WO2013075643A1 - Olefin polymerization catalyst, preparation method therefor, and application thereof - Google Patents

Olefin polymerization catalyst, preparation method therefor, and application thereof Download PDF

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WO2013075643A1
WO2013075643A1 PCT/CN2012/085049 CN2012085049W WO2013075643A1 WO 2013075643 A1 WO2013075643 A1 WO 2013075643A1 CN 2012085049 W CN2012085049 W CN 2012085049W WO 2013075643 A1 WO2013075643 A1 WO 2013075643A1
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alcohol
olefin polymerization
group
polymerization catalyst
catalyst
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PCT/CN2012/085049
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French (fr)
Chinese (zh)
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黄启谷
李凤娇
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北京化工大学
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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
    • 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
    • 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

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  • Olefin polymerization catalyst preparation method and application thereof
  • the present invention relates to the field of olefin polymerization catalysts and olefin polymerization, and in particular to a catalyst for the homopolymerization or copolymerization of olefins and a process for preparing the catalyst. Background technique
  • the olefin polymerization catalyst is the core of the polyolefin polymerization technology. From the development of the olefin polymerization catalyst, there are mainly two aspects in general: (1) development of a polyolefin resin catalyst capable of producing special properties or properties, such as Metallocene catalysts and non-post-expansion transition metal catalysts; (2) For the production of general-purpose polyolefin resins, on the basis of further improving the performance of the catalyst, the catalyst preparation process, reducing the catalyst cost, and developing environmentally friendly technologies To improve efficiency and enhance competitiveness. Before the 1980s, the focus of research on polyethylene catalysts was to pursue catalyst efficiency. After nearly 30 years of efforts, the catalytic efficiency of polyethylene catalysts was increased by orders of magnitude, thereby reducing the production process of polyolefins and reducing energy consumption and material consumption. .
  • the Ziegler-Natta catalyst has been around for 60 years. Although there have been polyolefin catalysts such as metallocene and non-metallocene, there are many industrialization problems, such as expensive catalysts and difficulties in the loading of the main catalyst. Wait. Therefore, in terms of current industrial production and market share, the traditional ZN catalyst will remain the dominant player in the field of olefin polymerization for some time to come. In recent years, ZN catalyst products at home and abroad have emerged in an endless stream, and catalyst stability and polymerization catalytic activity have also been continuously improved. However, there are still deficiencies in hydrogen sensitivity, control of catalyst particle regularity and particle size distribution.
  • Patent 96106647.4 X discloses an olefin polymerization catalyst and a process for the preparation thereof, which are prepared by dissolving a carrier MgCl 2 in a mixture of an alcohol and an alkane to form a liquid MgCl 2 alcohol adduct, such a liquid MgCl 2 alcohol adduct. Contact with TiCl 4 gives an olefin polymerization catalyst.
  • Patent 200480008242.X discloses an olefin polymerization catalyst and a preparation method thereof, wherein a carrier MgCl 2 is directly dissolved in ethanol to prepare a MgCl 2 alcohol adduct, and then TiCl 4 is supported on a MgCl 2 alcohol adduct. An olefin polymerization catalyst is added to the alcohol having a carbon number of less than 6 in the preparation of the MgCl 2 alcohol adduct.
  • This patent finds that during the preparation of the catalyst, two or more alcohols having different carbon numbers are added, an organic alcohol ether compound is added, an organosilicon compound is added, a liquid MgCl 2 alcohol adduct is prepared, and then TiCl is added. 4 Contact with the liquid MgCl 2 alcohol adduct to obtain an olefin polymerization catalyst which can improve the particle morphology of the solid procatalyst and the hydrogen modulating property of the catalyst catalyzed olefin polymerization.
  • the olefin polymerization catalyst provided by the invention has good particle shape and uniform particle size distribution; excellent hydrogen hydrogenation performance of the catalyst; high catalyst loading and high catalyst activity; good polymer particle morphology, high bulk density and less fine powder; Slurry polymerization process, gas phase polymerization process or combined polymerization process; the main catalyst preparation process is simple, requires low equipment, low energy consumption and small environmental pollution. Summary of the invention
  • An object of the present invention is to provide a catalyst and a catalyst preparation method for olefin polymerization or copolymerization of ethylene and a comonomer.
  • the olefin polymerization provided by the present invention or a spherical catalyst in which ethylene is copolymerized with a comonomer is composed of a main catalyst and a cocatalyst; the main catalyst is composed of a magnesium support, a transition metal compound, an alcohol of less than C5 or equal to C5.
  • the composition of the alcohol, the organosilicon compound and the organic alcohol ether compound greater than C5; the molar ratio of the magnesium halide, the transition metal halide, the alcohol smaller than C5, the alcohol larger than C5 and the organosilicon compound is: 1 : ( 1-40 ) : ( 0.1-5): (0.01-10): (0.01-10);
  • the mass ratio of magnesium halide to organic alcohol ether compound is: 100: (0.1-20).
  • the relationship between the amount of the main catalyst and the cocatalyst is as follows: The molar ratio of the transition metal halide to the cocatalyst in the main catalyst is 1: (10-500).
  • magnesium dichloride Specifically selected from the group consisting of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium oxychloride, magnesium oxychloride, magnesium propoxide, magnesium butoxide, magnesium phenoxide And at least one of ethoxy magnesium, magnesium isopropoxide, magnesium butoxide, magnesium isopropoxide chloride, butyl magnesium chloride, and the like.
  • magnesium dichloride is preferred.
  • the transition metal halide is selected from at least one of the compounds of the formula (2) which is M(Rl)4-mXm, wherein M is Ti, Zr, Hf, Fe, Co, Ni or the like; X is a halogen atom selected from CI, Br, F; m is an integer from 0 to 4; R1 is selected from an aliphatic hydrocarbon group of CI ⁇ C20, a fatty alkoxy group of CI ⁇ C20, and a cyclopentane of CI ⁇ C20.
  • the base group and its derivatives, the aromatic hydrocarbon group of C1 ⁇ C20, COR; or COOR, R; are aliphatic groups having C1 ⁇ C10 or aromatic groups having C1 ⁇ C10.
  • R1 may be specifically selected from the group consisting of: mercapto, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, isobutyl, tert-butyl, isopentyl, tert-amyl , 2-ethylhexyl, phenyl, zekeyl, o-nonylphenyl, m-nonylphenyl, p-nonylphenyl, o-sulfophenyl, decanoyl, acetyl or benzoyl, etc. At least one of them.
  • the transition metal halides such as Ti, Zr, Hf, Fe, Co, Ni, etc., specifically selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, Monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, n-butyl titanate, isopropyl titanate, decyloxytitanium trichloride, dibutoxydichloride A mixture of one or more of titanium, tributoxytitanium chloride, tetraphenoxytitanium, monochlorotriphenoxytitanium, dichlorodiphenoxytitanium, and trichloromonophenoxytitanium. Among them, titanium tetrachloride is preferred.
  • the molar ratio of the transition metal compound to the magnesium oxide is
  • an alcohol smaller than C5 or equal to C5 means an alcohol having a carbon number of 5 or less.
  • the alcohol less than C5 or equal to C5 is a fatty alcohol having a carbon number of less than or equal to 5, preferably ethanol, decyl alcohol, propanol, butanol or pentanol or any combination thereof, more preferably ethanol.
  • the molar ratio of the alcohol less than C5 to the magnesium halide is preferably (0.1-5): 1.
  • the addition of an alcohol having less than C5 or equal to C5, especially ethanol can significantly improve the hydrogen-adjusting properties of the catalyst.
  • an alcohol larger than C5 means an alcohol having a carbon number of more than 5.
  • the alcohol larger than C5 is a fatty alcohol having 6 to 20 carbon atoms or an alicyclic alcohol or an aromatic alcohol, preferably a fatty alcohol, and among the fatty alcohols, heptanol, isooctanol, octanol, decyl alcohol, hydrazine are preferred. Alcohol, undecyl alcohol, decadiol, tridecyl alcohol, tetradecanol, pentadecyl alcohol or cetyl alcohol or any combination thereof, more preferably isooctanol.
  • the molar ratio of the alcohol larger than C5 to the magnesium halide is preferably (0.01-10): 1.
  • the organosilicon compound is selected from the group consisting of diethoxyisopropoxy tert-butoxysilane, triisopropoxy tert-butoxysilane, diisopropoxydi-tert-butoxysilane, diethoxycyclohexyloxy Tert-butoxysilane, diethoxyphenoxy-tert-butoxysilane, monoethoxydiisopropoxy-tert-butoxysilane, ethoxyisopropoxy-tert-butoxycyclohexyloxysilane , tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, ethyltrimethoxysilane, ethyltriethoxy Silane, mercaptotrimethoxysilane, mercaptotriethoxysi
  • the organic alcohol ether compound is characterized in that the terminal group is a hydroxyl group selected from the group consisting of the general formula (3) HO(CH2)f O(CH2)nR2; wherein, f is an integer from 1 to 20, preferably 1 to 15; n is an integer of 1 to 10, preferably 1 to 6.
  • R is selected from the group consisting of an aliphatic hydrocarbon group of C1 to C30, a cycloalkyl group of C3 to C30, an aromatic hydrocarbon group of C6 to C30, and a heterocycloalkyl group of C2 to C30.
  • ethylene glycol monoterpene ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, propylene glycol monoethyl ether, butanediol monopropyl ether, 2-( 2 -cyclopentane) Ethyl ethoxy)ethanol, 3-( 2 -cyclohexylethoxy)propanol, 2-(5-phenylpentyloxy)ethanol, 4- (3-(caiyl)propoxy)butanol, 2- (3-Ethoxyethylpropoxy)ethanol, 2- ( 2 -furylethoxy)ethanol, 3-(3-pyridylpropoxy)propanol.
  • the mass ratio of the magnesium halide to the organic alcohol ether compound is: 100: (0.1 - 20).
  • One of the features of the present invention is that two or more alcohols having different carbon numbers are added during the preparation of the solid procatalyst, that is, an alcohol smaller than C5 or equal to C5 and an alcohol larger than C5, which is less than C5.
  • the alcohol equal to or greater than C5 is a fatty alcohol having a carbon number of less than or equal to 5, and is selected from the group consisting of ethanol, decyl alcohol, propanol, butanol or pentanol or any combination thereof, preferably ethanol.
  • the molar ratio of the alcohol to the magnesium halide of less than C5 or equal to C5 is preferably (0.3-5): 1; the alcohol larger than C5 is a fatty alcohol having a carbon number of C6 - C20 or an alicyclic alcohol or an aromatic alcohol, preferably a fat. Alcohol, a fatty alcohol selected from heptyl alcohol, isooctanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, decadiol, tridecyl alcohol, tetradecanol, pentadecyl alcohol or cetyl alcohol or any combination thereof, preferably Isooctanol.
  • the molar ratio of the alcohol larger than C5 to the magnesium halide is preferably (0.01 - 10): 1.
  • the addition of an alcohol less than C5 or equal to C5, especially ethanol, can significantly improve the hydrogen regulation performance of the catalyst.
  • One of the features of the present invention is that an organic alcohol ether compound repairing agent is added during the preparation of the solid procatalyst to improve the morphology and particle size distribution of the catalyst particles.
  • the method for preparing an olefin polymerization catalyst provided by the present invention comprises the following steps:
  • step 3 Adding a transition metal halide to the system obtained in step 2) at -25 to 30 ° C, after the addition, reacting at -25 to 30 ° C for 0.5-5 h, and then heating the system to 20-150 ° C, preferably 50-120 ° C, reaction 0.5-5 h, during the heating process, the solid particles gradually precipitated, after the reaction is finished, the product is washed 4-6 times with toluene or n-hexane, the unreacted matter is removed by filtration, and dried under vacuum.
  • the powdery solid procatalyst has a vacuum drying temperature of 40 ° C to 130 ° C, preferably 50 ° C to 100 ° C; and a vacuum drying time of 0.5 hours to 5 hours, preferably 1 hour to 4 hours.
  • the organic solvent is selected from the group consisting of C 5 ⁇ C 15 saturated hydrocarbons, C 5 ⁇ C 10 alicyclic hydrocarbons, C 6 ⁇ C 15 aromatic hydrocarbons or C 3 ⁇ d.
  • the saturated heterocyclic hydrocarbon is preferably anthracene, diphenyl, hexane, heptane, octane, decane or tetrahydrofuran, or a mixed solvent thereof.
  • the olefin polymerization catalyst provided by the present invention also requires a cocatalyst composition.
  • the cocatalyst is a common organoaluminum compound, preferably triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, ethylachlorodiethylaluminum, mercaptoaluminoxane MAO, etc.; moles of catalyst and cocatalyst The ratio is 1: 10-500.
  • the olefin polymerization catalyst provided by the present invention is as follows: It can be used as an ethylene polymerization or propylene polymerization or a copolymerization catalyst of ethylene (or propylene) and an ⁇ -olefin, wherein the ⁇ -olefin is selected from C 3 ⁇
  • C 20 olefin preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-mercapto-1-butene, cyclopentene, 4-mercapto-1-pentane Alkene, 1,3-butadiene, isoprene, styrene, mercaptostyrene, and the like.
  • the olefin polymerization catalyst provided by the present invention has the following beneficial effects:
  • the object of the present invention is to provide an olefin copolymerization catalyst with good particle morphology and a spherical shape; excellent hydrogen-tuning performance of the catalyst; high catalyst activity; suitable for slurry process, gas phase polymerization process or combined polymerization process; Single, low requirements on equipment and low environmental pollution.
  • n-decane 20 ml was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 70 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
  • the system was lowered to -10 ° C, 20 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 100 ° C for 3 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 10 ° C, 40 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h.
  • the system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stop stirring, let stand, stratify, filter, wash twice with hexane (30 each time) ML), after drying at 70 ° C for 2 hours under vacuum, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h.
  • n-decane 20 ml was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 70 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 100 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
  • n-decane 20 ml was added to the reactor at 20 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and vacuum dried at 60 ° C for 3 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
  • Embodiment 8 [0042] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 4 ml of ethanol, 6 ml of decyl alcohol, and the mixture is heated to 110 ° C for 2 h, and the solid is completely dissolved. A homogeneous solution. After cooling to 50 ° C, 5 ml of diethoxyisopropoxy tert-butoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence for 3 h.
  • n-decane 20 ml was added to the reactor at 15 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 ° C for 4 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
  • n-decane 20 ml was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 110 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
  • n-decane 20 ml was added to the reactor at 10 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 120 ° C for 2 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. .
  • n-decane 20 ml was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 2 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 ° C for 4 hours to obtain a powdery solid with good fluidity, particle size distribution and spherical shape. catalyst.
  • Example 15 [0056] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of ethanol, 6.5 ml of isooctanol, and the mixture is heated to 120 ° C for 0.5 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 6 ml of succinate was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h.
  • the stirring was stopped, allowed to stand, layered, filtered, washed with hexane four times (30 ml each time), and dried under vacuum at 60 ° C for 2 hours to obtain a powdery solid catalyst.
  • the MgCl 2 alcohol adduct precipitates a solid at a lower temperature.
  • the main catalyst has a poor particle morphology.
  • Ethylene polymerization After fully replacing the 2 liter stainless steel autoclave with nitrogen, the main catalyst component component 20 mg, dehydrated hexane 1000 ml, and the cocatalyst AlEt 3 solution 1.17 ml (2 mmol/ml) were sequentially added to the kettle. After heating to 80 °C, it is filled with hydrogen 0.28 MPa, charged with ethylene to 0.73 MPa, and reacted at constant pressure for 2 h.
  • Ethylene copolymerization After fully replacing the 2 liter stainless steel autoclave with nitrogen, the main catalyst component 20 mg, dehydrated hexane 1000 ml, AlEt 3 solution 1.17 ml (2 mmol/ml) were added to the kettle in turn, and added. Ml 1-self woman. After heating to 80 °C, it was charged with 0.28 MPa of hydrogen, charged with ethylene to 0.73 MPa, and reacted at constant pressure for 2 h.

Abstract

An Olefin polymerization catalyst, a preparation method therefor, and an application thereof belong to the field of Olefin polymerization catalyst and olefin polymerization. The Olefin polymerization catalyst is formed of a primary catalyst and a cocatalyst. The primary catalyst is formed of a magnesium halide carrier, transition metal halide, alcohol with 5 or less carbon atoms, alcohol with more than 5 carbon atoms, an organic silicon compound, and an organic alcohol ether compound. A molar ratio of the magnesium halide, to the transition metal halide, to the alcohol with 5 or less carbon atoms, to the alcohol with more than 5 carbon atoms, and to the organic silicon compound is 1:(1-40):(0.1-5):(0.01-10):(0.01-10). A mass ratio of the magnesium halide to the organic ether compound is 100:(0.1-20). The cocatalyst is an organic aluminum compound. The particles of the catalyst of the present invention have a good shape and are spherical. The catalyst has high activity and desirable hydrogen regulation performance, is applicable to a slurry polymerization process, a gas phase polymerization process, or a combined polymerization process.

Description

烯烃聚合催化剂及制备方法和应用  Olefin polymerization catalyst, preparation method and application thereof
[0001]本申请要求了 2011年 11月 26日提交的、 申请号为 201110382706.5、 发明名称为 "烯烃聚合催化剂及制备方法和应用"的中国专利申请的优先权， 其全部内容通过引用结合在本申请中。 技术领域 [0001] The present application claims the priority of the Chinese Patent Application No. 201110382706.5, entitled "Olefin Polymerization Catalyst and Preparation Method and Application", filed on November 26, 2011, the entire contents of In the application. Technical field
[0002]本发明属于烯烃聚合催化剂和烯烃聚合领域,具体涉及用于烯烃均聚 合或共聚合的催化剂及催化剂的制备方法。 背景技术  The present invention relates to the field of olefin polymerization catalysts and olefin polymerization, and in particular to a catalyst for the homopolymerization or copolymerization of olefins and a process for preparing the catalyst. Background technique
[0003]烯烃聚合催化剂是聚烯烃聚合技术的核心， 从烯烃聚合催化剂的发展 来看， 概括起来主要有两个方面： （ 1 )开发能够制备特殊性能或性能更优 异的聚烯烃树脂催化剂， 如茂金属催化剂及非茂后过渡金属催化剂等； （2 ) 对于通用聚烯烃树脂的生产而言， 在进一步改善催化剂性能的基础上， 筒化 催化剂制备工艺， 降低催化剂成本， 开发对环境友好的技术， 以提高效益， 增强竟争力。 20世纪 80年代以前， 聚乙烯催化剂研究的重点是追求催化剂 效率， 经过近 30年的努力， 聚乙烯催化剂的催化效率呈数量级提高， 从而 筒化了聚烯烃的生产工艺， 降低了能耗和物耗。  [0003] The olefin polymerization catalyst is the core of the polyolefin polymerization technology. From the development of the olefin polymerization catalyst, there are mainly two aspects in general: (1) development of a polyolefin resin catalyst capable of producing special properties or properties, such as Metallocene catalysts and non-post-expansion transition metal catalysts; (2) For the production of general-purpose polyolefin resins, on the basis of further improving the performance of the catalyst, the catalyst preparation process, reducing the catalyst cost, and developing environmentally friendly technologies To improve efficiency and enhance competitiveness. Before the 1980s, the focus of research on polyethylene catalysts was to pursue catalyst efficiency. After nearly 30 years of efforts, the catalytic efficiency of polyethylene catalysts was increased by orders of magnitude, thereby reducing the production process of polyolefins and reducing energy consumption and material consumption. .
[0004] Ziegler-Natta催化剂问世至今已有近 60年历史，期间尽管出现了如茂 金属与非茂金属等聚烯烃催化剂， 但其工业化问题较多， 如助催化剂昂贵， 主催化剂负载还存在困难等。 因此， 就目前工业生产与市场占有率来看， 传 统的 Z-N催化剂仍将是未来一段时间内烯烃聚合领域的主导者。 近年来， 国 内外的 Z-N催化剂产品层出不穷， 催化剂稳定性与聚合催化活性也不断提 高。 但在氢调敏感性、 控制催化剂颗粒规整性及粒径分布方面仍有不足。 目 前生产中需开发出制备工艺筒单、 氢调敏感性好、 粒径分布均匀的球形或类 球形催化剂。 [0005]专利 96106647.4 X公开了一种烯烃聚合催化剂及其制备方法，将载体 MgCl2溶于一种醇和烷烃的混合物中， 形成液体 MgCl2醇加合物， 这种液体 MgCl2醇加合物与 TiCl4接触， 得到烯烃聚合催化剂。 [0004] The Ziegler-Natta catalyst has been around for 60 years. Although there have been polyolefin catalysts such as metallocene and non-metallocene, there are many industrialization problems, such as expensive catalysts and difficulties in the loading of the main catalyst. Wait. Therefore, in terms of current industrial production and market share, the traditional ZN catalyst will remain the dominant player in the field of olefin polymerization for some time to come. In recent years, ZN catalyst products at home and abroad have emerged in an endless stream, and catalyst stability and polymerization catalytic activity have also been continuously improved. However, there are still deficiencies in hydrogen sensitivity, control of catalyst particle regularity and particle size distribution. At present, it is necessary to develop a spherical or spheroidal catalyst which has a preparation process, a hydrogen sensitivity, and a uniform particle size distribution. [0005] Patent 96106647.4 X discloses an olefin polymerization catalyst and a process for the preparation thereof, which are prepared by dissolving a carrier MgCl 2 in a mixture of an alcohol and an alkane to form a liquid MgCl 2 alcohol adduct, such a liquid MgCl 2 alcohol adduct. Contact with TiCl 4 gives an olefin polymerization catalyst.
[0006]专利 200480008242.X公开了一种烯烃聚合催化剂及其制备方法， 将 载体 MgCl2直接溶于乙醇制备了 MgCl2醇加合物， 再将 TiCl4负载在 MgCl2 醇加合物上得到了烯烃聚合催化剂，在制备 MgCl2醇加合物时加入了另一种 碳原子数小于 6的醇。 [0006] Patent 200480008242.X discloses an olefin polymerization catalyst and a preparation method thereof, wherein a carrier MgCl 2 is directly dissolved in ethanol to prepare a MgCl 2 alcohol adduct, and then TiCl 4 is supported on a MgCl 2 alcohol adduct. An olefin polymerization catalyst is added to the alcohol having a carbon number of less than 6 in the preparation of the MgCl 2 alcohol adduct.
[0007】本专利发现， 在催化剂制备过程中， 加入两种或两种以上碳原子数不 同的醇， 加入有机醇醚化合物， 加入有机硅化合物， 制备液体 MgCl2醇加合 物， 再将 TiCl4与这种液体 MgCl2醇加合物接触， 得到烯烃聚合催化剂， 可 以改善固体主催化剂的颗粒形态和催化剂催化烯烃聚合的氢调性能。本发明 所提供的烯烃聚合催化剂的颗粒形态良好， 且粒径分布均匀； 催化剂氢调性 能优异； 催化剂负载量高，催化剂活性高； 聚合物颗粒形态好， 堆积密度高， 细粉少； 适用于淤浆聚合工艺、 气相聚合工艺或组合聚合工艺； 主催化剂的 制备工艺筒单， 对设备要求低， 能耗小， 环境污染小。 发明内容 [0007] This patent finds that during the preparation of the catalyst, two or more alcohols having different carbon numbers are added, an organic alcohol ether compound is added, an organosilicon compound is added, a liquid MgCl 2 alcohol adduct is prepared, and then TiCl is added. 4 Contact with the liquid MgCl 2 alcohol adduct to obtain an olefin polymerization catalyst which can improve the particle morphology of the solid procatalyst and the hydrogen modulating property of the catalyst catalyzed olefin polymerization. The olefin polymerization catalyst provided by the invention has good particle shape and uniform particle size distribution; excellent hydrogen hydrogenation performance of the catalyst; high catalyst loading and high catalyst activity; good polymer particle morphology, high bulk density and less fine powder; Slurry polymerization process, gas phase polymerization process or combined polymerization process; the main catalyst preparation process is simple, requires low equipment, low energy consumption and small environmental pollution. Summary of the invention
[0008]本发明的目的在于提供一种用于烯烃聚合或乙烯与共聚单体共聚合 的催化剂及催化剂的制备方法。  SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst and a catalyst preparation method for olefin polymerization or copolymerization of ethylene and a comonomer.
[0009]本发明所提供的烯烃聚合或乙烯与共聚单体共聚合的球形催化剂由 主催化剂和助催化剂组成；所述的主催化剂由 化镁载体、过渡金属 化物、 小于 C5或等于 C5的醇、 大于 C5的醇、 有机硅化合物和有机醇醚化合物组 成； 卤化镁、 过渡金属卤化物、 小于 C5的醇、 大于 C5的醇和有机硅化合 物的摩尔比为： 1 : ( 1-40 ) : ( 0.1-5 )： ( 0.01-10 )： ( 0.01-10 ) ； 卤化镁 与有机醇醚化合物的质量比为： 100: ( 0.1-20 )。 主催化剂与助催化剂的用 量关系为： 主催化剂中的过渡金属卤化物与助催化剂的摩尔比为 1 : ( 10-500 ) 。 [0010]其中， 所述的卤化镁作为载体选自通式（ 1 ) 为 Mg(R)aXb的化合物 中的至少一种， R选自 C1 - C20的脂肪烃基、 CI ~ C20的脂肪烷氧基、 C3 ~ C20的脂环基或 C6 - C20的芳香烃基； X选自卤素； a = 0、 1或 2 , b = 0、 1 或 2, a + b = 2。 具体选自二氯化镁、 二溴化镁、 二碘化镁、 氯化曱氧基镁、 氯化乙氧基镁、 氯化丙氧基镁、 氯化丁氧基镁、 氯化苯氧基镁、 乙氧基镁、 异丙氧基镁、 丁氧基镁、 氯化异丙氧基镁、 氯化丁基镁等中的至少一种， 其 中， 优选二氯化镁。 [0009] The olefin polymerization provided by the present invention or a spherical catalyst in which ethylene is copolymerized with a comonomer is composed of a main catalyst and a cocatalyst; the main catalyst is composed of a magnesium support, a transition metal compound, an alcohol of less than C5 or equal to C5. The composition of the alcohol, the organosilicon compound and the organic alcohol ether compound greater than C5; the molar ratio of the magnesium halide, the transition metal halide, the alcohol smaller than C5, the alcohol larger than C5 and the organosilicon compound is: 1 : ( 1-40 ) : ( 0.1-5): (0.01-10): (0.01-10); The mass ratio of magnesium halide to organic alcohol ether compound is: 100: (0.1-20). The relationship between the amount of the main catalyst and the cocatalyst is as follows: The molar ratio of the transition metal halide to the cocatalyst in the main catalyst is 1: (10-500). [0010] wherein, the magnesium halide is selected as a carrier from at least one of the compounds of the formula (1) which is Mg(R)aXb, and R is selected from the group consisting of C1 - C20 aliphatic hydrocarbon groups, CI ~ C20 fatty alkoxy groups. a C3 to C20 alicyclic group or a C6-C20 aromatic hydrocarbon group; X is selected from a halogen; a = 0, 1 or 2, b = 0, 1 or 2, a + b = 2. Specifically selected from the group consisting of magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium oxychloride, magnesium oxychloride, magnesium propoxide, magnesium butoxide, magnesium phenoxide And at least one of ethoxy magnesium, magnesium isopropoxide, magnesium butoxide, magnesium isopropoxide chloride, butyl magnesium chloride, and the like. Among them, magnesium dichloride is preferred.
[0011]其中， 所述的过渡金属卤化物选自通式（ 2 ) 为 M(Rl)4-mXm的化合 物中的至少一种， 式中， M是 Ti, Zr, Hf, Fe, Co, Ni等； X是卤原子， 选自 CI, Br, F; m为 0到 4的整数； R1选自 CI ~ C20的脂肪烃基、 CI ~ C20的 脂肪烷氧基、 CI ~ C20的环戊二婦基及其衍生物、 C1 ~ C20的芳香烃基、 COR;或 COOR、 R;是具有 C1 ~ C10的脂肪族基或具有 C1 ~ C10的芳香基。 R1具体可选自： 曱基、 乙基、 丙基、 丁基、 戊基、 己基、 庚基、 辛基、 壬 基、 癸基、 异丁基、 叔丁基、 异戊基、 叔戊基、 2-乙基己基、 苯基、 蔡基、 邻 -曱基苯基、 间 -曱基苯基、 对 -曱基苯基、 邻-磺 苯基、 曱酰基、 乙酰 基或苯曱酰基等中的至少一种。 所述的 Ti, Zr, Hf, Fe, Co, Ni等过渡金属卤 化物， 具体可选用四氯化钛、 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、 三氯一乙氧基钛、 钛酸正丁酯、 钛 酸异丙酯、 曱氧基三氯化钛、 二丁氧基二氯化钛、 三丁氧基氯化钛、 四苯氧 基钛、 一氯三苯氧基钛、 二氯二苯氧基钛、 三氯一苯氧基钛中的一种或几种 的混合。 其中， 优选四氯化钛。 过渡金属 化物与 化镁的摩尔比优选 ( 1-40 ) ： 1。  [0011] wherein, the transition metal halide is selected from at least one of the compounds of the formula (2) which is M(Rl)4-mXm, wherein M is Ti, Zr, Hf, Fe, Co, Ni or the like; X is a halogen atom selected from CI, Br, F; m is an integer from 0 to 4; R1 is selected from an aliphatic hydrocarbon group of CI ~ C20, a fatty alkoxy group of CI ~ C20, and a cyclopentane of CI ~ C20 The base group and its derivatives, the aromatic hydrocarbon group of C1 ~ C20, COR; or COOR, R; are aliphatic groups having C1 ~ C10 or aromatic groups having C1 ~ C10. R1 may be specifically selected from the group consisting of: mercapto, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, isobutyl, tert-butyl, isopentyl, tert-amyl , 2-ethylhexyl, phenyl, zekeyl, o-nonylphenyl, m-nonylphenyl, p-nonylphenyl, o-sulfophenyl, decanoyl, acetyl or benzoyl, etc. At least one of them. The transition metal halides such as Ti, Zr, Hf, Fe, Co, Ni, etc., specifically selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, Monochlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, n-butyl titanate, isopropyl titanate, decyloxytitanium trichloride, dibutoxydichloride A mixture of one or more of titanium, tributoxytitanium chloride, tetraphenoxytitanium, monochlorotriphenoxytitanium, dichlorodiphenoxytitanium, and trichloromonophenoxytitanium. Among them, titanium tetrachloride is preferred. The molar ratio of the transition metal compound to the magnesium oxide is preferably (1-40): 1.
[0012]本发明中， 小于 C5或等于 C5的醇是指碳原子数小于或等于 5的醇。 例如， 所述的小于 C5或等于 C5的醇是碳原子数小于或等于 5的脂肪醇， 优选为乙醇、 曱醇、 丙醇、 丁醇或戊醇或其任意组合， 更优选为乙醇。 小于 C5的醇与卤化镁的摩尔比优选（0.1-5 ) ： 1。 本发明中， 加入小于 C5或等 于 C5的醇尤其是乙醇可以明显提高催化剂的氢调性能。 [0013】本发明中， 大于 C5的醇是指碳原子数大于 5的醇。 例如， 所述的大 于 C5的醇是碳原子数为 6-20的脂肪醇或脂环醇或芳香醇， 优选脂肪醇， 脂 肪醇中优选庚醇、 异辛醇、 辛醇、 壬醇、 癸醇、 十一醇、 十二醇、 十三醇、 十四醇、 十五醇或十六醇或其任意组合， 更优选异辛醇。 大于 C5的醇与卤 化镁的摩尔比优选 ( 0.01-10 ) ： 1。 [0012] In the present invention, an alcohol smaller than C5 or equal to C5 means an alcohol having a carbon number of 5 or less. For example, the alcohol less than C5 or equal to C5 is a fatty alcohol having a carbon number of less than or equal to 5, preferably ethanol, decyl alcohol, propanol, butanol or pentanol or any combination thereof, more preferably ethanol. The molar ratio of the alcohol less than C5 to the magnesium halide is preferably (0.1-5): 1. In the present invention, the addition of an alcohol having less than C5 or equal to C5, especially ethanol, can significantly improve the hydrogen-adjusting properties of the catalyst. [0013] In the present invention, an alcohol larger than C5 means an alcohol having a carbon number of more than 5. For example, the alcohol larger than C5 is a fatty alcohol having 6 to 20 carbon atoms or an alicyclic alcohol or an aromatic alcohol, preferably a fatty alcohol, and among the fatty alcohols, heptanol, isooctanol, octanol, decyl alcohol, hydrazine are preferred. Alcohol, undecyl alcohol, decadiol, tridecyl alcohol, tetradecanol, pentadecyl alcohol or cetyl alcohol or any combination thereof, more preferably isooctanol. The molar ratio of the alcohol larger than C5 to the magnesium halide is preferably (0.01-10): 1.
[0014]其中， 所述的有机硅化合物符合通式 Rx3Ry4Si(OR5)z, 其中 R3和 R4分另) J为 S基或 素， R5是 S基， 0<x < 2, 0<y < 2, 和 0 < z≤4, x+y+z = 4。 有机硅化合物选自二乙氧基异丙氧基叔丁氧基硅烷、三异丙氧基叔丁氧基硅 烷、 二异丙氧基二叔丁氧基硅烷、 二乙氧基环己氧基叔丁氧基硅烷、 二乙氧 基苯氧基叔丁氧基硅烷、 一乙氧基二异丙氧基叔丁氧基硅烷、 乙氧基异丙氧 基叔丁氧基环己氧基硅烷、 四曱氧基硅烷、 四乙氧基硅烷、 四丙氧基硅烷、 四丁氧基硅烷、 四 (2-乙基己氧基)硅烷、 乙基三曱氧基硅烷、 乙基三乙氧基 硅烷、 曱基三曱氧基硅烷、 曱基三乙氧基硅烷、 正丙基三乙氧基硅烷、 正丙 基三曱氧基硅烷、 癸基三曱氧基硅烷、 癸基三乙氧基硅烷、 环戊基三曱氧基 硅烷、 环戊基三乙氧基硅烷、 2-曱基环戊基三曱氧基硅烷、 2, 3-二曱基环戊 基三曱氧基硅烷、 环己基三曱氧基硅烷、 环己基三乙氧基硅烷、 曱基三曱氧 基硅烷、 曱基三乙氧基硅烷、 乙基三乙氧基硅烷、 乙烯基三曱氧基硅烷、 乙 婦基三乙氧基硅烷、 叔丁基三乙氧基硅烷、 正丁基三曱氧基硅烷、 正丁基三 乙氧基硅烷、 异丁基三乙氧基硅烷、 环己基三乙氧基硅烷、 环己基三曱氧基 硅烷、 苯基三曱氧基硅烷、 苯基三乙氧基硅烷、 一氯三曱氧基硅烷、 一氯三 乙氧基硅烷、 乙基三异丙氧基硅烷、 乙烯基三丁氧基硅烷、 三曱基苯氧基硅 烷、 曱基三烯丙氧基硅烷、 乙烯基三乙 ½硅烷、 二曱基二曱氧基硅烷、 二 曱基二乙氧基硅烷、 二丁基二曱氧基硅烷、 二异丙基二曱氧基硅烷、 二异丙 基二乙氧基硅烷、 叔丁基曱基二曱氧基硅烷、 叔丁基曱基二乙氧基硅烷、 叔 戊基曱基二乙氧基硅烷、 二环戊基二曱氧基硅烷、 二环戊基二乙氧基硅烷、 曱基环己基二曱氧基硅烷、 曱基环戊基二乙氧基硅烷、 曱基环戊基二曱氧基 硅烷、二苯基二曱氧基硅烷、二苯基二乙氧基硅烷、 曱基苯基二乙氧基硅烷、 曱基苯基二曱氧基硅烷、 双邻曱苯基二曱氧基硅烷、 双邻曱苯基二乙氧基硅 烷、 双间曱苯基二曱氧基硅烷、 双间曱苯基二乙氧基硅烷、 双对曱苯基二曱 氧基硅烷、 双对曱苯基二乙氧基硅烷、 三曱基曱氧基硅烷、 三曱基乙氧基硅 烷、 三环戊基曱氧基硅烷、 三环戊基乙氧基硅烷、 二环戊基曱基曱氧基硅烷 和环戊基二曱基曱氧基硅烷等中的一种或几种。 优选四曱氧基硅烷、 四乙氧 基硅烷中的一种。 有机硅化合物与卤化镁的摩尔比为 （0.01-10 ) : 1。 [0014] wherein, the organosilicon compound conforms to the general formula Rx3Ry4Si(OR5)z, wherein R3 and R4 are separately) J is a S group or a prime, R5 is a S group, 0<x < 2, 0<y < 2 , and 0 < z≤4, x+y+z = 4. The organosilicon compound is selected from the group consisting of diethoxyisopropoxy tert-butoxysilane, triisopropoxy tert-butoxysilane, diisopropoxydi-tert-butoxysilane, diethoxycyclohexyloxy Tert-butoxysilane, diethoxyphenoxy-tert-butoxysilane, monoethoxydiisopropoxy-tert-butoxysilane, ethoxyisopropoxy-tert-butoxycyclohexyloxysilane , tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, ethyltrimethoxysilane, ethyltriethoxy Silane, mercaptotrimethoxysilane, mercaptotriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, mercaptotrimethoxysilane, mercaptotriethoxy Silane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, 2-mercaptocyclopentyltrimethoxysilane, 2,3-didecylcyclopentyltrimethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, ethyltriethoxysilane, vinyltrioxane Silane, ethenyltriethoxysilane, tert-butyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, cyclohexyl Ethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, monochlorotrimethoxysilane, monochlorotriethoxysilane, ethyltriisopropyl Oxysilane, vinyl tributoxysilane, trimercaptophenoxysilane, mercaptotriallyloxysilane, vinyltrimethylsilane, dimercaptodimethoxysilane, dimercaptodiyl Oxysilane, dibutyldimethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, tert-butyldecyldimethoxysilane, tert-butylfluorenyl Ethoxysilane, tert-amyldecyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, nonylcyclohexyldimethoxysilane, decylcyclopentanyl Diethoxysilane, nonylcyclopentyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Nonylphenyldiethoxysilane, nonylphenyldimethoxysilane, di-o-nonylphenyldimethoxysilane, di-o-nonylphenyldiethoxysilane Alkane, bis-indolyl phenyl dimethoxy silane, bis-indenyl phenyl diethoxy silane, bis - fluorenyl phenyl dimethoxy silane, bis - fluorenyl phenyl diethoxy silane , triterpene fluorene Oxysilane, trimethyl ethoxy silane, tricyclopentyl methoxy silane, tricyclopentyl ethoxy silane, dicyclopentyl decyl methoxy silane, and cyclopentyl decyl decyloxy One or several of silanes and the like. One of tetramethoxysilane and tetraethoxysilane is preferred. The molar ratio of the organosilicon compound to the magnesium halide is (0.01-10): 1.
[0015】其中， 所述的有机醇醚化合物其特征为末端基为羟基， 选自符合通式 (3) HO(CH2)f O(CH2)nR2; 其中， f为 1到 20的整数， 优选 1到 15; n为 1 到 10的整数， 优选 1到 6。 R选自 C1~C30的脂肪烃基， C3~C30的环烷基， C6~C30的芳香烃基， C2~C30的杂环烷基。 具体可选自乙二醇单曱醚、 乙二 醇单***、 乙二醇单丁醚、 乙二醇单正丙醚、 丙二醇单***、 丁二醇单丙醚、 2-(2-环戊基乙氧基）乙醇、 3-(2-环己基乙氧基)丙醇、 2-(5-苯基戊氧基）乙醇、 4-(3- (蔡基)丙氧基)丁醇、 2-(3-环氧乙基丙氧基）乙醇、 2-(2-呋喃基乙氧基）乙 醇、 3-(3-吡啶基丙氧基)丙醇。 卤化镁与有机醇醚化合物的质量比为： 100: ( 0.1 - 20 ) 。 [0015] wherein the organic alcohol ether compound is characterized in that the terminal group is a hydroxyl group selected from the group consisting of the general formula (3) HO(CH2)f O(CH2)nR2; wherein, f is an integer from 1 to 20, preferably 1 to 15; n is an integer of 1 to 10, preferably 1 to 6. R is selected from the group consisting of an aliphatic hydrocarbon group of C1 to C30, a cycloalkyl group of C3 to C30, an aromatic hydrocarbon group of C6 to C30, and a heterocycloalkyl group of C2 to C30. Specifically, it may be selected from the group consisting of ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-n-propyl ether, propylene glycol monoethyl ether, butanediol monopropyl ether, 2-( 2 -cyclopentane) Ethyl ethoxy)ethanol, 3-( 2 -cyclohexylethoxy)propanol, 2-(5-phenylpentyloxy)ethanol, 4- (3-(caiyl)propoxy)butanol, 2- (3-Ethoxyethylpropoxy)ethanol, 2- ( 2 -furylethoxy)ethanol, 3-(3-pyridylpropoxy)propanol. The mass ratio of the magnesium halide to the organic alcohol ether compound is: 100: (0.1 - 20).
[0016]本发明的特征之一是固体主催化剂的制备过程中加入两种或两种以 上的碳原子数不同的醇， 即小于 C5或等于 C5的醇和大于 C5的醇， 所述的 小于 C5或等于 C5的醇是碳原子数小于或等于 5的脂肪醇， 选自乙醇、 曱 醇、 丙醇、 丁醇或戊醇或其任意组合， 优选乙醇。 小于 C5或等于 C5的醇 与卤化镁的摩尔比优选（ 0.3-5 ) ： 1 ; 所述的大于 C5的醇是碳原子数为 C6 - C20的脂肪醇或脂环醇或芳香醇， 优选脂肪醇， 脂肪醇中选庚醇、 异辛醇、 辛醇、 壬醇、 癸醇、 十一醇、 十二醇、 十三醇、 十四醇、 十五醇或十六醇或 其任意组合， 优选异辛醇。 大于 C5的醇与卤化镁的摩尔比优选（0.01-10 )： 1。加入小于 C5或等于 C5的醇尤其是乙醇可以明显提高催化剂的氢调性能。  [0016] One of the features of the present invention is that two or more alcohols having different carbon numbers are added during the preparation of the solid procatalyst, that is, an alcohol smaller than C5 or equal to C5 and an alcohol larger than C5, which is less than C5. The alcohol equal to or greater than C5 is a fatty alcohol having a carbon number of less than or equal to 5, and is selected from the group consisting of ethanol, decyl alcohol, propanol, butanol or pentanol or any combination thereof, preferably ethanol. The molar ratio of the alcohol to the magnesium halide of less than C5 or equal to C5 is preferably (0.3-5): 1; the alcohol larger than C5 is a fatty alcohol having a carbon number of C6 - C20 or an alicyclic alcohol or an aromatic alcohol, preferably a fat. Alcohol, a fatty alcohol selected from heptyl alcohol, isooctanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, decadiol, tridecyl alcohol, tetradecanol, pentadecyl alcohol or cetyl alcohol or any combination thereof, preferably Isooctanol. The molar ratio of the alcohol larger than C5 to the magnesium halide is preferably (0.01 - 10): 1. The addition of an alcohol less than C5 or equal to C5, especially ethanol, can significantly improve the hydrogen regulation performance of the catalyst.
[0017]本发明的特征之一是固体主催化剂的制备过程中加入了有机醇醚化 合物修复剂改善催化剂颗粒形态及粒径分布情况。 [0017] One of the features of the present invention is that an organic alcohol ether compound repairing agent is added during the preparation of the solid procatalyst to improve the morphology and particle size distribution of the catalyst particles.
[0018]本发明所提供的烯烃聚合催化剂的制备方法包括以下步骤： [0018] The method for preparing an olefin polymerization catalyst provided by the present invention comprises the following steps:
1 ) 将卤化镁载体分散于有机溶剂中， 加入小于 C5或等于 C5的醇和大于 C5的醇， 于 30至 150°C下搅拌溶解 1至 5h, 优选 60°C至 130°C。 2 ) 将 1)溶液降温至 10至 80°C ,依次加入有机硅化合物和有机醇醚化合物， 反应 0.5至 3h。 1) Dispersing the magnesium halide carrier in an organic solvent, adding an alcohol smaller than C5 or equal to C5 and an alcohol larger than C5, and stirring and dissolving at 30 to 150 ° C for 1 to 5 hours, preferably 60 to 130 °C. 2) The 1) solution is cooled to 10 to 80 ° C, and the organosilicon compound and the organic alcohol ether compound are sequentially added, and the reaction is carried out for 0.5 to 3 hours.
3 ) 在 -25至 30°C下， 向步骤 2 )得到的体系中加入过渡金属卤化物， 加完 后在 -25至 30°C下反应 0.5-5h, 再将体系升温至 20-150°C , 优选 50-120°C , 反应 0.5-5h, 在升温过程中， 固体颗粒逐渐析出， 反应结束后， 以曱苯或正 己烷洗涤产物 4-6次， 过滤除去未反应物， 真空干燥得到粉末状固体主催化 剂，真空干燥温度为 40°C至 130°C ,优选 50°C至 100°C ;真空干燥时间为 0.5 小时至 5小时， 优选 1小时至 4小时。  3) Adding a transition metal halide to the system obtained in step 2) at -25 to 30 ° C, after the addition, reacting at -25 to 30 ° C for 0.5-5 h, and then heating the system to 20-150 ° C, preferably 50-120 ° C, reaction 0.5-5 h, during the heating process, the solid particles gradually precipitated, after the reaction is finished, the product is washed 4-6 times with toluene or n-hexane, the unreacted matter is removed by filtration, and dried under vacuum. The powdery solid procatalyst has a vacuum drying temperature of 40 ° C to 130 ° C, preferably 50 ° C to 100 ° C; and a vacuum drying time of 0.5 hours to 5 hours, preferably 1 hour to 4 hours.
[0019]所述的有机溶剂选自 C5 ~ C15的饱和烃、 C5 ~ C10的脂环烃、 C6 ~ C15 的芳香烃或 C3 ~ d。的饱和杂环烃， 优选曱苯、 二曱苯、 己烷、 庚烷、 辛烷、 癸烷或四氢呋喃， 或它们的混合溶剂。 [0019] The organic solvent is selected from the group consisting of C 5 ~ C 15 saturated hydrocarbons, C 5 ~ C 10 alicyclic hydrocarbons, C 6 ~ C 15 aromatic hydrocarbons or C 3 ~ d. The saturated heterocyclic hydrocarbon is preferably anthracene, diphenyl, hexane, heptane, octane, decane or tetrahydrofuran, or a mixed solvent thereof.
[0020]本发明所提供的烯烃聚合催化剂还需有助催化剂组成。 所述的助催化 剂为常见的有机铝化合物， 优选三乙基铝， 三异丁基铝， 三正己基铝， 乙氯 二乙基铝， 曱基铝氧烷 MAO等； 催化剂与助催化剂的摩尔比为 1 : 10-500。  [0020] The olefin polymerization catalyst provided by the present invention also requires a cocatalyst composition. The cocatalyst is a common organoaluminum compound, preferably triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, ethylachlorodiethylaluminum, mercaptoaluminoxane MAO, etc.; moles of catalyst and cocatalyst The ratio is 1: 10-500.
[0021]本发明所提供的烯烃聚合催化剂的用途为： 可作为乙烯聚合或丙烯聚 合或乙烯 (或丙烯)与 α-烯烃的共聚合催化剂， 其中， 所述的 α-烯烃选自 C3 ~[0021] The use of the olefin polymerization catalyst provided by the present invention is as follows: It can be used as an ethylene polymerization or propylene polymerization or a copolymerization catalyst of ethylene (or propylene) and an α-olefin, wherein the α-olefin is selected from C 3 ~
C20的烯烃， 优选丙烯， 1-丁烯， 1-己烯， 1-辛烯， 1-癸烯， 3-曱基 -1-丁烯， 环戊烯， 4-曱基 -1-戊烯， 1,3-丁二烯， 异戊二烯， 苯乙烯， 曱基苯乙烯等。 C 20 olefin, preferably propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 3-mercapto-1-butene, cyclopentene, 4-mercapto-1-pentane Alkene, 1,3-butadiene, isoprene, styrene, mercaptostyrene, and the like.
[0022]本发明所提供的烯烃聚合催化剂具有以下有益效果：  [0022] The olefin polymerization catalyst provided by the present invention has the following beneficial effects:
[0023]本发明的目的是提供的烯烃共聚合催化剂的颗粒形态良好， 呈球形； 催化剂的氢调性能优异； 催化剂活性高； 适用于淤浆法、 气相聚合工艺或组 合聚合工艺； 制备方法筒单， 对设备要求低， 对环境污染小。  [0023] The object of the present invention is to provide an olefin copolymerization catalyst with good particle morphology and a spherical shape; excellent hydrogen-tuning performance of the catalyst; high catalyst activity; suitable for slurry process, gas phase polymerization process or combined polymerization process; Single, low requirements on equipment and low environmental pollution.
[0024]采用 GC测定主催化剂中乙醇和其它醇的质量百分含量，结果见表 1。  [0024] The mass percentage of ethanol and other alcohols in the main catalyst was determined by GC, and the results are shown in Table 1.
[0025]采用 ICP测定主催化剂中 Mg, Ti和 Si的质量百分含量。  [0025] The mass percentage of Mg, Ti and Si in the main catalyst was determined by ICP.
[0026]以下结合具体实施方式对本发明作进一步说明， 但本发明的保护范围 不仅限于下述实施例。 具体实施方式 [0027]实施例 1 The present invention will be further described in conjunction with the specific embodiments, but the scope of the present invention is not limited to the embodiments described below. detailed description [0027] Embodiment 1
[0028]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 3 ml, 异辛醇 6.5 ml, 搅拌升温至 110°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 50 °C下， 依次加入四乙氧基硅烷 5 ml, 乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升 温至 70°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 l h, 升温至 80°C反应 2 h。停止搅拌，静置， 分层， 过滤， 己烷洗涤两次（每 次 30 毫升） 。 又在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化 钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗 涤四次（每次 30 毫升） ， 于 70°C真空干燥 2小时， 得到流动性好、 粒径分 布均勾、 呈球形的粉末状固体主催化剂。  [0028] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of ethanol, 6.5 ml of isooctanol, and the mixture is heated to 110 ° C for 2 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 °C, 5 ml of tetraethoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence for 2 h. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 70 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 70 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0029]实施例 2 [0029] Example 2
[0030]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 30 ml, 乙醇 1.5 ml, 异辛醇 7 ml, 搅拌升温至 120°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 60°C下， 依次加入四乙氧基硅烷 0.5 ml, 乙二醇单曱醚 0. 2 ml, 反应 2 h。 将体系降至 -10°C下， 滴加 20 ml四氯化钛， 反应 1 h, 升 温至 100°C反应 3 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 在 10°C往反应器中加入正癸烷 20 ml, 滴加入 40 ml四氯化钛， 反应 l h, 升温至 65°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四 次（每次 30 毫升） ， 于 60°C真空干燥 3小时， 得到流动性好、 粒径分布均 匀、 呈球形的粉末状固体主催化剂。  [0030] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 30 ml of n-decane, 1.5 ml of ethanol, 7 ml of isooctanol, and the mixture is heated to 120 ° C for 2 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 60 ° C, 0.5 ml of tetraethoxysilane, 0.2 ml of ethylene glycol monoterpene ether were added in sequence, and the reaction was carried out for 2 h. The system was lowered to -10 ° C, 20 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 100 ° C for 3 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 10 ° C, 40 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 ° C for 3 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. .
[0031]实施例 3 Embodiment 3
[0032]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 0.2 ml, 异辛醇 8 ml, 搅拌升温至 100°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 50°C下， 依次加入四乙氧基硅烷 2ml, 乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升 温至 65°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） ， 于 70°C真空干燥 2小时后， 在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 65°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 又在 0°C往反应器中加入正 癸烷 30 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 65°C反应 2 h。 停止 搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 50°C真空干 燥 4小时， 得到流动性好、 粒径分布均勾、 呈球形的粉末状固体主催化剂。 [0032] In a reactor that has been sufficiently replaced with nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 0.2 ml of ethanol, 8 ml of isooctanol, and the mixture is heated to 100 ° C for 2 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 2 ml of tetraethoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence for 2 h. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stop stirring, let stand, stratify, filter, wash twice with hexane (30 each time) ML), after drying at 70 ° C for 2 hours under vacuum, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 30 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 ° C for 4 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0033]实施例 4 Embodiment 4
[0034]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 2 ml, 异辛醇 7 ml, 搅拌升温至 90 °C , 反应 4 h, 固体完全溶解形成均 一的溶液。降温至 50 °C下，依次加入二乙氧基异丙氧基叔丁氧基硅烷 0.5 ml, 乙二醇单曱醚 0.02 ml,反应 2 h。将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 l h, 升温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两 次（每次 30 毫升） ， 于 70°C真空干燥 2小时后， 在 0°C往反应器中加入正 癸烷 40 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C反应 2 h。 停止 搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 又在 0°C往反 应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C反 应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 80°C真空干燥 2小时， 得到流动性好、 粒径分布均勾、 呈球形的粉末状固体 主催化剂。  [0034] In a reactor that has been thoroughly replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 2 ml of ethanol, 7 ml of isooctanol, and the mixture is heated to 90 ° C for 4 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 °C, 0.5 ml of diethoxyisopropoxybutoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence for 2 h. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed twice with hexane (30 ml each time), dried under vacuum at 70 ° C for 2 hours, then added to the reactor at 40 ° C, 40 ml of n-decane, added dropwise 25 ml of titanium tetrachloride, reacted for 1 h, and heated to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 80 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0035]实施例 5 [0035] Example 5
[0036]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 3 ml, 异辛醇 4 ml, 搅拌升温至 80°C , 反应 5 h, 固体完全溶解形成均 一的溶液。 降温至 50°C下， 依次加入四乙氧基硅烷 4ml, 乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 3 h, 升温至 90°C反应 2 h。停止搅拌，静置，分层，过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升 温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 又在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反 应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次 (每次 30 毫升）， 于 90°C真空干燥 2小时，得到流动性好、粒径分布均匀、 呈球形的粉末状固体主催化剂。 [0036] In a reactor that has been thoroughly replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of ethanol, 4 ml of isooctanol, and the mixture is heated to 80 ° C for 5 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 4 ml of tetraethoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence, and the reaction was carried out for 2 h. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 3 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Add 20 ml of n-decane to the reactor at 0 ° C, and add 25 ml of titanium tetrachloride dropwise. Should be lh, warm to 80 ° C reaction for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 90 ° C for 2 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. .
[0037]实施例 6 [0037] Example 6
[0038]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 3.2 ml, 异辛醇 2 ml, 搅拌升温至 110°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 50°C下， 依次加入四乙氧基硅烷 8 ml, 乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15°C下， 滴加 40 ml四氯化钛， 反应 1 h, 升 温至 70°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 l h, 升温至 70°C反应 2 h。停止搅拌，静置， 分层， 过滤， 己烷洗涤两次（每 次 30 毫升） 。 又在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化 钛， 反应 l h, 升温至 70°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗 涤四次（每次 30 毫升） ， 于 100°C真空干燥 2小时， 得到流动性好、 粒径 分布均勾、 呈球形的粉末状固体主催化剂。  [0038] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3.2 ml of ethanol, 2 ml of isooctanol, and the mixture is heated to 110 ° C for 2 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 8 ml of tetraethoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence for 2 h. The system was lowered to -15 ° C, 40 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 70 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 70 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 70 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 100 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0039]实施例 7 [0039] Example 7
[0040]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 曱醇 3.5 ml, 异辛醇 6.5 ml, 搅拌升温至 60°C , 反应 4 h, 固体完全溶解形 成均一的溶液。 降温至 50°C下， 依次加入二乙氧基异丙氧基叔丁氧基硅烷 3 ml, 乙二醇单曱醚 0.02 ml, 反应 3 h。 将体系降至 -15°C下， 滴加 15 ml四氯 化钛， 反应 l h, 升温至 65°C反应 4 h。 停止搅拌， 静置， 分层， 过滤， 己烷 洗涤两次（每次 30 毫升） 。 在 20 °C往反应器中加入正癸烷 20 ml, 滴加入 40 ml四氯化钛， 反应 l h, 升温至 65°C反应 3 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 又在 20 °C往反应器中加入正癸烷 20 ml, 滴加入 15 ml四氯化钛， 反应 1 h, 升温至 65°C反应 2 h。 停止搅拌， 静 置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升）， 于 60°C真空干燥 3小时， 得到流动性好、 粒径分布均勾、 呈球形的粉末状固体主催化剂。  [0040] In a reactor that has been thoroughly replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3.5 ml of decyl alcohol, 6.5 ml of isooctanol, and the mixture is heated to 60 ° C for 4 h, and the solid is completely Dissolved to form a uniform solution. After cooling to 50 ° C, 3 ml of diethoxyisopropoxy tert-butoxysilane, 0.02 ml of ethylene glycol monoterpene ether, and 3 h of reaction were sequentially added. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 4 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 20 ° C, 40 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 3 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 20 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 65 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and vacuum dried at 60 ° C for 3 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0041]实施例 8 [0042]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 4 ml, 癸醇 6 ml, 搅拌升温至 110°C , 反应 2 h, 固体完全溶解形成均 一的溶液。 降温至 50°C下， 依次加入二乙氧基异丙氧基叔丁氧基硅烷 5 ml, 乙二醇单曱醚 0.02 ml,反应 3 h。将体系降至 -10°C下， 滴加 30 ml四氯化钛， 反应 l h, 升温至 80°C反应 3 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两 次（每次 30 毫升） 。 在 15 °C往反应器中加入正癸烷 20 ml, 滴加入 25 ml 四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 又在 15 °C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 60°C真空干燥 4小时， 得 到流动性好、 粒径分布均勾、 呈球形的粉末状固体主催化剂。 Embodiment 8 [0042] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 4 ml of ethanol, 6 ml of decyl alcohol, and the mixture is heated to 110 ° C for 2 h, and the solid is completely dissolved. A homogeneous solution. After cooling to 50 ° C, 5 ml of diethoxyisopropoxy tert-butoxysilane and 0.02 ml of ethylene glycol monoterpene ether were added in sequence for 3 h. The system was lowered to -10 ° C, 30 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 3 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 15 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 15 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 ° C for 4 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0043]实施例 9 Embodiment 9
[0044]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 丙醇 3 ml, 异辛醇 6.5 ml, 搅拌升温至 50°C , 反应 5 h, 固体完全溶解形成 均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 6 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 0°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升 温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 l h, 升温至 80°C反应 2 h。停止搅拌，静置， 分层， 过滤， 己烷洗涤两次（每 次 30 毫升） 。 又在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化 钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗 涤四次（每次 30 毫升） ， 于 110°C真空干燥 2小时， 得到流动性好、 粒径 分布均勾、 呈球形的粉末状固体主催化剂。  [0044] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of propanol, 6.5 ml of isooctanol, and the mixture is heated to 50 ° C for 5 h, and the solid is completely Dissolved to form a uniform solution. After cooling to 50 ° C, 6 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. The system was lowered to 0 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 110 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0045]实施例 10 [0045] Example 10
[0046]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 30 ml, 丁醇 4 ml, 异辛醇 6.5 ml, 搅拌升温至 110°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 50 °C下， 加入四乙氧基硅烷 6 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -5°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升 温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 在 10°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反 应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次 (每次 30 毫升） 。 又在 10°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml 四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 120°C真空干燥 2小时， 得到流动性好、 粒径分布均匀、 呈球形的粉末状固体主催化剂。 [0046] In a reactor that has been sufficiently replaced with nitrogen, 1 g of magnesium dichloride, 30 ml of n-decane, 4 ml of butanol, 6.5 ml of isooctanol, and the mixture is heated to 110 ° C for 2 h, and the solid is completely Dissolved to form a uniform solution. After cooling to 50 ° C, 6 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. Reduce the system to -5 ° C, add 15 ml of titanium tetrachloride, react for 1 h, liter The reaction was carried out at 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 10 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 10 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 120 ° C for 2 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. .
[0047]实施例 11 Embodiment 11
[0048]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 5 ml, 十二醇 5 ml, 搅拌升温至 110°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 6 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 0°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升 温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每 次 30 毫升）。 又在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四 次（每次 30 毫升） ， 于 50°C真空干燥 3小时， 得到流动性好、 粒径分布均 匀、 呈球形的粉末状固体主催化剂。  [0048] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 5 ml of ethanol, 5 ml of decadiol, and the mixture is heated to 110 ° C for 2 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 6 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. The system was lowered to 0 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each). Further, 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and vacuum dried at 50 ° C for 3 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. .
[0049]实施例 12 Embodiment 12
[0050】在经过氮气充分置换过的反应器中， 加入 l g二氯化镁， 曱苯 20 ml, 丙醇 3 ml, 异辛醇 6.5 ml, 搅拌升温至 120°C , 反应 2 h, 固体完全溶解形成 均一的溶液。 降温至 50 °C下， 加入四乙氧基硅烷 6 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 0°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升 温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每 次 30 毫升）。 又在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 3 h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四 次（每次 30 毫升） ， 于 70°C真空干燥 3小时， 得到流动性好、 粒径分布均 匀、 呈球形的粉末状固体主催化剂。 [0050] In a reactor that has been sufficiently replaced with nitrogen, lg magnesium dichloride, 20 ml of toluene, 3 ml of propanol, 6.5 ml of isooctanol, and the mixture is heated to 120 ° C for 2 h, and the solid is completely dissolved. A homogeneous solution. After cooling to 50 ° C, 6 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. The system was lowered to 0 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, and 25 ml of titanium tetrachloride was added dropwise. The reaction was carried out for 3 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 70 ° C for 3 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. .
[0051]实施例 13 Embodiment 13
[0052]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 3 ml, 异辛醇 6.5 ml, 搅拌升温至 110°C , 反应 3 h, 固体完全溶解形成 均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 2 ml, 反应 2 h。 将体系降 至 0°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 在 0°C往反应器中加 入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C反应 3 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 又在 0°C 往反应器中加入正癸烷 20 ml,滴加入 25 ml四氯化钛，反应 2 h,升温至 80°C 反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 50°C真空干燥 4小时， 得到流动性好、粒径分布均勾、 呈球形的粉末状固 体主催化剂。  [0052] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of ethanol, 6.5 ml of isooctanol, and the mixture is heated to 110 ° C, and reacted for 3 h, the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 2 ml of tetraethoxysilane was added and reacted for 2 h. The system was lowered to 0 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 3 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 2 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 50 ° C for 4 hours to obtain a powdery solid with good fluidity, particle size distribution and spherical shape. catalyst.
[0053]实施例 14 Embodiment 14
[0054]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 3 ml, 异辛醇 6.5 ml, 搅拌升温至 100°C , 反应 4 h, 固体完全溶解形成 均一的溶液。 将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升温至 90°C反应 2 h。停止搅拌，静置，分层，过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升 温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 又在 0°C往反应器中加入正癸烷 20 ml, 滴加入 25 ml四氯化钛， 反 应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次 (每次 30 毫升）， 于 60°C真空干燥 2小时，得到流动性好、粒径分布均匀、 呈球形的粉末状固体主催化剂。  [0054] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of ethanol, 6.5 ml of isooctanol, and the mixture is heated to 100 ° C for 4 h, and the solid is completely dissolved. A uniform solution is formed. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 ° C for 2 hours to obtain a powdery solid catalyst with good fluidity, uniform particle size distribution and spherical shape. .
[0055]实施例 15 [0056]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 3 ml, 异辛醇 6.5 ml, 搅拌升温至 120°C , 反应 0.5 h, 固体完全溶解形 成均一的溶液。 降温至 50°C下， 加入琥珀酸酯 6 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升温至 90°C反应 2 h。停止搅拌，静置，分层，过滤， 己烷洗涤两次（每次 30 毫升）， 于 60 °C真空干燥 2小时后在 0°C往反应器中加入正癸烷 20 ml,滴加入 25 ml 四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 又在 0°C往反应器中加入正癸烷 20 ml, 滴 加入 25 ml四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分 层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 60°C真空干燥 2小时， 得到 流动性好、 粒径分布均勾、 呈球形的粉末状固体主催化剂。 Example 15 [0056] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 3 ml of ethanol, 6.5 ml of isooctanol, and the mixture is heated to 120 ° C for 0.5 h, and the solid is completely dissolved. A uniform solution is formed. After cooling to 50 ° C, 6 ml of succinate was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed twice with hexane (30 ml each time), dried under vacuum at 60 °C for 2 hours, then 20 ml of n-decane was added to the reactor at 0 °C, and 25 ml was added dropwise. Ml Titanium tetrachloride, react for 1 h, and warm to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of n-decane was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 60 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0057]实施例 16 Embodiment 16
[0058]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 5 ml, 曱醇 3 ml, 异辛醇 7 ml, 搅拌升温至 100°C , 反应 2 h, 固体完 全溶解形成均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 6 ml, 加入乙 二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 0°C下， 滴加 15 ml四氯化钛， 反应 l h, 升温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两 次（每次 30 毫升） 。 在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯 化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷 洗涤两次（每次 30 毫升） 。 又在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 70°C真空干燥 2小时， 得到流动 性好、 粒径分布均勾、 呈球形的粉末状固体主催化剂。  [0058] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 5 ml of ethanol, 3 ml of sterol, 7 ml of isooctanol, and stirred to 100 ° C, reaction 2 h, the solid is completely dissolved to form a uniform solution. After cooling to 50 ° C, 6 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. The system was lowered to 0 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 70 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
[0059]实施例 17 Embodiment 17
[0060]在经过氮气充分置换过的反应器中，加入 1 g二氯化镁，正癸烷 20 ml, 乙醇 5 ml, 丙醇 1 ml, 异辛醇 6 ml, 搅拌升温至 110°C , 反应 2 h, 固体完 全溶解形成均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 6 ml, 加入乙 二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 0°C下， 滴加 15 ml四氯化钛， 反应 l h, 升温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两 次（每次 30 毫升） 。 在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯 化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷 洗涤两次（每次 30 毫升） 。 又在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 l h, 升温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 70°C真空干燥 2小时， 得到流动 性好、 粒径分布均勾、 呈球形的粉末状固体主催化剂。 [0060] In a reactor that has been sufficiently replaced by nitrogen, 1 g of magnesium dichloride, 20 ml of n-decane, 5 ml of ethanol, 1 ml of propanol, 6 ml of isooctanol, and the temperature is raised to 110 ° C, and the reaction is carried out. h, the solid is completely dissolved to form a uniform solution. After cooling to 50 ° C, 6 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. Reduce the system to 0 ° C, add 15 ml of titanium tetrachloride, The reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 hour, and the temperature was raised to 80 ° C for 2 hours. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 70 ° C for 2 hours to obtain a powdery solid with good fluidity and particle size distribution. catalyst.
对比例 1 Comparative example 1
[0061]在经过氮气充分置换过的反应器中， 加入 1 g二氯化镁， 癸烷 20 ml, 异辛醇 6.5 ml,搅拌升温至 110°C ,反应 2 h, 固体完全溶解形成均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 5 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15 °C下， 滴加 15 ml四氯化钛， 反应 1 h, 升温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C 往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C 反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 又在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升 温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升）， 于 80°C真空干燥 2小时， 得到流动性好、 粒径分布均匀、 呈球形的 粉末状固体主催化剂。 催化剂的氢调性能较差。  [0061] In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 ml of decane and 6.5 ml of isooctanol were added, and the mixture was heated to 110 ° C with stirring, and reacted for 2 h, and the solid was completely dissolved to form a uniform solution. After cooling to 50 ° C, 5 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added for 2 h. The system was lowered to -15 °C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Further, 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, washed four times with hexane (30 ml each time), and dried under vacuum at 80 ° C for 2 hours to obtain a powdery solid procatalyst with good fluidity, uniform particle size distribution and spherical shape. . The hydrogenation performance of the catalyst is poor.
对比例 2 Comparative example 2
[0062]在经过氮气充分置换过的反应器中， 加入 1 g二氯化镁， 癸烷 20 ml, 乙醇 5 ml, 搅拌升温至 120°C , 反应 3 h, 固体完全溶解形成均一的溶液。 降温至 50°C下， 加入四乙氧基硅烷 5 ml, 加入乙二醇单曱醚 0.02 ml, 反应 2 h。 将体系降至 -15°C下， 滴加 15 ml四氯化钛， 反应 1 h, 升温至 90°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升）。 在 0°C 往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升温至 80°C 反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤两次（每次 30 毫升） 。 又在 0°C往反应器中加入曱苯 20 ml, 滴加入 25 ml四氯化钛， 反应 1 h, 升 温至 80°C反应 2 h。 停止搅拌， 静置， 分层， 过滤， 己烷洗涤四次（每次 30 毫升） ， 于 60°C真空干燥 2小时， 得到粉末状固体主催化剂。 MgCl2醇加合 物在较低温度时析出固体。 主催化剂的颗粒形态差。 [0062] In a reactor sufficiently purged with nitrogen, 1 g of magnesium dichloride, 20 ml of decane, and 5 ml of ethanol were added, and the mixture was heated to 120 ° C with stirring, and reacted for 3 hours, and the solid was completely dissolved to form a uniform solution. After cooling to 50 ° C, 5 ml of tetraethoxysilane was added, and 0.02 ml of ethylene glycol monoterpene ether was added, and the reaction was carried out for 2 h. The system was lowered to -15 ° C, 15 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 90 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). 20 ml of toluene was added to the reactor at 0 ° C, 25 ml of titanium tetrachloride was added dropwise, and the reaction was carried out for 1 h, and the temperature was raised to 80 ° C for 2 h. Stirring was stopped, allowed to stand, layered, filtered, and washed twice with hexane (30 mL each time). Add 20 ml of toluene to the reactor at 0 ° C, add 25 ml of titanium tetrachloride, and react for 1 h, liter The temperature was raised to 80 ° C for 2 h. The stirring was stopped, allowed to stand, layered, filtered, washed with hexane four times (30 ml each time), and dried under vacuum at 60 ° C for 2 hours to obtain a powdery solid catalyst. The MgCl 2 alcohol adduct precipitates a solid at a lower temperature. The main catalyst has a poor particle morphology.
[0063]应用方式一 [0063] Application Method 1
[0064] 乙烯聚合： 将 2升不锈钢高压釜经氮气充分置换后， 依次向釜中加入 主催化剂组分组分 20 mg, 脱水己烷 1000 ml, 助催化剂 AlEt3溶液 1.17 ml(2 mmol/ml), 升温至 80 °C后充入氢气 0.28 MPa, 充入乙烯至 0.73 MPa, 恒压 恒温反应 2 h。 [0064] Ethylene polymerization: After fully replacing the 2 liter stainless steel autoclave with nitrogen, the main catalyst component component 20 mg, dehydrated hexane 1000 ml, and the cocatalyst AlEt 3 solution 1.17 ml (2 mmol/ml) were sequentially added to the kettle. After heating to 80 °C, it is filled with hydrogen 0.28 MPa, charged with ethylene to 0.73 MPa, and reacted at constant pressure for 2 h.
[0065]应用方式二 [0065] Application Method 2
[0066] 乙烯共聚合： 将 2升不锈钢高压釜经氮气充分置换后， 依次向釜中加 入主催化剂组分 20 mg , 脱水己烷 1000 ml , AlEt3溶液 1.17 ml(2mmol/ml) , 加入 30 ml 1-己婦。 升温至 80 °C后， 充入氢气 0.28 MPa, 充入乙烯至 0.73 MPa, 恒压恒温反应 2 h。 [0066] Ethylene copolymerization: After fully replacing the 2 liter stainless steel autoclave with nitrogen, the main catalyst component 20 mg, dehydrated hexane 1000 ml, AlEt 3 solution 1.17 ml (2 mmol/ml) were added to the kettle in turn, and added. Ml 1-self woman. After heating to 80 °C, it was charged with 0.28 MPa of hydrogen, charged with ethylene to 0.73 MPa, and reacted at constant pressure for 2 h.
[0067]应用方式三 [0067] Application Mode 3
[0068]丙烯聚合： 将 2升不锈钢高压釜经氮气充分置换后， 依次向釜中加入 主催化剂组分 20 mg , 脱水己烷 1000 ml , AlEt3溶液 1.17 ml(2mmol/ml) , 升 温至 80 °C后， 充入丙烯至 3MPa, 恒压恒温反应 2 h。 [0068] Propylene polymerization: After fully replacing the 2 liter stainless steel autoclave with nitrogen, the main catalyst component 20 mg, dehydrated hexane 1000 ml, AlEt 3 solution 1.17 ml (2 mmol/ml) were sequentially added to the kettle, and the temperature was raised to 80. After °C, it was charged with propylene to 3 MPa, and reacted at constant pressure for 2 h.
[0069]结果见表 2。 [0069] The results are shown in Table 2.
表 1 主催化剂中 Mg, Si, 小于 C5的醇和大于 C5的醇的质量百分含量 Table 1 Mass percentage of Mg, Si, alcohol less than C5 and alcohol larger than C5 in the main catalyst
Figure imgf000017_0001
表 2
Figure imgf000017_0001
Table 2
Figure imgf000018_0001
Figure imgf000018_0001

Claims

权 利 要 求 Rights request
1. 烯烃聚合催化剂由主催化剂和助催化剂组成， 其特征在于： 所述的 主催化剂由卤化镁、 过渡金属卤化物、 小于或等于 C5的醇、 大于 C5的醇、 有机硅化合物和有机醇醚化合物组成； 化镁、 过渡金属 化物、 小于 C5 的醇、 大于 C5的醇和有机硅化合物的摩尔比为： 1: ( 1-40) : (0.1-5) ：1. An olefin polymerization catalyst consisting of a main catalyst and a cocatalyst, characterized in that: the main catalyst comprises a magnesium halide, a transition metal halide, an alcohol lower than or equal to C5, an alcohol larger than C5, an organosilicon compound and an organic alcohol ether. Compound composition; molar ratio of magnesium, transition metallization, alcohol less than C5, alcohol larger than C5 and organosilicon compound: 1: (1-40) : (0.1-5) :
(0.01-10 ):(0.01-10)；卤化镁与有机醇醚化合物的质量比为: 100: (0.1-20); 所述的助催化剂为有机铝化合物； 主催化剂中的过渡金属 化物与助催化剂 的摩尔比为 1: 10-500。 (0.01-10): (0.01-10); the mass ratio of the magnesium halide to the organic alcohol ether compound is: 100: (0.1-20); the cocatalyst is an organoaluminum compound; the transition metal compound in the main catalyst and The molar ratio of the cocatalyst is 1: 10-500.
2.根据权利要求 1所述的烯烃聚合催化剂， 其特征在于： 所述的 化镁 载体选自通式（ 1 ) 为 Mg(R)aXb的化合物中的至少一种， R选自 CI ~ C20 的脂肪烃基、 CI ~ C20的脂肪烷氧基、 C3 ~ C20的脂环基或 C6 ~ C20的芳 香烃基； X选自卤素； a = 0、 1或 2, b = 0、 1或 2, 且 a + b = 2。 The olefin polymerization catalyst according to claim 1, wherein the magnesium support is at least one selected from the group consisting of compounds of the formula (1) of Mg(R)aXb, and R is selected from CI to C20. An aliphatic hydrocarbon group, a CI to C20 fatty alkoxy group, a C3 to C20 alicyclic group or a C6 to C20 aromatic hydrocarbon group; X is selected from a halogen; a = 0, 1 or 2, b = 0, 1 or 2, and a + b = 2.
3.根据权利要求 1所述的烯烃聚合催化剂， 其特征在于： 过渡金属卤化 物选自通式（2) 为 M(Rl)4-mXm的化合物中的至少一种， 式中， M是 Ti, Zr, Hf, Fe, Co或 Ni; X是卤原子， 选自 CI, Br, F; m为 0到 4的整数； Rl 选自 CI ~ C20的脂肪烃基、 CI ~ C20的脂肪烷氧基、 CI ~ C20的环戊二烯 基及其衍生物、 ci ~ C20的芳香烃基、 COR;或 COOR; , R;是 C1 ~ C10的脂 肪族基或 CI ~C10的芳香基， 优选过渡金属卤化物与卤化镁的摩尔比为 ( 1-40) ： 1。 The olefin polymerization catalyst according to claim 1, wherein the transition metal halide is at least one selected from the group consisting of compounds of the formula (2) of M(Rl)4-mXm, wherein M is Ti , Zr, Hf, Fe, Co or Ni; X is a halogen atom selected from CI, Br, F; m is an integer from 0 to 4; Rl is selected from an aliphatic hydrocarbon group of CI ~ C20, a fatty alkoxy group of CI ~ C20 , CI ~ C20 cyclopentadienyl and its derivatives, ci ~ C20 aromatic hydrocarbon group, COR; or COOR;, R; is a C1 ~ C10 aliphatic group or CI ~ C10 aromatic group, preferably transition metal halogenation The molar ratio of the substance to the magnesium halide is (1-40): 1.
4. 根据权利要求 1所述的烯烃聚合催化剂，其特征在于： 所述的小于或 等于 C5的醇是碳原子数小于或等于 5的脂肪醇或脂环醇， 优选小于 C5的 醇与卤化镁的摩尔比为 （0.1-5) ： 1。 The olefin polymerization catalyst according to claim 1, wherein the alcohol of less than or equal to C5 is a fatty alcohol or an alicyclic alcohol having a carbon number of 5 or less, preferably an alcohol of less than C5 and a magnesium halide. The molar ratio is (0.1-5): 1.
5.根据权利要求 1所述的烯烃聚合催化剂， 其特征在于： 所述的大于 C5 的醇是碳原子数为 C6-C20的脂肪醇或脂环醇或芳香醇，优选大于 C5的醇 与卤化镁的摩尔比为 (0.01-10) ： 1。 The olefin polymerization catalyst according to claim 1, wherein the alcohol larger than C5 is a C6-C20 fatty alcohol or an alicyclic alcohol or an aromatic alcohol, preferably an alcohol larger than C5 and halogenated. The molar ratio of magnesium is (0.01-10): 1.
6. 根据权利要求 1所述的烯烃聚合催化剂，其特征在于： 所述的有机硅 化合物符合通式 Rx3Ry4Si(OR5)，其中 R3为烃基或卤素， R4为烃基或卤素， R5是烃基， 0<x < 2, 0<y < 2, 和 0 < z≤4, x+y+z = 4, 优选有机硅化合物与 卤化镁的摩尔比为 （0.01-10 ) ： 1。 The olefin polymerization catalyst according to claim 1, wherein the organosilicon compound conforms to the formula Rx3Ry4Si(OR5), wherein R3 is a hydrocarbon group or a halogen, R4 is a hydrocarbon group or a halogen, and R5 is a hydrocarbon group, 0< x < 2, 0 < y < 2, and 0 < z ≤ 4, x + y + z = 4, preferably the molar ratio of the organosilicon compound to the magnesium halide is (0.01 - 10 ) : 1.
7. 根据权利要求 1所述的烯烃聚合催化剂，其特征在于： 所述的有机醇 醚化合物其特征为末端基为羟基， 选自符合通式 (3) HO(CH2)fO(CH2)nR2; 其 中， f为 1到 20的整数， n为 1到 10的整数， R选自 C广 C30的脂肪烃基、 C3~C3。的环烷基、 C6~C3。的芳香烃基或 C2~C3。的杂环烷基，优选卤化镁与有 机醇醚化合物的质量比为： 100: ( 0.1 - 20 ) 。 The olefin polymerization catalyst according to claim 1, wherein the organic alcohol ether compound is characterized in that the terminal group is a hydroxyl group selected from the group consisting of the formula (3) HO(CH 2 )fO(CH 2 ) n R 2 ; wherein, f is an integer from 1 to 20, n is an integer from 1 to 10, and R is selected from C- C30 aliphatic hydrocarbon groups, C 3 to C 3 . Cycloalkyl, C 6 ~ C 3 . Aromatic hydrocarbon group or C 2 ~ C 3 . The mass ratio of the heterocycloalkyl group, preferably the magnesium halide to the organic alcohol ether compound, is: 100: (0.1 - 20 ).
8. 根据权利要求 1所述的烯烃聚合催化剂， 其特征在于： 所述的小于 C5或等于 C5的醇为乙醇、 曱醇、 丙醇、 丁醇或戊醇或其任意组合， 更优选 为乙醇。 The olefin polymerization catalyst according to claim 1, wherein the alcohol less than C5 or equal to C5 is ethanol, decyl alcohol, propanol, butanol or pentanol or any combination thereof, more preferably ethanol. .
9. 根据权利要求 1所述的烯烃聚合催化剂， 其特征在于： 所述大于 C5 的醇为庚醇、 异辛醇、 辛醇、 壬醇、 癸醇、 十一醇、 十二醇、 十三醇、 十四 醇、 十五醇或十六醇或其任意组合， 优选异辛醇。 The olefin polymerization catalyst according to claim 1, wherein the alcohol having a C5 content is heptanol, isooctanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, decadiol, and thirteen Alcohol, tetradecanol, pentadecyl alcohol or cetyl alcohol or any combination thereof, preferably isooctanol.
10. 根据权利要求 1所述的烯烃聚合催化剂， 其特征在于： 所述的小于 或等于 C5的醇是乙醇， 以及大于 C5的醇是碳原子数为异辛醇。 The olefin polymerization catalyst according to claim 1, wherein the alcohol of C5 or less is ethanol, and the alcohol of C5 is an isooctyl alcohol.
11. 根据权利要求 1所述的烯烃聚合催化剂的制备方法， 其特征在于： 包括以下步骤： The method for preparing an olefin polymerization catalyst according to claim 1, comprising the steps of:
1 )将卤化镁载体分散于有机溶剂中， 加入小于或等于 C5的醇和大于 C5的醇， 于 50至 150°C下搅拌溶解 1至 5h;  1) dispersing the magnesium halide carrier in an organic solvent, adding an alcohol less than or equal to C5 and an alcohol greater than C5, and stirring and dissolving at 50 to 150 ° C for 1 to 5 hours;
2 )将 1)溶液降温至 10°C至 80°C , 依次加入有机硅化合物和有机醇醚化 合物， 反应 0.5至 3h; 3)在 -25至 30°C下， 向步骤 2)得到的体系中加入过渡金属卤化物， 加 完后在 -25至 30°C下反应 0.5-5h, 再将体系升温至 20-150°C, 反应 0.5-5h; 静置， 分层， 过滤， 己烷洗涤； 每次过渡金属卤化物与卤化镁的摩尔比为： ( 1-40) ： 1; 2) 1) the solution is cooled to 10 ° C to 80 ° C, the organosilicon compound and the organic alcohol ether compound are sequentially added, the reaction is 0.5 to 3 h; 3) Adding a transition metal halide to the system obtained in the step 2) at -25 to 30 ° C, after the addition, reacting at -25 to 30 ° C for 0.5-5 h, and then heating the system to 20-150 ° C, reaction 0.5-5h; standing, layering, filtration, hexane washing; each molar ratio of transition metal halide to magnesium halide is: (1-40): 1;
4) 以曱苯或己烷洗涤产物， 过滤除去未反应物， 真空干燥得到粉末状 固体主催化剂；  4) washing the product with terpene or hexane, removing unreacted materials by filtration, and drying in vacuo to obtain a powdery solid main catalyst;
其中， 所述的有机溶剂选自 C5~C15的饱和烃、 Cs-Ci。的脂环烃、 C6~ C15的芳香烃或 C3 ~ C10的饱和杂环烃或它们的混合溶剂。 Wherein, the organic solvent is selected from the group consisting of C 5 - C 15 saturated hydrocarbons and Cs-Ci. An alicyclic hydrocarbon, a C 6 - C 15 aromatic hydrocarbon or a C 3 - C 10 saturated heterocyclic hydrocarbon or a mixed solvent thereof.
12. 根据权利要求 11所述的烯烃聚合催化剂的制备方法， 其特征在于： 在步骤 3 )之后还包括以下步骤： The method for preparing an olefin polymerization catalyst according to claim 11, further comprising the following steps after the step 3):
再在 -25至 30°C下， 加入过渡金属 化物以及有机溶剂， 加完后在 -25 至 30°C下反应 0.5-5h,再将体系升温至 20-150°C,反应 0.5-5h; 静置， 分层， 过滤， 己烷洗涤； 每次过渡金属卤化物与卤化镁的摩尔比为： （1-40) : 1; 本步骤操作的次数是 1次 -3次。  Further adding a transition metal compound and an organic solvent at -25 to 30 ° C, after the addition, the reaction is carried out at -25 to 30 ° C for 0.5-5 h, and then the system is heated to 20-150 ° C, the reaction is 0.5-5 h; The mixture is allowed to stand, layered, filtered, and washed with hexane; the molar ratio of each transition metal halide to magnesium halide is: (1-40): 1; The number of operations in this step is 1 - 3 times.
13. 根据权利要求 1所述的烯烃聚合催化剂的应用， 其特征在于： 所述 的烯烃聚合催化剂作为乙烯聚合、 丙烯聚合、 乙烯与 α-烯烃的共聚合、 或丙 烯与 α-烯烃的共聚合催化剂， 其中， 所述的 α-烯烃选自 C3~C2。的烯烃。 The use of the olefin polymerization catalyst according to claim 1, wherein the olefin polymerization catalyst is used as an ethylene polymerization, a propylene polymerization, a copolymerization of ethylene and an α-olefin, or a copolymerization of propylene and an α-olefin. a catalyst, wherein the α-olefin is selected from the group consisting of C 3 to C 2 . Olefins.
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