WO2025190884A1 - Métallocènes pour la fabrication de copolymères de propylène - Google Patents

Métallocènes pour la fabrication de copolymères de propylène

Info

Publication number
WO2025190884A1
WO2025190884A1 PCT/EP2025/056498 EP2025056498W WO2025190884A1 WO 2025190884 A1 WO2025190884 A1 WO 2025190884A1 EP 2025056498 W EP2025056498 W EP 2025056498W WO 2025190884 A1 WO2025190884 A1 WO 2025190884A1
Authority
WO
WIPO (PCT)
Prior art keywords
propylene
hydrocarbyl
alkyl
methyl
ethylene
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
PCT/EP2025/056498
Other languages
English (en)
Inventor
Luigi Maria Cristoforo RESCONI
Martin NEUHEIMER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Borealis GmbH
Original Assignee
Borealis GmbH
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 GmbH filed Critical Borealis GmbH
Publication of WO2025190884A1 publication Critical patent/WO2025190884A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • 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
    • 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
    • C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by 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
    • 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

Definitions

  • the present disclosure relates to the use of bisindenyl metallocene catalysts for the production of polypropylene copolymers, especially with ethylene and/or butene, in particular propylene- ethylene-butene terpolymers, having an excellent balance between high catalyst productivity and high copolymer molecular weight, and hence low MFR at high catalyst productivity even at relatively high comonomer content, therefore enabling the production of copolymers having both low MFR and low sealing initiation temperatures.
  • BACKGROUND OF THE DISCLOSURE Metallocene catalysts have been used to manufacture polyolefins for many years.
  • Metallocenes are now used industrially and polyethylenes and polypropylenes in particular are often produced using cyclopentadienyl based catalyst systems with different substitution patterns. Metallocene catalysts have been used also in the production of propylene-butene copolymers and propylene-ethylene-butene terpolymers. These copolymers and terpolymers are used especially for films, for example for blown or cast films, and to produce the sealing layer of multilayer BOPP films.
  • copolymers and terpolymers must have specific MFR 2 values, such as MFR 2 between 0.5 and 3 for blown films, 8-10 for cast films, and MFR 2 matching that of the core hPP layer, typically MFR 2 between 6 and 8, in the case of the sealing layer of multilayer BOPP films.
  • MFR 2 between 0.5 and 3 for blown films, 8-10 for cast films
  • MFR 2 matching that of the core hPP layer typically MFR 2 between 6 and 8, in the case of the sealing layer of multilayer BOPP films.
  • the main advantage in using metallocene catalysts for producing propylene-butene copolymers and propylene-ethylene-butene terpolymers is that metallocene catalysts have a much higher reactivity for higher olefins like 1-butene and 1-hexene compared to Ziegler-Natta catalysts.
  • WO2019179959 describes C 1 -symmetric bisindenyl complexes comprising an indenyl moiety bearing 5-methoxy and 6-tert-butyl substituents and an indacenyl moiety bearing two aryl substituents on its 4,8 positions.
  • metallocenes formulated in silica catalysts containing both methylaluminoxane and trityl tetrakis(pentafluorophenyl)borate activators, has been described also for the production of propylene-butene copolymers in WO2023046573 and WO2023046824. It can sometimes be difficult to obtain high molecular weight e.g.
  • propylene-butene copolymers and propylene-ethylene-butene terpolymers while maintaining desirable levels of catalyst productivity with such prior art catalysts.
  • the present inventors thus sought to identify new metallocenes, which are able to provide high molecular weight e.g. propylene-butene copolymers and propylene-ethylene-butene terpolymers while maintaining desirable levels of catalyst productivity, especially in the case of the terpolymerization of propylene, in particular between propylene, butene, and ethylene.
  • the desired catalysts should also have improved performance in high temperature polymerization, in particular in loop reactors.
  • An object of the present disclosure is to provide a new process for producing a propylene copolymer resin, comprising polymerizing propylene and at least one comonomer selected from ethylene and C4-C10 alpha olefin comonomers, that can be used to provide copolymer resins with sufficiently low MFR2 at desirable levels of productivity.
  • the object of the disclosure is achieved by a process utilizing metallocene complexes of formula (I) which is characterized by what is stated in the independent claims. The preferred embodiments are disclosed in the dependent claims.
  • C 1 -C 20 -hydrocarbyl includes C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkynyl, C 3 -C 20- cycloalkyl, C 3 -C 20 -cycloalkenyl, C 6 -C 20 -aryl, C 7 -C 20- alkylaryl, and C 7 -C 20 -arylalkyl groups or, of course, mixtures of these groups, such as cycloalkyl substituted by alkyl.
  • preferred C 1 -C 20 -hydrocarbyl groups are C 1 -C 20 -alkyl, C 4 -C 20 -cycloalkyl, C 5 -C 20 - cycloalkyl-alkyl groups, C 7 -C 20 -alkylaryl groups, C 7 -C 20 -arylalkyl groups, and C 6 -C 20 -aryl groups, especially C 1 -C 10 -alkyl groups, C 6 -C 10 -aryl groups, and C 7 -C 12 -arylalkyl groups, e.g. C 1 -C 8 -alkyl groups.
  • hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 5 -C 6 -cycloalkyl, cyclohexylmethyl, phenyl, and benzyl.
  • C 1 -C 10 -hydrocarbyl includes C 1 -C 10 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 - cycloalkyl, C3-C10-cycloalkenyl, C6-C10-aryl, C7-C10-alkylaryl, and C7-C10-arylalkyl groups or, of course, mixtures of these groups, such as cycloalkyl substituted by alkyl.
  • preferred C 1 -C 10 -hydrocarbyl groups are C 1 -C 10 -alkyl, C 4 -C 10 -cycloalkyl, C 5 -C 10 - cycloalkyl-alkyl groups, C7-C10-alkylaryl groups, C7-C10-arylalkyl groups, and C6-C10-aryl groups, especially C1-C6-alkyl groups, C6-aryl groups, and C7-C10-arylalkyl groups, e.g. C1-C6- alkyl groups.
  • hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, and benzyl.
  • linear and branched hydrocarbyl groups cannot contain cyclic units.
  • Aliphatic hydrocarbyl groups cannot contain aryl rings.
  • heteroatoms of Group 14-16 of the Periodic Table includes for example Si, N, O or S.
  • C4-C8-ring refers to a cyclic group containing 4 to 8 carbon atoms.
  • C4-C8-ring refers to a cyclic group containing 4 to 8 carbon atoms and a Si atom, and includes for example silacycloalkane groups, such as silacyclobutane, silacyclopentane, or 9-silafluorene. The numbering of these rings will be evident from the structures indicated herein.
  • alkoxy refers to an alkyl-oxy-group, where the alkyl group is as defined herein, such as given in relation to the C1-C20-hydrocarbyl group above.
  • the alkoxy group is C1-C10-alkoxy, more preferably C1-C6- alkoxy, especially methoxy or ethoxy.
  • halogen includes fluoro, chloro, bromo, and iodo groups, especially chloro or fluoro groups, when relating to the complex definition.
  • the oxidation state of the metal ion is governed primarily by the nature of the metal ion in question and the stability of the individual oxidation states of each metal ion. It is appreciated that in the complexes of the invention, the metal ion is coordinated by ligands X to satisfy the valence of the metal ion and to fill its available coordination sites.
  • Catalyst activity is defined in this application to be the amount of polymer produced/g catalyst/h.
  • Metallocene is defined here to be the amount of polymer produced/g metallocene/h.
  • productivity is also sometimes used to indicate the catalyst activity although herein it designates the amount of polymer produced per unit weight of catalyst.
  • molecular weight is used herein to refer to weight average molecular weight Mw unless otherwise stated.
  • Consisting essentially of is used herein to refer to that further components may be present namely those not materially affecting the essential characteristics of the compound or composition e.g. minor amounts of impurities.
  • the present invention relates to a process for producing a propylene copolymer resin, comprising polymerizing propylene and at least one C4-C10 alpha olefin comonomer and optionally ethylene in the presence of a polymerization catalyst comprising a specific metallocene catalyst comprising, preferably essentially consisting of, more preferably consisting of: (i) a metallocene complex of formula (I) as discussed herein; (ii) a cocatalyst system comprising a cocatalyst comprising a group 13 element; and (iii) optionally a support.
  • the process for producing a propylene copolymer resin preferably comprises polymerizing propylene with either (a) ethylene and a C 4 -C 10 alpha olefin comonomer or (b) at least two different C 4 -C 10 alpha olefin comonomers. Details of the polymerization catalyst are discussed under section Polymerization catalyst. Polymerization in the process of the invention may be effected in one or more, e.g.1, 2, or 3, step(s). Preferably, the same polymerization catalyst is used in each step and ideally, it is transferred from pre-polymerization to subsequent polymerization steps in sequence in a well- known manner.
  • the process of the invention may utilise an in-line pre-polymerization step.
  • the in-line pre- polymerization step takes place just before the first polymerization step (I) and may be effected in the presence of hydrogen although the concentration of hydrogen should be low if it is present.
  • the concentration of hydrogen may be from 0 to 1 mol(hydrogen)/ kmol(propylene), preferably from 0.001 to 0.1 mol(hydrogen)/kmol(propylene).
  • the temperature conditions within the pre-polymerization step are ideally kept low such as 0 to 50°C, preferably 5 to 40°C, more preferably 10 to 30°C.
  • the pre-polymerization stage preferably polymerizes propylene monomer only.
  • the average (e.g. mean) residence time in the pre-polymerization reaction stage is short, typically 5 to 30 min.
  • the pre-polymerization stage preferably generates less than 5 wt% of the total polymer formed, such as 3 wt% or less.
  • Pre-polymerization preferably takes place in its own dedicated reactor, ideally in liquid propylene slurry.
  • the prepolymerized catalyst is then transferred over to the first polymerization step.
  • pre- polymerization is carried out in the same reactor as the first polymerization step.
  • Polymerization step(s) The present invention involves polymerizing propylene and at least one C4-C10 alpha olefin comonomer and optionally ethylene.
  • the propylene may be copolymerized with either (a) ethylene and a C4-C10 alpha olefin comonomer or (b) at least two different C4-C10 alpha olefin comonomers.
  • propylene is polymerized with ethylene and 1-butene.
  • the polymerization process may comprise one or more polymerization steps, provided that at least one polymerization step involves providing a propylene copolymer fraction, preferably a terpolymer fraction.
  • Polymerization in the process of the invention may be effected in one or more, e.g.1, 2, or 3, polymerization reactors, using conventional polymerization techniques, e.g.
  • the process comprises the step of (I) polymerizing propylene and at least one C 4 -C 10 alpha olefin comonomer and optionally ethylene, preferably (a) a C 4 -C 10 alpha olefin comonomer and ethylene or (b) at least two different C 4 -C 10 alpha olefin comonomers, in a slurry reactor to produce a propylene terpolymer.
  • the process is carried out in at least one slurry reactor.
  • a slurry polymerization reactor this is typically effected in at least one loop reactor.
  • the polymerization takes place in bulk, i.e. in a medium of liquid propylene.
  • the reaction temperature will generally be in the range 60 to 100 ⁇ C, preferably 70 to 85°C.
  • the reactor pressure will generally be in the range 5 to 80 bar-g (e.g.20 to 60 bar-g), and the average (e.g. mean) residence time will generally be in the range 0.1 to 5 hours (e.g.0.3 to 2 hours).
  • hydrogen is used in the polymerization step.
  • the amount of hydrogen employed is typically considerably larger than the amount used in the prepolymerization stage.
  • the propylene copolymer (e.g. propylene terpolymer) resin is produced in a multistage process comprising at least two reactors connected in series.
  • the present process is a multistage polymerization process, said process comprising an optional but preferred pre-polymerization step, followed by a first, and a second polymerization step.
  • At least one of the polymerization steps in the multistage polymerization process may be carried out in a gas phase reactor.
  • One preferred process configuration is based on a Borstar ® type cascade.
  • the process comprises (I) polymerizing in at least one slurry reactor propylene and at least one C4-C10 alpha olefin comonomer and optionally ethylene, preferably propylene and either (a) ethylene and a C4-C10 alpha olefin comonomer or (b) at least two different C4-C10 alpha olefin comonomers, more preferably propylene, at least one C4-C10 alpha olefin comonomer and ethylene, in a slurry reactor to produce a propylene copolymer in 50 to 99 wt% of the total weight of the propylene copolymer resin end product, and the process further comprises the step of (II) transferring the reaction mixture of step (I) into a gas phase reactor for producing propylene copolymer amounting to 1 to 50 wt% of the propylene copolymer resin end product.
  • the process comprises (I) polymerizing in at least one slurry reactor propylene, ethylene and a C 4 -C 10 alpha olefin comonomer, more preferably propylene, ethylene and butene, in a slurry reactor to produce a propylene terpolymer in 50 to 99 wt% of the total weight of the propylene terpolymer resin end product, and the process further comprises the step of (II) transferring the reaction mixture of step (I) into a gas phase reactor for producing propylene terpolymer amounting to 1 to 50 wt% of the propylene terpolymer resin end product.
  • the present process for the preparation of a propylene terpolymer resin comprises: (I’) in a first polymerization step, preferably in at least one slurry reactor, polymerizing propylene and at least one C4-C10 alpha olefin comonomer and optionally ethylene, preferably polymerizing propylene and butene, in the presence of the polymerization catalyst to produce a propylene copolymer matrix (A); and subsequently (II’) in a second polymerization step, preferably in at least one gas phase reactor, polymerizing propylene and at least one comonomer selected from ethylene and C4-C10 alpha olefin comonomers, preferably at least two different comonomers selected from ethylene and C4-C10 alpha olefin comonomers, more preferably ethylene and at least one C4-C10 alpha olefin comonomer, such as
  • propylene terpolymer phase (B) dispersed in the propylene copolymer matrix (A) e.g. to provide the propylene copolymer, preferably, propylene terpolymer resin.
  • the propylene copolymer matrix (A) produced in step (I’) is produced in an amount of less than or equal to 90 wt %
  • the propylene terpolymer phase (B) produced in step (II”) is produced in an amount of more than or equal to 10 wt %,of the total weight of the produced propylene terpolymer resin.
  • the first polymerization step involves polymerizing propylene and at least one C 4 -C 10 alpha olefin comonomer.
  • the comonomer polymerized with the propylene may be ethylene or a C 4 -C 10 alpha olefin comonomer or a mixture of comonomers might be used such as a mixture of ethylene and a C 4 -C 10 alpha olefin comonomer.
  • comonomers to propylene are preferably used ethylene, 1-butene, 1-hexene, 1-octene or any mixtures thereof, preferably ethylene.
  • ethylene comonomer When ethylene comonomer is present in the polymer produced in the first polymerization step (I), its content may be up to 5 mol%, or 3.4 wt%, while when butene comonomer is present, then its content can be up to 5 mol%, or 6.6 wt%, provided that their combined content is at most 5 mol%, relative to the polymer as a whole.
  • the first polymerization step may take place in any suitable reactor or series of reactors.
  • the first polymerization step may take place in a slurry polymerization reactor such as a loop reactor or in a gas phase polymerization reactor, or a combination thereof.
  • a slurry polymerization reactor such as a loop reactor or in a gas phase polymerization reactor, or a combination thereof.
  • the reaction temperature is greater than 60 ⁇ C, preferably greater than 65 ⁇ C, more preferably greater than greater than 70 ⁇ C.
  • the reaction temperature is than 65 to 85 ⁇ C, such as 65 to 75 ⁇ C, more preferably 70 to 75 ⁇ C.
  • this is typically effected in at least one loop reactor.
  • the polymerization takes place in bulk, i.e. in a medium of liquid propylene.
  • the reaction temperature will generally be in the range of 60 to 80 ⁇ C, preferably 65 to 75°C.
  • the reactor pressure will generally be in the range 5 to 80 bar (e.g.20 to 60 bar), and the average (e.g. mean) residence time will generally be in the range 0.1 to 5 hours (e.g. 0.3 to 2 hours).
  • the reaction temperature will generally be in the range of 60 to 100°C, preferably 70 to 90°C.
  • the reactor pressure will generally be in the range 10 to 35 bar (e.g. 15 to 30 bar), and the average (e.g. mean) residence time will generally be in the range 0.5 to 5 hours (e.g.1 to 2 hours).
  • the first polymerization step takes place in a slurry loop reactor connected in cascade to a gas phase reactor.
  • the polymer produced in the loop reactor is transferred into the first gas phase reactor.
  • hydrogen is used in the first polymerization step.
  • the amount of hydrogen employed is typically considerably larger than the amount used in the prepolymerization stage.
  • the second polymerization step (II) of the process of the invention may be a gas phase polymerization step in which propylene and, preferably, at least two different comonomers selected from ethylene and C 4 -C 10 alpha olefin comonomers are polymerized in the presence of the polymerization catalyst and polymer from step (I).
  • This polymerization step takes place in at least one gas phase reactor, optionally in the presence of an inert gas such as propane.
  • the second polymerization step may take place in a single gas phase reactor or more than one gas phase reactor connected in series or parallel.
  • the C 4 -C 10 alpha olefin comonomer(s) may be, for example, 1-butene, 1-hexene, 1-octene or any mixtures thereof.
  • step (II) involves the polymerization of propylene, ethylene and butene.
  • the temperature in the gas phase reactor will generally be in the range of 60 to 120°C, preferably in the range of 65 and 110 ⁇ C, more preferably in the range of 65 and 100°C, more preferably in the range of 70 to 90°C. Higher gas phase reactor temperatures will favour e.g. higher levels of productivity and, in some embodiments, comonomer (e.g. ethylene) reactivity.
  • the reactor pressure is at least 10 bar, preferably at least 15 bar, more preferably at least 16 bar, typically in the range of 10 to 60 bar, preferably in the range of 15 to 50 bar.
  • the average (e.g. mean) residence time within any gas phase reactor will generally be 0.5 to 8 hours (e.g.0.5 to 4 hours).
  • the gas used will be the monomer mixture optionally as mixture with a non-reactive gas such as propane.
  • the hydrogen content within the gas phase reactor(s) is important for controlling polymer properties but is independent of the hydrogen added to prepolymerization and first polymerization steps.
  • the production ratio or split (by weight) between the first and second polymerization steps is ideally 55:45 to 90:10.
  • Polymerization catalyst comprising, preferably essentially consisting of, more preferably consisting of (i) a metallocene complex of formula (I); (ii) a cocatalyst system comprising a cocatalyst comprising a group 13 element; and (iii) optionally a support.
  • 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 below.
  • Racemic Anti Racemic Syn In the present invention, formula (I), and any sub formulae, are intended to cover both syn- and anti-configurations. Preferred metallocene catalyst complexes are in the anti- configuration.
  • each indenyl group has an aryl group at the 4-position
  • 2 a hydrocarbyloxy moiety at the 5-position of each indenyl group, preferably a 5-alkoxy group (e.g.5-methoxy group) or a 5,6-dioxoalkylene ring
  • 3 at least one alkyl substituent on the 2-position of each indenyl group.
  • the present metallocene catalyst complexes are also distinctive in having a hydrocarbyloxy moiety at the 6-position of each indenyl group.
  • the present invention accordingly utilizes metallocene complexes of formula (I) (I) wherein: Mt is Zr or Hf; X is a sigma ligand; R 1 are each independently selected from C 1 -C 20 -hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form, together with the Si atom to which they are attached, a C 4 -C 8 -ring; R 2 and R 2 ’ are each independently CH 2 -R 21 , with R 21 being H or C 1 -C 10 -hydrocarbyl; n are each independently selected from an integer of from 1 to 5; each R 3 and R 4 is independently selected from H; C 1 -C 10 -hydrocarbyl; or -OR, -SR or -NR 2 , where R is C 1 -C 10 -hydrocarbyl; and/or wherein two adjacent R 3 groups or two adjacent R 4 groups form a ring together with the two C atoms of
  • each X is a sigma ligand.
  • each X is independently, same or different from each other, H, halogen, C 1 -C 6 -alkoxy, or R ⁇ group, where R ⁇ is C 1- C 6 -alkyl, phenyl, or benzyl. More preferably, each X is independently, same or different from each other, Cl, benzyl, or methyl. It is preferred that both X groups are the same.
  • both X are Cl, methyl, or benzyl, especially Cl.
  • R 1 are each independently, same or different from each other, C1-C10-hydrocarbyl, more preferably C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl, C7-C10-arylalkyl, C6-C10-aryl, or C7-C10-alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C3- C8-cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C1-C6-alkyl, C5-C6-cycloalkyl, or C6-aryl.
  • R 2 and R 2 ’ are each independently, same or different from each other, CH2-R 21 , with R 21 being H, C1-C6-alkyl, or C3-C8-cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl. More preferably R 21 is H, linear C1-C3-alkyl, or branched C3-alkyl.
  • R 21 is preferably H, linear C1-C6-alkyl or branched C3-C6-alkyl, more preferably, R 21 is H, C1-C3-alkyl or branched C3-alkyl. R 21 is more preferably H or methyl. It is further preferred that R 2 is methyl or ethyl. Most preferably, R 2 is methyl or ethyl and R 2 ’ is methyl or ethyl. In some embodiments, R 2 and R 2 ’ are independently methyl or ethyl. R 2 and R 2 ’ may be both methyl or both ethyl.
  • R 2 and R 2 ’ are each independently, same or different from each other, CH 2 -R 21 , with R 21 being H or C 1 -C 6 -alkyl; preferably H or linear C 1 -C 6 -alkyl, more preferably H or linear C 1 -C 4 -alkyl; preferably H, methyl or ethyl.
  • one of R 2 and R 2 ’ is methyl, and the other is of the formula CH 2 -R 21 , with R 21 being C 1 -C 6 -alkyl.
  • the R 21 of the R 2 and R 2 ’ that is not methyl is preferably C 1 -C 4 -alkyl; more preferably linear C 1 -C 4 -alkyl, even more preferably methyl or ethyl.
  • R 2 is methyl
  • R 2 ’ is of the formula CH 2 -R 21 , with R 21 being C 1 -C 6 -alkyl.
  • the R 21 of R 2 ’ is preferably C 1 -C 4 -alkyl; more preferably linear C 1 -C 4 -alkyl, even more preferably methyl or ethyl.
  • R 2 is methyl or ethyl and R 2 ’ is methyl or ethyl. In more preferred embodiments, R 2 and R 2 ’ are independently methyl or ethyl. Most preferably, R 2 and R 2 ’ are both methyl or both ethyl.
  • Two adjacent R 3 or two adjacent R 4 form a ring together with the two C atoms of the phenyl ring to which they are bonded.
  • the ring is preferably a C4-C8-ring, more preferably a C5-C6-ring, even more preferably a C6-ring.
  • R 3 and R 4 are each independently, same or different from each other, H, C1-C6-alkyl, or C6-C20-aryl, more preferably H, C1-C4-alkyl, or -OR 31 , with R 31 being a C1-C4-hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R 3 per phenyl group, for example, two R 3 per phenyl group and at least one R 4 , for example, two R 4 per phenyl group is not H.
  • each of the phenyl rings have the same substitution pattern or that the phenyl rings have different substitution patterns. It is preferred that one or two R 3 and/or R 4 groups is H.
  • R 3 and/or R 4 groups are H then the remaining R 3 and/or R 4 group, respectively, is preferably in the para position. If one R 3 and/or R 4 group is H then the remaining R 3 and/or R 4 groups are preferably in the meta positions.
  • one or two R 3 is H, more preferably, one R 3 is H.
  • the remaining R 3 may be the same, like 3 ⁇ ,5 ⁇ -di-methyl. Alternatively, only one R 3 is not H, for example, 4 ⁇ -tert-butyl.
  • one or two R 4 is H, more preferably one R 4 is H.
  • the remaining two R 4 may be the same like 3 ⁇ ,5 ⁇ -di-methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl.
  • two R 3 are not H and are C 1 -C 6 -alkyl, preferably methyl, and two R 4 are not H and these two R 4 are C 1 -C 6 alkyl, preferably methyl.
  • the two R 3 and/or two R 4 that are not H are in the 3, 5-positions.
  • R 5 may be C 1 -C 10 -hydrocarbyl
  • R 6 may be OR 8 , where R 8 is a C 1 -C 10 -hydrocarbyl.
  • R 5 is C 1 -C 10 -hydrocarbyl
  • R 5 may be linear C 1 -C 6 -alkyl, branched C 3 -C 6 -alkyl, or C 3- C 8 cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl. More preferably, R 5 may be methyl or ethyl, yet more preferably methyl.
  • R 8 is a C 1 -C 10 -hydrocarbyl
  • R 8 may be linear C 1 -C 6 -alkyl, branched C 3 -C 6 -alkyl, or C 3- C8 cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl.
  • R 6 may be OR 9 , wherein R 5 and R 9 form a C3 to C7 carbocycle together with the O groups of -OR 5 and -OR 9 and two C atoms of the phenyl ring to which the O groups of -OR 5 and -OR 9 are bonded.
  • the carbocycle may be a C4 carbocycle.
  • R 5 , R 9 , the two O groups of -OR 5 and -OR 9 and the two carbon atoms of the phenyl ring to which the O groups of -OR 5 and -OR 9 are bonded form a 6-membered ring.
  • the carbocycle may be substituted, for example, with one or more C1 to C3 alkyl groups, or preferably unsubstituted.
  • R 5 ’ may be C1-C10-hydrocarbyl
  • R 6 ’ may be OR 8 ’, where R 8 ’ is a C1-C10-hydrocarbyl.
  • R 5 ’ is C1-C10-hydrocarbyl
  • R 5 ’ may be linear C1-C6-alkyl, branched C3-C6-alkyl, or C3- C8-cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl. More preferably, R 5 ’ may be methyl or ethyl, yet more preferably methyl.
  • R 8 ’ is a C1-C10-hydrocarbyl
  • R 8 ’ may be linear C1-C6-alkyl, branched C3-C6-alkyl, or C3-C8-cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl.
  • R 6 ’ may be OR 9 ’, wherein R 5 ’ and R 9 ’ form a C 3 to C 7 carbocycle together with the O groups of -OR 5 ’ and -OR 9 ’ and two C atoms of the phenyl ring to which the O groups of -OR 5 ’ and -OR 9 ’ are bonded.
  • the carbocycle may be a C 4 carbocycle.
  • R 5 ’, R 9 ’, the two O groups of -OR 5 ’ and -OR 9 ’ and the two carbon atoms of the phenyl ring to which the O groups of -OR 5 ’ and -OR 9 ’ are bonded form a 6-membered ring.
  • the carbocycle may be substituted, for example, with one or more C 1 -C 3 -alkyl groups, or preferably unsubstituted.
  • R 5 ’ may be the same as R 5 .
  • R 6 may be the same as R 6 ’. More preferably, R 5 ’ may be the same as R 5 , and R 6 may be the same as R 6 ’.
  • R 7 is H, Me, OMe, or C 6 -C 20 -aryl, whereby C 6 -C 20 -aryl is optionally substituted 1 to 5 times with R 3 , whereby at least one R 3 per said aryl group is not H.
  • R 3 is H, C 1 -C 6 -alkyl, or C 6 -C 20 -aryl, more preferably H, C 1 -C 4 -alkyl, or -OR 31 , with R 31 being a C 1 -C 4 -hydrocarbyl.
  • R 3 is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R 3 per phenyl group, for example, two R 3 per phenyl group is not H.
  • R 7 is a C6-C20-aryl being substituted 1 to 5 times with R 3
  • one or two R 3 groups is H. If two R 3 groups is H then the remaining R 3 is preferably in the para position. If one R 3 is H then the remaining R 3 groups are preferably in the meta positions.
  • one or two R 3 is H, more preferably, one R 3 is H.
  • the remaining R 3 may be the same, like 3 ⁇ ,5 ⁇ -di-methyl. Alternatively, only one R 3 is not H, for example, 4 ⁇ -tert-butyl.
  • two R 3 are not H and are C1-C6-alkyl, preferably methyl.
  • the two R 3 that are not H e.g.
  • R 7 is H.
  • the invention utilizes a metallocene catalyst complex of formula (I-a): (I-a) wherein: Mt is Zr or Hf; X is a sigma ligand; R 1 are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form, together with the Si atom they are attached to, a C4-C8 ring; R 2 and R 2 ’ are each independently, same or different from each other, CH 2 -R 21 , with R 21 being H or C 1 -C 10 -hydrocarbyl; R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -
  • each of the definitions for Mt, X, R 1 , R 2 , R 2 ’, R 3 , R 4 and R 7 described herein for the metallocene complex of formula (I) also applies to the metallocene complex of formula (I-a), unless the context indicates otherwise.
  • the above-defined metallocene complexes of formula (I-a) the following represent preferable embodiments, which can be selected alone or in combination: m are each independently, same or different from each other, an integer from 2 to 4, preferably 2.
  • Each R 61 is independently, same or different from each other, -CH2-, -CHR*-, or -C(R*)2- group, with R* being C1-C2-alkyl, preferably C1-alkyl.
  • each R 61 is -CH2-.
  • the invention utilizes a metallocene catalyst complex of formula (I-b)
  • R 1 are each independently, same or different from each other, C 1 -C 20 -hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C 4 -C 8 ring;
  • R 2 and R 2 ’ are each independently, same or different from each other, CH 2 -R 21 , with R 21 being H or C 1 -C 10 -hydrocarbyl;
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, or -OR 31 , with R 31 being C 1 -C 10 -hydrocarbyl, whereby at least one R 3 and at least one R
  • each of the definitions for Mt, X, R 1 , R 2 , R 2 ’, R 3 and R 4 described herein for the metallocene complex of formula (I) also applies to the metallocene complex of formula (I-b), unless the context indicates otherwise.
  • each of the definitions for R 61 and m described herein for the metallocene complex of formula (I-a) also applies to the metallocene complex of formula (I-b), unless the context indicates otherwise.
  • the invention utilizes a metallocene catalyst complex of formula (I-c): (I-c) wherein: Mt is Zr or Hf; X is a sigma ligand; R 1 are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C 4 -C 8 ring; R 2 and R 2 ’ are each independently, same or different from each other, CH 2 -R 21 , with R 21 being H or linear or branched C 1-6 -alkyl; R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, or -OR 31 , with R 31 being C 1
  • the invention utilizes a metallocene catalyst complex of formula (I-d): (I-d)
  • Mt is Zr or Hf, preferably Zr.
  • Each X is a sigma ligand.
  • each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R ⁇ group, where R ⁇ is C1-C6-alkyl, phenyl, or benzyl. More preferably, each X is independently, same or different from each other, Cl, benzyl, or methyl. It is preferred that both X groups are the same.
  • both X are Cl, methyl, or benzyl, especially Cl.
  • R 1 are each independently, same or different from each other, C 1 -C 10 -hydrocarbyl, more preferably C 1 -C 10 -alkyl, C 4 -C 10 -cycloalkyl, C 5 -C 10 -cycloalkyl-alkyl, C 7 -C 10 -arylalkyl, C 6 -C 10 -aryl, or C 7 -C 10 -alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 3 -C 8 -cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C 1 -C 6 -alkyl, C 5 -C 6 -cycloalkyl, or C 6 -aryl.
  • each R 1 is independently, same or different from each other, C 1 -C 10 -alkyl, optionally substituted with C 1 -C 10 -alkoxy. It is preferred that both R 1 groups are the same. Most preferably, both R 1 are methyl.
  • R 2 and R 2’ are each independently, same or different from each other, CH 2 -R 21 , with R 21 being H, C 1 -C 6 -alkyl, or C 3 -C 8 -cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl.
  • R 21 is H, linear C 1 -C 3 -alkyl, or branched C 3 -alkyl.
  • R 21 is preferably H, linear C 1 -C 6 -alkyl or branched C 3 -C 6 -alkyl, more preferably, R 21 is H, C 1 -C 3 -alkyl or branched C 3 -alkyl.
  • R 21 is more preferably H or methyl.
  • R 2 is methyl or ethyl. Most preferably, R 2 is methyl or ethyl and R 2’ is methyl or ethyl. In some embodiments, R 2 and R 2’ are independently methyl or ethyl.
  • R 2 and R 2’ may be both methyl or both ethyl.
  • R 2 and R 2 ’ are each independently, same or different from each other, CH 2 -R 21 , with R 21 being H or C 1 -C 6 -alkyl; preferably H or linear C 1 -C 6 -alkyl, more preferably H or linear C1-C4 alkyl; preferably H, methyl or ethyl.
  • one of R 2 and R 2 ’ is methyl, and the other is of the formula CH 2 -R 21 , with R 21 being C1-C6-alkyl.
  • the R 21 of the R 2 and R 2’ that is not methyl is preferably C1-C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl.
  • R 2 is methyl
  • R 2 ’ is of the formula CH2-R 21 , with R 21 being C1-C6-alkyl.
  • the R 21 of R 2’ is preferably C1-C4-alkyl; more preferably linear C1-C4-alkyl, even more preferably methyl or ethyl.
  • R 2 is methyl or ethyl and R 2’ is methyl or ethyl.
  • R 2 and R 2 ’ are independently methyl or ethyl. Most preferably, R 2 and R 2 ’ are both methyl or both ethyl.
  • R 3 and R 4 are each independently, same or different from each other, H, C1-C6-alkyl, or C6-C20-aryl, more preferably H, C1-C4-alkyl, or -OR 31 , with R 31 being a C1-C4-hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R 3 per phenyl group, for example, two R 3 per phenyl group and at least one R 4 , for example, two R 4 per phenyl group is not H.
  • each of the phenyl rings have the same substitution pattern or that the phenyl rings have different substitution patterns. It is preferred that one or two R 3 and/or R 4 groups is H.
  • R 3 and/or R 4 groups are H then the remaining R 3 and/or R 4 group, respectively, is preferably in the para position. If one R 3 and/or R 4 group is H then the remaining R 3 and/or R 4 groups are preferably in the meta positions.
  • one or two R 3 is H, more preferably, one R 3 is H.
  • the remaining R 3 may be the same, like 3 ⁇ ,5 ⁇ -di-methyl. Alternatively, only one R 3 is not H, for example, 4 ⁇ -tert-butyl.
  • one or two R 4 is H, more preferably one R 4 is H.
  • the remaining two R 4 may be the same like 3 ⁇ ,5 ⁇ -di-methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl .
  • two R 3 are not H and are C 1 -C 6 -alkyl, preferably methyl, and two R 4 are not H and these two R 4 are C1-C6 alkyl, preferably methyl.
  • the two R 3 and/or two R 4 that are not H (e.g. methyl) are in the 3, 5– positions.
  • R 5 may be C1-C10-hydrocarbyl
  • R 6 may be OR 8 , where R 8 is a C1-C10-hydrocarbyl.
  • R 5 may be linear C1-C6-alkyl, branched C3-C6-alkyl, or C3-C8 cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl. More preferably, R 5 may be methyl or ethyl, yet more preferably methyl.
  • R 8 is a C1-C10-hydrocarbyl
  • R 8 may be linear C1-C6-alkyl, branched C3-C6-alkyl, or C3-C8-cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl.
  • R 5 ’ may be C1-C10-hydrocarbyl
  • R 6 ’ may be OR 8 ’, where R 8 ’ is a C1-C10-hydrocarbyl.
  • R 5 ’ is C1-C10-hydrocarbyl
  • R 5 ’ may be linear C1-C6-alkyl, branched C3-C6-alkyl, or C3- C8-cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl. More preferably, R 5 ’ may be methyl or ethyl, yet more preferably methyl.
  • R 8 ’ is a C1-C10-hydrocarbyl
  • R 8 ’ may be linear C1-C6-alkyl, branched C3-C6-alkyl, or C3-C8-cycloalkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, or cyclohexyl.
  • R 5 ’ may be the same as R 5 .
  • R 6 may be the same as R 6 ’. More preferably, R 5 ’ may be the same as R 5 , and R 6 may be the same as R 6 ’.
  • R 5 may be methyl or ethyl, yet more preferably methyl
  • R 5 ’ may be methyl or ethyl, yet more preferably methyl.
  • R 5 and R 5 ’ is methyl.
  • R 7 is H, Me, OMe, or C 6 -C 20 -aryl, whereby C 6 -C 20 -aryl is optionally substituted 1 to 5 times with R 3 , whereby at least one R 3 per said aryl group is not H.
  • R 3 is H, C 1 -C 6 -alkyl, or C 6 -C 20 -aryl, more preferably H, C 1 -C 4 -alkyl, or -OR 31 , with R 31 being a C 1 -C 4 -hydrocarbyl.
  • R 3 is H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R 3 per phenyl group, for example, two R 3 per phenyl group is not H.
  • R 7 is a C 6 -C 20 -aryl being substituted 1 to 5 times with R 3
  • one or two R 3 groups is H. If two R 3 groups is H then the remaining R 3 is preferably in the para position. If one R 3 is H then the remaining R 3 groups are preferably in the meta positions.
  • one or two R 3 is H, more preferably, one R 3 is H.
  • the remaining R 3 may be the same, like 3 ⁇ ,5 ⁇ -di-methyl. Alternatively, only one R 3 is not H, for example, 4 ⁇ -tert-butyl.
  • two R 3 are not H and are C 1 -C 6 -alkyl, preferably methyl.
  • the two R 3 that are not H are in the 3,5-positions.
  • R 7 is H.
  • the invention utilizes a metallocene catalyst complex of formula
  • Mt, X, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 described herein for the metallocene complex of formula (I) or formula (I-d) also applies to the metallocene complex of formula (I-e), unless the context indicates otherwise.
  • the metallocene complex of formula (I-e) is C 2 -symmetric.
  • R 5 is a C1-C3-alkyl.
  • the metallocene catalyst complexes of the invention are preferably symmetrical, more preferably C2- symmetric. Symmetrical means simply that the two ligands forming the metallocene are the same, that is, each ligand bears a set of substituents that are chemically identical.
  • the metallocene complexes of the invention are preferably chiral, racemic, bridged bisindenyl C 1 -symmetric metallocenes in their anti-configuration.
  • the complexes of the invention are formally C 1 -symmetric, the complexes ideally retain a pseudo-C 2 -symmetry since they maintain C2-symmetry in close proximity of the metal center although not at the ligand periphery.
  • the metallocene complexes of the invention are preferably chiral, racemic, bridged bisindenyl C2-symmetric metallocenes in their anti-configuration.
  • Preferred metallocenes are selected from: dimethylsilanediyl-bis[9-(3,5-dimethylphenyl)-7-methyl-2,3-dihydro-indeno[5,6- b][1,4]dioxin-6-yl]zirconium dichloride; and dimethylsilanediyl-bis[9-(3,5-dimethylphenyl)-7-ethyl-2,3-dihydro-indeno[5,6- b][1,4]dioxin-6-yl]zirconium dichloride.
  • Cocatalyst To form active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art.
  • Cocatalysts comprising one or more compounds of Group 13 metals, like organoaluminium, organoboron, and/or borate compounds used to activate metallocene catalysts are suitable for use in this invention. In some examples, organoboron and/or borate compounds are not used. According to the present invention a cocatalyst system comprising an aluminoxane cocatalyst and optionally a boron containing cocatalyst is advantageously used in combination with the above defined metallocene catalyst complex. Preferably only cocatalysts comprising aluminium, like organoaluminium compounds used to activate metallocene catalysts, are utilized in this invention.
  • a cocatalyst system essentially consisting of, preferably consisting of, an aluminoxane cocatalyst is advantageously used in combination with the above defined metallocene catalyst complex.
  • no further cocatalysts comprising one or more compounds of Group 13 metals other than aluminium, like organoboron and/or borate compounds, used to activate metallocene catalysts are comprised in the polymerization catalyst.
  • Suitable amounts of cocatalyst will be well known to the person skilled in the art.
  • the amount of cocatalyst is chosen to reach below defined molar ratios.
  • the molar ratio of Al from the aluminoxane to the metal ion (Mt) (preferably zirconium) of the metallocene Al/Mt may be in the range 10:1 to 2000:1 mol/mol, preferably 50:1 to 1000:1, and more preferably 100:1 to 600:1 mol/mol.
  • the molar ratio of boron (B) to the metal ion (Mt) (preferably zirconium) of the metallocene B/Mt may be in the range 0.1:1 to 10:1 mol/mol, preferably 0.3:1 to 7:1, especially 0.5:1 to 3:1 mol/mol.
  • the molar ratio of feed amounts of boron (B) to metal ion (Mt), preferably zirconium, of the metallocene B/Mt is from 0.5:1 to 2:1
  • Aluminoxane cocatalyst can be one of formula (A): 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, C1-C10-alkyl, preferably C1-C5-alkyl, or C3-C10-cycloalkyl, C7-C12-arylalkyl or -alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C10-alkoxy, preferably methoxy or ethoxy.
  • the resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (A).
  • 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. Boron containing cocatalyst According to the present invention, the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst. It will be appreciated by the person skilled in the art that where boron based cocatalysts are employed, it is normal to pre-alkylate the complex by reaction thereof with an aluminium alkyl compound, such as TIBA.
  • an aluminium alkyl compound such as TIBA.
  • aluminium alkyl e.g. Al(C1-C6 alkyl)3
  • Preferred aluminium alkyl compounds are triethylaluminium, tri- isobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium.
  • the metallocene complex is in its alkylated version, that is for example a dimethyl or dibenzyl metallocene complex can be used.
  • Boron containing cocatalysts of interest include those of formula (B): BY3 (B) wherein Y is the same or different and is hydrogen, C1-C10-haloalkyl, or C6-C20-haloaryl, or fluorine, chlorine, bromine or iodine.
  • Y are fluorine, trifluoromethyl, unsaturated groups such as haloaryl like p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5- trifluorophenyl and 3,5-di(trifluoromethyl)phenyl.
  • Y are fluorine, trifluoromethyl, aromatic fluorinated groups such as p- fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5- di(trifluoromethyl)phenyl.
  • Preferred boron containing cocatalysts of formula (B) are trifluoroborane, tris(4- fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)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.
  • Z4B –- W + (C) wherein Z is a substituted phenyl derivative, said substituent being halo-C1-C6-alkyl or halogen; and W + is a cationic counterion.
  • the substituents of Z are fluoro or trifluoromethyl.
  • the phenyl group is perfluorinated.
  • the borate anion Z4B – is preferably a weakly-coordinating anion such as tetrakis(pentafluorophenyl)borate.
  • Suitable cationic counterions W + are triarylcarbenium such as triphenylcarbenium or 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.
  • triarylcarbenium such as triphenylcarbenium or protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethy
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • the metallocene catalysts can be used in supported or unsupported 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.
  • a silica support is preferred.
  • 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 WO94/14856, WO95/12622 and WO2006/097497.
  • the particle size is not critical but is preferably in the range 5 to 200 ⁇ m, more preferably 20 to 80 ⁇ m.
  • the complex may be loaded into the pores of the particulate support, e.g. using a process analogous to those described in W094/14856, W095/12622, W02006/097497, and EP18282666.
  • the average particle size of the support such as 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 inorganic porous support such as silica support can be in the range from 10 to 100 nm and the pore volume from 1 to 3 mL/g.
  • the pore diameter of the inorganic porous support such as silica support can be in the range from 20 to 40 nm.
  • the surface area of the inorganic porous support such as silica support can be typically in the range from 100 to 400 m 2 /g.
  • suitable 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.
  • the catalyst can contain from 5 to 500 ⁇ mol, such as 10 to 100 ⁇ mol of transition metal of the metallocene per gram of support such as silica, and 3 to 15 mmol of Al per gram of support such as silica.
  • the present polymerization catalyst may be produced by e.g. as described in WO2020/239603 or WO2020/239598.
  • a polymerization catalyst containing such metallocenes may be produced by a process including the steps of P1-a) combining the porous inorganic support with a first portion of the aluminoxane cocatalyst in a hydrocarbon solvent to obtain aluminoxane cocatalyst treated support, optionally followed by thermal treatment of the aluminoxane treated support; P1-b) dissolving the metallocene complex in a hydrocarbon solvent, preferably an aromatic solvent, more preferably toluene, optionally adding a second portion of the aluminoxane cocatalyst in the hydrocarbon solvent optionally the boron containing cocatalyst wherein the amount of the first portion of the aluminoxane cocatalyst added in step P1-a) is 75.0 to 100.0 wt% of the total amount of aluminoxane cocatalyst and the amount the second portion of the aluminoxane cocata
  • the components can be mixed in any order.
  • the optional boron containing cocatalyst can be mixed with the metallocene complex dissolved in the hydrocarbon solvent and followed by addition the optional aluminoxane, or the metallocene complex dissolved in the hydrocarbon solvent can be mixed with the optional aluminoxane and a hydrocarbon followed by addition of boron containing cocatalyst and so on.
  • all components might be combined simultaneously. Only one impregnation step is used, i.e. the treated support of step P1-a) is loaded only in one step with the metallocene.
  • the process comprises P2-a) combining the porous inorganic support with aluminoxane cocatalyst in a hydrocarbon solvent to obtain aluminoxane cocatalyst treated support, optionally followed by thermal treatment of the aluminoxane treated support, filtering off the hydrocarbon solvent, optionally washing with an aromatic solvent, repeating the filtration and washing steps to remove unreacted aluminium compounds; drying the final aluminoxane cocatalyst treated support; P2-b) dissolving the metallocene in a hydrocarbon solvent optionally adding a methylaluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of methylaluminoxane cocatalyst added in step P2-a) is 75.0 to 100.0 wt% of the total amount of methylaluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step P2-b
  • the obtained supported catalyst system may be provided as an oil slurry with a desired solid content.
  • the solid catalyst content in the slurry may be e.g. up to 30 wt%, like up to 25 wt%.
  • the amounts of support, aluminoxane, preferably MAO, boron containing cocatalyst and metallocene depend on the desired herein defined ratios (boron/M, Al/M, Al/SiO 2 , M/SiO 2 ).
  • Polymers It is a feature of the invention that the claimed process enables the formation of polypropylene with very high melting point. These features can be achieved at commercially interesting polymerization temperatures, e.g.
  • the polydispersity index (Mw/Mn) of the polymers depend on the polymerization conditions in each reactor, and can be between 2.0 and 7.0.
  • the propylene polymers obtained using the catalysts of the invention have a narrow polydispersity index (Mw/Mn), between 2.0 and 4.0.
  • Propylene copolymers Propylene copolymers with ethylene or with C4-C10 alpha olefin comonomers, preferably propylene terpolymers with ethylene and with C4-C10 alpha olefin comonomers, more preferably propylene-ethylene-butene terpolymers, made by the process of the invention can be made with high productivity.
  • the productivity of the polymerization process may be at least 13 kg of polymer per gram of catalyst, preferably at least 14 kg of polymer per gram of catalyst, more preferably at least 14.5 kg polymer per gram of catalyst.
  • the polymerization temperature may be above 60°C, preferably above 65°C.
  • the process of the invention may be used to produce propylene copolymers, preferably propylene terpolymers, having relatively low MFR2.
  • the MFR2 may below 15, preferably below 10 and, for example, below 8.
  • the MFR2 may be below 10, preferably below 8.
  • the propylene copolymers may have a total comonomer content of 0.5 to 10 weight %, preferably 1.0 to 8.0 weight %, for example, 2 to 7 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 0.5 to 2 weight %, and a C 4 -C 10 alpha olefin comonomer content of 4.0 to 8.0 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 0.5 to 3.0 weight %, preferably 0.8 to 1.8 weight %.
  • the propylene copolymer may be a terpolymer having a C 4 -C 10 alpha olefin comonomer content of 2.0 to 10 weight %, preferably 4.5 to 7.0 weight %, such as 5.0 to 6.0 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 0.9 to 1.5 weight %, and a C 4 -C 10 alpha olefin comonomer content of 4.8 to 6.5 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 1.0 to 1.3 weight %, and a C 4 - C 10 alpha olefin comonomer content of 5.0 to 6.0 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 0.8 to 1.8 weight %, and a C4 alpha olefin comonomer content of 4.5 to 7 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 0.9 to 1.5 weight %, and a C 4 alpha olefin comonomer content of 4.8 to 6.5 weight %.
  • the propylene copolymer may be a terpolymer having an ethylene content of 1.0 to 1.3 weight %, and a C4 alpha olefin comonomer content of 5.0 to 6.0 weight %.
  • the propylene copolymer is a terpolymer having an ethylene content and C4-C10 alpha olefin comonomer (e.g.
  • C4 alpha olefin comonomer) content as described above in combination with an MFR2 may below 15, preferably below 10 and, for example, below 8.
  • An advantage of certain embodiments of the present disclosure is that propylene copolymers having such MFR2 properties may be produced at desirable levels of productivity.
  • such propylene copolymers may be produced at relatively high levels of productivity, for example, of at least 13 kg of polymer per gram of catalyst, preferably at least 14 kg of polymer per gram of catalyst, more preferably at least 14.5 kg polymer per gram of catalyst.
  • the propylene copolymer has an MFR2 of 0.5 to 20 g/10min, more preferably 1.0 to 10 g/10min, especially 2.0 to 8.0 g/10min.
  • the polymers made by the catalysts of the description are useful in all kinds of end articles such as pipes, films (cast, blown or BOPP films, such as for example BOPP for capacitor film), fibers (such as spun-bond and melt-blown fibers), moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on.
  • end articles such as pipes, films (cast, blown or BOPP films, such as for example BOPP for capacitor film), fibers (such as spun-bond and melt-blown fibers), moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on.
  • end articles such as pipes, films (cast, blown or BOPP films, such as for example BOPP for capacitor film), fiber
  • 6-tert-Butyl-5-methoxy-2-ethylindan-1-one -ethylacrylic acid (47.6 g, 475.5 mmol, 1.27 equiv.) was added to Eaton's reagent obtained from 103.5 g of P 4 O 10 and 520 ml of MeSO 3 H at 50 °C.
  • 1-tert- butyl-2-methoxybenzene (61.7 g, 375.7 mmol) was added dropwise over ca.1 h at 50-53 °C (hot water bath). The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature, and poured on a mixture of 1.0 liter of cold water and 1 kg of ice.
  • the crude product was extracted with 3 ⁇ 400 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K 2 CO 3 , dried over K 2 CO 3 , filtered through a short pad of silica gel 60 (40-63 ⁇ m) and then evaporated to dryness.
  • the residue was purified by vacuum distillation to give 81.18 g (87.7 %, ca. 90% purity) of 6-tert-butyl-5-methoxy-2-ethylindan-1-one as a yellowish oil (bp 150-170 o C/5 mm Hg).
  • 6-tert-Butyl-2-ethyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 64.08 g (197.0 mmol) of 4-bromo-6-tert-butyl-2-ethyl-5-methoxyindan-1-one, 37.32 g (248.8 mmol, 1.26 equiv.) of 3,5-dimethylphenylboronic acid, 1.02 g (2.0 mmol, 1 mol.%) of Pd(P t Bu3)2, 63.4 g of Na2CO3, 325 ml of 2-methyltetrahydrofurane, and 290 ml of water was refluxed for 6 h.
  • Methacryloyl chloride (94.39 g, 903.0 mmol) was added dropwise over 15 min to a suspension of AlCl 3 (126.4 g, 947.7 mmol) in 750 ml of dichloromethane cooled to –78 °C a, followed by dropwise addition of benzo-1,4-dioxane (123.0 g, 903.4 mmol).
  • the reaction mixture was heated to room temperature in 1 hour, then the reaction mixture was stirred for 19 h at room temperature. The resulting mixture was poured onto 2000 cm 3 of crushed ice.
  • the organic layer was separated, the aqueous layer was extracted with 300 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K 2 CO 3 , dried over K 2 CO 3 , and passed through a short pad of silica gel 60 (40-63 ⁇ m) which was additionally washed with 200 ml of dichloromethane.
  • the combined organic elute was evaporated to dryness to give 167.5 g (90.8%, purity ca.90%) of 7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one as a white solid mass which was used without further purification.
  • the obtained elute was evaporated to dryness to give a white solid mass which was dissolved in 800 ml of toluene, preheated to ca.60 °C, then TsOH (1.0 g) was added. This mixture was refluxed with Dean-Stark head for 10 min. Then, the reaction mixture was quickly cooled to room temperature using an ice-water bath. The formed solution was washed with 10% aqueous K2CO3, the organic layer was separated, the aqueous layer was extracted with 100 ml of dichloromethane. The combined organic extract was dried over K2CO3, passed through a pad of silica gel 6040-63 ⁇ m), and the so obtained elute was evaporated to dryness.
  • the precipitated white solid was filtered off (G3), washed with 2x10 ml of n-hexane, and dried under vacuum to give 13.69 g of a 93:7 mixture of 5,9-dibromo-7-methyl-2,3,7,8-tetrahydro- 6H-indeno[5,6-b][1,4]dioxin-6-one and 9-bromo-7-methyl-2,3,7,8-tetrahydro-6H-indeno[5,6- b][1,4]dioxin-6-one, respectively.
  • the organic layer was separated, the aqueous layer was extracted with 150 ml of dichloromethane.
  • the combined organic extract was dried over K 2 CO 3 , passed through a pad of silica gel 60 (40-63 ⁇ m), and the so obtained elute was evaporated to dryness.
  • the crude product was triturated with 200 ml of n-hexane, the formed precipitate was filtered off (G3), washed with 2x50 ml of n-hexane, and dried under vacuum.
  • the organic layer was separated, the aqueous layer was extracted with 2x100 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K 2 CO 3 , dried over K2CO3, and passed through a short pad of silica gel 60 (40-63 ⁇ m), which was additionally washed with 100 ml of dichloromethane.
  • the combined organic elute was evaporated to dryness.
  • the residue was washed with a mixture of 50 ml of n-hexane and ca. 4 ml of dichloromethane and then dried under vacuum to give 31.5 g (62%) of the title material as a white solid mass.
  • the organic layer was separated, the aqueous layer was extracted with 2x200 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K 2 CO 3 , dried over K2CO3 and passed through a short pad of silica gel 60 (40-63 ⁇ m), which was additionally washed with 200 ml of dichloromethane.
  • the combined organic elute was evaporated to dryness.
  • the residue was washed with 300 ml of n-hexane and dried under vacuum to give 105.4 g (77.1%) of the title material as a white solid mass.
  • Catalyst Preparations All catalysts were prepared using silica Sunspera AGC DM-L-303, calcined at 600 °C. MAO Axion CA1330 was used as received and stored at –20 °C not longer than 6 months. The catalysts were prepared by following a two-step preparation method.
  • First step is the preparation of SiO2/MAO (activated carrier), followed by a second step where a toluene solution of the metallocene complex is impregnated on the dry support from the first step. Only in case the metallocene is not enough soluble in toluene, a second aliquot of MAO is added to the metallocene/toluene slurry in order to promote the full dissolution of the metallocene.
  • Preparation of SiO2/MAO activated carrier A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen. 10 kg of SiO2 carrier was first added from a feeding drum into the reactor, followed by careful pressurizing and depressurizing with nitrogen.
  • toluene (43.5 kg) was added.
  • the SiO2/toluene slurry was stirred for 25 min at 22 °C.
  • 18 kg of 30 wt% MAO in toluene (Axion CA 1330) was added slowly (140 min) through a 12 mm line on the top of the reactor keeping the temperature around 22 °C.
  • MAO addition the reactor temperature was quickly increased to 90 °C and the mixture was stirred at this temperature for 120 min.
  • the hot toluene was filtered out and the solid cake was washed twice with hot toluene while stirring (43.5 kg, 90 °C, 30 min, 40 rpm). Each time the hot toluene was filtered out.
  • Table 1 catalysts tested and their metallocene content a b Al in Al MC in catalyst Catalyst atalyst c Al/Zr in catalyst c wt% wt% wt% molar CE1 12,7 1,56 12,7 401 IE1 13,3 1,14 14,3 513 IE2 12,3 1,30 n.m. 311 IE3 12,3 1,15 12,8 484 IE4 12,4 1,21 n.m.
  • DSC The DSC curves and data have been produced on a DSC Q200 TA Instrument, by placing a 5-7 mg sample cut from the polymer MFR string, into a closed DSC aluminum pan, heating the sample from -10 °C to 225 °C at 10 °C/min, holding for 10 min at 225 °C, cooling from 225 °C to –30 °C, holding for 5 min at –30 °C, heating from –30 °C to 225 °C at 10 °C/min.
  • the reported T m values are those of the peak of the endothermic heat flow determined from the second heating scan.
  • GPC Gel Permeation Chromatography
  • ⁇ ⁇ ° ⁇ ⁇ ⁇ ⁇ 0,8772 ⁇
  • w25 polymer weight
  • V25 Volume of TCB at 25°C
  • the column set was calibrated using universal calibration (according to ISO 16014-2:2019) with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11500 kg/mol.
  • PS polystyrene
  • the PS standards were dissolved at 160°C for 15 min or alternatively at room temperatures at a concentration of 0.2 mg/ml for molecular weight higher and equal 899 kg/mol and at a concentration of 1 mg/ml for molecular weight below 899 kg/mol.
  • NMR nuclear-magnetic resonance
  • Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3 s ⁇ as described in Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004;37:813; Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006;207:382 ⁇ and the RS-HEPT decoupling scheme ⁇ Filip, X., Tripon, C., Filip, C., J. Mag.
  • the presence of isolated 2,1-erythro regio defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm, by the methylene site at 42.4 ppm and confirmed by other characteristic sites.
  • the presence of 2,1 regio defect adjacent an ethylene unit was indicated by the two inequivalent S ⁇ signals at 34.8 ppm and 34.4 ppm respectively and the T ⁇ at 33.7 ppm.
  • Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) is added using a stream of 250 g propylene. Then the chosen amount of H2 is added via mass flow controller in one minute. The reactor temperature is stabilized at the desired temperature of the prepolymerization step by using a thermostat. The solution is stirred at 250 rpm for at least 20 min. Then the catalyst is injected as described in the following. The desired amount of catalyst (solid or as oil slurry) is loaded into a stainless-steel vial in a glovebox. Then the catalyst vial is mounted on a port on the lid of the reactor. The catalyst is fed into the reactor by flushing 350 g propylene from the balance through the catalyst vial.
  • the temperature is held constant by thermostat and the pressure of 21 bar-g is kept constant by feeding via mass flow controller a C2/C3 and C4/C3 gas mixture of composition corresponding to the target polymer composition, until the set duration for this step has lapsed. Then the reactor is cooled down to about 30°C and the volatile components flashed out. After purging the reactor 2 times with N2 and one vacuum/N2 cycle, the product is taken out and dried overnight in a fume hood.100 g of the polymer is additivated with 0.5 wt% Irganox B225 (solution in acetone) and dried overnight in a fume hood, followed by one hour in a vacuum drying oven at 60°C. Propylene/butene/ethylene terpolymerization results The catalyst performances were compared. Results are summarised in the following tables.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La divulgation concerne un procédé de production d'une résine de copolymère de propylène, comprenant la polymérisation de propylène et d'au moins un comonomère d'alpha oléfine en C4-C10 et éventuellement d'éthylène en présence d'un catalyseur de polymérisation comprenant, (i) un complexe métallocène de formule (I) ; (ii) un système cocatalyseur comprenant un cocatalyseur comprenant un élément du groupe 13 ; et (iii) éventuellement un support ; le complexe métallocène de formule (I) étant (I), ou Mt est Zr ou Hf ; X est un ligand sigma ; R1 sont chacun indépendamment choisis parmi hydrocarbyle en C1-C20, contenant éventuellement jusqu'à deux hétéroatomes des groupes 14 à 16 du tableau périodique, ou forment, conjointement avec l'atome Si auquel ils sont attachés, un cycle C4-C8 ; R2 et R2' sont chacun indépendamment CH2-R21, R21 étant H ou hydrocarbyle en C1-10 ; n sont chacun indépendamment choisis parmi un nombre entier de 1 à 5 ; chaque R3 et R4 est indépendamment choisi parmi H ; hydrocarbyle en C1-C10 ; ou -OR, -SR ou -NR2, où R est hydrocarbyle en C1-C10 ; et/ou deux R3 adjacents ou deux R4 adjacents formant un cycle conjointement avec les deux atomes C du cycle phényle auquel ils sont liés ; R5 est hydrocarbyle en C1-C10, et R6 est OR8, où R8 est un hydrocarbyle en C1-C10 ; ou R6 est OR9, R5 et R9 formant un carbocycle en C3 à C7 conjointement avec les groupes O et deux atomes C du cycle phényle auquel les groupes O de -OR5 et -OR9 sont liés ; R5' est hydrocarbyle en C1-10 et R6' est OR8', où R8' est un hydrocarbyle en C1-C10 ; ou R6' est OR9', R5' et R9' formant un carbocycle en C3 à C7 avec les groupes O et deux atomes C du cycle phényle auquel les groupes O de -OR5' et -OR9 sont liés ; et R7 est H, Me, OMe ou aryle en C6-C20, moyennant quoi l'aryle en C 6-C20 est éventuellement substitué 1 à 5 fois par R3, moyennant quoi au moins un R3 par ledit groupe aryle n'est pas H.
PCT/EP2025/056498 2024-03-13 2025-03-10 Métallocènes pour la fabrication de copolymères de propylène Pending WO2025190884A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP24163251.2 2024-03-13
EP24163251 2024-03-13

Publications (1)

Publication Number Publication Date
WO2025190884A1 true WO2025190884A1 (fr) 2025-09-18

Family

ID=90365073

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2025/056498 Pending WO2025190884A1 (fr) 2024-03-13 2025-03-10 Métallocènes pour la fabrication de copolymères de propylène

Country Status (1)

Country Link
WO (1) WO2025190884A1 (fr)

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014856A1 (fr) 1992-12-28 1994-07-07 Mobil Oil Corporation Procede de production d'un materiau porteur
WO1995012622A1 (fr) 1993-11-05 1995-05-11 Borealis Holding A/S Catalyseur de polymerisation d'olefines sur support, sa preparation et son utilisation
WO2003051934A2 (fr) 2001-12-19 2003-06-26 Borealis Technology Oy Production de catalyseurs de polymerisation d'olefines
WO2006097497A1 (fr) 2005-03-18 2006-09-21 Basell Polyolefine Gmbh Composes de type metallocene
WO2007116034A1 (fr) * 2006-04-12 2007-10-18 Basell Polyolefine Gmbh Composes de metallocene
US20090221772A1 (en) * 2005-03-18 2009-09-03 Basell Polylefine Gmbh Metallocene Compounds
WO2014060540A1 (fr) 2012-10-18 2014-04-24 Borealis Ag Procédé de polymérisation et catalyseur
WO2018091684A1 (fr) 2016-11-18 2018-05-24 Borealis Ag Catalyseurs
WO2019007655A1 (fr) * 2017-07-07 2019-01-10 Borealis Ag Procédé de préparation de copolymères de propylène hétérophasiques
WO2019179959A1 (fr) 2018-03-19 2019-09-26 Borealis Ag Catalyseurs pour la polymérisation d'oléfines
WO2019215122A1 (fr) 2018-05-09 2019-11-14 Borealis Ag Procédé de préparation de copolymères de propylène comprenant des unités comonomères d'alpha-oléfines c4-c12
WO2020239603A1 (fr) 2019-05-29 2020-12-03 Borealis Ag Préparation améliorée d'un système de catalyseur
WO2023046824A1 (fr) 2021-09-23 2023-03-30 Borealis Ag Compositions de terpolymère statistique de propylène/éthylène/1-butène bimodales monophasiques présentant des propriétés optiques et d'étanchéité améliorées
WO2023046573A1 (fr) 2021-09-23 2023-03-30 Borealis Ag Procédé de production d'un copolymère de propylène
WO2025016570A1 (fr) * 2023-07-14 2025-01-23 Borealis Ag Catalyseurs pour polymérisation d'oléfines
WO2025016564A1 (fr) * 2023-07-14 2025-01-23 Borealis Ag Métallocènes pour fabrication de polypropylène

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014856A1 (fr) 1992-12-28 1994-07-07 Mobil Oil Corporation Procede de production d'un materiau porteur
WO1995012622A1 (fr) 1993-11-05 1995-05-11 Borealis Holding A/S Catalyseur de polymerisation d'olefines sur support, sa preparation et son utilisation
WO2003051934A2 (fr) 2001-12-19 2003-06-26 Borealis Technology Oy Production de catalyseurs de polymerisation d'olefines
WO2006097497A1 (fr) 2005-03-18 2006-09-21 Basell Polyolefine Gmbh Composes de type metallocene
US20090221772A1 (en) * 2005-03-18 2009-09-03 Basell Polylefine Gmbh Metallocene Compounds
WO2007116034A1 (fr) * 2006-04-12 2007-10-18 Basell Polyolefine Gmbh Composes de metallocene
WO2014060540A1 (fr) 2012-10-18 2014-04-24 Borealis Ag Procédé de polymérisation et catalyseur
WO2018091684A1 (fr) 2016-11-18 2018-05-24 Borealis Ag Catalyseurs
WO2019007655A1 (fr) * 2017-07-07 2019-01-10 Borealis Ag Procédé de préparation de copolymères de propylène hétérophasiques
WO2019179959A1 (fr) 2018-03-19 2019-09-26 Borealis Ag Catalyseurs pour la polymérisation d'oléfines
WO2019215122A1 (fr) 2018-05-09 2019-11-14 Borealis Ag Procédé de préparation de copolymères de propylène comprenant des unités comonomères d'alpha-oléfines c4-c12
US20210002397A1 (en) * 2018-05-09 2021-01-07 Borealis Ag Process for preparing propylene copolymers comprising c4-c12-apha olefin comonomer units
WO2020239603A1 (fr) 2019-05-29 2020-12-03 Borealis Ag Préparation améliorée d'un système de catalyseur
WO2020239598A1 (fr) 2019-05-29 2020-12-03 Borealis Ag Préparation améliorée d'un système de catalyseur
WO2023046824A1 (fr) 2021-09-23 2023-03-30 Borealis Ag Compositions de terpolymère statistique de propylène/éthylène/1-butène bimodales monophasiques présentant des propriétés optiques et d'étanchéité améliorées
WO2023046573A1 (fr) 2021-09-23 2023-03-30 Borealis Ag Procédé de production d'un copolymère de propylène
WO2025016570A1 (fr) * 2023-07-14 2025-01-23 Borealis Ag Catalyseurs pour polymérisation d'oléfines
WO2025016564A1 (fr) * 2023-07-14 2025-01-23 Borealis Ag Métallocènes pour fabrication de polypropylène

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CASTIGNOLLES, P.GRAF, R.PARKINSON, M.WILHELM, M.GABORIEAU, M., POLYMER, vol. 50, 2009, pages 2373
FILIP, X.TRIPON, C.FILIP, C., J. MAG. RESN., vol. 176, 2005, pages 239
GRIFFIN, J.M.TRIPON, C.SAMOSON, A.FILIP, C.BROWN, S.P., MAG. RES. IN CHEM., vol. 45, no. 1, 2007, pages 198
KLIMKE, K.PARKINSON, M.PIEL, C.KAMINSKY, W.SPIESS, H.W.WILHELM, M., MACROMOL. CHEM. PHYS., vol. 207, no. 493-09-4, 2006, pages 382
PARKINSON, M.KLIMKE, K.SPIESS, H.W.WILHELM, M., MACROMOL. CHEM. PHYS., vol. 208, 2007, pages 2128
POLLARD, M.KLIMKE, K.GRAF, R.SPIESS, H.W.WILHELM, M.SPERBER, O.PIEL, C.KAMINSKY, W., MACROMOLECULES, vol. 37, 2004, pages 813
RESCONI, L.CAVALLO, L.FAIT, A.PIEMONTESI, F., CHEM. REV., vol. 100, 2000, pages 1253

Similar Documents

Publication Publication Date Title
US12473320B2 (en) Catalyst system
EP3131935B1 (fr) Nouveau système de catalyseur pour la production de copolymères de polyéthylène dans un procédé de polymérisation en solution à haute température
EP2746289B1 (fr) Catalyseurs
EP3131934B1 (fr) Système de catalyseur amélioré pour la production de copolymères de polyéthylène dans un procédé de polymérisation en solution à haute température
KR20130125311A (ko) 안사-메탈로센 화합물 및 이를 이용한 담지 촉매의 제조방법
WO2012001051A1 (fr) Procédé pour la polymérisation d'oléfines utilisant un métallocène du groupe 4 comme catalyseur
EP2215129A2 (fr) Catalyseurs
KR102338106B1 (ko) 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리올레핀의 제조 방법
JP2013510221A (ja) 混合メタロセン触媒組成物およびこれを用いたポリオレフィンの製造方法
CN106414470A (zh) 作为聚合催化剂的第iva族金属的甲硅烷基二(六甲基茚基)络合物
US20230002605A1 (en) Heterophasic polypropylene copolymers
US20230023983A1 (en) Method of Preparing Supported Metallocene Catalyst and Method of Preparing Polypropylene Using Catalyst Prepared Thereby
JP2011506313A (ja) テトラゾール基を含む非メタロセン系オレフィン重合触媒およびこれを用いたオレフィン重合方法
JP2006182778A (ja) アルファオレフィンの重合及び共重合用触媒組成物
KR100958676B1 (ko) 이핵으로 구속된 배열을 갖는 균일계 촉매의 합성방법 및이를 이용하여 제조한 선형알파올레핀 공중합체
WO2025016570A1 (fr) Catalyseurs pour polymérisation d'oléfines
WO2025016564A1 (fr) Métallocènes pour fabrication de polypropylène
KR102022686B1 (ko) 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조방법
JP2024007403A (ja) 新規な遷移金属化合物、それを含む遷移金属触媒組成物、およびそれを用いたエチレンとα－オレフィンの共重合体の製造方法
WO2025016567A1 (fr) Métallocènes pour la fabrication de copolymères de propylène
EP2933276A1 (fr) Système de catalyseur amélioré de production de copolymères de polyéthylène dans un processus de polymérisation en solution à température élevée
WO2025016565A1 (fr) Catalyseurs pour polymérisation d'oléfines
WO2025016566A1 (fr) Métallocènes pour la fabrication de polypropylène
WO2025016568A1 (fr) Métallocènes pour fabrication de polypropylène
TW202440670A (zh) 聚丙烯共聚物的製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25709731

Country of ref document: EP

Kind code of ref document: A1