EP4514864A1 - Procédé de production de copolymères de propylène aléatoires comprenant des unités comonomères d'oléfine en c4-c12-alpha - Google Patents

Procédé de production de copolymères de propylène aléatoires comprenant des unités comonomères d'oléfine en c4-c12-alpha

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Publication number
EP4514864A1
EP4514864A1 EP23722851.5A EP23722851A EP4514864A1 EP 4514864 A1 EP4514864 A1 EP 4514864A1 EP 23722851 A EP23722851 A EP 23722851A EP 4514864 A1 EP4514864 A1 EP 4514864A1
Authority
EP
European Patent Office
Prior art keywords
group
propylene
carbon atoms
comonomer
catalyst
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23722851.5A
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German (de)
English (en)
Inventor
Luigi Resconi
Simon Schwarzenberger
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Borealis GmbH
Original Assignee
Borealis GmbH
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Filing date
Publication date
Application filed by Borealis GmbH filed Critical Borealis GmbH
Publication of EP4514864A1 publication Critical patent/EP4514864A1/fr
Pending legal-status Critical Current

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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to a process for producing a random copolymer of propylene, optionally ethylene, and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms using a specific class of hafnocene complexes in combination with a cocatalyst system comprising a boron containing cocatalyst and an aluminoxane cocatalyst, preferably in a multistage polymerisation process including a gas phase polymerisation step.
  • Metallocene catalysts have been used to manufacture polyolefins for many years.
  • Metallocene catalysts for polypropylene generally show a very steep molecular weight capability response to hydrogen, that is, the melt flow rate of metallocene catalysed polypropylene strongly increases by even a mild increase in hydrogen concentration in the polymerisation medium.
  • the use of hydrogen is needed to reach acceptable catalyst productivities.
  • metallocene catalysts are mostly used for the production of high flow polypropylene materials.
  • the higher alpha- olefin tends to lower both catalyst activity and copolymer molecular weight.
  • the desired catalysts should also have improved performance in the production of high molecular weight propylene random copolymers comprising C4-C12-alpha olefin comonomer units, whereby the propylene copolymer comprising C 4 -C 12 -alpha olefin comonomer units should have higher melting points compared to propylene random copolymers comprising C4-C12-alpha olefin comonomer units produced with metallocene catalyst systems of the prior art.
  • MI low melt index
  • the specific hafnocene catalyst system gives a higher flexibility/freedom in the design of propylene/C 4 -C 12 -alpha olefin random polymers than prior art catalyst systems.
  • Summary of the invention provides a process for producing a random copolymer of propylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms, and optionally ethylene, in the presence of a single-site catalyst comprising (i) a complex of formula (I) wherein each X independently is a sigma-donor ligand in the group R2Si- at least one R is methyl or ethyl, and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl; each R 1 independently is the same or can be different and are a CH 2
  • the catalyst of the invention can be used in non-supported form or in solid form.
  • the catalyst of the invention may be used as a homogeneous catalyst or heterogeneous catalyst.
  • the catalyst of the invention in solid form, preferably in solid particulate form can be either supported on an external carrier material, like silica or alumina, or, in a particularly preferred embodiment, is free from an external carrier, however still being in solid form.
  • the solid catalyst is obtainable by a process in which (x) a liquid/liquid emulsion system is formed, said liquid/liquid emulsion system comprising a solution of the catalyst components (i) and (ii) dispersed in a solvent so as to form dispersed droplets; and (y) solid particles are formed by solidifying said dispersed droplets.
  • the present invention relates to a random copolymer of propylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms or a random terpolymer of propylene, ethylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms obtainable from the process according to the invention as defined above or below, wherein the random copolymer of propylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms or random terpolymer of propylene, ethylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms follows the following relation (A) in behalf of its polymerisation process: metallocene productivity / MFR 21 ⁇ 15 [kg/(g ⁇ h) / g/10 min] (A) with metallocene productivity overall productivity of the single site catalyst as kg random copoly
  • the complexes and hence catalysts of the invention are based on formula (I) as hereinbefore defined.
  • the complexes of the invention are asymmetrical. Asymmetrical means simply that the two indenyl ligands forming the hafnocene are different, that is, each indenyl ligand bears a set of substituents that are either chemically different, or located in different positions with respect to the other indenyl ligand.
  • Symmetrical complexes are based on two identical indenyl ligands.
  • the hafnocene complexes of the invention are preferably chiral, racemic bridged bisindenyl C 1 -symmetric hafnocenes in their anti-configuration.
  • the complexes of the invention are formally C 1 -symmetric, the complexes ideally retain a pseudo-C2-symmetry since they maintain C2-symmetry in close proximity of the metal center although not at the ligand periphery.
  • the complexes By nature of their chemistry both anti and syn enantiomer pairs (in case of C 1 -symmetric complexes) are formed during the synthesis of the complexes.
  • racemic-anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane
  • racemic-syn means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the scheme exemplified for zirconocene complexes below. The same approach also counts for the hafnocene compexes of the invention.
  • Racemic Anti Racemic Syn Formula (I), and any sub formulae are intended to represent complexes in their anti- configurations.
  • hafnocene complexes of the invention are preferably employed as the racemic- anti-isomers. ldeally, therefore at least 95 mol%, such as at least 98 mol%, especially at least 99 mol% of the hafnocene catalyst complex is in the racemic anti-isomeric form.
  • hydrocarbyl group includes alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, alkylaryl groups or arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl.
  • Each X independently is a sigma -donor ligand.
  • each X is independently a hydrogen atom, a halogen atom, C1-C6-alkoxy group or an R' group, where R' is a C 1 -C 6 -alkyl, phenyl or benzyl group. More preferably, X is chlorine, benzyl or a methyl group. Preferably, both X groups are the same. The most preferred options are two chlorides, two methyl or two benzyl groups, especially two chlorides.
  • R2Si- at least one R is methyl or ethyl, and the other R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, pentyl, hexyl, cyclohexyl and phenyl.
  • R 2 Si- represents Me 2 Si-, Et 2 Si- or (cyclohexyl)Me-Si-.
  • the bridge is -Si(CH3)2 or Et2Si-.
  • each R 3 and R 4 are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially hydrogen, methyl or tert-butyl, wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen; or at least one R 3 is a methoxy group in the 4-position of each phenyl group and the two other R 3 groups are tert-butyl groups; and/or at least one R 4 is a methoxy group in the 4-position of the phenyl ring and the two other R 4 are tert-butyl groups.
  • one or two R 3 per phenyl group are not hydrogen and one or two R 3 groups are hydrogen. If there are two non-hydrogen R 3 groups per phenyl group then the R 3 group representing hydrogen is preferably at the 4-position of the ring. If there are two R 3 groups representing hydrogen then the non-hydrogen R 3 group is preferably present at the 4-position of the ring. Most preferably the two R 3 groups are the same.
  • a preferred structure is 3',5'-di- methyl or 4'-tert-butyl for both phenyl groups substituted by R 3 groups. Alternatively, the structure is 3,5-di-tert-butyl-4-methoxyphenyl.
  • R 5 is a linear or branched C 1 -C 6 -alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl group or C6-C20-aryl group.
  • R 5 is a preferably a linear or branched C1-C6-alkyl group or C6-C20-aryl group, more preferably a linear C 1 -C 4 -alkyl group, even more preferably a C 1 or C 2 -alkyl group and most preferably methyl.
  • the invention provides a hafnocene complex of formula (II) with each X is a sigma-donor ligand selected from chloro, benzyl and C1-C6-alkyl; R2Si is Me2Si or Et2Si; each R 3 and R 4 are independently the same or can be different and are hydrogen, a linear or branched C1-6-alkyl group or -OY group where Y is a C1-C6-alkyl group; wherein (A) at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and at least one R 3 per phenyl group and at least one R 4 is hydrogen; or (B) at least one R 3 is an -OY group, wherein Y is a is a C1-C6-hydrocarbyl group, in the 4-position of each phenyl ring and the two other R 3 groups are tert-butyl groups; and/or (C) at least one R
  • the hafnocene complex of the invention is one of formula (III) with each X is the same and is a sigma-donor ligand selected from chloro, benzyl and C1- C6-alkyl;
  • R 2 Si is Me 2 Si or Et 2 Si;
  • each non-hydrogen R 3 is the same and each non-hydrogen R 4 is the same;
  • R 3 is hydrogen, a linear or branched C1-C6-alkyl group;
  • R 4 is hydrogen, a linear or branched C 1 -C 6 -alkyl group; wherein at least one R 3 per phenyl group and at least one R 4 is not hydrogen, and wherein at least one R 3 per phenyl group and at least one R 4 is hydrogen,
  • R 5 is a linear or branched C 1 -C 4 -alkyl group;
  • R 6 is a -C(R 8 ) 3 group, with R 8 being a linear or branched C 1 or C 2 -
  • hafnocene complexes of the invention include: rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3’,5’-dimethylphenyl)-1 ⁇ 5,6 ⁇ 7- tetrahydro-s-indacen-1-yl] [2-methyl-4-(3’,5’-dimethylphenyI)-5-methoxy-6-tert- butylinden-1-yl] Hafnium dichloride (MC-1), rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4’-tert-butylphenyl)-1 ⁇ 5,6,7- tetrahydro-s-indacen-1-yl][2-methyl-4-(3’,5’-dimethyl-phenyl)-5-methoxy-6-tert- butylinden-1-yl] Hafnium dichloride (MC-2), rac-anti-dimethylsilanediyl[2-
  • ligands required to form the catalysts of the invention can be synthesised by any process and the skilled organic chemist would be able to devise various synthetic protocols for the manufacture of the necessary ligand materials.
  • WO 2007/116034 discloses the necessary chemistry and is herein incorporated by reference. Synthetic protocols can also generally be found in WO 2002/02576, WO 2011/135004, WO 2012/084961, WO 2012/001052, WO 2011/076780, WO 2015/158790 and WO 2019/179959.
  • a cocatalyst system comprising a boron containing cocatalyst as well as an aluminoxane cocatalyst is used in combination with the above defined complex.
  • the aluminoxane cocatalyst can be one of formula (X): where n is usually from 6 to 20 and R has the meaning below.
  • Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR3, AlR2Y and Al2R3Y3 where R can be, for example, C 1 -C 10 alkyl, preferably C 1 -C 5 alkyl, or C 3 -C 10 -cycloalkyl, C 7 -C 12 -arylalkyl or alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C 1 -C 10 alkoxy, preferably methoxy or ethoxy.
  • the resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (X).
  • the preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content. According to the present invention the aluminoxane cocatalyst is used in combination with a boron containing cocatalyst.
  • MAO methylaluminoxane
  • Boron based cocatalysts of interest include those of formula (Z) BY 3 (Z) wherein Y independently is the same or can be different and is a halogen, a halogenated alkylaryl group or a halogenated aryl group, each alkylaryl or aryl group containing from 6 to 20 carbon atoms and at least one fluorine atom as substituent.
  • Y independently is the same or can be different and is a halogen, a halogenated alkylaryl group or a halogenated aryl group, each alkylaryl or aryl group containing from 6 to 20 carbon atoms and at least one fluorine atom as substituent.
  • Preferred examples for Y are p-fluorophenyl, 3,5- difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5- di(trifluoromethyl)phenyl.
  • Preferred options are trifluoroborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4- fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta- fluorophenyl)borane, tris(3,5-difluorophenyl)borane and/or tris (3,4,5- trifluorophenyl)borane. Particular preference is given to tris(pentafluorophenyl)borane.
  • borates are used, i.e. compounds containing a borate anion.
  • Such ionic cocatalysts preferably contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate.
  • Suitable counterions are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N- dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N- dimethylanilinium or p-nitro- N,N-dimethylanilinium.
  • Preferred ionic compounds which can be used according to the present invention include: tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenyl
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • triphenylcarbeniumtetrakis(pentafluorophenyl)borate and N,N- dimethylaniliniumtetrakis(pentafluorophenyl)borate are especially preferred.
  • Ph 3 CB(PhF 5 ) 4 and analogues therefore are especially favoured.
  • the preferred cocatalysts are alumoxanes, most preferably methylalumoxanes in combination with a borate cocatalyst such as N,N-dimethylammonium- tetrakis(pentafluorophenyl)borate and Ph3CB(PhF5)4.
  • a borate cocatalyst such as N,N-dimethylammonium- tetrakis(pentafluorophenyl)borate and Ph3CB(PhF5)4.
  • the combination of methylalumoxane and a tritylborate is especially preferred. Suitable amounts of cocatalyst will be well known to the skilled man.
  • the catalyst may contain from 10 to 100 ⁇ mol of the hafnium ion of the hafnocene per gram of silica, and 5 to 10 mmol of Al per gram of silica.
  • a suitable cocatalyst as a catalyst for the polymerisation of propylene, e.g.
  • the catalyst of the invention can be used in supported or unsupported form.
  • the catalyst system of the invention is used in supported form.
  • the particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina.
  • the use of a silica support is preferred. The skilled man is aware of the procedures required to support a metallocene catalyst.
  • the support is a porous material so that the complex may be loaded into the pores of the support, e.g. using a process analogous to those described in WO 94/14856, WO 95/12622 and WO 2006/097497.
  • the average particle size of the silica support can be typically from 10 to 100 ⁇ m. However, it has turned out that special advantages can be obtained if the support has an average particle size from 15 to 80 ⁇ m, preferably from 18 to 50 ⁇ m.
  • the average pore size of the silica support can be in the range 10 to 100 nm and the pore volume from 1 to 3 mL/g.
  • support materials are, for instance, ES757 produced and marketed by PQ Corporation, Sylopol 948 produced and marketed by Grace or SUNSPERA DM-L-303 silica produced by AGC Si-Tech Co. Supports can be optionally calcined prior to the use in catalyst preparation in order to reach optimal silanol group content. The use of these supports is routine in the art. In an alternative embodiment, no support is used at all.
  • Such a catalyst can be prepared in solution, for example in an aromatic solvent like toluene, by contacting the hafnocene (as a solid or as a solution) with the cocatalyst, for example methylaluminoxane and/or a borane or a borate salt previously dissolved in an aromatic solvent, or can be prepared by sequentially adding the dissolved catalyst components to the polymerisation medium.
  • the cocatalyst for example methylaluminoxane and/or a borane or a borate salt previously dissolved in an aromatic solvent
  • no external carrier is used but the catalyst is still presented in solid particulate form.
  • no external support material such as inert organic or inorganic carrier, for example silica as described above is employed, but the solid catalyst is prepared using an emulsion-solidification method.
  • the preparation of the catalyst system according to the present invention comprises the steps of: a’) reacting a silica support with aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene with optional subsequent washings and drying, to obtain an aluminoxane cocatalyst treated support, b’) reacting the hafnocene complex of formula (I) with a borate cocatalyst and optionally an aluminoxane cocatalyst, in particular methylaluminoxane, in a suitable hydrocarbon solvent, such as toluene or xylene, to obtain a solution of activated hafnocene complex of formula (I), borate cocatalyst and optionally aluminoxane cocatalyst, whereby the borate cocatalyst is added in an amount that a
  • the preparation of the catalyst system according to the present invention comprises the steps of: a) reacting a silica support with an aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene with optional subsequent washings and drying, to obtain aluminoxane cocatalyst treated support, b) reacting the hafnocene complex of formula (I) with an aluminoxane cocatalyst in a suitable hydrocarbon solvent, such as toluene, c) adding borate cocatalyst to the solution obtained in step b) to obtain a solution of hafnocene complex of formula (l), borate cocatalyst and aluminoxane cocatalyst whereby the borate cocatalyst is added in an amount that a boron/hafnium molar ratio of feed amounts in the range of 0.1:1 to 10:1 is reached, d) adding the solution obtained in step
  • the self-supported catalysts generate, due to the high amount of catalytically active species in the catalyst system, high temperatures at the beginning of the polymerisation which may cause melting of the product material. Both effects, i.e. the partial dissolving of the catalyst system and the heat generation, might cause fouling, sheeting and deterioration of the polymer material morphology.
  • prepolymerisation in this regard is part of the catalyst preparation process, being a step carried out after a solid catalyst is formed.
  • This catalyst prepolymerisation step is not part of the actual polymerisation configuration, which might comprise a conventional process prepolymerisation step as well.
  • a solid catalyst is obtained and used in polymerisation.
  • Catalyst "prepolymerisation” takes place following the solidification step of the liquid-liquid emulsion process hereinbefore described.
  • Prepolymerisation may take place by known methods described in the art, such as that described in WO 2010/052263, WO 2010/052260 or WO 2010/052264.
  • Preferable embodiments of this aspect of the invention are described herein.
  • As monomers in the catalyst prepolymerisation step preferably alpha-olefins are used.
  • C 2 -C 10 olefins such as ethylene, propylene, 1-butene, 1-pentene, 1- hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene 1-decene, styrene and vinylcyclohexene are used.
  • Most preferred alpha-olefins are ethylene and propylene.
  • the catalyst prepolymerisation may be carried out in gas phase or in an inert diluent, typically oil or fluorinated hydrocarbon, preferably in fluorinated hydrocarbons or mixture of fluorinated hydrocarbons. Preferably perfluorinated hydrocarbons are used.
  • the melting point of such (per)fluorinated hydrocarbons is typically in the range of 0 to 140°C, preferably 30 to 120°C , like 50 to 110°C .
  • the temperature for the prepolymerisation step is below 70°C, e.g. in the range of -30 to 70°C, preferably 0-65°C and more preferably in the range 20 to 55°C.
  • Pressure within the prepolymerisation vessel is preferably higher than atmospheric pressure to minimize the eventual leaching of air and/or moisture into the catalyst vessel.
  • the pressure is in the range of at least 1 to 15 bar, preferably 2 to 10 bar.
  • the prepolymerisation vessel is preferably kept in an inert atmosphere, such as under nitrogen or argon or similar atmosphere.
  • Prepolymerisation is continued until the prepolymerisation degree (DP) defined as weight of polymer matrix/weight of solid catalyst before prepolymerisation step is reached.
  • the degree is below 25, preferably 0.5 to 10.0, more preferably 1.0 to 8.0, most preferably 2.0 to 6.0.
  • Use of the catalyst prepolymerisation step offers the advantage of minimising leaching of catalyst components and thus local overheating.
  • the catalyst can be isolated and stored.
  • the hafnocene catalysts used according to the present invention possess excellent catalyst activity and good comonomer response.
  • the catalysts are also able to provide propylene copolymers of high weight average molecular weight Mw. Moreover, the copolymerisation behaviour of hafnocene catalysts used according to the invention shows a reduced tendency of chain transfer to ethylene. Polymers obtained with the hafnocenes of the invention have normal particle morphologies. In general therefore the inventive catalysts can provide: - high activity in bulk propylene polymerisation; - very high molecular weight capability; - improved comonomer incorporation in propylene copolymers; - good polymer morphology.
  • the present invention relates to a process for producing a random copolymer of propylene and at least one comonomer selected from alpha-olefins having from 4 to 12 carbon atoms and optionally ethylene using the specific class of hafnocene complexes in combination with a boron containing cocatalyst as well as with an aluminoxane cocatalyst, as defined above or below.
  • copolymer means random copolymer
  • terpolymer means random terpolymer.
  • a random copolymer or terpolymer is a copolymer or terpolymer in which the comonomer units are randomly distributed in the polymer chain.
  • a random copolymer or terpolymer is to distinguish from a block copolymer or terpolymer, in which the comonomer units are arranged in comonomer rich blocks within the polymer chain.
  • random copolymers and terpolymers are characterized by a lower comonomer content compared to block copolymers or terpolymers.
  • Random copolymers and terpolymers are usually monophasic, i.e. they do not contain an elastomeric phase dispersed in a matrix phase, like e.g. heterophasic copolymers or terpolymers.
  • a random copolymer or terpolymer of propylene is a copolymer or terpolymer with a molar majority of propylene monomer units, in which the comonomers are randomly distributed in the polymer chain.
  • copolymer of propylene and at least one comonomer selected from alpha- olefins having from 4 to 12 carbon atoms and “propylene copolymer” are used equally in the following for defining the polymer of propylene produced by the process of the invention.
  • copolymer of propylene is also used is the following as abbreviation for the embodiment of the random terpolymer of propylene, ethylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms.
  • the at least one comonomer is selected from alpha-olefins having from 4 to 12 carbon atoms, preferably from alpha-olefins having from 4 to 10 carbon atoms, more preferably from alpha-olefins having from 4 to 8 carbon atoms, such as 1-butene, 1- hexene and 1-octene.
  • 1-hexene and 1-octene are especially preferred.
  • the propylene copolymer can comprise more than one of said comonomer as defined such as two, three or four different of said comonomer, such as 1-hexene and 1- octene.
  • the propylene copolymer includes propylene monomer units, comonomer units selected from at least one, preferably one, alpha-olefin having from 4 to 12 carbon atoms as defined above and ethylene comonomer units.
  • the propylene copolymer is a terpolymer of propylene, ethylene and at least one comonomer selected from alpha olefins having from 4 to 12 carbon atoms It is, however, preferred that the propylene copolymer only includes one of said comonomers as defined above.
  • the process can be a one-stage process in which the propylene copolymer is produced in one polymerisation reactor.
  • the process can also be a multistage polymerisation process comprising at least two reactors connected in series preferably including a gas phase polymerisation step.
  • Polymerisation in the process of the invention may be effected in at least two or more, e.g.2, 3 or 4, polymerisation reactors connected in series of which at least one reactor is preferably a gas phase reactor.
  • the process may also involve a prepolymerisation step.
  • This prepolymerisation step is a conventional step used routinely in polymer synthesis and is to be distinguished from the catalyst prepolymerisation step discussed above.
  • the process of the invention employs one reactor or two reactors wherein for the latter case at least one reactor of the two reactors is a gas phase reactor.
  • the process of the invention preferably employs one reactor, suitably for producing a unimodal propylene copolymer, or two reactors connected in series wherein at least one reactor is a gas phase reactor, suitably for producing a bimodal propylene copolymer.
  • the process according to the invention can also employ three or more reactors connected in series wherein at least one reactor is a gas phase reactor.
  • the process of the invention for producing the propylene copolymer employs a first reactor operating in bulk and optionally a second reactor being a gas phase reactor. Any optional additional subsequent reactor after the second reactor is preferably a gas phase reactor.
  • the process may also utilise a prepolymerisation step.
  • Bulk reactions may take place in a loop reactor.
  • the reaction temperature used will generally be in the range 60 to 115°C (e.g.70 to 90°C)
  • the reactor pressure will generally be in the range 10 to 25 bar for gas phase reactions with bulk polymerisation operating at higher pressures.
  • the residence time will generally be 0.25 to 8 hours (e.g.0.5 to 4 hours).
  • the gas used will be the monomer optionally as mixture with a non-reactive gas such as nitrogen or propane. It is a particular feature of the invention that polymerisation takes place at temperatures of at least 60°C.
  • the quantity of catalyst used will depend upon the nature of the catalyst, the reactor types and conditions and the properties desired for the polymer product. As is well known in the art hydrogen can be used for controlling the molecular weight of the polymer. Splits between the various reactors can vary. When two reactors are used, splits are generally in the range of 30 to 70 wt% to 70 to 30 wt% bulk to gas phase, preferably 40 to 60 to 60 to 40 wt%. Where three reactors are used, it is preferred that each reactor preferably produces at least 20 wt% of the polymer, such as at least 25 wt%. The sum of the polymer produced in gas phase reactors should preferably exceed the amount produced in bulk.
  • the process comprises the following steps: a) introducing propylene monomer units, alpha-olefin comonomer units having from 4 to 12 carbon atoms, optionally ethylene comonomer units, and hydrogen into a polymerisation reactor; b) polymerizing the propylene monomer units, optional ethylene comonomer units, and alpha-olefin comonomer units having from 4 to 12 carbon atoms to form a copolymer of propylene and at least one comonomer selected from alpha-olefins having from 4 to 12 carbon atoms in the presence of the single-site catalyst.
  • This embodiment is especially suitable for the production of a unimodal propylene copolymer.
  • the process may further comprise the following steps: c) transferring the polymerisation mixture from process step b) comprising the copolymer of propylene and at least one comonomer selected from alpha-olefins having from 4 to 12 carbon atoms and the single site catalyst into a second polymerisation reactor; d) introducing propylene monomer units, optionally alpha-olefin comonomer units having from 4 to 12 carbon atoms and hydrogen into said second polymerisation reactor; e) polymerizing the propylene monomer units and optionally alpha-olefin comonomer units having from 4 to 12 carbon atoms, optionally ethylene comonomer units and optionally hydrogen to form a second polymer of propylene which is selected from a propylene homopolymer or a copolymer of propylene and at least one comonomer alpha-olefin having from 4 to 12 carbon atoms in the presence of the single-site catalyst and the copolymer
  • Said embodiment is especially suitable for the production of a bimodal or multimodal propylene copolymer.
  • a propylene homopolymer can be polymerized so that the propylene copolymer polymerized according to the process of said embodiment comprises a copolymer component of propylene and at least one comonomer selected alpha-olefins from having from 4 to 12 carbon atoms and a propylene homopolymer component.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de production d'un copolymère aléatoire de propylène, éventuellement d'éthylène, et d'au moins un comonomère choisi parmi les alpha oléfines présentant de 4 à 12 atomes de carbone, utilisant une classe spécifique de complexes d'hafnocène en combinaison avec un système de cocatalyseurs comprenant un cocatalyseur contenant du bore et un cocatalyseur d'aluminoxane, de préférence dans un procédé de polymérisation en plusieurs étapes comprenant une étape de polymérisation en phase gazeuse.
EP23722851.5A 2022-04-28 2023-04-26 Procédé de production de copolymères de propylène aléatoires comprenant des unités comonomères d'oléfine en c4-c12-alpha Pending EP4514864A1 (fr)

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EP22170438 2022-04-28
PCT/EP2023/060889 WO2023208984A1 (fr) 2022-04-28 2023-04-26 Procédé de production de copolymères de propylène aléatoires comprenant des unités comonomères d'oléfine en c4-c12-alpha

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