WO2011028178A1 - Catalyseur ziegler-natta, à morphologie contrôlée, hautement actif, pour la fabrication du polyéthylène et procédé de fabrication de ce catalyseur - Google Patents

Catalyseur ziegler-natta, à morphologie contrôlée, hautement actif, pour la fabrication du polyéthylène et procédé de fabrication de ce catalyseur Download PDF

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Publication number
WO2011028178A1
WO2011028178A1 PCT/SG2009/000316 SG2009000316W WO2011028178A1 WO 2011028178 A1 WO2011028178 A1 WO 2011028178A1 SG 2009000316 W SG2009000316 W SG 2009000316W WO 2011028178 A1 WO2011028178 A1 WO 2011028178A1
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catalyst
magnesium
based support
chloride based
magnesium chloride
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PCT/SG2009/000316
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English (en)
Inventor
Likhasit Sinthusai
Roman Strauss
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Irpc Public Company Limited
Axis Ip Holding Pte Ltd
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Priority to PCT/SG2009/000316 priority Critical patent/WO2011028178A1/fr
Publication of WO2011028178A1 publication Critical patent/WO2011028178A1/fr

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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
    • C08F110/02—Ethene

Definitions

  • the present disclosure generally relates to a stable, morphologically controlled Ziegler- Natta polyethylene catalyst with high activity and lifespan. More particularly, the present disclosure describes various preparation processes for making the catalyst. The present disclosure further describes various processes for using the catalyst to make polyethylene and other polyolefins.
  • Catalysts are usually used in the production of polymers of 1-alkenes (a-olefins).
  • properties of a polymer such as stereoregularity and morphology, are dependent on the type of catalyst used during the polymerization process.
  • ZN catalyst Ziegler-Natta catalyst
  • ZN catalysts are used extensively in industry to produce commercially important polymers with high stereoselectivity.
  • ZN catalysts are usually based on titanium compounds and organometallic aluminium compounds.
  • Cossee-Arlman mechanism describes a restriction in binding of the incoming monomers at any random chlorine site on titanium surfaces of the catalyst. Instead, incoming monomers are directed to a specific vacant chlorine site on a titanium surface, thereby imposing stereoregularity on the growing polymer chain. Details of the Cossee-Arlman reaction mechanism can be found in "Bochmann, M., Organometallics 1, Complexes with Transition Metal-Carbon ⁇ -Bonds, Oxford University Press, New York, 1994: pp. 69-71".
  • a method for preparing a ZN catalyst includes contacting a magnesium compound with an alcohol, triethyl aluminium, a binding agent such as an organosilane and an internal electron donor such as a monoester to form a soluble magnesium complex; chlorinating the soluble magnesium complex with ethylaluminium dichloride to obtain a magnesium chloride based support; purifying the magnesium chloride based support; titanating and aging the magnesium chloride based support; and separating the titanated magnesium chloride based support to obtain the ZN catalyst.
  • a ZN catalyst produced by the above process and having particular catalyst properties is disclosed.
  • a ZN catalyst according to the disclosure can include approximately 21.0 to 27.5 wt-% of magnesium and approximately 5.5 to 6.0 wt-% of titanium.
  • a polyethylene co-polymer can be produced by a process involving contacting ethylene with one or more a-olefin monomers in the presence of a ZN catalyst of the present disclosure under polymerization conditions.
  • a ZN catalyst is capable of facilitating the production of a polyethylene homo- or co-polymer with an average particle size of 500 to 600 ⁇ and a fine particle content of less than approximately 2 v-%.
  • FIG. 1A shows a scanning electron microscope micrograph of a representative catalyst obtained according to an embodiment of the disclosure at 200X magnification
  • FIG. IB shows a scanning electron microscope micrograph of a representative catalyst obtained according to an embodiment of the disclosure at 1500X magnification
  • FIG. 2A shows a scanning electron microscope micrograph of a representative polyethylene produced with a catalyst synthesized according to an embodiment of the disclosure at 200X magnification
  • FIG. 2B shows a scanning electron microscope micrograph of a representative polyethylene produced with a catalyst synthesized according to an embodiment of the disclosure at 75 OX magnification.
  • the present disclosure relates to ZN catalysts having desirable properties such as high stability, high activity, effective particle morphology control, long catalyst lifespan and an ability to meet a satisfactory performance-cost target.
  • the present disclosure also relates to techniques, processes or methods for making, manufacturing or synthesizing such catalysts.
  • the present disclosure relates to polyethylene homo- and co- polymer that can be made, manufactured or synthesized using such ZN catalysts.
  • a process for making a ZN catalyst in accordance with various embodiments of the disclosure generally includes multiple reaction steps.
  • the process can include preparing a disordered MgCl 2 support; titanating and aging the disordered MgCl 2 support; and decantation and purification to obtain the catalyst.
  • the reaction steps can be carried in a single reaction vessel.
  • the multiple reaction steps can be carried out in one- liter glass reactor under inert gas atmosphere, which is coupled or connected to an agitator and a condenser.
  • Preparation of a disordered MgCl 2 support involves reacting a magnesium compound with an alcohol.
  • a suitable magnesium compound include one or more of butyloctyl magnesium (BOMAG), ethyl magnesium chloride, butyl ethylmagnesium (BEM) and the like.
  • a suitable alcohol for this reaction include one or more of 2- ethyl- 1-hexanol (2-EHA), isopropyl alcohol, n- butyl alcohol and the like.
  • the alcohol is 2-ethyl-l- hexanol.
  • the molar ratio of alcohol/Mg is between 0.5 to 4.0. Typically, the molar ratio of alcohol/Mg is maintained at about 3.5.
  • the viscosity of the magnesium compound can be high.
  • preparation of a disordered MgCl 2 support can include addition of triethylaluminium (TEA) as a viscosity reducing agent.
  • TAA triethylaluminium
  • the molar ratio of viscosity reducing agent/Mg is between -0.1 to 0.6. Typically, the molar ratio of the viscosity reducing agent/Mg is maintained at about 0.5.
  • the reaction between a magnesium source and an alcohol can be carried out in the presence of an internal electron donor.
  • the internal electron donor acts to increase hydrogen sensitivity and thermal stability of the catalyst end-product.
  • the internal electron donor additionally acts as an MgCl 2 coordinating agent during a titanation and an aging process sequence. During titanation and aging, the internal electron donor creates a disordered MgCl 2 support crystal structure and facilitates coordination of a catalyst precursor (for example, titanium compounds) onto the MgCl 2 support.
  • the internal electron donor is a monoester such as ethyl benzoate (EB), n-propyl benzoate, isopropyl benzoate, n-butyl benzoate or the like.
  • the molar ratio of internal electron donor/Mg can be varied between about 0.05 to about 0.15. In various embodiments, the molar ratio of an internal electron donor/Mg is about 0.05 to 0.06 for producing a catalyst with optimum properties.
  • the reaction between the magnesium compound and alcohol can be carried out in the presence of a binding agent or catalyst particle stabilizer.
  • the binding agent can be incorporated during the synthesis process of a ZN catalyst to produce a catalyst end-product with a binding agent component.
  • the binding agent acts to improve catalyst particle stability.
  • the binding agent component in the catalyst can act to improve polymer particle stability, thereby resulting in production of polymers with low fine polymer content.
  • the binding agent component of the catalyst also acts as a co-internal electron donor during an ethylene homo- or co-polymerization process.
  • an organosilane such as one or more of dicyclopentyl dimethoxysilane (DCPMS), diisopropyl dimethoxysilane, cyclohexyl methyl dimethoxysilane, isobutyl isopropyl dimethoxysilane and the like, is used as a binding agent.
  • the molar ratio between the binding agent and Mg can be varied between 0.25 and 1.0, which will be illustrated by examples described in detail below.
  • molar ratio of binding agent/Mg is selected in view of manufacturing cost considerations, for instance, a lower binding agent/Mg molar ratio may reduce manufacturing cost.
  • the binding agent/Mg molar ratio is maintained between about 0.25 to about 0.50.
  • the reaction between a magnesium source and an alcohol in the presence of a viscosity reducing agent, an internal electron donor and a binding agent is an exothermic reaction.
  • the reaction is usually carried out at a temperature below 60°C, for example, above approximately 50°C, or at about 55°C to about 58°C.
  • the intermediate resulting from the reaction between a magnesium compound and an alcohol in the presence of a viscosity reducing agent, an internal electron donor and a binding agent is a soluble magnesium complex.
  • the intermediate can be reacted with a chlorinating agent to form a solid precipitate.
  • the solid precipitate is a disordered MgCl 2 based support.
  • a chlorinating agent include one or more of ethyl aluminium dichloride (EADC), diethyl aluminium chloride (DEAC), ethyl aluminium sesquichloride (EASC), titanium tetrachloride and the like.
  • the chlorinating agent is EADC.
  • the molar ratio of chlorinating agent/Mg can range from 0.5 to 2.0.
  • the molar ratio of chlorinating agent/Mg is typically maintained at 1.0 for optimum results.
  • the chlorination process can be performed at room temperature.
  • the process further includes purification of a disordered MgCl 2 based support.
  • a supernatant liquid phase can be removed, decanted or siphoned off and the solid precipitate can be washed or extracted, e.g., with a hydrocarbon solvent.
  • the solid precipitate can be subjected to at least two washing procedures (e.g., the solid precipitate can be washed at least two times).
  • Suitable hydrocarbon solvents for washing include heptane, hexane and the like.
  • titanating and aging of MgCl 2 based support includes adding a titanium compound to the MgCl 2 based support.
  • suitable titanium compounds include titanium tetrachloride (TiCl 4 ) and the like.
  • TiCl 4 titanium tetrachloride
  • the molar ratio of Ti/Mg ranges between about 2.0 and about 4.0, as further detailed in examples described below. To obtain a catalyst with desired properties, the molar ratio of Ti/Mg can be about 4.0.
  • the titanation and aging reaction can be carried out at an elevated temperature for a suitable period of time. The titanation and aging process can be performed over a wide range of temperatures.
  • very high temperature for example, over approximately 100°C
  • very low temperature for example, under approximately 80°C
  • a high titanating and aging temperature often results in coordination of titanium compounds on nonspecific active sites on the MgCl 2 based support.
  • the use of such catalysts for ethylene homo- and co-polymerization processes can give rise to polymers with undesirable properties such as a broad molecular weight distribution (MWD).
  • a very low temperature should be avoided as the titanium compound cannot be properly coordinated to the MgCl 2 based support under such a temperature condition.
  • the mixture can be heated to a temperature of about 80°C to 100°C.
  • the mixture can be heated up to approximately 85°C.
  • the performance of the catalyst is generally affected by the aging time.
  • the aging time is generally kept below 8 hours.
  • the aging time can be between about 3 hours to about 8 hours.
  • aging can be performed over a period of about 5 hours.
  • the process for making a ZN catalyst further includes separation of the catalyst, for example, by decantation and purification of the catalyst.
  • the supernatant liquid phase can be removed, extracted, decanted or siphoned off after titanating and aging of the MgCl 2 based support.
  • the solid precipitate can be washed several times with a hydrocarbon solvent until the titanium content in a mother liquor is less than about 8-15mmol/L (for example, lOmmol/L). In several embodiments, the solid precipitate is washed at least seven times. Suitable hydrocarbon solvents for washing include heptane, hexane and the like.
  • FIG. 1 shows a SEM micrograph of a catalyst obtained in accordance with a representative embodiment of the disclosure.
  • Catalysts obtained in accordance with various embodiments of the disclosure generally have a spherical shape.
  • the particle size of the catalyst generally varies with the specific type of reagents used during the production process, as shown in later examples. In some embodiments, the particle size of the catalyst can range from 3 micrometers to 60 micrometers, for example, from 10 micrometers to 40 micrometers. In a representative embodiment as illustrated in FIG. IB, size of the catalyst is approximately 40 micrometers.
  • Polymerization of ethylene in accordance with the present disclosure can be carried out in the presence of a catalyst that is synthesized in accordance with any of the above embodiments.
  • ethylene can be introduced or brought into contact with one or more a-olefin monomers in the presence of a ZN catalyst under suitable polymerization conditions to form polyolefins such as polyethylene, high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear-low-density polyethylene (LLDPE) and the like.
  • HDPE high-density polyethylene
  • MDPE medium-density polyethylene
  • LLDPE linear-low-density polyethylene
  • the polymerization process can be carried out in the presence of an organoaluminium compound as a co-catalyst, with hexane as a reaction medium.
  • organoaluminium compounds include triethylaluminium (TEA), tri-isobutylylaluminium (TIBAL), isoprenylaluminium (IPRA), which is a reaction product of aluminiumtrialkyl or aluminiumdialkyl hydride with isoprene, and the like.
  • TAA triethylaluminium
  • TIBAL tri-isobutylylaluminium
  • IPRA isoprenylaluminium
  • the amount of organoaluminium added can be dependent on the purity of hexane (for example, an amount of organoaluminium can be added until an Al/Ti molar ratio ranges from 10 to 200).
  • the Al/Ti molar ratio can be established or maintained at about 50.
  • the polymerization process is usually carried out in a slurry phase within a reactor.
  • the catalyst suspension can be first introduced into the reactor followed by the introduction of ethylene in the gaseous phase through a control valve that is coupled to the reactor.
  • the polymerization process can be carried out at a temperature between about 70°C to about 90°C and under total pressure of about 6-10 bars.
  • pressure within the reactor can come from the partial pressures of hydrogen gas, hexane vapour and the ethylene gas. Hence, constant pressure within the reactor can be maintained throughout the polymerization reaction by adjusting the flow rate of ethylene gas input.
  • the polymerization process can be carried out under the following conditions: polymerization temperature of about 80°C; total pressure of about 8 bar made up of partial pressure of about 4.4 bar ethylene gas, about 1.0 bar hydrogen gas, and the remaining partial pressure from hexane vapor; and reaction time of about two hours.
  • This set of reaction conditions will be referred hereafter as the standard polymerization conditions.
  • the catalyst system can provide a high level of activity of at least about 40 Kg PE/g cat under standard polymerization conditions. In another embodiment, the catalyst activity can be at least about 45 Kg PE/g cat.
  • the lifespan of the catalyst obtained in accordance with the present disclosure is expected to be longer than conventional catalysts. In view of such a lifespan, catalysts in accordance with the embodiments of the disclosure are promising catalyst candidates for use in multimodal high-density polyethylene (HDPE) production processes, e.g., multi-reactor cascade slurry or gas phase processes.
  • HDPE high-density polyethylene
  • Fig. 2 shows a SEM micrograph of polyethylene produced with a catalyst synthesized in accordance with an embodiment of the disclosure.
  • the polyethylene is produced in the presence of the catalyst under standard polymerization condition.
  • the polymer macroparticles are composed of primary particles in accordance with the "Multi Grain Model”. Fibril linkages between the primary particles can also be observed as illustrated in Fig. 2B. It is possible that these linkages play a role in preventing fragmentation of macroparticles during the polymer particle growth process.
  • Particle size of the polymers so obtained can range between about 500 ⁇ ⁇ ⁇ to 750 ⁇ in most embodiments. In some embodiments, the particle size of the polymers can be between about 500 ⁇ to 600 ⁇ .
  • the span of polymer particle size can be less than about 2.0, as further detailed below. This indicates that the distribution of the polymer particle size can be narrow.
  • the polymers so obtained can also have very low fine polymer content. Specifically, the percentage volume of polymers with particle size smaller than ⁇ can be less than about 2% in most embodiments. In some embodiments, the fine polymer content can be less than about 1.5%.
  • Polyethylene homo- and co-polymers produced in accordance with various embodiments of the disclosure can have one or more desirable properties such as good morphology control, large particle size, low fine polymer content and narrow particle size distribution. Due to the low fine polymer content of the polyethylene polymers produced, less clogging is expected in a filter used in a drying column for polyethylene powder drying. As a result, the filter need not be changed as frequently, thereby saving on cost and time incurred for replacing the filter. Furthermore, in view of the good morphology control, large particle size and narrow particle size distribution, the polyethylene produced can have a high bulk density. This implies that the polyethylene powder has high flowability.
  • the polyethylene homo- and co-polymers produced in accordance with the disclosure and after melt-homogenization and stabilization according to procedures known in the art are suitable for film, injection molding, pipe, sheet, profile extrusion blow molding, and other applications.
  • Examples 1A - 1C correspond to catalyst synthesis conditions under different DCPMS/Mg molar ratio conditions while other catalyst synthesis conditions are held constant.
  • the molar ratio of TEA/Mg is held at 0.5, that of 2-EHA/Mg at 3.5, that of EB/Mg at 0.125, that of EADC/Mg at 1.0, that of Ti/Mg at 3.0; while the temperature is maintained at 85°C during titanation, and titanation is performed over a period of 5 hours.
  • Examples 2A - 2C correspond to catalyst synthesis conditions under different Ti/Mg molar ratios, while other catalyst synthesis conditions remain constant.
  • Examples 2A - 2C the molar ratio of TEA/Mg is held at 0.5, that of 2-EHA/Mg at 3.5, that of EB/Mg at 0.125, that of DCPMS/Mg at 0.5, that of EADC/Mg at 1.0; while the temperature is maintained at 85°C during titanation, and titanation is performed over a period of 5 hours.
  • Examples 3A - 3C correspond to different catalyst aging times, where other catalyst synthesis conditions remain constant.
  • the molar ratio of TEA/Mg is held at 0.5, that of 2-EHA/Mg at 3.5, that of EB/Mg at 0.125, that of DCPMS/Mg at 0.5, that of EADC/Mg at 1.0, that of Ti/Mg at 3.0; while the temperature is maintained at 85°C during titanation.
  • Examples 4A - 4E correspond to catalyst synthesis conditions under different EB/Mg and DCPMS/Mg molar ratio conditions while other catalyst synthesis conditions are held constant.
  • the molar ratio of TEA/Mg is held at 0.5, that of 2-EHA/Mg at 3.5, that of EADC/Mg at 1.0, and that of Ti/Mg at 4.0; while the temperature is maintained at 85°C during titanation, and titanation is performed over a period of 5 hours.
  • a process for making a ZN catalyst is carried out under nitrogen atmosphere. 200ml
  • heptane After washing, 200ml of heptane is added to the reactor.
  • the reactor is heated up to 85°C.
  • 57.7ml (525.1mmol) of TiCl 4 is added into the reactor via a dropping funnel at a dropping rate of lml/min to initiate the titanating process.
  • the content within the reactor is stirred at a rate of 300rpm.
  • the agitator is switched off after 5h to allow the catalyst to settle.
  • the supernatant is siphoned off and TiCl 4 catalyst with MgCl 2 -based support is washed at least 7 times with 400ml of heptane at a temperature of 60-70°C.
  • the resulting catalyst is referred hereinafter as Catalyst 1A.
  • the titanium content of the mother liquor should be less than 1 Ommol/L.
  • the polymerization reaction is earned out in a 2-liter reactor equipped with a mechanical stirrer.
  • A1(C 2 H 5 ) 3 (TEA) is added to 1000ml of dried hexane (after N 2 stripping) in the reactor.
  • the amount of TEA is fixed at a molar ratio of Al/Ti of 50.
  • 0.01 mmol of catalyst suspension is introduced into the reactor using a pipette.
  • the content of the reactor is purged 3 times under a pressure of 5 bar of nitrogen gas, followed by purging 3 times under a 10 bar hydrogen gas pressure.
  • the reactor is heated ; up to 80°C and is pressurized with 1 bar of hydrogen gas and ethylene gas to a constant pressure of 8 bar for 2h.
  • a constant pressure is maintained during the polymerization process by controlling the ethylene gas flow rate.
  • the polymerization process is stopped after 2h by shutting off the valve that controls the flow of ethylene gas.
  • the suspension is allowed to cool to room temperature and the resulting polymer suspension can be separated and dried at 80°C in a vacuum drying oven for 2h.
  • Catalyst IB can be prepared in a similar manner to that of Example 1A except that DCPMS is not added into the reactor.
  • Example 1C
  • Catalyst 1C can be prepared in a similar manner to that of Example 1A except that 40.8 ml (175mmol) of DCPMS is added to provide a DCPMS/Mg molar ratio of 1.
  • Certain aspects or characteristics of Catalysts 1A, IB, 1C and corresponding polymer characteristics when Catalyst 1A, IB and 1C are used in an ethylene polymerization process are described in Tables 1 and 2.
  • the listed catalyst and polymer characteristics can be obtained by standard measures known and understood by one skilled in the art. Particularly, Mg (wt-%) refers to the weight percentage magnesium content in the catalyst.
  • Mg (wt-%) can be obtained by performing complexation titration with a standard solution of ethylenediaminetetraacetic acid (EDTA).
  • Ti (wt-%) refers to the weight percentage titanium content in the catalyst.
  • Ti (wt-%) can be calculated based on results obtained by performing redox titration of a catalyst sample with Ce(IV) sulfate.
  • CI (wt-%) refers to the weight percentage chlorine content in the catalyst.
  • CI (wt-%) can be obtained by using potentiometric methods such as potentiometric titration with a standard solution of silver nitrate.
  • the morphology of the catalyst and polymer can be observed using standard scanning electron microscopy techniques.
  • Particle diameters, sizes and/or size distributions of the catalyst and the polymer(s) can be measured using a particle sizing system such as a Sympatec particle sizer.
  • Span is a measure of the characteristics (e.g., width) of a particle size distribution, which can be determined in accordance with the following formula:
  • d 90 is an upper diameter threshold, relative to which 90% of the total particulate volume exhibits a diameter that is equal to or smaller than d 90 ; and d 10 is a lower diameter threshold, relative to which 10% of the total particulate volume exhibits a diameter that is equal to or smaller than d 10 .
  • d 5 o is an average diameter threshold, relative to which 50% of the total particulate volume exhibits a diameter that is equal to or smaller than d 50 .
  • Activity of the catalyst can be measured in terms of a number of kilograms of polyethylene produced per gram of catalyst.
  • MFI 2 is the melt flow index measured according to ASTM standard D 1238 under conditions of 190°C and a 2.16 Kg load
  • MFI 5 refers to the melt flow index according to ASTM standard D 1238 under conditions of 190°C and a 5 Kg load. Both MFI 2 and MFI 5 can be measured using a melt indexer such as Goettfert MPX 62.92.
  • MFR refers to the melt flow rate of the polymer. MFR is the ratio between MFI 5 and MFI 2 .
  • fine content (v-%) refers to a volume percentage of particles having a diameter or size equal to or smaller than a fine content threshold, such as ⁇ .
  • Table 1 shows particular catalyst properties of Catalysts 1A, IB and 1C.
  • the magnesium content in each catalyst increases from 16.5 to 32.7 wt-% as the DCPMS/Mg ratio used in the preparation of the catalyst is increased from 0 to 1.0.
  • the titanium content in these catalysts decreases from 5.7 wt-% to 3.5 wt-% as the DCPMS/Mg ratio used in the preparation of the catalyst is increased.
  • the results imply that the ratio of DCPMS/Mg used in the preparation of the catalyst plays a role in controlling the amount of Ti incorporated into the MgCl 2 crystal lattice structure.
  • Chlorine content in the catalysts remains relatively constant and is generally or somewhat independent of the DCPMS/Mg ratio used in the preparation of the catalyst.
  • Catalyst particle size notably increases when the DCPMS/Mg ratio used in the preparation of the catalyst is increased. Specifically, the particle sizes of Catalyst 1 A and 1C are 26.5 ⁇ and 31.4 ⁇ , respectively, thereby demonstrating that DCPMS is involved in the morphology formation process of catalyst particles. The span of the catalyst particles is between 2.0 and 2.5 when DCPMS/Mg ratio is between 0 and 1.0. Catalyst
  • Table 2 lists particular polymer characteristics corresponding to polymerization reactions that involve Catalysts 1A, IB and IC.
  • the activity of Catalysts 1A, IB and IC ranges between 15.0 Kg PE/g cat and 27.0 Kg PE/g cat.
  • Catalyst 1A which is prepared with DCPMS/Mg ratio of 0.5, provides the highest activity level of 27.0 Kg PE/g cat.
  • Melt flow rates of the polymers produced using Catalysts 1A, IB and IC are relatively constant.
  • the average particle sizes of the polymers produced by Catalysts 1A and IC are 630 ⁇ and 524 ⁇ , respectively, while the average particle size of the polymers produced with Catalyst IB is 126 ⁇ .
  • the particle size span for all three catalysts is between 1.2 and 1.6, which indicates that the size distribution of polymer particles is narrow.
  • the fine polymer content of the polymers produced with Catalysts 1A and IC is respectively 0.8 v-% and 1.6 v-%, while the fine polymer content of the polymer produced with Catalyst IB (without DCPMS) is 25 v-%.
  • DCPMS may act as an internal binding agent for improving the mechanical stability of the catalyst particles and preventing fragmentation of polymer particles in early stage of particle growth.
  • Catalyst 2 A can be prepared in a similar mam er to that of Example 1A except that 38.5ml (350.1mmol) of TiCl 4 is added into the reactor via a dropping funnel to create a Ti/Mg molar ratio of 2.0.
  • Catalyst 2B can be prepared in a similar manner to that of Example 1A except that 48.1 ml (437.6mmol) of TiCl 4 is added into the reactor to give a Ti/Mg molar ratio of 2.5.
  • Catalyst 2C can be prepared in a similar manner to that of Example 1A except that 57.7 ml (525.1mmol) of TiCl 4 is added into the reactor to create a Ti/Mg molar ratio of 3.0.
  • Table 3 shows various aspects of catalyst properties of Catalysts 2 A, 2B and 2C.
  • the magnesium content in the catalyst increases with increasing Ti/Mg ratio used in catalyst preparation. Specifically, the magnesium content in the catalyst increases from 9.5 wt-% to 28.3 wt-%) when Ti/Mg ratio is increased from 2.0 to 3.0. Also, the titanium content in the catalyst increases from 1.5 wt-% to 5.3 wt-% when Ti/Mg ratio used in the preparation of the catalyst is increased from 2.0 to 3.0.
  • the chlorine content in the catalysts remains relatively stable or similar for each of the three catalysts.
  • the quantity of titanium incorporated into onto MgCl 2 based support crystal lattice structure is directly dependent on the quantity of TiCl 4 that is added during the preparation of the catalyst.
  • a higher Ti content is fixed onto MgCl 2 based support when more TiCl 4 is added during the preparation of the catalyst.
  • catalyst particle size is generally independent of the Ti/Mg ratio.
  • the particle size distribution spans corresponding to Catalysts 2A, 2B and 2C range between 1.5 and 2.0.
  • Table 4 illustrate various polymer characteristics when Catalysts 2A, 2B and 2C are used for the polymerization of ethylene.
  • Catalyst activity increases with increasing Ti/Mg ratio used in catalyst preparation.
  • the MFI of Catalyst 2B is relatively higher than that of Catalysts 2A and 2C.
  • the particle size of polymers produced with Catalysts 2 A, 2B and 2C are relatively large, at around 450-630 ⁇ . Polymer particle spans are generally low, which indicates that the size distribution of polymer particles is narrow.
  • Table 3 and 4 it can be seen that the use of a higher Ti/Mg ratio in the preparation of the catalyst results in the production of catalysts having desirable catalyst properties and polymers having desired polymer properties or characteristics.
  • Catalyst 3B can be prepared in a similar manner to that of Example 3 A except that, after TiCl 4 is added into the reactor, the catalyst is not left to age.
  • Catalyst 3C can be prepared in a similar manner to that of Example 3 A except that T1CI4 is added into the reactor at a dropping rate of 1 ml/min and the catalyst is left to age for approximately 8 hours.
  • Table 5 shows particular catalyst properties of Catalysts 3 A, 3B and 3C.
  • the magnesium content in the catalysts slightly decreases from 28.3 wt-% without aging to about 24.7 wt- % at an aging time of 5 and 8 h.
  • the titanium content is approximately 5.2 wt-% - 5.3 wt-% at aging time of 0-5 h, and increases to approximately 7.1 wt-% at an aging time of 8 h.
  • the chlorine content in Catalysts 3 A, 3B and 3C ranges around 52-54 wt-%. Additionally, the average particle sizes of the three catalysts are in the range of 26-30 ⁇ with a span of 1.7-2.0.
  • Average polymer particles sizes corresponding to Catalysts 3 A, 3B and 3C are in the range of 489-630 ⁇ , and generally decrease with an increase in aging time. Polymer particle distribution spans range between 1.2 and 1.5. In addition, fine polymer content increases from 0.8 v-% to 2.8 v-% as aging time is increased from 0 h to 8 h. Hence, the results indicate that a catalyst prepared with an aging time of more than 8 hours may produce polyethylene with certain undesirable characteristics. The results further indicate that a catalyst prepared with an aging time of approximately 5 hours can give rise to a polyethylene having acceptable, desired, or optimized characteristics.
  • Catalyst 4A can be prepared in a similar manner to that of Example 1A except that 1.32 ml (9.6mmol) of EB and 20.4 ml (87.5mmol) of DCPMS are added into the reactor and 79.9ml (700mmol) of TiCl 4 was added via dropping funnel to create a EB/Mg molar ratio of 0.050, a DCPMS/Mg molar ratio of 0.50 and a Ti/Mg molar ratio of 4.0.
  • Example 4B
  • Catalyst 4B can be prepared in a similar manner to that of Example 4A except that 1.6ml (l l .Ommol) of EB and 10.2ml (43.75mmol) of DCPMS are added into the reactor to create a EB/Mg molar ratio of 0.055 and a DCPMS/Mg molar ratio of 0.25.
  • Example 4C
  • Catalyst 4C can be prepared in a similar manner to that of Example 4A except that 1.75 ml (12.0mmol) of EB and 20.4ml (87.5mmol) of DCPMS are added into the reactor to create a EB/Mg molar ratio of 0.06 and a DCPMS/Mg molar ratio of 0.50.
  • Example 4D
  • Catalyst 4D can be prepared in a similar manner to that of Example 4 A except that 3.2 ml (21.7mmol) of EB and 20.4ml (87.5mmol) of DCPMS are added into the reactor to create a EB/Mg molar ratio of 0.125 and a DCPMS/Mg molar ratio of 0.50.
  • Example 4E
  • Catalyst 4E can be prepared in a similar manner to that of Example 4 A except that 3.94 ml (27mmol) of EB and 20.4ml (87.5mmol) of DCPMS are added into the reactor to create a EB/Mg molar ratio of 0.135 and a DCPMS/Mg molar ratio of 0.50.
  • Table 7 shows various catalyst properties corresponding to Catalysts 4A - 4E. Based on Table 7, the magnesium content in Catalysts 4A - 4E ranges from 21.0- 27.5 wt-% and is generally independent of EB/Mg ratio.
  • each of Catalysts 4A, 4C, 4D and 4E produces polymers of around 578 ⁇ to 735 ⁇ .
  • Catalyst 4C is able to produce polymers with the largest particle size.
  • an EB/Mg molar ratio between 0.050 to 0.060 can be construed as a desirable or optimum ratio to produce a catalyst with desirable or optimum activity, hydrogen response, and an ability to control polymer particle morphology, mechanical stability of particles in the early stage(s) of the polymerization process and MWD of polymer.

Abstract

L'invention concerne diverses techniques, méthodes et procédés qui peuvent être utilisés dans la fabrication d'un catalyseur Ziegler-Natta (ZN). Dans un mode de réalisation, un procédé de fabrication d'un catalyseur ZN comprend les opérations consistant à préparer un support à base de chlorure de magnésium à l'aide d'une source de magnésium (par exemple, le butyloctyl magnésium), un alcool (par exemple le 2-éthyl-1-hexanol), le dicyclopentyl diméthoxysilane comme agent de liaison, un donneur d'électrons interne (par exemple le benzoate d'éthyle), du triétyl aluminium comme agent de réduction de la viscosité et du dichlorure d'éthyl aluminium comme agent de chloration ; purifier le support à base de chlorure de magnésium ; effectuer une titanation (par exemple à l'aide de tétrachlorure de titane) et faire vieillir (par exemple pendant approximativement 5 heures) le support à base de chlorure de magnésium ; et purifier le composé final afin d'obtenir un catalyseur ZN. Des rapports particuliers entre certains des agents mentionnés ci-dessus sont décrits pour générer des catalyseurs ZN ayant des propriétés visées ou spécifiées, telles que l'activité, la stabilité mécanique, la dimension de particule et la distribution de la dimension de particule. Dans certains modes de réalisation, des homopolymères ou copolymères de polyéthylène avec des α-oléfines supérieures obtenues avec de tels catalyseurs ZN sont décrits, et les caractéristiques des homopolymères correspondants sont également décrites.
PCT/SG2009/000316 2009-09-07 2009-09-07 Catalyseur ziegler-natta, à morphologie contrôlée, hautement actif, pour la fabrication du polyéthylène et procédé de fabrication de ce catalyseur WO2011028178A1 (fr)

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CN109678998A (zh) * 2017-10-19 2019-04-26 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及催化剂体系和预聚合催化剂体系及烯烃聚合方法

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US4581342A (en) * 1984-11-26 1986-04-08 Standard Oil Company (Indiana) Supported olefin polymerization catalyst
US4603183A (en) * 1983-08-18 1986-07-29 E. I. Du Pont De Nemours & Co. Hydrocarbon soluble catalyst supports and resultant polymerization catalysts
US4804726A (en) * 1984-06-11 1989-02-14 Ioyo Soda Manufacturing Co., Ltd. Manufacturing method of polyolefin
US5672665A (en) * 1994-03-25 1997-09-30 Exxon Chemical Patents, Inc. Process for transitioning between incompatible polymerization catalysts
US7078467B1 (en) * 2005-06-14 2006-07-18 Univation Technologies, Llc Single catalyst low, medium and high density polyethylenes
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US4603183A (en) * 1983-08-18 1986-07-29 E. I. Du Pont De Nemours & Co. Hydrocarbon soluble catalyst supports and resultant polymerization catalysts
US4804726A (en) * 1984-06-11 1989-02-14 Ioyo Soda Manufacturing Co., Ltd. Manufacturing method of polyolefin
US4581342A (en) * 1984-11-26 1986-04-08 Standard Oil Company (Indiana) Supported olefin polymerization catalyst
US5672665A (en) * 1994-03-25 1997-09-30 Exxon Chemical Patents, Inc. Process for transitioning between incompatible polymerization catalysts
US7078467B1 (en) * 2005-06-14 2006-07-18 Univation Technologies, Llc Single catalyst low, medium and high density polyethylenes
EP1980576A1 (fr) * 2006-02-03 2008-10-15 Japan Polypropylene Corporation Polymere de propylene, son procede de fabrication, composition de polymere de propylene et article moule fabrique a partir de la composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678998A (zh) * 2017-10-19 2019-04-26 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及催化剂体系和预聚合催化剂体系及烯烃聚合方法
CN109678998B (zh) * 2017-10-19 2021-11-19 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及催化剂体系和预聚合催化剂体系及烯烃聚合方法

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