔体积为10％-90％，优选为15％-70％；同时，孔径不小于30nm的孔的孔体积占总孔体积为5％-70％，优选为10％-60％。
在本发明的一些优选的实施方式中，所述固体物的比表面积不低于100m 2/g，优选为不低于150m 2/g。
根据本发明，所述内给电子体可以为本领域常用的各种内给电子体，优选自酯、醚、酮、胺、硅烷的一种或多种，优选为一元或多元脂肪族羧酸酯、芳香族羧酸酯、二醇酯类化合物、二醚类化合物至少一种，优选为包括二元的脂肪族羧酸酯、芳香族羧酸酯、二元醇酯类和二醚类化合物中的至少一种。
适用于本发明的内给电子体化合物的具体实例包括但不限于：邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二正丁酯、邻苯二甲酸二异辛酯、邻苯二甲酸二正辛酯、丙二酸二乙酯、丙二酸二丁酯、己二酸二乙酯、己二酸二丁酯、癸二酸二乙酯、癸二酸二丁酯、顺丁烯二酸二乙酯、顺丁烯二酸二正丁酯、萘二羧酸二乙酯、萘二羧酸二丁酯、偏苯三酸三乙酯、偏苯三酸三丁酯、联苯三酸三乙酯、联苯三酸三丁酯、均苯四酸四乙酯、均苯四酸四丁酯、1,3-丙二醇二苯甲酸酯、2-甲基-1,3-丙二醇二苯甲酸酯、2-乙基-1,3-丙二醇二苯甲酸酯、2-丙基-1,3-丙二醇二苯甲酸酯、2-丁基-1,3-丙二醇二苯甲酸酯、2,2-二甲基-1,3-丙二醇二苯甲酸酯、2-乙基-2-丁基-1,3-丙二醇二苯甲酸酯、2,2-二乙基-1,3-丙二醇二苯甲酸酯、2-甲基-2-丙基-1,3-丙二醇二苯甲酸酯、2-异丙基-2-异戊基-1,3-丙二醇二苯甲酸酯、2,4-戊二醇二苯甲酸酯、3-甲基-2,4-戊二醇二苯甲酸酯、3-乙基-2,4-戊二醇二苯甲酸酯、3-丙基-2,4-戊二醇二苯甲酸酯、3-丁基-2,4-戊二醇二苯甲酸酯、3,3-二甲基-2,4-戊二醇二苯甲酸酯、2-甲基-1,3-戊二醇二苯甲酸酯、2,2-二甲基-1,3-戊二醇二苯甲酸酯、2-乙基-1,3-戊二醇二苯甲酸酯、2-丁基-1,3-戊二醇二苯甲酸酯、2-甲基-1,3-戊二醇二苯甲酸酯、2-乙基-1,3-戊二醇二苯甲酸酯、2-丙基-1,3-戊二醇二苯甲酸酯、2-丁基-1,3-戊二醇二苯甲酸酯、2,2-二甲基-1,3-戊二醇二苯甲酸酯、2-甲基-1,3-戊二醇二苯甲酸酯、2,2-二甲基-1,3-戊二醇二苯甲酸酯、2-乙基-1,3-戊二醇二苯甲酸酯、2-丁基-1,3-戊二醇二苯甲酸酯、2,2,4-三甲基-1,3-戊二醇二苯甲酸酯、3-甲基-3-丁基-2,4-戊二醇二苯甲酸酯、2,2-二甲基-1,5-戊二醇二苯甲酸酯、1,6-己二醇二苯甲酸酯、6-庚烯-2,4-庚二醇二苯甲酸酯、2-甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、 3-甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、4-甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、5-甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、6-甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、3-乙基-6-庚烯-2,4-庚二醇二苯甲酸酯、4-乙基-6-庚烯-2,4-庚二醇二苯甲酸酯、5-乙基-6-庚烯-2,4-庚二醇二苯甲酸酯、6-乙基-6-庚烯-2,4-庚二醇二苯甲酸酯、3-丙基-6-庚烯-2,4-庚二醇二苯甲酸酯、4-丙基-6-庚烯-2,4-庚二醇二苯甲酸酯、5-丙基-6-庚烯-2,4-庚二醇二苯甲酸酯、6-丙基-6-庚烯-2,4-庚二醇二苯甲酸酯、3-丁基-6-庚烯-2,4-庚二醇二苯甲酸酯、4-丁基-6-庚烯-2,4-庚二醇二苯甲酸酯、5-丁基-6-庚烯-2,4-庚二醇二苯甲酸酯、6-丁基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,5-二甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,5-二乙基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,5-二丙基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,5-二丁基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,3-二甲基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,3-二乙基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,3-二丙基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,3-二丁基-6-庚烯-2,4-庚二醇二苯甲酸酯、3,5-庚二醇二苯甲酸酯、2-甲基-3,5-庚二醇二苯甲酸酯、3-甲基-3,5-庚二醇二苯甲酸酯、4-甲基-3,5-庚二醇二苯甲酸酯、5-甲基-3,5-庚二醇二苯甲酸酯、6-甲基-3,5-庚二醇二苯甲酸酯、3-乙基-3,5-庚二醇二苯甲酸酯、4-乙基-3,5-庚二醇二苯甲酸酯、5-乙基-3,5-庚二醇二苯甲酸酯、3-丙基-3,5-庚二醇二苯甲酸酯、4-丙基-3,5-庚二醇二苯甲酸酯、3-丁基-3,5-庚二醇二苯甲酸酯、2,3-二甲基-3,5-庚二醇二苯甲酸酯、2,4-二甲基-3,5-庚二醇二苯甲酸酯、2,5-二甲基-3,5-庚二醇二苯甲酸酯、2,6-二甲基-3,5-庚二醇二苯甲酸酯、3,3-二甲基-3,5-庚二醇二苯甲酸酯、4,4-二甲基-3,5-庚二醇二苯甲酸酯、6,6-二甲基-3,5-庚二醇二苯甲酸酯、2,6-二甲基-3,5-庚二醇二苯甲酸酯、3,4-二甲基-3,5-庚二醇二苯甲酸酯、3,5-二甲基-3,5-庚二醇二苯甲酸酯、3,6-二甲基-3,5-庚二醇二苯甲酸酯、4,5-二甲基-3,5-庚二醇二苯甲酸酯、4,6-二甲基-3,5-庚二醇二苯甲酸酯、4,4-二甲基-3,5-庚二醇二苯甲酸酯、6,6-二甲基-3,5-庚二醇二苯甲酸酯、2-甲基-3-乙基-3,5-庚二醇二苯甲酸酯、2-甲基-4-乙基-3,5-庚二醇二苯甲酸酯、2-甲基-5-乙基-3,5-庚二醇二苯甲酸酯、3-甲基-3-乙基-3,5-庚二醇二苯甲酸酯、3-甲基-4-乙基-3,5-庚二醇二苯甲酸酯、3-甲基-5-乙基-3,5-庚二醇二苯甲酸酯、4-甲基-3-乙基-3,5-庚二醇二苯甲酸酯、4-甲基-4-乙基-3,5-庚二醇二苯甲酸酯、4-甲基-5-乙基-3,5-庚二醇二苯甲酸酯、2-甲基-3-丙基-3,5-庚二醇二苯甲酸酯、2-甲基-4-丙基-3,5-庚二醇二苯甲酸酯、2-甲基-5-丙基-3,5-庚二醇二苯甲酸酯、3-甲基-3-丙基-3,5-庚二醇二苯甲酸酯、3-甲基-4-丙基-3,5-庚二醇二苯甲酸酯、3-甲基-5-丙基-3,5-庚二醇二苯甲酸酯、4-甲基-3-丙基-3,5-庚二醇二苯甲酸酯、4-甲基-4-丙基-3,5-庚二醇二苯甲酸酯、4-甲基-5-丙基-3,5-庚二醇二苯甲酸酯、2-(2-乙基己基)-1,3-二甲氧基丙 烷、2-异丙基-1,3-二甲氧基丙烷、2-丁基-1,3-二甲氧基丙烷、2-仲基-1,3-二甲氧基丙烷、2-环己基-1,3-二甲氧基丙烷、2-苯基-1,3-二甲氧基丙烷、2-(2-苯基乙基)-1,3-二甲氧基丙烷、2-(2-环己基乙基)-1,3-二甲氧基丙烷、2-(对-氯苯基)-1,3-二甲氧基丙烷、2-(二苯基甲基)-1,3-二甲氧基丙烷、2,2-二环己基-1,3-二甲氧基丙烷、2,2-二环戊基-1,3-二甲氧基丙烷、2,2-二乙基-1,3-二甲氧基丙烷、2,2-二丙基-1,3-二甲氧基丙烷、2,2-二异丙基-1,3-二甲氧基丙烷、2,2-二丁基-1,3-二甲氧基丙烷、2-甲基-2-丙基-1,3-二甲氧基丙烷、2-甲基-2-苄基-1,3-二甲氧基丙烷、2-甲基-2-乙基-1,3-二甲氧基丙烷、2-甲基-2-异丙基-1,3-二甲氧基丙烷、2-甲基-2-苯基-1,3-二甲氧基丙烷、2-甲基-2-环己基-1,3-二甲氧基丙烷、2,2-双(2-环己基乙基)-1,3-二甲氧基丙烷、2-甲基-2-异丁基-1,3-二甲氧基丙烷、2-甲基-2-(2-乙基己基)-1,3-二甲氧基丙烷、2,2-二异丁基-1,3-二甲氧基丙烷、2,2-二苯基-1,3-二甲氧基丙烷、2,2-二苄基-1,3-二甲氧基丙烷、2,2-双(环己基甲基)-1,3-二甲氧基丙烷、2-异丁基-2-异丙基-1,3-二甲氧基丙烷、2-(1-甲基丁基)-2-异丙基-1,3-二甲氧基丙烷、2-异丙基-2-异戊基-1,3-二甲氧基丙烷、2-苯基-2-异丙基-1,3-二甲氧基丙烷、2-苯基-2-仲丁基-1,3-二甲氧基丙烷、2-苄基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-异丙基-1,3-二甲氧基丙烷、2-环戊基-2-仲丁基1,3-二甲氧基丙烷、2-环己基-2-异丙基-1,3-二甲氧基丙烷、2-环己基-2-仲丁基-1,3-二甲氧基丙烷、2-异丙基-2-仲丁基-1,3-二甲氧基丙烷、2-环己基-2-环己基甲基-1,3-二甲氧基丙烷，9,9-二甲氧基甲基芴、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、丁二醇二甲醚、丁二醇二乙醚、丁二醇二丁醚、己二醇二甲醚、己二醇二乙醚、己二醇二丁醚、2,2-二甲基琥珀酸二乙酯、2-乙基-2-甲基琥珀酸二乙酯、2-苄基-2-异丙基琥珀酸二乙酯、2-环己基甲基-2-异丁基琥珀酸二乙酯、2-环戊基-2-正丁基琥珀酸二乙酯、2,2-二异丁基琥珀酸二乙酯、2-环己基-2-乙基琥珀酸二乙酯、2-异丙基-2-甲基琥珀酸二乙酯、2-十四烷基-2-乙基琥珀酸二乙酯、2-异丁基-2-乙基琥珀酸二乙酯、2-(1-三氟甲基-乙基)-2-甲基琥珀酸二乙酯、2-异戊基-2-异丁基琥珀酸二乙酯、2-苯基-2-正丁基琥珀酸二乙酯、2,2-二甲基琥珀酸二异丁酯、2-乙基-2-甲基琥珀酸二异丁酯、2-苄基-2异丙基琥珀酸二异丁酯、2-环己基甲基-2-异丁基琥珀酸二异丁酯、2-环戊基-2-正丁基琥珀酸二异丁酯、2,2-二异丁基琥珀酸二异丁酯、2-环己基-2-乙基琥珀酸二异丁酯、2-异丙基-2-甲基琥珀酸二异丁酯、2-十四烷基-2-乙基琥珀酸二异丁酯、2-异丁基-2-乙基琥珀酸二异丁酯、2-(1-三氟甲基-乙基)-2-甲基琥珀酸二异丁酯、2-异戊基-2-异丁基琥珀酸二异丁酯、2-苯基-2-正丁基-琥珀酸二异丁酯、2,2-二甲基琥珀酸二新戊酯、2-乙基-2-甲基琥珀酸二新戊酯、2-苄基-2-异丙基琥珀酸二新戊酯、2-环己基甲基-2-异丁基琥珀酸二新戊酯、2-环戊基-2- 正丁基琥珀酸二新戊酯、2,2-二异丁基琥珀酸二新戊酯、2-环己基-2-乙基琥珀酸二新戊酯、2-异丙基-2-甲基琥珀酸二新戊酯、2-十四烷基-2-乙基琥珀酸二新戊酯、2-异丁基-2-乙基琥珀酸二新戊酯、2-(1-三氟甲基-乙基)-2-甲基琥珀酸二新戊酯、2-异戊基-2-异丁基琥珀酸二新戊酯、2-苯基-2-正丁基琥珀酸二新戊酯、2,3-双(三甲基甲硅烷基)琥珀酸二乙酯、2,2-仲丁基-3-甲基琥珀酸二乙酯、2-(3,3,3,三氟丙基)-3-甲基琥珀酸二乙酯、2,3-双(2-乙基-丁基)琥珀酸二乙酯、2,3-二乙基-2-异丙基琥珀酸二乙酯、2,3-二异丙基-2-甲基琥珀酸二乙酯、2,3-二环己基-2-甲基琥珀酸二乙酯、2,3-二苄基琥珀酸二乙酯、2,3-二异丙基琥珀酸二乙酯、2,3-双(环己基甲基)琥珀酸二乙酯、2,3-二-叔丁基琥珀酸二乙酯、2,3-二异丁基琥珀酸二乙酯、2,3-二新戊基琥珀酸二乙酯、2,3-二异戊基琥珀酸二乙酯、2,3-(1-三氟甲基-乙基)琥珀酸二乙酯、2,3-十四烷基琥珀酸二乙酯、2,3-芴基琥珀酸二乙酯、2-异丙基-3-异丁基琥珀酸二乙酯、2-叔丁基-3-异丙基琥珀酸二乙酯、2-异丙基-3-环己基琥珀酸二乙酯、2-异戊基-3-环己基琥珀酸二乙酯、2-十四烷基-3-环己基甲基琥珀酸二乙酯、2-环己基-3-环戊基琥珀酸二乙酯、2,3-二乙基-2-异丙基琥珀酸二异丁酯、2,3-二异丙基-2-甲基琥珀酸二异丁酯、2,3-二环己基-2-甲基琥珀酸二异丁酯、2,3-二苄基琥珀酸二异丁酯、2,3-二异丙基琥珀酸二异丁酯、2,3-双(环己基甲基)琥珀酸二异丁酯、2,3-二叔丁基琥珀酸二异丁酯、2,3-二异丁基琥珀酸二异丁酯、2,3-二新戊基琥珀酸二异丁酯、2,3-二异戊基琥珀酸二异丁酯、2,3-(1-三氟甲基-乙基)琥珀酸二异丁酯、2,3-十四烷基琥珀酸二异丁酯、2,3-芴基琥珀酸二异丁酯、2-异丙基-3-异丁基琥珀酸二异丁酯、2-叔丁基-3-异丙基琥珀酸二异丁酯、2-异丙基-3-环己基琥珀酸二异丁酯、2-异戊基-3-环己基琥珀酸二异丁酯、2-十四烷基-3-环己基甲基琥珀酸二异丁酯、2-环己基-3-环戊基琥珀酸二异丁酯、2,3-双(三甲基甲硅烷基)琥珀酸二新戊酯、2,2-仲丁基-3-甲基琥珀酸二新戊酯、2-(3,3,3-三氟丙基)-3-甲基琥珀酸二新戊酯、2,3-双(2-乙基-丁基)琥珀酸二新戊酯、2,3-二乙基-2-异丙基琥珀酸二新戊酯、2,3-二异丙基-2-甲基琥珀酸二新戊酯、2,3-二环己基-2-甲基琥珀酸二新戊酯、2,3-二苄基琥珀酸二新戊酯、2,3-二异丙基琥珀酸二新戊酯、2,3-双(环己基甲基)琥珀酸二新戊酯、2,3-二叔丁基琥珀酸二新戊酯、2,3-二异丁基琥珀酸二新戊酯、2,3-二新戊基琥珀酸二新戊酯、2,3-二异戊基琥珀酸二新戊酯、2,3-(1-三氟甲基-乙基)琥珀酸二新戊酯、2,3-十四烷基琥珀酸二新戊酯、2,3-芴基琥珀酸二新戊酯、2-异丙基-3-异丁基琥珀酸二新戊酯、2-叔丁基-3-异丙基琥珀酸二新戊酯、2-异丙基-3-环己基琥珀酸二新戊酯、2-异戊基-3-环己基琥珀酸二新戊酯、2-十四烷基-3-环己基甲基琥珀酸二新戊酯、2-环己基-3-环戊基琥珀酸二新戊酯。
进一步，优选的内给电子体为邻苯二甲酸二正丁酯、邻苯二甲酸二异丁酯、2,4-戊二醇二苯甲酸酯、3,5-庚二醇二苯甲酸酯、2,3-二异丙基琥珀酸二乙酯、2,3-二异丙基琥珀酸二异丁酯、2,3-二异丙基琥珀酸二正丁酯、2,3-二异丙基琥珀酸二甲基酯、2,2-二甲基琥珀酸二异丁酯、2-乙基-2-甲基琥珀酸二异丁酯、2-乙基-2-甲基琥珀酸二乙酯、2-异丙基-2-异戊基-1,3-二甲氧基丙烷、9,9-二甲氧基甲基芴、乙二醇二丁醚中的至少一种。
根据本发明，所述内给电子体的加入量无特殊要求，为本领域常规加入量即可。优选地，所述内给电子体与卤化镁的摩尔比为0.001-1:1，优选的为0.01-1:1。
在第四方面，本发明提供了一种烯烃聚合用固体催化剂组分的制备方法，包括：
方法1：至少一种内给电子体在上述镁基固体物的制备过程中加入，得到所述烯烃聚合用固体催化剂组分；
或方法2：至少一种内给电子体在上述镁基固体物的制备过程中加入，析出的固体物继续与至少一种内给电子体接触，得到所述烯烃聚合用固体催化剂组分；
或方法3：至少一种内给电子体与上述镁基固体物接触，得到所述烯烃聚合用固体催化剂组分。
根据本发明，所述方法1和方法2中内给电子加入位置可以是在所述镁基固体物的制备过程中的任意位置，可以为整体或者分批加入。
根据本发明，所述方法1和方法2的内给电子加入的位置，包括可以是整体或者部分加入到步骤S1的含镁元素均匀溶液之中；可以是整体或者部分在步骤S2的混合物形成后以及步骤S3的固化升温析出的过程中加入。
在第五方面，本发明提供了一种烯烃聚合用催化剂体系，包括：
(1)上述的固体催化剂组分；
(2)烷基铝化合物；以及
任选地(3)外给电子体。
在本发明的一些优选的实施方式中，所述烷基铝化合物中的铝与所述固体催化剂组分中的钛的摩尔比为(5-5000):1，优选(20-800):1。
在本发明的一些优选的实施方式中，以铝计所述烷基铝化合物和所述外给电子体化合物的摩尔比为(0.1-500):1，优选(1-100):1，更优选(3-100):1。
根据本发明的一些优选的实施方式，所述烷基铝化合物通式为AlR nX 3-n所示的化合物，其中，R为氢、碳原子数为1-20的烃基，特别是烷基、芳烷基、芳基等；X为卤素，n为1-3的整数。具体地可以为三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氢二乙基铝、 一氢二异丁基铝、一氯二乙基铝、一氯二异丁基铝、倍半乙基氯化铝和二氯乙基铝中的至少一种，优选为三乙基铝和/或三异丁基铝。
根据本发明，外给电子体化合物优选为有机硅化合物。在一些实施方案中，所述有机硅化合物的通式为R nSi(OR y) 4-n，式中n为0-3的整数，R为烷基、环烷基、芳基、卤化烷基、卤素和氢原子中的一种或多种，R y为烷基、环烷基、芳基和卤化烷基中的一种或多种；优选所述有机硅化合物为三甲基甲氧基硅烷、三甲基乙氧基硅烷、三甲基苯氧基硅烷、二甲基二甲氧基硅烷、二甲基二乙氧基硅烷、甲基叔丁基二甲氧基硅烷、二苯基二甲氧基硅烷、二苯基二乙氧基硅烷、二环已基二甲氧基硅烷、苯基三甲氧基硅烷、苯基三乙氧基硅烷、乙烯基三甲氧基硅烷、甲基环己基二甲氧基硅烷、二环戊基二甲氧基硅烷、2-乙基哌啶基-2-叔丁基二甲氧基硅烷、(1,1,1-三氟-2-丙基)-2-乙基哌啶基二甲氧基硅烷和(1,1,1-三氟-2-丙基)-甲基二甲氧基硅烷中的至少一种，优选为甲基环己基二甲氧基硅烷。
在第六方面，本发明提供了一种上述的固体催化剂组分或上述的催化剂体系在烯烃聚合反应中的应用。
根据本发明，本发明的烯烃聚合催化剂可以用于烯烃的均聚合，也可以用于将多种烯烃进行共聚合。所述烯烃中的至少一种为由式CH 2＝CHR表示的烯烃，其中R是氢或C 1-C 6的直链或支链烷基。所述由式CH 2＝CHR表示的烯烃的具体实例可以包括：乙烯、丙烯、1-正丁烯、1-正戊烯、1-正己烯、1-正辛烯和4-甲基-1-戊烯。优选情况下，所述由式CH 2＝CHR表示的烯烃为乙烯、丙烯、1-正丁烯、1-正己烯和4-甲基-1-戊烯中的一种或多种。更优选地，所述由式CH 2＝CHR表示的烯烃为丙烯，或丙烯与其他烯烃的共聚合。
在一些优选的实施方案中，本发明提供了一种上述的固体催化剂组分或上述的催化剂体系在丙烯聚合反应中的应用。
在第七方面，本发明提供了一种烯烃聚合方法，包括使烯烃在上述的固体催化剂组分或上述的催化剂体系的存在下进行聚合反应。
根据本发明，烯烃的聚合按照已知方法进行，在液相单体或单体于惰性溶剂中的溶液的液相中，或在气相中，或通过在气液相中的组合聚合工艺进行操作。
在本发明的一些优选的实施方式中，所述聚合反应的条件包括：温度为0℃-150℃，优选为60℃-100℃；压力为0.1MPa-10.0MPa。
本发明的有益效果至少在于：固体催化剂组分具有独特多峰孔分布特征，采用本发明催化剂用于丙烯聚合制备的聚合物具有较宽分子量分布。
附图简要说明
图1显示了实施例1制备的镁基固体物采用氮气吸附法测试并运用NLDFT算法计算的孔径分布图。
图2显示了实施例2制备的镁基固体物采用氮气吸附法测试并运用NLDFT算法计算的孔径分布图。
图3显示了实施例3制备的镁基固体物采用氮气吸附法测试并运用NLDFT算法计算的孔径分布图。
图4显示了对比例1制备的镁基固体物采用氮气吸附法测试并运用NLDFT算法计算的孔径分布图。
图5显示了实施例7制备的催化剂组分采用氮气吸附法测试并运用NLDFT算法计算的孔径分布图。
图6显示了对比例5制备的催化剂组分采用氮气吸附法测试并运用NLDFT算法计算的孔径分布图。
图7显示了实施例1制备的镁基固体物的显微镜图。
实施例
以下通过实施例对本发明进行详细说明，但本发明的保护范围并不限于下述说明。
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购途径获得的常规产品。
下述实施例中，涉及的测试方法如下：
1、催化剂中钛含量的测定：采用紫外-可见分光光度计722型进行比色测定；
2、催化剂中镁含量的测定：采用镁离子和EDTA络合滴定法测得；
3、含镁载体或催化剂粒度分布：根据激光衍射法测量，采用马尔文2000粒度分析仪，正己烷分散剂；
4、催化剂中内给电子体化合物含量测定：用催化剂干粉经稀酸(如稀硫酸等)分解后，用萃取剂(如己烷等)萃取其中的内给电子体化合物，采用色谱法测定；醚类给电子体采用Agilent 6890N气相色谱仪测定；酯类给电子体采用Waters600E高效液相色谱仪测定。
5、含镁载体或催化剂比表面和孔径分布：用美国Micromeritics公司ASAP2460比表面与孔隙度分析仪采用氮气吸附法测定；
6、聚合物堆积密度(BD)的测定参照ASTM D1895-96标准；
7、丙烯聚合物等规度指数(II)采用庚烷抽提法测定：2克干燥的聚合物样品，放在 抽提器中用沸腾庚烷抽提6小时后，将剩余物干燥至恒重，所得的聚合物重量(g)与2(g)的比值即为等规度；
8、聚合物分子量分布MWD(MWD＝Mw/Mn)：采用PL-GPC220以三氯苯为溶剂在150℃下的测定(标样：聚苯乙烯，流速：1.0ml/min，柱子：3xPlgel 10μm MlxED-B 300x7.5nm)；
9、聚合物的熔体流动指数(MI)：采用德国GOTTFERT公司的MI-4型熔体流动指数测定仪进行测定，根据GB/T 3682.1-2018标准测定。
下面给出的实施例是为了说明本发明，而不是对本发明的限制。
实施例1
实施例1用于说明镁基固体物的制备。
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、249mL甲苯、10.75g环氧氯丙烷、70.7g磷酸三丁酯，在60℃温度条件下，在300rmp的搅拌条件下维持2小时。然后加入2.56g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到14℃。提前将2.1g表面活性剂(马来酸酐-甲基丙烯酸酯共聚物的醇解物，可由广州锐圣研化工科技有限公司以商品名T632商购获得)与220ml食品级100号的白油(运动黏度(40℃)在100mm 2/s)混合均匀形成混合物A。40min内同时开始分别滴入151ml四氯化钛和混合物A。滴加完毕后，在400rmp转速下搅拌1小时。随后在3小时内逐渐升温到80℃。过滤母液，固体用热甲苯洗涤2次后，再用己烷洗涤2次，干燥得到含钛的镁基固体物。所得固体物的平均粒径D50是34.2μm，SPAN值(即(D90-D10)/D50)为0.60，钛含量是2.0％(重量)，Mg含量是20.3％(重量)。固体物的显微镜照片见于图7。
该固体物采用氮气吸附法测试并运用NLDFT算法的孔径分布图于图1所示。从图1可见其孔径分布显示为多峰孔径分布，孔径在10nm以下至少包含一个峰孔径分布，并且同时孔径在10nm以上还至少包含另一个峰的孔径分布。
采用氮气吸附法测得固体物孔径数据见于表1。
实施例2
实施例2用于说明镁基固体物的制备。
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、194ml甲苯、10.75g环氧氯丙烷、75.12磷酸三丁酯，在60℃温度条件下，在搅拌下维持2小时。然后加入3.2g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到24℃，加入40ml甲苯稀释的2.5g表面活性剂(马来酸酐-甲基丙烯酸酯共聚物的醇解物，可由广州锐圣研化工科技有限公司以商品名T632商购获得)，继续搅拌1小时。40min内同时开始分别滴入136ml 四氯化钛和240ml食品级100号的白油(运动黏度(40℃)在100mm2/s)。滴加完毕后，在400rmp转速下搅拌1小时。随后逐渐升温到80℃。过滤母液，固体用热甲苯洗涤2次后，再用己烷洗涤2次，干燥得到含钛的镁基固体物。所得固体物的平均粒径D50是62.1μm，SPAN值0.63，钛含量是2.3％(重量)，Mg含量是21.1％(重量)。
该固体物采用氮气吸附法测试并运用NLDFT算法的孔径分布图于图2所示。从图2可见其孔径分布显示为多峰孔径分布，孔径在10nm以下至少包含一个峰孔径分布，并且同时孔径在10nm以上还至少包含另一个峰的孔径分布。
采用氮气吸附法测得固体物孔径数据见于表1。
实施例3
采用实施例1的方法制备镁基固体物，不同之处在于所用的环氧氯丙烷量改为14.2g，磷酸三丁酯的量改为53.2g，甲苯量改为197ml，四氯化钛量改为133ml,加入邻苯二甲酸酐，在60℃再维持1小时后，将溶液降温到8℃。所得固体物钛含量是2.1％(重量)，Mg含量是21.2％(重量)。
该固体物采用氮气吸附法测试并运用NLDFT算法的孔径分布图于图3所示。从图3可见其孔径分布显示为多峰孔径分布，孔径在10nm以下至少包含一个峰孔径分布，并且同时孔径在10nm以上还至少包含另一个峰的孔径分布。
采用氮气吸附法测得固体物孔径数据见于表1。
实施例4
采用实施例1的方法制备镁基固体物，不同之处在于所用的环氧氯丙烷量改为7.2g，磷酸三丁酯的量改为65.1g，并且加入磷酸三丁酯后继续加入2.2g乙醇，白油量改为184ml，四氯化钛量改为203ml,加入邻苯二甲酸酐，在60℃再维持1小时后，将溶液降温到0℃。所得固体物钛含量是3.6％(重量)，Mg含量是20.2％(重量)。
采用氮气吸附法测得固体物孔径数据见于表1，其孔径分布显示为多峰孔径分布。
实施例5
采用实施例1的方法制备含钛镁基固体物，不同之处在于所用的环氧氯丙烷量10.75g，磷酸三丁酯的量改为33.2g，甲苯量改为72ml，白油量改为120ml，四氯化钛量改为112ml，加入邻苯二甲酸酐，在60℃再维持1小时后，将溶液降温到0℃，所得固体物钛含量是2.6％(重量)，Mg含量是21.4％(重量)。
采用氮气吸附法测得固体物孔径数据见于表1，其孔径分布显示为单峰孔径分布。
对比例1
采用专利CN107207657A中实施例1的制备方法制备的固体物，不同之处将表面活性剂VISCOPLEX改为本发明实施例1所用表面活性剂。所得固体物的平均粒径D50是27.1μm，SPAN值1.24，钛含量是2.1％(重量)，Mg含量是20.2％(重量)。
采用氮气吸附法测得固体物孔径数据见于表1，其孔径分布图于图4所示，显示为单峰孔径分布。图4为NLDFT算法孔径分布图。
对比例2
采用专利CN1097597C中实施例1的制备方法制备的固体物，不同之处在于不加入给电子体邻苯二甲酸二异丁酯以及将后续步骤改为，析出固体物后过滤母液，固体用热甲苯洗涤2次后，再用己烷洗涤2次，干燥得到含钛的镁基固体物。所得固体物的平均粒径D50是24.1μm，SPAN值1.14，钛含量是2.3％(重量)，Mg含量是21.1％(重量)。
采用氮气吸附法测得固体物孔径数据见于表1，其孔径分布为单峰孔径分布。
表1
Figure PCTCN2021124050-appb-000002
注：NLDFT算法下孔径＜5nm的孔体积占比是指采用NLDFT算法得到的孔径＜5nm的孔体积与在该算法下计算的总孔体积的比值，其他表示方式的意思据此类推。表1给出孔体积是BJH算法孔体积。
实施例6
A、固体催化剂组分的制备
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、249mL甲苯、 10.75g环氧氯丙烷、70.7g磷酸三丁酯，在60℃温度条件下，在300rmp搅拌下维持2小时。然后加入2.5g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到15℃。提前将2.1g表面活性剂(马来酸酐-甲基丙烯酸酯共聚物的醇解物，可由广州锐圣研化工科技有限公司以商品名T632商购获得)与220mL食品级100号的白油(运动黏度(40℃)在100mm2/s)混合均匀形成混合物1。40min内同时开始分别滴入151mL四氯化钛和混合物1。滴加完毕后，在400rmp转速下搅拌1小时。随后在3小时内逐渐升温到80℃。加入3mL邻苯二甲酸二正丁酯给电子体，升温到85℃，恒温1小时。过滤，固体用热甲苯洗涤两次。再加入四氯化钛80mL和甲苯120mL在110℃恒温0.5小时并过滤，重复此操作。然后将所得固体用己烷洗涤5次后真空干燥得到烯烃聚合催化剂组分固体物。催化剂组分数据见于表3。
采用氮气吸附法测得固体物孔径数据见于表2。该催化剂的孔径分布为多峰孔径分布。
B、丙烯聚合
在一个5升高压反应釜中，经氮气充分置换后，在室温下加入5mL三乙基铝的己烷溶液(三乙基铝的浓度为0.5mmol/mL)、1mL环己基甲基二甲氧基硅烷(CHMMS)的己烷溶液(CHMMS的浓度为0.1mmol/mL)、10mL无水己烷和10mg实施例6的催化剂组分。引入1升标准状态下的氢气和1.15千克的液体丙烯。升温至70℃，在70℃下聚合反应1小时，反应结束后，将反应釜降温并停搅拌排出反应产物，得到烯烃聚合物，催化剂的聚合结果和聚合物数据见表3。
实施例7
A、固体催化剂组分的制备
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、272mL甲苯、9.76g环氧氯丙烷、78g磷酸三丁酯，在60℃温度条件下，在300rmp搅拌下维持2小时。然后加入3g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到10℃。提前将3.2g表面活性剂(马来酸酐-甲基丙烯酸酯共聚物的醇解物，可由广州锐圣研化工科技有限公司以商品名T632商购获得)与240mL食品级100号的白油(运动黏度(40℃)在100mm2/s)混合均匀形成混合物1。40min内同时开始分别滴入135mL四氯化钛和混合物1。滴加完毕后，在400rmp转速下搅拌2小时。随后在3小时内逐渐升温到85℃。升温过程中加入2,4-戊二醇二苯甲酸酯给电子体3mL，升温到85℃，恒温1小时。过滤，固体用热甲苯洗涤两次。再加入四氯化钛80mL和甲苯120mL在110℃恒温0.5小时并过滤，重复此操作。然后将所得固体用己烷洗涤5次后真空干燥得到烯烃聚合催化剂组分固体物。催化剂组分数据见于表3。
该固体物采用氮气吸附法测试并运用NLDFT算法的孔径分布图于图5所示。从图5可见其孔径分布显示为多峰孔径分布，孔径在10nm以下至少包含一个峰孔径分布，并且同时孔径在10nm以上还至少包含另一个峰的孔径分布。采用氮气吸附法测得固体物孔径数据见于表2。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
实施例8
A、固体催化剂组分的制备
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、211mL甲苯、11.5g环氧氯丙烷、68g磷酸三丁酯，在60℃温度条件下，在搅拌下维持2小时。然后加入2.5g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到0℃，加入9,9-二甲氧基甲基芴3g，继续搅拌60min。提前将2.5g表面活性剂(马来酸酐-甲基丙烯酸酯共聚物的醇解物，可由广州锐圣研化工科技有限公司以商品名T632商购获得)与260mL食品级100号的白油(运动黏度(40℃)在100mm 2/s)混合均匀形成混合物1。40min内同时开始分别滴入165mL四氯化钛和混合物1，滴加完毕后，在400rmp转速下搅拌1小时。随后在4小时内逐渐升温到85℃，恒温1小时。过滤，固体用热甲苯洗涤两次。再加入四氯化钛80mL和甲苯120mL在110℃恒温0.5小时并过滤，重复此操作。然后将所得固体用己烷洗涤5次后真空干燥得到烯烃聚合催化剂组分固体物。催化剂组分数据见于表3。
采用氮气吸附法测得固体物孔径数据见于表2。该催化剂的孔径分布为多峰孔径分布。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
实施例9
A、固体催化剂组分的制备
基本上与实施例6相同，不同之处仅在于环氧氯丙烷量改为14.2g，磷酸三丁酯的量改为53.2g，甲苯量改为197ml，四氯化钛量改为133ml，加入邻苯二甲酸酐，在60℃再维持1小时后，将溶液降温到8℃。催化剂组分数据见于表3。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为多峰孔径分布。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
实施例10
A、固体催化剂组分的制备
基本上与实施例6相同，不同之处在于所用的环氧氯丙烷量改为7.2g，磷酸三丁酯的量改为65.1g，并且加入磷酸三丁酯后继续加入2.2g乙醇，白油量改为184ml，四氯化钛量改为203ml,加入邻苯二甲酸酐，在60℃再维持1小时后，将溶液降温到0℃。催化剂组分数据见于表3。
采用氮气吸附法测得固体物孔径数据见于表2，其孔径分布显示为多峰孔径分布。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
实施例11
A、固体催化剂组分的制备
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、104g甲苯、10.5g环氧氯丙烷、70.0g磷酸三丁酯，1.5mL乙二醇二丁醚在60℃温度条件下，以300RMP的转速搅拌维持2小时。然后加入3.4g邻苯二甲酸酐，在60℃继续搅拌1小时。将溶液降温到14℃。提高搅拌到400RMP。提前将128.5g食品级100号白油(运动黏度(40℃)在100mm 2/s)和5.7g表面活性剂(T602，可由广州锐圣研化工科技有限公司商购获得)混合形成混合物1。在60min内同时将181.7mL四氯化钛和混合物1滴入溶液中。滴加完毕继续维持1小时，得到混合物2。逐渐升温到80℃。加入2-异丙基-2-异戊基-1,3-二甲氧基丙烷2.0mL，升温到85℃继续维持1小时。过滤清液后，固体物用200mL甲苯洗涤3次。加入120mL甲苯，80mL四氯化钛，90℃处理1小时，除去滤液。加入120mL甲苯，80mL四氯化钛，110℃处理1小时，除去滤液。再用200mL己烷重复洗涤4次后，得烯烃聚合催化剂组分固体物。催化剂物性数据见于表3。催化剂孔径数据见于表2。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
实施例12
A、固体催化剂组分的制备
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、104g甲苯、7.2g环氧氯丙烷、75.2g磷酸三丁酯，1.5mL 2-异丙基-2-异戊基-1,3-二甲氧基丙烷，在60℃ 温度条件下，以300RMP搅拌维持2小时。然后加入4.59g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到14℃。提高搅拌到400RMP。提前将128.5g食品级100号白油(运动黏度(40℃)在100mm 2/s)和5.7g表面活性剂(T602，可由广州锐圣研化工科技有限公司商购获得)混合形成混合物1。在60min内同时将81.7mL四氯化钛和混合物1滴入溶液中。滴加完毕继续维持1小时。逐渐升温到80℃并保持1小时。过滤清液后，固体物用200mL甲苯洗涤2次。加入160mL甲苯，40mL四氯化钛，和2-异丙基-2-异戊基-1,3-二甲氧基丙烷2.6mL，升温到85℃继续维持2小时。除去滤液，加入120mL甲苯，80mL四氯化钛，90℃处理1小时，除去滤液。加入120mL甲苯，80mL四氯化钛，110℃处理1小时，除去滤液。固体物再用200mL己烷重复洗涤5次后，得烯烃聚合催化剂组分固体物。催化剂物性数据见于表3。催化剂孔径数据见于表2。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
实施例13
A、固体催化剂组分的制备
在经过高纯氮气重复置换的反应釜中，依次加入10.86g无水氯化镁、104g甲苯、12.43g环氧氯丙烷、75.2g磷酸三丁酯，在60℃温度条件下，以300RMP搅拌维持2小时。然后加入4.59g邻苯二甲酸酐，在60℃再维持1小时。将溶液降温到14℃。提高搅拌到400RMP。提前将128.5g食品级100号白油(运动黏度(40℃)在100mm 2/s)和5.7g表面活性剂(T602，可由广州锐圣研化工科技有限公司商购获得)混合形成混合物1。在60min内同时将81.7mL四氯化钛和混合物1滴入溶液中。滴加完毕继续维持1小时。逐渐升温到80℃并保持1小时。过滤清液后，固体物用200mL甲苯洗涤2次。加入160mL甲苯，40mL四氯化钛，和2-异丙基-2-异戊基-1,3-二甲氧基丙烷3.6mL，升温到85℃继续维持2小时。除去滤液，加入120mL甲苯，80mL四氯化钛，90℃处理1小时，除去滤液。加入120mL甲苯，80mL四氯化钛，110℃处理1小时，除去滤液。固体物再用200mL己烷重复洗涤5次后，得烯烃聚合催化剂组分固体物。催化剂物性数据见于表3。催化剂孔径数据见于表2。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
对比例3
A、固体催化剂组分的制备
基本上与实施例6相同，不同之处在于所用的环氧氯丙烷量10.75g，磷酸三丁酯的量改为33.2g，甲苯量改为72ml，白油量改为120ml，四氯化钛量改为112ml，加入邻苯二甲酸酐，在60℃再维持1小时后，将溶液降温到0℃。催化剂组分数据见于表3。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为单峰孔径分布。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
对比例4
A、固体催化剂组分的制备
基本上与实施例6相同，不同之处在于所用的磷酸三丁酯的量改为38.8g。催化剂组分数据见于表3。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为单峰孔径分布。
B、丙烯聚合
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
对比例5
采用专利CN107207657A中实施1的制备方法制备的固体物，不同之处将表面活性剂VISCOPLEX改为实施例1所用表面活性剂。然后将固体物与260ml含20％四氯化钛的甲苯溶液和3ml邻苯二甲酸二正丁酯给电子体在85℃恒温1小时。过滤，固体用甲苯洗涤两次。再加入四氯化钛100毫升和甲苯150毫升在110℃恒温0.5小时并过滤，重复此操作。然后将所得固体用己烷洗涤5次后真空干燥得到烯烃聚合催化剂组分固体物。催化剂组分数据见于表3。
该固体物采用氮气吸附法测试并运用NLDFT算法的孔径分布图于图6所示。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为单峰孔径分布。
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
对比例6
采用专利CN1097597C中实施1的制备方法制备的固体物，不同之处在于将邻苯二甲酸二异丁酯改为9,9-二甲氧基甲基芴1.5g。催化剂组分数据见于表3。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为单峰孔径分布。
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
对比例7
采用专利CN1097597C中实施1的制备方法制备的固体物，不同之处在于所用的邻苯二甲酸二异丁酯改为2,4-戊二醇二苯甲酸酯1.5ml。催化剂组分数据见于表3。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为单峰孔径分布。
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
对比例8
采用专利CN1097597C中实施1的制备方法制备的固体物，不同之处在于所用的邻苯二甲酸二异酯改为2-异丙基-2-异戊基-1,3-二甲氧基丙烷1.5ml。催化剂组分数据见于表3。
采用氮气吸附法测得催化剂孔径数据见于表2。该催化剂的孔径分布为单峰孔径分布。
丙烯聚合方法同实施例6，催化剂聚合数据和聚合物数据见表3。
表2
Figure PCTCN2021124050-appb-000003
注：NLDFT算法下孔径＜5nm的孔体积占比是指采用NLDFT算法得到的孔径＜5nm的孔 体积与在该算法下计算的总孔体积的比值，其他表示方式的意思据此类推。表2给出孔体积是BJH算法孔体积。
表3
Figure PCTCN2021124050-appb-000004
*实施例11内给电子含量为2-异丙基-2-异戊基-1,3-二甲氧基丙烷的含量
由表1-3和图1-6的数据可看出，本发明获得的含钛的镁基固体物和氯化镁负载型烯烃聚合催化剂组分均具有多峰孔径分布特征，并且比表面积较高。而对比例所示的同为氯化镁负载型烯烃聚合催化剂则只具有单峰孔径分布特征。基于本发明催化剂用于丙烯聚合时，具有较高的聚合活性和较高立构定向能力，所制备的聚合物的分子量分布较宽。
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (15)

  1. 一种具有多峰孔分布的镁基固体物，其以卤化镁为载体且含有钛元素，并且，通过氮气吸附法测定，所述镁基固体物具有不低于50m 2/g的比表面积，并且所述镁基固体物的孔径分布在1nm-300nm的范围内，其中，在小于10nm的孔径范围和在不小于10nm的孔径范围，分别具有至少一个峰；优选地在小于10nm的孔径范围的峰的最可几孔径为2nm-8nm，优选为2nm-6nm；同时，在不小于10nm的孔径范围的峰的最可几孔径为15nm-200nm，优选为20nm-100nm，更优选为30nm-90nm。
  2. 权利要求1所述的镁基固体物，其特征在于，所述镁基固体物中，孔径小于10nm的孔的孔体积与孔径不小于10nm的孔的孔体积的比值为(0.1-20):1，优选为(0.25-15):1。
  3. 权利要求1或2所述的镁基固体物，其特征在于，孔径小于5nm的孔的孔体积占总孔体积的10％-90％，优选为15％-70％；孔径不小于30nm的孔的孔体积占总孔体积的5％-70％，优选为10％-60％。
  4. 一种权利要求1-3中任一项所述的镁基固体物的制备方法，包括：
    S1.使卤化镁与路易斯碱在有机溶剂中接触，形成含镁溶液；
    S2.使所述含镁溶液、惰性分散介质和路易斯酸接触，形成混合物；
    S3.在助析出剂和表面活性剂的存在下，使所述镁基固体物从所述混合物中析出，
    其中，步骤S1中，所述路易斯碱包括有机磷化合物，且以每摩尔卤化镁计，所述有机磷化合物的用量为1.5-10摩尔，优选2-5摩尔；更优选地，所述路易斯碱还包括有机环氧化合物；步骤S2中，所述路易斯酸包含钛化合物。
  5. 权利要求4所述的制备方法，其特征在于，步骤S1中，所述卤化镁的通式如式(1)所示：
    MgX 1 2  式(1)
    式(1)中，X 1为卤素，优选为氯、溴或碘，优选地，所述卤化镁为二氯化镁；和/或
    所述有机磷化合物选自式(2)或式(3)所示的化合物中的一种或多种：
    Figure PCTCN2021124050-appb-100001
    式(2)和式(3)中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自1-20个碳原子的直链或支链烷基、环烷基或芳香烃基及带有取代基的芳香烃基，优选地所述有机磷化合物为磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三戊酯、磷酸三苯酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丁酯和亚磷酸苯甲酯中的一种或多种；和/或
    所述有机溶剂选自芳香族烃类化合物和卤代烃类化合物中的一种或多种，优选为甲苯、乙苯、苯、二甲苯和氯苯中的一种或多种，更优选地，以每摩尔卤化镁计，所述有机溶剂的用量为1-40摩尔，优选为2-30摩尔。
  6. 权利要求4-5中任一项所述的制备方法，其特征在于，步骤S2中，所述惰性分散介质选自煤油、石蜡油、白油、凡士林油、甲基硅油、脂族和环脂族烃类中的一种或多种，优选为白油、己烷和癸烷中的一种或多种，更优选地以每克卤化镁计，所述惰性分散介质的用量为0.1g-300g，优选为1g-150g；和/或
    所述路易斯酸包括含钛化合物，所述含钛化合物的通式如式(4)所示：
    TiX 2 m(OR 1) 4-m  式(4)
    式(4)中，X 2为卤素，优选为氯、溴或碘，R 1为1-20个碳原子的烃基，m为1-4的整数，优选地所述含钛化合物选自四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、四乙氧基钛、一氯三乙氧基钛、二氯二乙氧基钛和三氯一乙氧基钛中的一种或多种，更优选地以每摩尔卤化镁计，所述含钛化合物的用量为0.5-25摩尔，优选为1-20摩尔。
  7. 权利要求4-6中任一项所述的制备方法，其特征在于，步骤S3中，所述助析出剂选自有机酸、有机酸酐、有机醚和有机酮中的一种或多种，优选为乙酸酐、邻苯二甲酸酐、丁二酸酐、顺丁烯二酸酐、均苯四甲酸二酐、醋酸、丙酸、丁酸、丙烯酸、甲基丙烯酸、丙酮、甲乙酮、二苯酮、甲醚、乙醚、丙醚、丁醚和戊醚中的一种或多种，更优选地以每摩尔卤化镁计，所述助析出剂的用量为0.01-1摩尔，优选为0.04-0.4摩尔；和/或
    所述表面活性剂选自高分子表面活性剂，优选自(甲基)丙烯酸烷基酯类聚合物和(甲基)丙烯酸烷基酯类的共聚物、马来酸酐聚合物的醇解物和马来酸酐类共聚物的醇解物中的一种或多种，更优选地以每克卤化镁计，所述表面活性剂的用量为0.01g-5g，优选为0.05g-1g。
  8. 一种具有多峰孔分布的烯烃聚合用固体催化剂组分，其包括：根据权利要求1-7中所述的镁基固体物和至少一种内给电子体。
  9. 权利要求8所述固体催化剂组分，其特征在于，通过氮气吸附法测定具有多个峰的孔径分布以及不低于50m 2/g的比表面积；其中所述固体物的多个峰的孔径分布情况为在1nm-10nm的孔径范围内具有至少第一个峰，同时在10nm-200nm的孔径范围内具有至少第 二个峰。
  10. 权利要求8-9所述的固体催化剂组分，其特征在于，所述固体物的多个峰的孔径分布情况为，在1nm-10nm的孔径范围内的峰的最可几孔径为2nm-8nm，进一步优选为2nm-6nm；在10nm-200nm的孔径范围内的峰的最可几孔径为15nm-200nm，优选为20nm-100nm，更优选为30nm-90nm。
  11. 权利要求8-10所述的固体催化剂组分，其特征在于，孔径小于5nm的孔的孔体积占总孔体积为10％-90％，优选为15％-70％；同时，孔径不小于30nm的孔的孔体积占总孔体积为5％-70％，优选为10％-60％。
  12. 权利要求8所述的固体催化剂组分，其中所述内给电子体选自酯、醚、酮、胺、硅烷的一种或多种，优选为一元或多元脂肪族羧酸酯、芳香族羧酸酯、二醇酯类化合物、二醚类化合物至少一种，优选为包括二元的脂肪族羧酸酯、芳香族羧酸酯、二元醇酯类和二醚类化合物中的至少一种，更优选包括邻苯二甲酸酯类、丙二酸酯类、琥珀酸酯类、戊二酸酯类、二醇酯类、二醚类、新戊酸酯或碳酸酯类中的至少一种。
  13. 一种权利要求8-12中任一项所述的烯烃聚合用固体催化剂组分的制备方法，包括：至少一种内给电子体在所述镁基固体物的制备过程中加入，或/和，至少一种内给电子体与所述镁基固体物接触，得到所述烯烃聚合用固体催化剂组分。
  14. 一种烯烃聚合用催化剂体系，包括：
    (1)权利要求8-12中任一项所述的固体催化剂组分；
    (2)烷基铝化合物；以及
    任选地(3)外给电子体。
  15. 一种权利要求8-12中任一项所述的固体催化剂组分或权利要求14所述的催化剂体系在烯烃聚合反应中、尤其是丙烯聚合反应中的应用。
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