WO2001004166A1 - Procede de production de polypropylene - Google Patents

Procede de production de polypropylene Download PDF

Info

Publication number
WO2001004166A1
WO2001004166A1 PCT/FI2000/000630 FI0000630W WO0104166A1 WO 2001004166 A1 WO2001004166 A1 WO 2001004166A1 FI 0000630 W FI0000630 W FI 0000630W WO 0104166 A1 WO0104166 A1 WO 0104166A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction zone
reactor
process according
catalyst
gas phase
Prior art date
Application number
PCT/FI2000/000630
Other languages
English (en)
Inventor
Thomas Garoff
Pauli Leskinen
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 AU61630/00A priority Critical patent/AU6163000A/en
Publication of WO2001004166A1 publication Critical patent/WO2001004166A1/fr

Links

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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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

  • the present invention relates to propylene polymerization.
  • the present invention concerns a process for producing homo- or random copolymers of propylene in the presence of a Ziegler-Natta type catalyst in a process comprising a combination of at least one bulk reactor and at least one gas phase reactor.
  • the polymerization is preferably carried out in a process comprising both bulk, e.g., loop and gas phase reactors, usually in that order.
  • the melt flow rate (MFR) of the fraction of the final product produced in bulk reactor is typically same as or lower than the MFR of the fraction produced in the gas phase reactor (depending on whether unimodal or multimodal polymer is produced).
  • the higher MFR is obtained by means of feeding hydrogen and/or ethylene into the gas phase reactor.
  • the final product can then exhibit a narrow or broad molecular weight distribution (MWD).
  • MWD molecular weight distribution
  • XS xylene solubles
  • the broadness of the molecular weight distribution of the final product depends on percentages of the fractions with different MFRs. Since a specific combination of the fractions is required in the end product, a split is also required in the production. In other words, a certain percentage of the material has to be produced in the loop reactor and a certain fraction in the gas phase reactor in order to obtain a desired final product.
  • the catalyst together with cocatalyst and the external donor are fed (optionally via prepolymerization) to the first reactor in the reactor sequence, which is typically a bulk reactor, e.g., a loop reactor.
  • the reactor sequence which is typically a bulk reactor, e.g., a loop reactor.
  • the problem with the processes of the prior art is that the lifetime of the catalyst is, however, restricted.
  • a high excess of the amount of the cocatalyst with regard to what is needed for activating the catalyst in the loop reactor creates a high activity in the loop reactor, and when the material enters to the gas phase reactor, the activity of the catalyst drops. This is due to the conditions in the gas phase reactor and the fact that a great portion of the catalyst activity has been used in the loop reactor.
  • the catalyst is already partly deactivated, and the deactivation process is still going on.
  • the residence time in the loop is typically short.
  • the catalyst activity in the gas phase reactor is low, long residence times are required in order to achieve an end product with desired properties.
  • the reactivity of the catalyst in the gas phase reactor has typically been 2 to 5 times poorer compared with the reactivity in the bulk polymerization. This will lead to the gas phase reactor becoming a capacity bottle neck in the polymerization process.
  • propylene is homo- or copolymerized in a process comprising a combination of at least one bulk reaction zone including at least one bulk reactor and at least one gas phase reaction zone including at least one gas phase reactor.
  • Polymerization is thus carried out in at least two subsequent polymerization reactors in the presence of a Ziegler-Natta type catalyst including a catalyst component, a cocatalyst component and an external donor.
  • the first reaction zone is a bulk polymerization zone and the second reaction zone is a gas phase polymerization zone.
  • the reactors are preferably arranged in series.
  • the present invention is based on the idea that, in order to improve the catalyst activity in the second reaction zone, the feed of the cocatalyst is split between the bulk polymerization zone and the gas phase polymerization zone. Only a fraction of the cocatalyst is fed into the first polymerization zone, together with an excess amount of external donor which blocks the catalyst to a certain amount. This leads to a slower reactivity of the catalyst in the first polymerization zone, since the Ti 4+ in the catalyst component is only partly reduced to Ti 3+ (I). The rest of the cocatalyst component is fed to the second polymerization zone. This increases the activity of the catalyst in the second polymerization, since fresh Ti 3+ which is not deactivated at all, is formed (II). Thus an equal productivity in both of the polymerization zones is achieved.
  • Cat' designates the deactivated catalyst.
  • the process according to the present invention is characterised by what is stated in the characterising part of claim 1.
  • the bimodal propylene polymer, being one embodiment of the present invention is characterised by what is stated in the characterising part of claim 18.
  • the typical way to operate a process for producing propylene homo- or random copolymers is to arrange the loop reactor before the gas phase reactor and to feed the whole catalyst composition to the loop reactor.
  • the activity of the catalyst in the gas phase reaction zone is considerably higher and thus the residence times in the gas phase reaction zone are shorter than in the processes of the prior art. This results in a faster process and thus increases the polymer production, or allows for decreasing of the size of the gas phase reactor, which decreases the investment costs.
  • residence times according to the present invention can be 60 - 70 % of the residence times required previously.
  • the reactivity of the catalyst in the gas phase reactor(s) and the lifetime of the catalyst are improved and thus it is possible to operate in even, e.g., three gas phase reactors in series after the bulk polymerization. This is important in view of the often desired modification of the polymer properties in additional gas phase reactors, in order to obtain, e.g., elastic properties for the material.
  • the production split can be controlled efficiently.
  • the split has been adjusted by pressure and surface level of the gas phase reactor, which is slow. Also grade changes can be made faster by using the process of the present invention.
  • the polypropylene material produced according to the present process can be made extremely isotactic even with a remote amount of donor. This is possible since, with the process of the present invention, the amount of donor in proportion to cocatalyst is high in the loop reactor (presuming loop reactor is the first reactor in series). Generally, more isotactic material can be produced in a gas phase reactor, and thus, after the gas phase reaction zone, an extremely isotactic and stiff material is obtained.
  • the present invention contributes to better odour and taste properties of the polymers, which is due to the fact that less alkyl is needed in the first polymerization stage, e.g., in loop reactor, and thus less oligomers are formed.
  • blocking problems in filters can be avoided due to the decrease in formation of aluminium oxides.
  • slurry reactor designates any reactor, such as a continuous or simple batch stirred tank reactor or loop reactor, operating in bulk or slurry and in which the polymer forms in particulate form.
  • Bok means a polymerization in reaction medium that comprises at least 60 wt-% monomer.
  • a bulk reactor is used in the process of the present invention. According to a preferred embodiment the bulk reactor comprises a loop reactor.
  • gas phase reactor any mechanically mixed or fluid bed reactor.
  • gas phase reactor comprises a mechanically agitated fluidized bed reactor with gas velocities of at least 0.2 m/sec.
  • reaction zone or "polymerization zone” stands for one or several reactors of similar type producing the same type or characteristics of polymer connected in the series.
  • catalyst or “catalyst system” is meant a system comprising a catalyst component, a cocatalyst component, an external donor and, optionally, an internal donor.
  • first cocatalyst feed designates the feed of the cocatalyst to the prepolymerization stage or to the first reaction zone
  • second cocatalyst feed designates the feed of the cocatalyst to the second reaction zone
  • the catalyst system used in the present process is preferably a propylene stereospecific, high yield Ziegler-Natta catalyst capable of polymerising propylene at reaction conditions.
  • the Ziegler-Natta catalyst system used in the present invention comprises a catalyst component, a cocatalyst component and an external electron donor.
  • Suitable catalyst systems are described in, for example, in US 5 234 879, EP 627 449, WO 92/19653 and WO 92/19658. Of these, the catalyst disclosed in WO 92/19653 is particularly preferred.
  • the catalyst component is the catalyst component
  • the catalyst component contains primarily a procatalyst component containing typically magnesium, titanium, halogen, and an internal electron donor.
  • a catalyst component useful in the present process can be prepared by reacting a magnesium halide compound with a titanium compound, preferably titanium tri- or tetrachloride, and an internal donor. Also other transition metal compounds, such as vanadium, zirconium, chromium, molybdenum and tungsten compounds can be mixed with the titanium compound.
  • the magnesium halide compound is, for example, selected from the group of magnesium chloride, a complex of magnesium chloride with lower alcohol and other derivatives of magnesium chloride.
  • MgCl 2 can be used as such or it can be combined with silica, e.g. by filling pores of the silica with a solution or slurry containing MgCl 2 .
  • the lower alcohol used can be preferably methanol or ethanol, particularly ethanol.
  • One particularly attractive catalyst type comprises a transesterified catalyst, in particular a catalyst transesterified with phthalic acid or its derivatives (cf. Finnish Patent No. 88047).
  • the alkoxy group of the phthalic acid ester used in the transesterified catalyst comprises at least five carbon atoms, preferably at least 8 carbon atoms.
  • the ester can be used for example propylhexyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, di-undecyl phthalate, ditridecyl phthalate or ditetradecyl phthalate.
  • the partial or complete transesterification of the phthalic acid ester can be carried out e.g. by selecting a phthalic acid ester - a lower alcohol pair, which spontaneously or with the aid of a catalyst, which does not damage the procatalyst composition, transesterifies the catalyst at an elevated temperatures. It is preferable to carry out the transesterification at a temperature, which lies in the range of 110 to 150 °C, preferably 120 to 140 °C.
  • the external donor is a compound added to the reactor in order increase the stereoselectivity of the catalyst.
  • the external donor used in the process of the present invention is, for example, a silane based donor having generally the formula (III), or a 1,3- di ether donor having the formula (IV).
  • R and R' can be the same or different and they stand for a linear, branched or cyclic aliphatic, or aromatic group
  • R" is methyl or ethyl; n is an integer 0 to 3; m is an integer 0 to 3; and n+m is 1 to 3.
  • R' and R" are the same or different and stand for a linear, branched or cyclic aliphatic or aromatic group.
  • the groups R and R' when being aliphatic, can be saturated or unsaturated.
  • Linear Ci to C 12 hydrocarbons include methyl, ethyl, propyl, butyl, octyl and decanyl.
  • suitable saturated branched Q.g alkyl groups the following can be mentioned: isopropyl, isobutyl, isopentyl, tert-butyl, tert-amyl and neopentyl.
  • Cyclic aliphatic groups containing 4 to 8 carbon atoms comprise, e.g., cyclopentyl, cyclohexyl, methyl cyclopentyl and cycloheptyl.
  • the donors used in the process of the present invention are strongly co-ordinating donors which form relatively strong complexes with catalyst surface, mainly with MgCl 2 surface in the presence of aluminium alkyl and TiCl .
  • the donor components are characterised by a strong complexation affinity towards catalyst surface and a sterically large and protective hydrocarbon. Strong co-ordination with MgCl 2 requires oxygen- oxygen distance of 2.5 to 2.9 A [Albizzati et al., Macromol. Symp. 89 (1995) 73-89].
  • this kind of donors have the structure of the general formula (V)
  • R' is a branched aliphatic or cyclic or aromatic group, and n is 1 or 2, preferably 2.
  • the external donor is selected from the group consisting of dicyclopentyl dimethoxysilane, diisopropyl dimethoxysilane, methylcyclohexyl dimethoxysilane, di- isobutyl dimethoxysilane, and di-t-butyl dimethoxysilane, dicyclopentyl dimethoxysilane being particularly preferred.
  • the cocatalyst component is selected from the group of organometallic compounds.
  • the cocatalysts are metal hydrides, or alkyls or aryls of metals.
  • the metal is typically aluminium, lithium, zinc, tin cadmium, beryllium or magnesium.
  • organoaluminium compound in particular trialkyl aluminium, dialkyl aluminium chloride or alkyl aluminium sesquichloride.
  • the cocatalyst is triethyl aluminium (TEA).
  • the present invention concerns a multistage process consisting of at least one bulk reaction zone including at least one bulk reactor, and at least one gas phase reaction zone including at least one gas phase reactor.
  • the at least one bulk reaction zone is arranged before the gas phase reaction zone, when the gas phase reaction zone is arranged in a cascade with at least one bulk reactor with a feed to the gas phase for homo- or random copolymerizing propylene.
  • the reaction system comprises at least one bulk reaction zone (referred to as “the first reaction zone”) and at least one gas phase reaction zone (referred to as “the second reaction zone”), in that order, which is a preferred process configuration for making homo- or random copolymer of propylene, and especially bimodal polypropylene.
  • the reactor system can comprise the reaction zones in any number and order.
  • Each of the reaction zones can, and typically do, contain more than one reactor.
  • the most typical process configuration comprises one bulk reactor, which preferably is a loop reactor, and one gas phase reactor. Still, combinations like two bulk reactors and one gas phase reactor or one bulk reactor and two or more gas phase reactors, connected in series in any order, are also possible.
  • the high MFR portion and the low MFR portion of the product can be prepared in any order in the reactors.
  • a separation stage can be employed between the reactors to prevent the carryover of reactants from the first polymerization stage into the second one.
  • the polymerization reaction system can also include a number of additional reactors, such as pre- and/or postreactors.
  • the prereactors include any reactor for prepolymerizing the catalyst with propylene and/or other ⁇ -olefm(s) and/or ethylene, if necessary.
  • the postreactors include reactors used for modifying and improving the properties of the polymer product. A typical example are additional gas phase reactors for obtaining elastic properties. All reactors of the reactor system are preferably arranged in series.
  • the polymerization process comprises at least the following steps of
  • the comonomer(s) optionally used in any or every reactor are preferably C 2 to C 10 olefins, e.g. ethylene, 1-butene, 4-methyl-l-pentene, 1-hexene, dienes, or cyclic olefins, or a mixture thereof.
  • olefins e.g. ethylene, 1-butene, 4-methyl-l-pentene, 1-hexene, dienes, or cyclic olefins, or a mixture thereof.
  • Different amounts of hydrogen can be used as a molar mass modifier or regulator in any or every reactor.
  • the polymerization is carried out in the presence of a catalyst described above.
  • the catalyst is fed to the process in at least two stages, so that the catalyst component and the external donor, and a part of the total amount of the cocatalyst component is fed to the first reaction zone to the first reactor in series. Additionally, the rest of the total amount of the cocatalyst component is fed to the second reaction zone, preferably to the first reactor of the second reaction zone.
  • the first reaction zone in series can optionally include also a prepolymerization stage.
  • the catalyst is then subjected to prepolymerization prior to feeding into the first actual polymerization reactor of the reaction zone.
  • the catalyst components are contacted with a monomer, such as an olefin monomer or a mixture of monomers, before feeding into the first actual polymerization reactor.
  • the monomer used in the prepolymerization is typically, but not necessarily the same as in the actual polymerization reactions. Examples of suitable systems are described in, for example, WO 97/33920.
  • the catalyst is prepolymerized, then preferably also the first feed of the cocatalyst is conducted to the prepolymerization.
  • the catalyst is flushed to the prepolymerization reactor with a monomer (e.g., propylene) and also the donor and part of the cocatalyst component are fed to the reactor.
  • a monomer e.g., propylene
  • the split of the cocatalyst component feed varies.
  • wt-% preferably 10 to 40 wt-%, preferably 20 to 30 wt-%, of the total cocatalyst component feed is fed to the first reaction zone, or to the prepolymerization stage optionally included in it, and 90 to 60 wt-%, preferably 80 to 70 wt-% of the total cocatalyst component feed is fed to the second reaction zone.
  • the reactor sequence comprises at least one prepolymerization reactor, at least one bulk reactor, and at least one gas phase reactor, connected in series, in that order.
  • the first feed of the cocatalyst is advantageously conducted to the prepolymerization reactor(s), and the rest of the cocatalyst is fed to the gas phase polymerization reactor(s).
  • the molar ratio of aluminium in the cocatalyst component to titanium (Al/Ti) in the catalyst component in the first feed of the cocatalyst is 10 - 150, preferably 30 - 100 and in particular 40 - 80.
  • the total molar ratio of aluminium to titanium (the first and the second feed of the cocatalyst together) is 200 - 500, preferably 200 - 350 and in particular 250 - 300.
  • the molar ratio of aluminium in the cocatalyst component to donor (Al/D) in the first feed of the cocatalyst is 1 - 10, preferably 1 - 5 and in particular 2 - 3.
  • the total molar ratio of aluminium to donor (the first and the second feed of the cocatalyst together) is 5 - 100, preferably 10 - 50 and in particular 10 - 30.
  • the prepolymerized slurry is conducted to the first reaction zone. If no prepolymerization is carried out, then the catalyst component and the external donor and part of the cocatalyst component are fed directly to the first reaction zone. Propylene and optionally copolymers are also fed to the first reaction zone.
  • the first reaction zone is preferably a bulk polymerization zone.
  • Bulk polymerization is carried out in a reaction medium, such as propene.
  • the bulk polymerization is preferably carried out in a loop reactor.
  • the temperature in the loop is typically in the range of 40 to 110 °C, preferably in the range of 50 to 100 °C, and even more preferably for homopolymers 80 to 100 °C and for copolymers of high comonomer content 60 to 75 °C and for copolymer with high comonomer randomness 75 to 85 °C.
  • the reaction pressure is in range of 30 to 100 bar, preferably 35 to 80 bar.
  • the polymerization heat is removed by cooling the reactor with a cooling jacket.
  • the residence time in the bulk polymerization zone depends on the catalyst activity and on the desired composition of the end products. Generally, the residence time in a bulk reactor must be at least 10 minutes, preferably 20-100 min for obtaining a sufficient degree of polymerization. A typical residence time is between 40 and 60 min.
  • the content of the bulk reactor, the polymerization product and reaction medium together with unreacted monomer and the catalyst, can be led directly to the second reaction zone, typically to a fluidized bed gas phase reactor.
  • some components e.g. hydrogen, can fully or partially be removed with various technical solutions before the flow enters the second reaction zone.
  • the second cocatalyst feed is preferably directed to the material flow of the first reactor to the second reaction zone.
  • the second cocatalyst feed can be introduced separately to the first reactor in the second reaction zone.
  • the second cocatalyst feed can be divided so that some fresh cocatalyst is fed to each of the reactors in the reaction zone. It is also possible to feed rest of the cocatalyst to part of the reactors in the second reaction zone.
  • the second reaction zone is preferably a gas phase reaction zone including at least one gas phase reactor, wherein propylene and optionally comonomer(s) are polymerized in a reaction medium comprising gas or vapour.
  • the gas phase reactor can be an ordinary fluidized bed reactor, although other types of gas phase reactors can be used.
  • the bed of the fluidized bed reactor consists of the formed and growing polymer particles and of the still active catalyst, which has come along with the polymer fraction from the bulk reactor.
  • the bed is kept in a fluidized state by introducing gaseous components, e.g. monomer on such flow rate (at least 0.2 m/s) which make the particles act as a fluid.
  • the fluidizing gas can contain also inert carrier gases, like nitrogen and also hydrogen as a molecular weight modifier.
  • the gas phase reactor used can be operated in the temperature range of 50 to 115 °C, preferably between 60 and 110 °C and reaction pressure between 10 and 40 bar and below the dew point.
  • the partial pressure of the monomer between 2 and 30 bar or more.
  • Fresh propylene is preferably, but not necessarily fed to the gas phase polymerization zone.
  • comonomer(s) are fed to the gas phase polymerization zone.
  • the residence time in the gas phase polymerization zone depends on the activity of the catalyst and on the desired composition of the end product. Since the catalyst activity in the second reaction zone is improved by means of the present invention, the residence times are generally shorter than in the prior art processes.
  • a typical residence time in a gas phase reactor is, according to the present invention, typically 1 - 2.5 h, preferably 1.5 - 2.2 h.
  • the pressure of the second polymerization product including the gaseous reaction medium is then reduced after the first gas phase reactor in order to separate part of the gaseous and possible volatile components (e.g. heavy comonomers and compounds used for catalyst feeds) of the product e.g. in a flash tank.
  • the overhead stream or part of can be circulated to the first gas phase reactor or to the bulk polymerization zone.
  • the polymerization product can be fed into additional gas phase reactor(s) to produce a modified polymerization product having, e.g., elastomeric properties, from which the polypropylene is separated and recovered.
  • the present invention facilitates this kind of production, since the high reactivity of the catalyst in the gas phase reaction zone enables the use of even three gas phase reactors in series with a reasonable production rate.
  • the production split between the bulk polymerization zone and the gas phase polymerization zone is 5 - 95 : 95 - 5, preferably 20 - 80 : 80 - 20 and in particular 40 - 60 : 60 - 40.
  • 5 to 60 %, in particular 20 to 60 %, of the propylene homopolymer or random copolymer is produced at conditions to provide the polymer fraction having a relatively high molecular weight and thus relatively low MFR 2
  • 95 to 40 %, in particular 80 to 40 %, of the propylene homopolymer or random copolymer is produced at such conditions that provide a polymer with a higher MFR 2 .
  • MFR 2 is in the range of 0.01 - 2000 g/10 min, preferably in 0.1 - 1000 g/10 min and in particular 1 - 400 g/10 min.
  • the xylene solubles fraction (XS) of the polymer material is typically 1.5 to 5 wt-%, in particular 1.8 - 3 wt-%.
  • bimodal polypropylene is produced in order to obtain a material with a broad MWD and thus also an enhanced processability.
  • the MFR 2 of the low molecular weight fraction of the bimodal polymer is approximately 50 g/10 min
  • the MFR 2 of the high molecular weight fraction is approximately 2 g/10 min or less, and in particular 0.01 - 1.6 g/10 min.
  • the xylene soluble fraction of the bimodal homopolymer material is typically for such polymers less than 1.8 wt-%, preferably less than 1.6 wt-%.
  • MFR The melt flow rate of the polymer material was determined according to ISO standard 1133 using a piston load of 2.16 kg and a temperature of 230 °C.
  • the abbreviation "MFR" is generally provided with a numerical subindex indicating the load of the piston in the test. Thus, e.g., MFR 2 designates a 2.16 kg load.
  • Xylene Solubles Determination of xylene soluble fraction (XS): 2.0 g of polymer is dissolved in 250 ml p-xylene at 135 °C under agitation. After 30 ⁇ 2 minutes the solution is allowed to cool for 15 minutes at ambient temperature and then allowed to settle for 30 minutes at 25 ⁇ 0.5 °C. The solution is filtered with filter paper into two 100 ml flasks.
  • V] volume of analysed sample (ml).
  • a highly active propylene polymerization catalyst of ZN type prepared according to WO
  • the CCSTR has been described in WO 97/33920.
  • the residence time of the particles was 8 - 10 minutes.
  • Hydrogen feed to the prepolymerization reactor was 0.1..0.2 mol-%.
  • the prepolymerized catalyst component was used in a loop reactor and a gas phase reactor connected in series.
  • the operating temperature in the loop reactor was 80 °C and the pressure was 55 bar.
  • the residence time in the loop reactor was 0.75 h.
  • the MFR 2 (measured according to ISO 1133, with a load of 2.16 kg and a temperature of 230 °C) was set to be 1.5 - 2 by adjusting the hydrogen feed accordingly.
  • the isotacticity was kept as high as possible by adjusting the donor feed accordingly, and at the same time, the xylene solubles (XS) values were kept as low as possible.
  • Direct feed line was used between loop and GPR.
  • the rest of TEA (the total molar ratio of Al Ti was 300) was fed to material stream between the loop reactor and the GPR.
  • the gas phase reactor was operated at 80 °C and 29 bar total pressure.
  • the production split between the loop reactor and the gas phase reactor was about 40/60.
  • the residence time in the GPR was 2.1 h.
  • the MFR 2 (2.16 kg / 230 °C) of the final product was set to be about 20 by adjusting the hydrogen feed accordingly.
  • the polymerization was carried out as in Example 1, except that the TEA split was not used.
  • Al/Ti molar ratio to the catalyst contacting stage was 250 and Al/D molar ratio was 10.
  • the greater amount of TEA fed in the catalyst contacting stage created a higher catalyst activity in the loop reactor.
  • the activity of the catalyst dropped when it entered the gas phase reactor.
  • the drop in activity was due to the conditions in the GPR and the fact that a great deal of the catalyst activity had already been used in the loop reactor.
  • the catalyst has a restricted living time, and thus also the deactivation of the catalyst was going on.
  • the reactivity of the catalyst was not so good in the GPR.
  • the production split turned from 40/60 to 60/40 despite the fact that the residence time in the GPR was longer (3.0 h).
  • Example 1 the XS value was not on such a level as in Example 1. Further, the molecular weight distribution of the final material (measured with MFR 2 ) was not as broad by using the same amounts of hydrogen as in Example 1.
  • Example 2 The polymerization conditions and a main product analysis are shown in Table 1.
  • Example 2 The polymerization conditions and a main product analysis are shown in Table 1.
  • Example 2 The polymerization was carried out as in Example 1, except that the molar ratio Al/Ti in the catalyst contacting stage was only 50 and the Al D ratio was 2. Compared to Example 1 even a higher catalyst activity in the GPR was reached, which can be seen accordingly in a shorter residence time in the GPR. Also the isotacticity (XS) of the product was better.
  • XS isotacticity

Abstract

L'invention concerne un procédé de production de propylène, et des polypropylènes ainsi produits. Selon ce procédé, le propylène est homo- ou copolymérisé dans une séquence de réactions comprenant une zone de réaction en vrac et au moins une zone de réaction par phase gazeuse disposées en série. La polymérisation est réalisée en présence d'un système catalyseur de type Ziegler-Natta contenant un composé catalyseur, un composé cocatalyseur et un donneur externe. Selon cette invention, le composé catalyseur, le donneur externe et une partie du composé cocatalyseur sont amenés vers une première zone de réaction, et le reste dudit composé cocatalyseur est amené vers une seconde zone de réaction.
PCT/FI2000/000630 1999-07-08 2000-07-07 Procede de production de polypropylene WO2001004166A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61630/00A AU6163000A (en) 1999-07-08 2000-07-07 Process for producing polypropylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI991572 1999-07-08
FI991572 1999-07-08

Publications (1)

Publication Number Publication Date
WO2001004166A1 true WO2001004166A1 (fr) 2001-01-18

Family

ID=8555051

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2000/000630 WO2001004166A1 (fr) 1999-07-08 2000-07-07 Procede de production de polypropylene

Country Status (2)

Country Link
AU (1) AU6163000A (fr)
WO (1) WO2001004166A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048041A1 (fr) * 1999-12-27 2001-07-05 Borealis Technology Oy Polymeres de propylene a vitesse d'ecoulement elevee a l'etat fondu
EP1270627A1 (fr) * 2001-06-27 2003-01-02 Borealis Technology Oy Resine de polymere de propylene presentant des proprietes ameliorees
CN100402560C (zh) * 2006-03-08 2008-07-16 南京金陵塑胶化工有限公司 聚丙烯的制备工艺及其反应装置
WO2013127707A1 (fr) * 2012-02-27 2013-09-06 Borealis Ag Procédé de préparation d'un polypropylène à faible teneur en cendres
WO2020136442A1 (fr) 2018-12-28 2020-07-02 Braskem S.A. Procédé pour l'introduction de catalyseur dans un processus de polymérisation
CN112375171A (zh) * 2020-10-28 2021-02-19 中国石油化工股份有限公司 一种聚丙烯材料的制备方法
US20210317236A1 (en) * 2018-09-28 2021-10-14 Borealis Ag A multi-stage process for producing a c2 to c8 olefin polymer composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192427A1 (fr) * 1985-02-19 1986-08-27 BP Chemicals Limited Polymérisation en plusieurs étapes d'alpha-oléfines en phase gazeuse
EP0697420A1 (fr) * 1994-08-19 1996-02-21 Union Carbide Chemicals & Plastics Technology Corporation Procédé pour la préparation de polypropylène
WO1998055519A1 (fr) * 1997-06-05 1998-12-10 Solvay Polyolefins Europe-Belgium (Societe Anonyme) Procede en continu de production de polymeres de polypropylene
EP0889064A2 (fr) * 1997-07-02 1999-01-07 Basf Aktiengesellschaft Procédé de préparation d'alcènes C2-C8 utilisant un système catalytique de type Ziegler-Natta

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192427A1 (fr) * 1985-02-19 1986-08-27 BP Chemicals Limited Polymérisation en plusieurs étapes d'alpha-oléfines en phase gazeuse
EP0697420A1 (fr) * 1994-08-19 1996-02-21 Union Carbide Chemicals & Plastics Technology Corporation Procédé pour la préparation de polypropylène
WO1998055519A1 (fr) * 1997-06-05 1998-12-10 Solvay Polyolefins Europe-Belgium (Societe Anonyme) Procede en continu de production de polymeres de polypropylene
EP0889064A2 (fr) * 1997-07-02 1999-01-07 Basf Aktiengesellschaft Procédé de préparation d'alcènes C2-C8 utilisant un système catalytique de type Ziegler-Natta

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048041A1 (fr) * 1999-12-27 2001-07-05 Borealis Technology Oy Polymeres de propylene a vitesse d'ecoulement elevee a l'etat fondu
EP1270627A1 (fr) * 2001-06-27 2003-01-02 Borealis Technology Oy Resine de polymere de propylene presentant des proprietes ameliorees
WO2003002626A1 (fr) * 2001-06-27 2003-01-09 Borealis Technology Oy Resine polymere de propylene a proprietes ameliorees
EP1359171A1 (fr) * 2001-06-27 2003-11-05 Borealis Technology Oy Resine de polmere de propylene presentant des proprietes ameliorees
US7220812B2 (en) 2001-06-27 2007-05-22 Borealis Technology Oy Propylene polymer resin with improved properties
CN100417672C (zh) * 2001-06-27 2008-09-10 北方技术股份有限公司 具有改善性能的丙烯聚合物树脂
CN100402560C (zh) * 2006-03-08 2008-07-16 南京金陵塑胶化工有限公司 聚丙烯的制备工艺及其反应装置
KR20140129264A (ko) * 2012-02-27 2014-11-06 보레알리스 아게 저 회분 함량을 갖는 폴리프로필렌의 제조 방법
WO2013127707A1 (fr) * 2012-02-27 2013-09-06 Borealis Ag Procédé de préparation d'un polypropylène à faible teneur en cendres
KR101672112B1 (ko) 2012-02-27 2016-11-02 보레알리스 아게 저 회분 함량을 갖는 폴리프로필렌의 제조 방법
US20210317236A1 (en) * 2018-09-28 2021-10-14 Borealis Ag A multi-stage process for producing a c2 to c8 olefin polymer composition
US11897975B2 (en) * 2018-09-28 2024-02-13 Borealis Ag Multi-stage process for producing a C2 to C8 olefin polymer composition
WO2020136442A1 (fr) 2018-12-28 2020-07-02 Braskem S.A. Procédé pour l'introduction de catalyseur dans un processus de polymérisation
US11866522B2 (en) 2018-12-28 2024-01-09 Braskem S.A. Process for introducing catalyst in a polymerization process
CN112375171A (zh) * 2020-10-28 2021-02-19 中国石油化工股份有限公司 一种聚丙烯材料的制备方法
CN112375171B (zh) * 2020-10-28 2022-07-26 中国石油化工股份有限公司 一种聚丙烯材料的制备方法

Also Published As

Publication number Publication date
AU6163000A (en) 2001-01-30

Similar Documents

Publication Publication Date Title
CA2295018C (fr) Procede et dispositif permettant de preparer des homopolymeres et des copolymeres de propylene
US6111039A (en) Dual donor catalyst system for the polymerization of olefin
US7157532B2 (en) Method for the production of olefin polymers and selected catalysts
US7038000B2 (en) Process for preparing propylene copolymers
US5122583A (en) Efficiency of a pre-polymerized catalyst
EP0250229B2 (fr) Procédé de polymérisation d'alpha-oléfine
EP0576411B1 (fr) Système catalytique amélioré pour la polymérisation d'oléfines
WO1996034899A1 (fr) Procede et constituant catalyseur pour la copolymerisation et l'homopolymerisation d'olefines
WO2004106387A2 (fr) Procede de formation d'un systeme catalyseur ziegler-natta presentant une morphologie controlee
WO2002096957A1 (fr) Compositions de catalyseur de polymerisation d'olefine et methode de preparation
US6339136B1 (en) Process for making propylene homo or copolymers
US4543389A (en) Copolymerization catalyst and process for polymerizing impact resistant ethylene-propylene polymers
US4520163A (en) Process of sequentially copolymerizing propylene-ethylene copolymers and catalyst therefor
WO2001004166A1 (fr) Procede de production de polypropylene
US20070142220A1 (en) Method for preparing ethylene polymerization catalysts
US20110245070A1 (en) Catalyst Components for the Polymerization of Olefins and Catalysts Therefrom Obtained
EP0576413B1 (fr) Donneurs d'électrons pour la polymérisation améliorée d'oléfines
EP1355954B1 (fr) Procede de preparation de polymeres de propylene
EP0576412B1 (fr) Donneurs d'électrons pour la polymérisation améliorée d'oléfines
EP0622382B1 (fr) Procédé pour améliorer la distribution statistique dans la copolymérisation des oléfins
GB2079759A (en) Polymerization of -olefins and catalysts therefor

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP