WO2013075643A1 - Catalyseur de polymérisation d'oléfines, procédé de préparation, et application associée - Google Patents

Catalyseur de polymérisation d'oléfines, procédé de préparation, et application associée 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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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

Definitions

  • 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.

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Abstract

La présente invention concerne un catalyseur de polymérisation d'oléfines, son procédé de préparation et son application et concerne le domaine du catalyseur de polymérisation d'oléfines et de la polymérisation d'oléfines. Le catalyseur de polymérisation d'oléfines est formé d'un catalyseur principal et d'un co-catalyseur. Le catalyseur principal est formé d'un support à base d'halogénure de magnésium, d'halogénure d'un métal de transition, d'alcool doté de 5 atomes de carbone ou moins, d'alcool doté de plus de 5 atomes de carbone, d'un composé de silicium organique et d'un composé éther d'alcool organique. Le rapport molaire entre l'halogénure de magnésium et l'halogénure de métal de transition, l'alcool doté de 5 atomes de carbone ou moins, l'alcool doté de plus de 5 atomes de carbone et le composé de silicium organique est 1/(1-40)/(0,1-5)/(0,01-10)/(0,01-10). Le rapport de masse entre l'halogénure de magnésium et le composé d'éther organique est 100/ (0,1-20). Le co-catalyseur est un composé d'aluminium organique. Les particules du catalyseur de la présente invention ont une bonne forme et sont sphériques. Le catalyseur présente une activité élevée et une performance de régulation de l'hydrogène souhaitable, est applicable à un procédé de polymérisation en suspension, un procédé de polymérisation en phase gazeuse ou à un procédé de polymérisation combinée.
PCT/CN2012/085049 2011-11-26 2012-11-22 Catalyseur de polymérisation d'oléfines, procédé de préparation, et application associée WO2013075643A1 (fr)

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CN102911299B (zh) * 2012-11-05 2015-03-04 北京化工大学 烯烃高效聚合催化剂及制备方法和应用
CN103113500B (zh) * 2013-01-29 2015-05-27 北京化工大学 烯烃配位聚合催化剂及其制备方法和应用
CN103073662B (zh) * 2013-01-29 2015-04-29 北京化工大学 烯烃聚合催化剂及其制备方法和应用
CN103159873A (zh) * 2013-03-06 2013-06-19 中国石油天然气股份有限公司 一种负载型聚烯烃催化剂及其制备和应用
CN103183754A (zh) * 2013-03-13 2013-07-03 中国石油天然气股份有限公司 一种烯烃聚合催化剂及制备方法
CN103613690A (zh) * 2013-11-25 2014-03-05 北京化工大学 一种烯烃聚合催化剂及其制备方法和应用
CN106519084B (zh) * 2015-09-15 2019-02-15 中国石油天然气股份有限公司 烯烃聚合催化剂用主催化剂及其制备方法与烯烃聚合催化剂
CN107344974B (zh) 2016-05-04 2020-06-09 中国石油天然气股份有限公司 烯烃配位聚合催化剂及制备方法与应用
CN108017735B (zh) * 2018-01-09 2020-07-21 为信（深圳）材料科技有限公司 一种球形烷氧基镁颗粒的组份及制备方法
CN108467442B (zh) 2018-02-11 2021-06-01 中国石油天然气股份有限公司 一种烯烃配位聚合催化剂及其应用

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