EP2142576A1 - Polyéthylène, procédé et composition catalytique pour sa préparation - Google Patents

Polyéthylène, procédé et composition catalytique pour sa préparation

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Publication number
EP2142576A1
EP2142576A1 EP08749587A EP08749587A EP2142576A1 EP 2142576 A1 EP2142576 A1 EP 2142576A1 EP 08749587 A EP08749587 A EP 08749587A EP 08749587 A EP08749587 A EP 08749587A EP 2142576 A1 EP2142576 A1 EP 2142576A1
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EP
European Patent Office
Prior art keywords
atoms
radicals
alkyl
aryl
independently
Prior art date
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EP08749587A
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German (de)
English (en)
Inventor
Lars KÖLLING
Shahram Mihan
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Basell Polyolefine GmbH
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Basell Polyolefine GmbH
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Priority to EP08749587A priority Critical patent/EP2142576A1/fr
Publication of EP2142576A1 publication Critical patent/EP2142576A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene

Definitions

  • the present invention relates to a polyethylene, as well as to a process and to a catalyst composition suitable for the preparation thereof.
  • Multimodal polyethylenes are known, whose properties essentially depend on the nature of the ethylene polymer fractions of which they are made, as well as on the way in which the polyethylenes are prepared and, in particular, on the kind of process used to prepare the same.
  • a key role is played by the catalyst system selected in the (co)polymerization step(s) which ⁇ s(are) carried out to obtain the polyethylene starting from the monomers, i.e. from ethylene and, optionally, one further comonomer or more further comonomers.
  • polymer is used to indicate both a homopolymer, i.e. a polymer comprising repeating monomeric units derived from equal species of monomers, and a copolymer, i.e a polymer comprising repeating monomeric units derived from at least two different species of monomers, in which case reference will be made to a binary copolymer, to a terpolymer, etc. depending on the number of different species of monomers present
  • polyethylene is used to indicate both an ethylene homopolymer and a copolymer of ethylene and at least a further comonomer.
  • polymerization is used to indicate both a homopolymerization, i e a polymerization of repeating monomeric units derived from equal species of monomers, and a copolyme ⁇ zation, i e a polymerization of at least two different species of monomers.
  • ethylene homopolymer is used to indicate a polymer comprising repeating ethylene monomeric units, possible comonomers of different species being present in a limited amount, in any case such that the melting temperature T m of the polymer is equal to or greater than 125 0 C, wherein the melting temperature T m is the temperature at the maximum of the melting peak as better described in the following.
  • T m is measured according to ISO 11357-3 by a first heating at a heating rate of 20°C/min until a temperature of 200°C is reached, a dynamic crystallization at a cooling rate of 20°C/min until a temperature of -10°C is reached, ad a second heating at a heating rate of 20°C/m ⁇ n until a temperature of 200 0 C is reached.
  • the melting temperature T m (maximum of the melting peak of the second heating) is therefore the temperature at which the curve of the enthalpy vs. temperature of the second heating has a maximum.
  • copolymer of ethylene is used to indicate a polymer comprising repeating ethylene monomeric units and at least one further comonomer of different species, said at least one comonomer of different species being present in an amount higher than a predetermined value, in any case such that the melting temperature T m of the polymer is lower than 125°C.
  • Multimodal polyethylenes exhibit reduced melt flow perturbations and are preferred to monomodal polyethylenes because of improved properties for applications such as blow molding and/or films having a predetermined mechanical strength.
  • Multimodal polyethylenes generally have a molecular mass distribution curve having more than one molecular mass peak due to the presence of a plurality of polymer fractions having distinct molecular masses.
  • Monomodal polyethylenes have a monomodal molecular mass distribution curve, i.e. a curve having a single peak due to the presence of a single polymer fraction having a given molecular mass. Thanks to a broader molecular mass distribution, multimodal polyethylenes can be processed more easily with respect to monomodal polyethylenes.
  • Prior art
  • the expression "molecular weight”, except where otherwise indicated, is used to indicate the weight average molar mass M w .
  • a disadvantage of this process for example with reference to a process performed in two reactors arranged in series, apart from the complexity and costs resulting from the performance of a process in two reactors, is that relatively large amounts of hydrogen have to be added to produce the fraction having the relatively lower molecular weight.
  • the polyethylenes obtained in this way have a low content of vinyl groups, especially in the low molecular weight fraction, generally lower than 0 3.
  • a single reactor can be used for the preparation of multimodal polyethylene by using catalyst compositions comprising at least two different ethylene polymerization catalysts giving rise to respective distinct polyethylene fractions.
  • catalyst compositions comprising at least two different ethylene polymerization catalysts of the Ziegler type or the metallocene type is known. So, for example, WO 95/11264 teaches to use a combination of such two catalysts producing respective polyolefins having distinct weight average molar masses, thus resulting in a polyethylene having a broad molecular mass distribution.
  • LLDPE linear low density polyethylene
  • SCBD short chain branching distribution
  • the number and the distribution of the side chains influence the crystallization behaviour of the ethylene copolymer and, as a result, the mechanical properties thereof
  • the flow properties and thus the processability of these ethylene copolymers mainly depend on their molecular mass and molecular mass distribution, however, the short chain branching distribution also plays a role in particular processing methods, e.g in film extrusion in which the crystallization behaviour of the ethylene copolymers during cooling of the film extrudate is an important factor in determining how quickly and in what quality a film can be extruded
  • Polyolefins prepared by means of transition metal complexes comprising other ligands than cyclopentadienyl ligands are also known WO 04/074333, for example, describes 2,6-b ⁇ s[1-(2,6- diisopropylphenylimino)ethyl]pyridine complexes of Yttrium, a lanthanide or an actinide metal as catalysts for polymerization of conjugated dienes.
  • WO 98/27124 discloses 2,6-bis(imino)pyridyl complexes of iron and cobalt as catalysts for homo- or co-polymerization of ethylene
  • WO 99/46302 discloses a catalyst composition for polymerization of alpha-olefins comprising (a) a 2,6- bis(imino)pyridyl iron component and (b) another catalysts, i.e. a zirconocene or Ziegler catalyst. J Am Chem.
  • the above-mentioned object is achieved by providing a multimodal polyethylene having an inverse comonomer distribution, which advantageously allows to attain improved mechanical properties, and predetermined values of polydispersity of the at least one first ethylene polymer fraction and, respectively, of the at least one second ethylene polymer fraction, which advantageously allows to attain improved processability.
  • the Applicant has found that the at least one first ethylene polymer fraction having a relatively lower molecular weight and including an ethylene homopolymer should have a relatively narrower molecular mass distribution, while the at least one second ethylene polymer fraction having a relatively higher molecular weight and including an ethylene copolymer, should have a relatively broader molecular mass distribution.
  • An inverse comonomer distribution is a comonomer distribution in which the comonomer is substantially incorporated only in the relatively higher molecular weight ethylene polymer fractions and is referred to in the field as inverse with respect to a comonomer distribution where the relatively lower molecular weight fractions have the relatively higher comonomer contents and vice versa as obtainable, for example, by the use of conventional non-single site catalysts for each ethylene polymer fraction such as the Ziegler-Natta catalysts, while multimodal ethylene polymers having all ethylene polymer fractions produced using single-site catalysts, for example metallocene catalysts, have a substantially uniform comonomer distribution.
  • the present invention provides a multimodal polyethylene comprising at least one first ethylene polymer fraction including an ethylene homopolymer having a first molecular weight, and at least one second ethylene polymer fraction including an ethylene copolymer having a second molecular weight higher than said first molecular weight, the multimodal polyethylene having a density of 0.915-0 970 g/cm 3 , a weight average molar mass M w of 100 000-900 000 g/mol, and a polydispersity M w /M n of at least 15, wherein the at least one homopolymer has a density of 0 950- 0.975 g/cm 3 , a weight average molar mass M w of 10 000-90 000 g/mol, and a polydispersity M w /M n higher than 3 and lower than 10, and wherein the at least one copolymer has a polydispersity M w /M n between 8 and 80.
  • the density of the multimodal polyethylene is preferably 0.920-0.960 g/cm 3 , more preferably 0.940-0 955 g/cm 3 According to an alternative preferred embodiment of the invention, the density of the multimodal polyethylene is in the range of 0.930-0.967g/cm 3 .
  • the weight average molecular mass M w of the multimodal polyethylene is preferably 150 000 - 800 000 g/mol, more preferably 200 000 - 750 000 g/mol.
  • the multimodal polyethylene has a polydispersity, i e the ratio between the weight average molecular mass M w and the number average molecular mass M n , of 15-180, more preferably of 15-150, more preferably of 20-150 and, still more preferably, of 20-130
  • the homopolymer of the multimodal polyethylene has a density of 0 955-0 975 g/cm 3 , more preferably of 0 960 - 0 970 g/cm 3
  • the homopolymer of the multimodal polyethylene has a weight average molecular mass M w of 20 000 - 80 000 g/mol, more preferably of 30 000 - 70 000 g/mol
  • the polydispersity of the homopolymer of the multimodal polyethylene is 3 ⁇ M w /M n ⁇ 10, preferably 3 ⁇ M w /M n ⁇ 8, preferably 4 ⁇ M w /M n ⁇ 8, still more preferably 4 ⁇ M w /M n ⁇ 7, especially 4 5 ⁇ M W /M n ⁇ 7
  • the copolymer of the multimodal polyethylene has a density of 0 910-0 965 g/cm 3 , preferably 0 920-0 960 g/cm 3 , more preferably 0 939-0 955 g/cm 3
  • the copolymer of the multimodal polyethylene has a weight average molecular mass M w of 150 000 - 2 000 000 g/mol, preferably 180 000-1 000 000 g/mol, more preferably 200 000 - 800 000 g/mol
  • the copolymer of the multimodal polyethylene has a polydispersity of 8-80, more preferably 10-50, and, still more preferably, of 12-30
  • the multimodal polyethylene has at least 1 5 CH 3 groups/1000 carbon atoms, preferably from 1 5 to 15 CH 3 groups /1000 carbon atoms and, still more preferably, 2 5 to 10 CH 3 groups /1000 carbon atoms
  • the CH 3 groups /1000 carbon atoms are determined by means of 13 C-NMR, as described by James C Randall, JMS-REV Macromol Chem Phys , C29 (2&3), 201-317 (1989), and refer to the total content of CH 3 groups/1000 carbon atoms
  • the multimodal polyethylene has at least 0 3 vinyl groups/1000 carbon atoms, preferably at least 0 5 vinyl groups/1000 carbon atoms, preferably from 0 5 to 3 vinyl groups/1000 carbon atoms, preferably from 0 5 to 2 vinyl groups/1000 carbon atoms, preferably from 0 5 to 1 5 vinyl groups/1000 carbon atoms
  • the multimodal polyethylene has preferably less than 5 vinyl groups/1000 carbon atoms, preferably from 1 to 3 vinyl groups/1000 carbon atoms, preferably from 2 to 3 vinyl groups/1000 carbon atoms
  • the at least one first ethylene polymer fraction has at least 0 3 vinyl groups/1000 carbon atoms, preferably at least 0 5 vinyl groups/1000 carbon atoms preferably from 0 5 to 5 vinyl groups/1000 carbon atoms, preferably from 0 5 to 3 vinyl groups/1000 carbon atoms, preferably from 0 5 to 2 vinyl groups/1000 carbon atoms, preferably from 0 5 to 1 5 vinyl groups/1000 carbon atoms
  • the at least one first ethylene polymer fraction has preferably less than 5 vinyl groups/1000 carbon atoms, preferably from 1 to 3 vinyl groups/1000 carbon atoms, preferably from 2 to 3 vinyl groups/1000 carbon atoms
  • the multimodal polyethylene has at least 0 1 vinylidene groups/1000 carbon atoms, more preferably from 0 1 to 0 5 vinylidene groups/1000 carbon atoms and still more preferably, from 0 1 to 0 25 vinylidene groups/1000 carbon atoms
  • Vinyl groups are usually attributed to a polymer termination reaction after an ethylene insertion, while vinylidene end groups are usually formed after a polymer termination reaction after a comonomer insertion
  • vinylidene and vinyl groups are subsequently functionalized or crosshnked, the vinyl groups usually being more suitable for these subsequent reactions
  • the multimodal polyethylene of the invention is therefore particularly useful in applications requiring subsequent functionalization or crosslinking, such as for example pipes or adhesives
  • the ethylene copolymer of the multimodal polyethylene preferably comprises at least one alpha- olefin as comonomer
  • Preferred alpha-olefins are all alpha-olefins having from 3 to 12 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1- octene and 1-decene
  • the ethylene copolymer of the multimodal polyethylene preferably comprises at least one 1— olefin having from 4 to 8 carbon atoms for example 1-butene, 1-pentene, 1-hexene 4-methyl pentene or 1-octene
  • Particular preference is given to at least one of the alpha-olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene
  • the multimodal polyethylene of the invention can be for example obtained by a process carried out in a single reactor in the presence of a mixed catalyst composition comprising two different polymerization catalysts as described in the following
  • the present invention provides a catalyst composition which is particularly suitable to prepare the multimodal polyethylene describe above
  • the catalyst composition of the present invention comprises (A) at least one chromium catalyst based on chromium oxide, and (B) at least one iron catalyst of formula (I),
  • F and G independently of one another, are selected from the group consisting of-
  • R A ,R a independently of one another denote hydrogen, CrC ⁇ o-alkyl, C 2 -C 2 o-alkenyl, C 6 - C 20 -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, or S ⁇ R 11A 3 , wherein the organic radicals R A ,R B can also be substituted by halogens, and/or in each case two radicals R A ,R 8 can also be bonded with one another to form a five- or six-membered nng,
  • R C ,R C independently of one another denote hydrogen, Ci-C 2 o-alkyl, C 2 -C 2 o-alkenyl, C 6 - C 2 o-aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, or SiR 11A 3 , wherein the organic radicals R C ,R° can also be substituted by halogens, and/or in each case two radicals R C ,R° can also be bonded with one another to form a five- or six-membered nng,
  • ,11A independently of one another denote hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, and/or two radicals R 11A can also be bonded with one another to form a five- or six-membered ring,
  • the at least one iron catalyst is of formula (II):
  • R 1 -R 2 independently of one another denote hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, or five-, six- or seven-mem bered heterocyclyl, which comprises at least one atom from the group consisting of N, P, O or S, wherein the organic radicals R 1 -R 2 can also be substituted by halogens, NR 1 ⁇ 2 , OR 16 or SiR 17 3 and/or the two radicals R 1 -R 2 can also be bonded with R 3 -R 5 to form a five-, six- or seven- membered ring,
  • R -R 15 independently of one another denote hydrogen, C 1 -C 22 -BlKyI, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical, NR 16 2 , OR 1 ⁇ , halogen, S ⁇ R 17 3 or five-, six- or seven-membered heterocyclyl, which comprises at least one atom from the group consisting of N, P, O or S, wherein the organic radicals R 3 - R 15 can also be substituted by halogens, NR 16 2 , OR 16 or SiR 17 3 and/or in each case two radicals R 3 -R 5 can be bonded with one another and/or in each case two radicals R 6 -R 10 can also be bonded with one another to form a five-, six- or seven-membered ring and/or in each case two radicals R 11 -
  • R 16 independently of one another denote hydrogen, CrC 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 2 2-aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical or SiR 17 3 , wherein the organic radicals R 16 can also be substituted by halogens and in each case two radicals R 16 can also be bonded to form a five- or six-mem bered ring,
  • R 17 independently of one another denote hydrogen, C r C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -
  • E 1 -E 3 independently of one another denote carbon, nitrogen or phosphorus, in particular carbon, and u independently of one another is 0 for E 1 -E 3 as nitrogen or phosphorus and 1 for E 1 - E 3 as carbon,
  • X independently of one another denote fluorine, chlorine, bromine, iodine, hydrogen
  • R 18 independently of one another denote hydrogen, C r C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 - C 20 -aryl, arylalkyl having 1 to 10 C atoms in the alkyl radical and 6-20 C atoms in the aryl radical or S ⁇ R 19 3 , wherein the organic radicals R 18 can also be substituted by halogens or nitrogen- and oxygen-containing groups and in each case two radicals R 18 can also be bonded to form a five- or six-membered ring,
  • R 19 independently of one another denote hydrogen, C r C 20 -alkyl, C 2 -C 20 -alkenyl, C 6 -
  • R 19 can also be bonded to form a five- or six-membered ring, s is 1 , 2, 3 or 4, in particular 2 or 3,
  • the present invention also provides a catalyst composition comprising (A) at least one chromium catalyst based on chromium oxide, and (B) at least one iron catalyst of formula (II)
  • E 1 -E 3 in a molecule can be identical or different If E 1 is phosphorus, then E 2 to E 3 are preferably each carbon If E 1 is nitrogen, then E 2 and E 3 are each preferably nitrogen or carbon, in particular carbon u independently of one another is 0 for E 1 -E 3 as nitrogen or phosphorus and 1 for E 1 -E 3 as carbon
  • R 1 -R 2 can be varied within a wide range Possible carboorganic substituents R 1 -R 2 are for example, the following Ci-C 22 -alkyl which may be linear or branched, e g methyl, ethyl n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n- dodecyl, 5- to 7-membered cycloalkyl which may in turn bear a C r C 10 -alkyl group and/or C 6 -C 10 - aryl group as substituents, e g cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloocty
  • the substituents R 3 -R 15 can be varied within a wide range, as long as at least one radical R of R 6 - R 15 is chlorine, bromine, and iodine, CF 3 or OR 11
  • Possible carboorganic substituents R 3 -R 15 are, for example, the following C- ⁇ -C 22 -alkyl which may be linear or branched, e g methyl, ethyl, n- propyl, isopropyl, n-butyl isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl, 5- to 7-membered cycloalkyl which may in turn bear a Ci-C 10 -alkyl group and/or C 6 - Cio-aryl group as substituents, e g
  • halogens such as fluorine, chlorine or bromine.
  • R 3 -R 15 can also be amino NR 1 ⁇ 2 or SiR 17 3 , alkoxy or aryloxy OR 16 , for example dimethylamino, N-pyrrolidinyl, picolinyl, methoxy, ethoxy or isopropoxy or halogen such as fluorine, chlorine or bromine
  • R 16 and R 17 are more fully described below.
  • Two R 16 and/or R 17 may also be joined to form a 5- or 6-membered ring.
  • the S ⁇ R 1? 3 radicals may also be bound to E 1 -E 3 via an oxygen or nitrogen.
  • Examples for R 17 are trimethylsilyloxy, triethylsilyloxy, butyldimethylsilyloxy, tributylsilyloxy or tri-tert-butylsilyloxy.
  • Preferred radicals R 3 -R 5 are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, ortho-dialkyl- or -dichloro-substituted phenyls, trialkyl- or trichloro-substituted phenyls, naphthyl, biphenyl and anthranyl.
  • Particularly preferred organosilicon substituents are trialkylsilyl groups having from 1 to 10 carbon atoms in the alkyl radical, in particular trimethylsilyl groups.
  • Preferred radicals R 6 -R 15 are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, vinyl, allyl, benzyl, phenyl, fluorine, chlorine and bromine, wherein at least one of the radicals R 6 -R 15 is chlorine, bromine, iodine, CF 3 or OR 11 .
  • At least one radical R of the group consisting of R 6 -R 8 , and R 11 -R 13 is chlorine, bromine, or CF 3 and at least one radical R of the group consisting of R s -R s , and R 11 -R 13 is hydrogen, or Ci-C 4 -alkyl, wherein the alkyl can be linear or branched, in particular, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert -butyl.
  • At least one radical R of the group consisting of R 6 -R 8 , and R 11 -R 13 is chlorine or bromine and at least one radical R of the group consisting of R 6 -R 8 , and R 11 -R 13 is hydrogen, or methyl.
  • R 6 and/or R 11 are chlorine or bromine and R 7 , R 8 , R 12 and/or R 13 are hydrogen, or methyl.
  • R 6 and R 8 , and/or R 11 and R 13 are chlorine or bromine, and R 7 and/or R 12 , are hydrogen or methyl.
  • R 6 and R 11 are identical, and/or R 7 and R 12 are identical, and/or R 8 and R 13 are identical, wherein at least one pair of identical rests R is chlorine or bromine.
  • R 5 and R 11 are different, and/or R 7 and R 12 are different, and/or R 8 and R 13 are different, wherein at least rest R is chlorine or bromine.
  • Particular preference is given to iron components in which at least one rest R R 6 -R 8 , and/or R 11 -R 13 is chlorine.
  • At least one radical R of the group consisting of R 9 , R 10 , R 14 , and R 15 is hydrogen, or C 1 -C 22 -alkyl which may also be substituted by halogens, e g. methyl, trifluoromethyl, ethyl, n- propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, or vinyl.
  • R 9 , R 10 , R 14 , and R 15 are identical.
  • Variation of the radicals R 15 enables, for example, physical properties such as solubility to be finely adjusted.
  • Possible carboorganic substituents R 16 are, for example, the following: Ci-C 20 - alkyl which may be linear or branched, e.g.
  • cyclopropyl cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclododecyl, C 2 -C 2 o-alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g.
  • radicals R 17 in organosilicon substituents SiR 17 3 are the same radicals which have been described above for R 1 -R 2 , where two radicals R 17 may also be joined to form a 5- or 6-membered ring, e.g. trimethylsilyl, t ⁇ ethylsilyl, butyldimethylsilyl, tributylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl.
  • Ci-C 10 -alkyl such as methyl, ethyl, n-propyl, n- butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and also vinyl allyl, benzyl and phenyl as radicals R 17 .
  • the ligands X result, for example, from the choice of the appropriate starting metal compounds used for the synthesis of the iron complexes, but can also be varied afterward.
  • Possible ligands X are, in particular, the halogens such as fluorine, chlorine, bromine or iodine, in particular chlorine.
  • Alkyl radicals such as methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl or benzyl are also usable ligands X, wherein the organic radicals X can also be substituted by R 18 .
  • ligands X mention may be made, purely by way of example and in no way exhaustively, of trifluoroacetate, BF 4 " , PF 6 " and weakly coordinating or non-coordinating anions (cf., for example, S Strauss in Chem. Rev. 1993, 93, 927-942), e g B(C 6 F 5 ) 4 ⁇ .
  • ligands X are also particularly useful ligands X. Some of these substituted ligands X are particularly preferably used since they are obtainable from cheap and readily available starting materials. Thus, a particularly preferred embodiment is that in which X is dimethylamide, methoxide, ethoxide, isopropoxide, phenoxide, naphthoxide, triflate, p-toluenesulfonate, acetate or acetylacetonate.
  • the number s of the hgands X depends on the oxidation state of the iron The number s can thus not be given in general terms.
  • the oxidation state of the iron in catalytically active complexes is usually known to those skilled in the art. However, it is also possible to use complexes whose oxidation state does not correspond to that of the active catalyst. Such complexes can then be appropriately reduced or oxidized by means of suitable activators. Preference is given to using iron complexes in the oxidation state +3 or +2.
  • D is an uncharged donor, in particular an uncharged Lewis base or Lewis acid, for example amines, alcohols, ethers, ketones, aldehydes, esters, sulfides or phosphines which may be bound to the iron centre or else still be present as residual solvent from the preparation of the iron complexes.
  • Lewis base or Lewis acid for example amines, alcohols, ethers, ketones, aldehydes, esters, sulfides or phosphines which may be bound to the iron centre or else still be present as residual solvent from the preparation of the iron complexes.
  • the number t of the hgands D can be from 0 to 4 and is often dependent on the solvent in which the iron complex is prepared and the time for which the resulting complexes are dried and can therefore also be a non-integer number such as 0.5 or 1.5. In particular, t is 0, 1 to 2.
  • Preferred complexes (B) are 2,6-b ⁇ s[1-(2-chloro-4,6-dimethylphenyl ⁇ mino)ethyl]pyridine iron(ll) chloride; 2,6-bis[1-(2-chloro-6-methylphenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-bis[1-(2,6- dichlorophenyl ⁇ mino)ethyl]pyridine ⁇ ron(ll) dichloride, 2,6-bis[1-(2,4-dichloro-6-methyl- phenylimino)ethyl]pyridine iron(ll) dichloride, 2,6-b ⁇ s[1-(2,6-difluorophenylimino)ethyl]-pyridine iron(ll) dichloride, 2,6-bis[1-(2,6-d ⁇ bromophenylimino)ethyl]-pyr ⁇ d ⁇ ne ⁇ ron(ll) dichloride or the respective
  • chromium catalysts based on chromium oxide can be used to prepare catalyst (A) of the catalyst composition of the invention, provided they give rise, together with iron catalyst (B), to an ethylene copolymer having the features defined in attached claim 1
  • these chromium catalysts are also referred to as Phillips catalysts and are well-known in the art (for instance, their composition and mode of preparation is described in M. P. McDaniel, Adv. Cat 33, 7-98 (19B5), US5,363,915, all of which are incorporated herein by reference .
  • supported chromium oxide or Phillips catalysts catalysts are used.
  • Chromium catalysts based on chromium oxide are well known in the art and commercially available from a number of producers. As is known, chromium catalysts are generally produced by doping inorganic supports such as silica gels or aluminum oxides with chromium (catalyst precursors) with the active component containing chromium preferably from a solution or, in the case of volatile compounds, from the vapour phase.
  • Suitable chromium compounds are chromium(Vl) oxide, chromium salts such as chromium(lll) nitrate and chrom ⁇ um(lll) acetate, complex compounds such as chrom ⁇ um(lll) acetylacetonate or chromium hexacarbonyl, or alternatively organometallic compounds of chromium such as bis(cyclopentadienyl)chromium(ll), organic chromic esters or bis(aren)chromium(0).
  • this chromium-doped catalyst precursor is thermally treated at predetermined temperatures, preferably from 500 and 900 0 C, more preferably from 550 to 650 0 C, in an oxidizing atmosphere, preferably in air
  • the oxidised catalyst precursor may be subjected to a prereduction step by means of a reducing agent, such as for example carbon monoxide or hydrogen
  • This pre-reduction step is preferably performed at a temperature within the range of 300 to 400 0 C, more preferably from 320 to 48O 0 C, preferably during a period from 5 minutes to 48 hours, more preferably from 1 to 10 hours
  • the molar ratio of chromium catalyst (A) to iron catalyst (B) is usually in the range from 1 100 to 100 1 , preferably from 1 10 to 10 1 and particularly preferably from 1 5 to 5 1
  • the preferred embodiments of (A) and (B) are likewise preferred in combinations of (A) and (B)
  • the catalyst composition of the invention can be used alone or together with further components as catalyst system for olefin polymerization Accordingly, the present invention also provides a catalyst system comprising, additionally to the catalysts (A) and (B), at least one organic or inorganic support (H), and/or at least one activating compound (J), and/or at least one metal compound of a metal of group 1 , 2 or 13 of the Periodic Table (K)
  • a supported chromium catalyst and a supported iron catalyst is used in an especially preferred embodiment the chromium catalyst and the iron catalyst are on the same, common support in order to ensure a relatively close spatial proximity of the different catalyst centres and thus to ensure good mixing of the different polymers formed
  • finely divided supports (H) which can be any organic or inorganic, inert solid
  • the support (H) can be a porous support such as talc, a sheet silicate, or an inorganic oxide
  • the support (H) preferably used has a specific surface
  • Inorganic oxides suitable as supports (H) may be found among oxides of the elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements Preference is given to oxides or mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and also corresponding oxide mixtures, optionally one may also use ZrO 2 or B 2 O 3 Preferred oxides are silicon dioxide, in particular in the form of a silica gel or a pyrogenic silica, or aluminum oxide Examples of particularly preferred supports are spray dried SiO 2 especially those having a pore volume of from 1 0 to 3 0 ml/g, preferably from 1 2 to 2 2 ml/g and more preferably from 1 4 to 1 9 ml/g and a surface area (BET) of from 100 to 500 m 2 /g and preferably from 200 to 400 m 2 /g Such products are commercially available, for example as Silica XPO 2107 sold by Grace
  • the inorganic support (H) can be subjected to a thermal treatment, e g for removing adsorbed water Such a drying treatment is generally carried out at from 80 to 300 0 C, preferably from 100 to 200 0 C and is preferably carried out under reduced pressure and/or in a stream of inert gas, for example nitrogen or argon
  • a thermal treatment is generally carried out at from 80 to 300 0 C, preferably from 100 to 200 0 C and is preferably carried out under reduced pressure and/or in a stream of inert gas, for example nitrogen or argon
  • the inorganic support (H) can also be calcined, in which case the concentration of OH groups on the surface is adjusted and the structure of the solid may be altered by a treatment at from 200 to 1000 0 C
  • the support can also be treated chemically using customary desiccants such as metal alkyls, preferably aluminum alkyls chlorosilanes or SiCI 4 , or else methyl-aluminoxane Appropri
  • the inorganic support (H) can also be chemically modified
  • the treatment of silica gel with NH 4 SiF 6 leads to fluorination of the silica gel surface
  • likewise treatment of silica gels with siianes containing nitrogen-, fluorine- or sulfur-containing groups gives correspondingly modified silica gel surfaces
  • the support (H) is generally loaded by contacting it, in a solvent with a chromium compound, removing the solvent and calcining the catalyst at a temperature of from 400 to 1 100° C
  • the support (H) can for this purpose be suspended in a solvent or in a solution of the chromium compound
  • the ratio by weight of chromium compounds to the support during application is generally from 0 001 1 to 200 1 , preferably from 0 005 1 to 100 1
  • the chromium catalyst (A) is prepared by adding small amounts of MgO and/or ZnO to the inactive pre-catalyst and subsequently activating this mixture in
  • a catalyst system comprising at least one chromium catalyst (A) at least one iron catalyst (B) at least one support component (H), and preferably at least one activating compound (J)
  • the catalyst system comprises at least one activating compound (J).
  • activating compound is preferably used in an excess or in stoichiometric amounts based on the catalysts which they activate.
  • the molar ratio of catalyst to activating compound (J) can be from 1 :0 1 to 1 :10000.
  • Such activator compounds are uncharged, strong Lewis acids, ionic compounds having a Lewis-acid cation or a ionic compound containing a Bronsted acid as cation in general.
  • activators of the polymerization catalysts of the present invention especially on definition of strong, uncharged Lewis acids and Lewis acid cations, and preferred embodiments of such activators, their mode of preparation as well as particularities and the stoichiometry of using them have already been set forth in detail in WO05/103096 from the same applicant Examples are aluminoxanes, hydroxyaluminoxanes, boranes, boroxins, boronic acids and borinic acids.
  • strong, uncharged Lewis acids for use as activating compounds are given in WO 03/31090 and WO05/103096 incorporated hereto by reference.
  • Suitable activating compounds (J) are both as an example and as a strongly preferred embodiment, compounds such as an aluminoxane, a strong uncharged Lewis acid, an ionic compound having a Lewis-acid cation or an ionic compound containing.
  • aluminoxanes it is possible to use, for example, the compounds described in WO 00/31090 incorporated hereto by reference Particularly useful aluminoxanes are open-chain or cyclic aluminoxane compounds of the general formula (III) or (IV)
  • R 1B -R 4B are each, independently of one another, a C ⁇ Ce-alkyl group, preferably a methyl, ethyl, butyl or isobutyl group and I is an integer from 1 to 40, preferably from 4 to 25.
  • a particularly useful aluminoxane compound is methyl aluminoxane (MAO).
  • modified aluminoxanes in which some of the hydrocarbon radicals have been replaced by hydrogen atoms or alkoxy, aryloxy, siloxy or amide radicals can also be used in place of the aluminoxane compounds of the formula (111) or (IV) as activating compound (J).
  • Boranes and boroxines are particularly useful as activating compound (J), such as trialkylborane, triarylborane or trimethylboroxine. Particular preference is given to using boranes which bear at least two perfluo ⁇ nated aryl radicals More preferably, a compound selected from the list consisting of t ⁇ phenylborane tr ⁇ s(4-fluorophenyl)borane, tr ⁇ s(3 5-d ⁇ fluorophenyl)borane tr ⁇ s(4- fluoromethylphenyl)borane t ⁇ s(pentafluorophenyl)borane tr ⁇ s(tolyl)borane, t ⁇ s(3,5- d ⁇ methylphenyl)borane t ⁇ s(3,5-d ⁇ fluorophenyl)borane or t ⁇ s(3 4 5-tr ⁇ fluorophenyl)borane is used most preferably the activating compound is tr ⁇
  • activating compounds (J) can also be used suitably as activating compounds (J)
  • Preferred ionic activating compounds (J) can contain borates bearing at least two perfluorinated aryl radicals Particular preference is given to N,N-d ⁇ methyl anilino tetrak ⁇ s(pentafluorophenyl)borate and in particular N,N-d ⁇ methylcyclohexylammon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate N,N-d ⁇ methylbenzyl- ammonium tetrak ⁇ s(pentafluorophenyl)borate or t ⁇ tyl tetrakispentafluorophenylborate It is also possible for two or more borate anions to
  • the catalyst system may further comprise, as additional component (K) a metal compound as defined both by way of generic formula, its mode and stoichiometric of use and specific examples in WO 05/103096, incorporated hereto by reference
  • additional component (K) a metal compound as defined both by way of generic formula, its mode and stoichiometric of use and specific examples in WO 05/103096, incorporated hereto by reference
  • the metal compound (K) can likewise be reacted in any order with the catalysts (A) and (B) and optionally with the activating compound (J) and the support (H)
  • support (H), chromium catalyst (A) iron catalyst (B) and the activating compounds (J) can be combined is in principle immaterial
  • the various intermediates can be washed with suitable inert solvents such as aliphatic or aromatic hydrocarbons
  • suitable inert solvents such as aliphatic or aromatic hydrocarbons
  • the supported catalyst is preferably obtained as a free-flowing powder Examples of the industrial implementation of the above process are described in WO 96/00243 WO 98/40419 or WO 00/05277
  • a further method of immobilization is prepolyme ⁇ zation of the catalyst system with or without prior application to a support -
  • the chromium catalyst (A) and the iron catalyst (B) may be contacted with the olefin to be polymerized in the form of a single catalyst system, for example a catalyst system according to any of the preferred embodiments optionally comprising further component as described above, or they may be added to the reactor separately.
  • the chromium catalyst (A) is preferably applied in such an amount that the concentration of the chromium from the chromium catalyst (A) in the finished catalyst system is from 1 to 200 ⁇ mol, preferably from 5 to 100 ⁇ mol and particularly preferably from 10 to 70 ⁇ mol, per g of support (H).
  • the iron catalyst (B) is preferably applied in such an amount that the concentration of iron from the iron catalyst (B) in the finished catalyst system is from 1 to 200 ⁇ mol, preferably from 5 to 100 ⁇ mol and particularly preferably from 10 to 70 ⁇ mol, per g of support (H).
  • the catalyst system firstly to be prepolyme ⁇ zed with alpha-olefins, preferably linear C 2 -C 10 -I -alkenes and more preferably ethylene or propylene, and the resulting prepolymerized catalyst solid then to be used in the actual polymerization.
  • the mass ratio of catalyst solid used in the prepolymerization to a monomer polymerized onto it is preferably in the range from 1 :0.1 to 1 :1000, preferably from 1 :1 to 1 200.
  • an olefin preferably an alpha-olefin, for example vinylcyclohexane, styrene or phenyldimethylvinylsilane
  • an antistatic or a suitable inert compound such as a wax or oil
  • the molar ratio of additives to the sum of chromium catalyst (A) and iron catalyst (B) is usually from 1 :1000 to 1000:1 , preferably from 1 :5 to 20 1.
  • the present invention provides the use of the above-mentioned catalyst composition for the polymerization of ethylene, and a process for preparing the multimodal polyethylene of the invention comprising the step of copolymerizing ethylene with at least one alpha-olefin.
  • the present invention further provides a process for polymerization of olefins in the presence of the catalyst composition of the invention.
  • alpha-olefins preferably having from 3 to 12 carbon atoms
  • Preferred alpha-olefins are linear or branched C 2 -Ci 2 -I -alkenes, in particular linear C 2 -Ci 0 -I -alkenes such as ethene, propene, 1- butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or branched C 2 -Ci 0 -I -alkenes such as 4-methyl-1-pentene.
  • Particularly preferred 1 -olefins are C 4 -C 12 -I -alkenes, in particular linear C 6 -C 10 -1-alkenes. It is also possible to polymerize mixtures of various 1-olefins.
  • Monomer mixtures containing at least 50 mol% of ethene are preferably used
  • the process of the invention for polymerizing ethylene with alpha-olefins can be carried out using industrially known polymerization methods at temperatures, preferably in the range from -60 to 350°C, more preferably in the range from 20 to 300 0 C, and still more preferably from 25 to 150 0 C, and preferably under pressures of from 0.5 to 4000 bar, more preferably from 1 to 100 bar and most preferably from 3 to 40 bar.
  • the polymerization can be carried out in a known manner in bulk, in suspension, in the gas phase or in a supercritical medium in the customary reactors used for the polymerization of olefins.
  • the polymerization can be carried out batchwise or preferably continuously in one or more stages. High-pressure polymerization processes in tube reactors or autoclaves, solution processes, suspension processes, stirred gas-phase processes and gas- phase fluidized-bed processes are all possible.
  • the mean residence times are preferably from 0.5 to 5 hours, more preferably from 0.5 to 3 hours.
  • the more suitable pressure and temperature ranges for carrying out the polymerizations usually depend on the polymerization method.
  • high polymerization temperatures are preferably also set.
  • Preferred temperature ranges for these high-pressure polymerization processes are from 200 to 32O 0 C, more preferably from 220 to 290 0 C
  • temperatures of from 50 to 180 0 C, preferably from 70 to 12O 0 C are preferably set in these polymerization processes.
  • the polymerization is preferably carried out in a suspension medium, preferably an inert hydrocarbon such as isobutane or mixtures of hydrocarbons or else in the monomers themselves.
  • the polymerization temperatures are preferably in the range from -20 to 115 0 C, and the pressure is generally in the range from 1 to 100 bar.
  • the solids content of the suspension is generally in the range from 10 to 80%.
  • the polymerization can be carried out either batchwise, e.g. in stirring autoclaves, or continuously, e g. in tube reactors, preferably in loop reactors.
  • the gas-phase polymerization is preferably carried out in the temperature range from 30 to 125°C, and preferably at pressures of from 1 to 50 bar.
  • gas-phase polymerization preferably carried out in gas-phase fluidized-bed reactors, to solution polymerization and to suspension polymerization, preferably in loop reactors and stirred tank reactors.
  • the gas-phase polymerization can also be carried out in the condensed or supercondensed mode, in which part of the circulating gas is cooled to below the dew point and is recirculated as a two-phase mixture to the reactor.
  • a multizone reactor comprising two distinct polymerization zones connected to one another, by passing the polymer alternately through these two zones a predetermined number of times.
  • the two zones preferably have different polymerization conditions, so as to perform two different polymerization stages.
  • Such a reactor is described, for example, in
  • the different or identical polymerization stages can also, if desired, be connected in series so as to form a polymerization cascade in two reactors arranged in series.
  • a parallel reactor arrangement using two or more identical or different processes is also possible.
  • molar mass regulators for example hydrogen, or customary additives such as antistatics can also be used in the polymerizations.
  • the polymerization is preferably carried out with smaller amounts or no hydrogen present.
  • the polymerization is preferably carried out in a single reactor, in particular in a gas-phase reactor.
  • the polymerization of ethylene with alpha-olefins preferably having from 3 to 12 carbon atoms allows to prepare the multimodal polyethylene of the invention when the catalyst composition of the invention is used.
  • the polyethylene powder obtained directly from the reactor displays a very high homogeneity, so that, unlike the case of cascade processes, subsequent extrusion is not necessary in order to obtain a homogeneous product.
  • the preparation of the multimodal polyethylene of the invention in the reactor advantageously reduces the energy consumption, requires no subsequent blending processes and makes simple control of the molecular mass distributions and the molecular mass fractions of the various polymers possible. In addition, good mixing of the polyethylenes is achieved.
  • melt flow rate MFR 2 i was determined according to ISO 1133 at a temperature of 190 0 C under a load of 21.6 kg (190°C/21.6 kg).
  • the melt flow rate MFR 5 was determined according to ISO 1133 at a temperature of 190 0 C under a load of 5 kg (190°C/5 kg)
  • the intrinsic viscosity was determined in accordance with EN ISO 1628-1.
  • the determination of the weight average molar mass M w number average molar mass M n , and polidispersity M w /M n derived there from was carried out by means of high-temperature gel permeation chromatography on a WATERS 150 C using a method based on DIN 55672-1 (version 1995-02 of issue hard 1995) and the following columns connected in series: 3x SHODEX AT 806 MS, 1x SHODEX UT 807 and 1x SHODEX AT-G under the following conditions: solvent: 1 ,2,4-trichlorobenzene (stabilized with 0.025% by weight of 2,6-di-tert-butyl-4- methylphenol), flow: 1 ml/m ⁇ n, 500 ⁇ l injection volume, temperature: 135°C, calibration using PE Standards. Evaluation was carried out using WIN-GPC.
  • the vinyl group content was determined by means of IR in accordance with ASTM D 6248-98.
  • the branches/1000 carbon atoms were determined by means of 13 C-NMR, as described by James. C. Randall, JMS-REV. Macromol. Chem. Phys , C29 (2&3), 201-317 (1989), and were based on the total content of CH 3 groups/1000 carbon atoms including end groups
  • the side chains larger than CH 3 and especially ethyl, butyl and hexyl side chain branches/1000 carbon atoms excluding end groups were likewise determined in this way
  • the degree of branching in the individual polymer fractions was determined by the method of Holtrup (W. Holtrup, Makromol. Chem. 178, 2335 (1977)) coupled with 13 C-NMR as described by James. C Randall, JMS-REV. Macromol. Chem. Phys., C29 (2&3), 201-317 (1989)
  • the content of comonomer side chains/1000 carbon atoms was determined by means of infrared spectroscopy by use of an FTIR 2000 of Perkin Elmer, and is based on the total CH 3 group content/1000 carbon atoms including end groups.
  • the comonomer content was determined by multiple variate data analysis.
  • Heptane and toluene have been dried over molecular sieves.
  • the support used was a spray dried SiU 2 support having a surface area (BET) of 300 m 2 /g and a pore volume of 1 60 ml/g.
  • BET surface area
  • Such a support is available commercially from Grace under the name XPO2107.
  • To 135 kg of such a support were added 192 I of a solution of Cr(N0 3 ) 3 9H 2 O in methanol (17 g/l) were added, and after 1 hour the solvent was removed by distillation under reduced pressure (900-300 mbar) at 70-75 0 C
  • the resulting intermediate contained 0.3 wt % of chromium.
  • IPRA-solution 8 5 ml of a solution of IPRA in hexane (70% by weight, Crompton) were provided and filled up with heptane to 100 ml
  • Costelan ® AS 100 from Costenoble were provided and filled up with heptane to 100 ml
  • M w /M n polydispersity index ratio of weight average molecular mass and number average molecular mass density polymer density tot CH 3 / 1000C is to total CH 3 / 1000 carbon atoms (including end groups) trans double bonds is the content of trans bonds/1000 carbon atoms as determined by means of IR, ASTM D 6248-98 vinyl double bonds is the content of vinyl groups/1000 carbon atoms as determined by means of IR, ASTM D 6248-98 C6 is the content of hexene comonomer

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Abstract

L'invention porte sur un polyéthylène multimodal ayant une distribution inverse de comonomères, ainsi que sur un procédé effectué dans un seul réacteur en présence d'une composition de catalyseurs mixtes comprenant deux différents catalyseurs de polymérisation. Le polyéthylène multimodal a une masse volumique de 0,915 - 0,970 g/cm3, une masse moléculaire moyenne en poids Mw de 100 000 - 900 000 g/mole, et une polydispersité Mw/Mn d'au moins 15. Le ou les homopolymères ont une masse volumique de 0,950 - 0,975 g/cm3, une masse moléculaire moyenne en poids Mw de 10 000 - 90 000 g/mole et une polydispersité Mw/Mn supérieure à 3 et inférieure à 10, et le ou les copolymères ont une polydispersité Mw/Mn entre 8 et 80.
EP08749587A 2007-04-30 2008-04-17 Polyéthylène, procédé et composition catalytique pour sa préparation Withdrawn EP2142576A1 (fr)

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US8846188B2 (en) 2008-09-25 2014-09-30 Basell Poliolefine GmbH Impact resistant LLDPE composition and films made thereof
EP2196480A1 (fr) * 2008-12-15 2010-06-16 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Catalyseur supporté
BR112013028810B1 (pt) 2011-05-10 2020-11-24 Basell Polyolefine Gmbh Processo para homogeneizaqao e peletizaqao de uma composiçao de polietileno, uso de uma composiçao de polietileno obtida por tal processo e produtos preparados a partir de tal composiçao
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