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WO2001000690A2 - Procede de production de polyethylene en plusieurs etapes - Google Patents

Procede de production de polyethylene en plusieurs etapes Download PDF

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Publication number
WO2001000690A2
WO2001000690A2 PCT/FI2000/000580 FI0000580W WO0100690A2 WO 2001000690 A2 WO2001000690 A2 WO 2001000690A2 FI 0000580 W FI0000580 W FI 0000580W WO 0100690 A2 WO0100690 A2 WO 0100690A2
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WO
WIPO (PCT)
Prior art keywords
process according
polymerisation
copolymer
produced
ethene
Prior art date
Application number
PCT/FI2000/000580
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English (en)
Other versions
WO2001000690A3 (fr
Inventor
Vidar Almqvist
Arild Follestad
Original Assignee
Borealis Technology Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to AU58297/00A priority Critical patent/AU5829700A/en
Publication of WO2001000690A2 publication Critical patent/WO2001000690A2/fr
Publication of WO2001000690A3 publication Critical patent/WO2001000690A3/fr

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Classifications

    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the invention relates to a multi-stage process for producing ethene homo or co- polymer, which multi-stage process comprises, in any order, at least a liquid-phase polymerisation step (a) and a gas-phase polymerisation step (b).
  • the invention also relates to the ethene homo or copolymer produced with said process.
  • Bimodal polyethene materials produced using Ziegler-Natta catalysts in a multistage process are known to have superior mechanical properties compared to uni- modal materials produced with Ziegler-Natta or chromium catalysts.
  • the bimodal materials also have an excellent processability, which allows them to be run in a variety of machines and machine settings, both in those specifically designed for low density polyethene (PE-LD) produced in a high pressure process and in those specifically designed for linear polymers (PE-LLD and PE-HD) produced in a low pressure process.
  • PE-LD low density polyethene
  • PE-LLD and PE-HD linear polymers
  • the molar mass of the polymer is function of the yield of the polymer on the catalyst particle: the lower the yield, the higher the molar mass.
  • Continuously operating reactors have typically an exponential catalyst particle residence time distribution. This means that a large portion of catalyst particles pass through the reactor very quickly. Thus the yield remains low for these catalyst particles, and consequently the molar mass of the polymer produced by these catalyst particles is high. This large portion of high molar mass polymer particles may cause homogeneity problems in the processing, resulting in gels and/or "fish-eyes" in the final product.
  • Melt flow rate (MFR), sometimes also called melt index (MI), is a generally used measure of the molar mass of the polymer.
  • the melt flow rate is measured by pressing the polymer melt through a standard cylindrical die at a preset temperature under a specified load.
  • the measurement temperature for polyethene is 190 °C.
  • the load is generally denoted as a subscript.
  • MFR 21 denotes the melt flow rate measured under 21.6 kg load
  • MFR 2 denotes the melt flow rate measured under 2.16 kg load.
  • Melt flow rate can be determined using e.g. ISO 1133 C4, ASTM D 1238 or DIN 53735 standards.
  • the preparation of bimodal polyethene using a Ziegler-Natta catalyst is disclosed e.g.
  • EP-B-517 868 discloses a process comprising a loop and a gas-phase reactor.
  • the loop reactor may be operated in supercritical conditions above the critical temperature and pressure of the fluid mixture contained within the reactor. While the inventors state that the invention disclosed in EP-B-517 868 is not catalyst specific, the examples they present only disclose the use of a Ziegler-Natta catalyst.
  • EP-A-829 495 discloses a process where polyethene is polymerised in a two-stage slurry process, using a chromium catalyst. In the first stage a low molar mass, high density polyethene is produced and in the second stage a high molar mass polyethene having a relatively low density is produced. According to the inventors, the polymerisation stages can thus be controlled independently from each other.
  • ethene homo or copolymer in a multi-stage process comprising, in any order, at least a liquid-phase polymerisation step (a) and a gas-phase polymerisation step (b).
  • the process is characterised in that the polymerisation is carried out in the presence of a chromium catalyst.
  • the polyethene produced in similar process with chromium catalyst exhibits a much higher melt strength at similar molar mass. This is especially advantageous for the blow moulding application, specially for the blow moulding of large containers.
  • the advantage of the invention is a better homogeneity of the final polymer product as well as a higher activity of the catalyst. Increased homogeneity results from the fact that the molar mass of the polymer increases with increased yield.
  • the catalyst particles have a more even reactor residence time distribution than in a one-stage process, resulting in less polymer particles having a very high molar mass. Consequently, there is a lower risk of inhomogeneities. Also, there are less non-reacted catalyst particles, which would lead to gels in the final product.
  • the process comprises first a liquid- phase polymerisation step (a) and a subsequent gas-phase polymerisation step (b).
  • the molar masses and or melt flow rates of the ethene homo or copolymers produced in the steps (a) and (b) are essentially identical.
  • the difference between the melt flow rates at a load of 21.6 kg of the polymers produced in steps (a) and (b) is at most 100%, preferably at most 50% of the melt flow rate of the final product.
  • the density of the ethene homo or copolymer produced in step (a) is at least 10 kg/m 3 , more preferably at least 15 kg/m , most preferably at least 20 kg/m higher or lower than the density of the ethene homo or copolymer produced in step (b).
  • the ethene homo or copolymer produced in step (a) has a higher density than the ethene homo or copolymer produced in step (b).
  • the difference in density results in difference in long chain branching and in the branching distribution in the polymer chain.
  • Materials with different molar masses can be produced by the process according to the invention.
  • the average molar mass of the polymer is controlled by adjusting the operating temperatures of the polymerisation steps, among other process parameters.
  • the molar mass of the material produced using the process according to the invention may vary so that its melt flow rate at a load of 21,6 kg (MFR 21 , determined at 190 °C according to the standard ISO 1133) ranges from 2,5 to 200 g/lO min.
  • the process according to the invention also allows the production of materials within a wide density range.
  • the density may be as high as 965 kg/m 3 , but it is also possible to produce materials having a density as low as 915 kg/m 3 .
  • the ratio of the amount of polymer produced in step (a) to the amount of polymer produced in step (b) is preferably between 30/70 and 70/30, more preferably between 40/60 and 60/40. If the fraction of relatively high density material produced in step (a) is too low, the mechanical properties of the final product are likely to suffer, since then the relatively low density material produced in step (b) contains too little comonomer. On the other hand, if the fraction of relatively high density material of step (a) is too high, then the final product contains too low an amount of copolymer having a relatively low density, and this again has an adverse effect on the mechanical properties.
  • an ethylene homopolymer having a melt index MFR 1 (melt flow rate measured at 190 °C under a load of 21.6 kg) of about 0.5-3 g/10 rnin is produced at the first polymerisation step and an ethylene copolymer is produced at the second polymerisation step so that the final polymer composition has an MFR 21 of 0.5-3.0 g/10 min and a density of 945-965 kg/m 3 , preferably of 950-960 kg/m 3 .
  • the ratio between the first step polymer and the second step polymer ranges from 30/70 to 70/30, preferably from 40/60 to 60/40 and more preferably from 40/60 to 50/50.
  • the chromium catalyst used in the invention may be any chromium oxide catalyst used in the art.
  • the chromium compound used in the catalyst is any convenient chromium compound that will become an oxide when calcinated.
  • the chromium compound can for example be chromium trioxide, a chromium halide, a chromium oxyhalide, a chromium nitrate, a chromium acetate, a chromium sulphate or a chromium alcoholate.
  • various chromates, such as potassium bichromate, ammonium chromate and various alkyl chromates are usable as well as chromium acetylacetonate. Mixtures of at least two chromium compounds can also be used.
  • the chromium compound is advantageously supported on a support, that is preferably silica.
  • the carrier may also contain minor amounts of other components than silica, like oxides of aluminium, titanium or zirconium.
  • the carrier is formed in a precipitation step together with the chromium compound.
  • the carrier may also consist primarily of aluminophosphate.
  • the surface area of the catalyst is preferably greater than 300 m 2 /g, and the pore volume is greater than 1 cmVg.
  • the catalyst needs to be activated prior to use.
  • the activation is performed at an elevated temperature in an oxidising atmosphere, and is called oxidat- ive calcination.
  • the catalyst may be activated in an air stream at a temperature between 400-950 °C, preferably between 500-900 °C. If after the oxidative calci- nation a prereduction of the catalyst is desired, it is preferably done at a somewhat lower temperature than the activation, e.g. between 250-500 °C.
  • MFR melt flow rate
  • the catalyst comprises about 0.5-5.0 wt-% of chromium.
  • the chromium is, after the oxidative oxidation stage, at an oxidation state of +VI and it is reduced in the reactor by ethene to oxidation state +11.
  • the catalyst may also be reduced prior to its introduction into the reactor by using a convenient reduction agent, like carbon monoxide.
  • the catalyst used in the process is preferably only slightly sensitive to hydrogen, since use of hydrogen results in a decreased content of long chain branches. This again has a negative effect on the melt strength of the polymer.
  • the catalyst is used without cocatalyst. If however specifically desired, a cocatalyst may be used.
  • a cocatalyst may be used.
  • An example of a cocatalyst that may be used in combi- nation with a chromium catalyst is triethylboron (TEB), which would lead to increased MFR 21 /MFR 2 , or triemylaluminium (TEA) which, when used in small amounts, primarily acts as an activity booster, probably by acting as a poison scavenger.
  • TEB triethylboron
  • TSA triemylaluminium
  • the polymerisation step (a) is carried out in a loop reactor, in the presence of a reaction medium, the monomer and optionally one or several comonomers as well as hydrogen. Preferably, no comonomer is used.
  • the ratio of hydrogen to ethene in step (a) is within the range of 0-1 mol/mol, preferably within 0-1.5 mol/mol. Most preferably, the polymerisation is carried out in the absence of hydrogen.
  • Non-polar hydrocarbons can be used as reaction medium in loop reactor.
  • Alkanes form one suitable group of hydrocarbons that can be used as the reaction medium. Examples of suitable alkanes are propane, i-butane, n-butane, pentane, hexane and heptane, as well as mixtures of at least two of them. It is especially suitable to use propane as the reaction medium, since then the critical temperature of the fluid mixture is sufficiently low to allow operation in supercritical conditions at a temperature below the softening point of the polymer.
  • the polymerisation step (a) is performed in supercritical conditions, whereby the polymerisation temperature and pressure are above the corresponding critical points of the reaction mixture formed by the reaction medium, monomer and optionally hydrogen and comonomer and the polymerisation temperature is lower than the melting point of the polymer formed.
  • the polymerisation in supercritical conditions in loop reactor is advantageous, because there is no risk of formation of gas bubbles in the reactor, which would lead to problems in the operation of the loop pump. Also, the separation of hydrocarbons from the polymer is economical since no additional energy is needed to evaporate the medium.
  • the molar mass of the material produced in the polymerisation step (a) is primarily controlled by adjusting the operating temperature of the reactor.
  • the catalyst should be able to produce the desired molar mass at a temperature which exceeds the critical temperature of the reaction mixture.
  • a suitable range of the operating temperature, when propane is used as medium is 90-110 °C, preferably 95-105 °C.
  • the operating pressure preferably exceeds the critical pressure of the mixture.
  • a suitable range, when propane is used as medium is between 50-75 bar, preferably between 55-70 bar.
  • the density of the polymer formed in the polymerisation step (a) is lower than the density of the final polymer.
  • comonomer is added into the loop reactor. The comonomer however increases the critical temperature of the reaction mixture and thus the operation requires more energy since the polymerisation temperature has to be increased.
  • the polymer slurry is discharged from the loop reactor either continuously or discontinuously by using any method known in the art.
  • An especially suitable method is to employ settling legs, where the slurry is allowed to concentrate before it is discharged from the reactor. In this way, a higher polymer concentration is reached at the outlet than is present in the reactor.
  • the slurry is transferred from the polymerisation step (a) into a separation step where the hydrocarbons are separated from the polymer.
  • the medium and unreacted monomer are recycled back into the polymerisation step (a).
  • the polymer containing the active catalyst is transferred into the polymerisation step (b).
  • the polymerisation step (b) is carried out in one or more gas phase reactors.
  • one gas-phase reactor is used, and most preferably said step (b) is carried out in a fluidised bed reactor.
  • Said fluidised bed reactor may also be equipped with an agitator.
  • the polymer bed is fluidised by the circulation gas, which is introduced to the bottom of the reactor, and has a sufficient velocity to fluidise the polymer particles.
  • the unreacted monomer and eventually comonomer is collected at the top of the reactor, compressed and cooled to remove the heat of polymerisation, and finally reintroduced to the reactor.
  • Other types of gas phase reactors like mixed bed reactors or fast fluidised bed reactors, may also be used.
  • Ethene, optionally one or more comonomers and one or more inert gases are introduced into the reactor so that a desired production rate and product density are reached.
  • comonomer is preferably a C 3 -C 12 ⁇ -olefin.
  • the operating temperature is set to such a level that the desired molar mass of the polymer is reached. Typically, the operating temperature is 75-110 °C, preferably 85-105 °C.
  • the operating pressure is typically 5-50 bar, preferably 10-30 bar.
  • the polymer produced in the polymerisation step (b) has a molar mass which is essentially equal to that of the material produced in the polymerisation step (a).
  • the density of the polymer is controlled so that the final product has the predefined target density. According to a preferred embodiment of the invention, the density of the polymer produced in step (b) is lower than the density of the polymer produced in step (a).
  • the most important process variables to control the molar mass and consequently the melt flow rate of the polymer produced in each step are the polymerisation temperatures.
  • the MFR is increased by decreasing the polymerisation temperature.
  • MFR is also increased by increasing the ratio between comonomer and ethene. However, this ratio is also used for controlling the density of the polymer.
  • the invention also relates to ethene homo or copolymer, which is characterised in that is comprises at least two fractions, which fractions have essentially the same molar mass and/or melt flow rate and essentially different densities.
  • the difference between the melt flow rates at a load of 21.6 kg of the first and second fractions is preferably at most 15%, more preferably at most 10% of the melt flow rate of the final product, and the difference of density of the at least two fractions is at least 10 kg/m 3 , more preferably at least 15 kg/m 3 , most preferably at least 20 kg/m 3 .
  • the polymer may be compounded and extruded into pellets using any method known in the art.
  • suitable devices are twin screw extruders, which homogenise the material to a certain extent before pelletising.
  • the extruder may be of either corotating or counterrotating type.
  • a chromium catalyst was activated at 650 °C for 6 hours.
  • the thus activated catalyst was used in polymerisation as follows:
  • a loop reactor of 500 dm was continuously introduced propane diluent, ethylene and the above polymerisation catalyst.
  • the reactor was operated at 82 °C and 60 bar, and the feeds were adjusted so that the production rate of ethylene homopolymer was 25 kg/h and the average residence time was 0.8 hours.
  • the MFR 21 of the ethylene homopolymer resin was 1.8 g/10 min and density of 962 kg/m 3 .
  • the polymer slurry was continuously withdrawn from the loop reactor, hydrocarbons were removed and the polymer was introduced into a fluidised bed gas phase reactor operated at 85 °C and 20 bar. Additional ethylene and 1-butene comonomer were introduced into the reactor so that 53 kg/h of copolymer of ethylene and 1-butene having MFR 21 of 2.0 g/10 min and density of 954 kg/m 3 was recovered from the reactor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé permettant de produire des homopolymères ou des copolymères éthyléniques en plusieurs étapes, ce procédé comprenant au moins une étape de polymérisation en phase liquide (a) et une étape de polymérisation en phase gazeuse (b), lesquelles peuvent se dérouler dans n'importe quel ordre. Selon ce procédé, la polymérisation s'effectue en présence d'un catalyseur de chrome. Dans un mode de réalisation de cette invention, les masses molaires et/ou les vitesses d'écoulement à chaud des homopolymères ou des copolymères éthyléniques produits au cours des étapes (a) et (b) sont essentiellement identiques.
PCT/FI2000/000580 1999-06-29 2000-06-28 Procede de production de polyethylene en plusieurs etapes WO2001000690A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58297/00A AU5829700A (en) 1999-06-29 2000-06-28 Multi-stage process for producing polyethene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI991480A FI991480A0 (fi) 1999-06-29 1999-06-29 Monivaiheprosessi polyeteenin valmistamiseksi Flerstegsprocess för produktion av polyeten
FI991480 1999-06-29

Publications (2)

Publication Number Publication Date
WO2001000690A2 true WO2001000690A2 (fr) 2001-01-04
WO2001000690A3 WO2001000690A3 (fr) 2001-05-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2000/000580 WO2001000690A2 (fr) 1999-06-29 2000-06-28 Procede de production de polyethylene en plusieurs etapes

Country Status (3)

Country Link
AU (1) AU5829700A (fr)
FI (1) FI991480A0 (fr)
WO (1) WO2001000690A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022082155A1 (fr) * 2020-10-15 2022-04-21 Chevron Phillips Chemical Company Lp Composition de polymère et ses méthodes de fabrication et d'utilisation

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI86867C (fi) * 1990-12-28 1992-10-26 Neste Oy Flerstegsprocess foer framstaellning av polyeten
NO960350A (no) * 1996-01-26 1997-04-28 Borealis As Fremgangsmåte og katalysatorsystem for polymerisering av etylen, eventuelt sammen med <alfa>-olefiner, og fremstilt polymermateriale
EP0829495A1 (fr) * 1996-09-13 1998-03-18 Fina Research S.A. Procédé de préparation de polyéthylène ayant une distribution large de poids moléculaire

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022082155A1 (fr) * 2020-10-15 2022-04-21 Chevron Phillips Chemical Company Lp Composition de polymère et ses méthodes de fabrication et d'utilisation
US11674023B2 (en) 2020-10-15 2023-06-13 Chevron Phillips Chemical Company Lp Polymer composition and methods of making and using same
US12037483B2 (en) 2020-10-15 2024-07-16 Chevron Phillips Chemical Company Lp Polymer composition and methods of making and using same

Also Published As

Publication number Publication date
AU5829700A (en) 2001-01-31
WO2001000690A3 (fr) 2001-05-10
FI991480A0 (fi) 1999-06-29

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