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WO2025016568A1 - Métallocènes pour fabrication de polypropylène - Google Patents

Métallocènes pour fabrication de polypropylène Download PDF

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Publication number
WO2025016568A1
WO2025016568A1 PCT/EP2024/057076 EP2024057076W WO2025016568A1 WO 2025016568 A1 WO2025016568 A1 WO 2025016568A1 EP 2024057076 W EP2024057076 W EP 2024057076W WO 2025016568 A1 WO2025016568 A1 WO 2025016568A1
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hydrocarbyl
butyl
independently
group
alkyl
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Dmitry S. Kononovich
Alexander Z. Voskoboynikov
Luigi Maria Cristoforo RESCONI
Vyatcheslav V. Izmer
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Borealis GmbH
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Borealis GmbH
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Priority to PCT/EP2024/069910 priority Critical patent/WO2025016933A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • 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
    • C08F4/65912—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
    • 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

Definitions

  • the present disclosure relates to new bisindenyl ligands, complexes thereof, and catalysts comprising those complexes.
  • the present disclosure also relates to the use of the new bisindenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers, with high activity levels, high molecular weight, and hence low MFR, and with ideal melting points.
  • Metallocene catalysts have been used to manufacture polyolefins for many years. Countless academic and patent publications describe the use of these catalysts in olefin polymerization.
  • WO2001048034 describes C1-symmetric bisindenyl complexes bearing 5-methoxy substituents and 6-tert-butyl substituents, but the 2-substituents are linear. Such catalysts produce relatively low melting hPP (148-150 °C).
  • WO2018091684 describes C2-symmetric rac-Me2Si(2-Me-4-(3,5-Me2Ph)-ind)2ZrCl2 complex, that produces hPP with low Tm of 150-151 °C.
  • WO2005058916 describes a series of C1-symmetric bisindenyl complexes combining one 2-iso-propyl-4-aryl-indenyl ligand and one 2-methyl-4-aryl-indacenyl ligand. While Tm of hPP is somewhat high varying from 152 to 160°C, catalyst activities are invariably low.
  • WO2019179959 describes C1-symmetric bisindenyl complexes comprising indenyl moiety bearing 5-methoxy substituents and 6-tert-butyl substituents and an indacenyl moiety. The catalysts provide somewhat high Tm of hPP varying from 154 to 156 °C in the presence of borate containing cocatalyst.
  • metallocene complexes of formula (I) polymerization catalyst comprising said metallocene complex of formula (I), and process for polymerization of polypropylene optionally with comonomers which are characterized by what is stated in the independent claims.
  • the preferred embodiments of the disclosure are disclosed in the dependent claims. It was surprisingly found that specific modification of C 2 -symmetric, metallocenes incorporating bulky aryl substituent at 4- and 7-position of indene ligand with no substitution at 5- and 6-positions in combination with specific substitution of indenyl ligand provide desired properties.
  • the inventors have identified a supported catalyst system composed of a specific class of metallocene catalysts in combination with an aluminium containing cocatalyst having improved polymerization behavior, higher catalyst productivity, improved performance in the production of propylene polymers, in particular, homopolymers compared to systems known in the art.
  • the specific catalyst system gives a higher flexibility/freedom in the design of propylene polymers than prior art catalyst systems.
  • the present disclosure also provides a polymerization catalyst, comprising, preferably consisting of (i) a metallocene complex of formula (I) as described herein; (ii) a cocatalyst comprising a group 13 element; and (iii) optionally a support.
  • the present disclosure provides a process for the polymerization of propylene, comprising polymerizing propylene in the presence of the polymerization catalyst described herein.
  • the process may be process for the preparation of a heterophasic polypropylene copolymer.
  • This process may comprise (I) polymerizing propylene in bulk in the presence of the polymerization catalyst as described herein to form a polypropylene homopolymer matrix; (II) in the presence of said matrix and said polymerizationcatalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber.
  • C 1-20 -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 6-20- 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, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, and benzyl. It is to be noted that 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 cyclic groups containing 4 to 8 carbon atoms and a Si atom and includes for example silacycloalkanediyls, such as silacyclobutane, silacyclopentane, or 9-silafluorene
  • 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.
  • the metal ion is coordinated by ligands X to satisfy the valency of the metal ion and to fill its available coordination sites.
  • ligands X The nature of these sigma-ligands can vary greatly. The numbering of these rings will be evident from the structures indicated herein.
  • Catalyst activity is defined in this application to be the amount of polymer produced/g catalyst/h.
  • Catalyst metal activity is defined here to be the amount of polymer produced/g Metal/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.
  • the term “molecular weight” is used herein to refer to weight average molecular weight Mw unless otherwise stated.
  • This invention relates to a series of new ligands, metallocene catalyst complexes and hence catalysts that are ideal for the polymerization of propylene.
  • Metallocene catalyst complex The metallocene catalyst complexes of the invention are asymmetrical. Asymmetrical means simply that the two ligands forming the metallocene are different, that is, each ligand bears a set of substituents that are chemically different.
  • 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 C1-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 C1-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 below.
  • Racemic Anti Racemic Syn Formula (I), and any sub formulae are intended to cover both syn- and anti- configurations.
  • Preferred metallocene catalyst complexes are in the anti-configuration.
  • the metallocene complexes of the invention are preferably employed as the racemic- anti-isomers.
  • the numbering scheme of the indenyl ligands is the following:
  • the present invention accordingly relates to compounds of formula (I): wherein Mt is Zr or Hf:
  • X is a sigma ligand;
  • 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, C 1 -C 10 - hydrocarbyl;
  • n are each independently an integer from 1 to 5;
  • R 3 and R 4 are each independently H, C 1 -C 10 hydrocarbyl group, or a –OR 31 , -SR 31 or
  • one of the indenyl ligands is unsubstituted at the 5 and 6 positions.
  • 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, C 1 -C 6 alkoxy, or R ⁇ group, where R ⁇ is a C 1- C 6 alkyl, phenyl, or benzyl group.
  • each X is independently, same or different from each other, chlorine, benzyl, or a methyl group. It is preferred that both X groups are the same. Most preferably 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 C1-C6-alkyl, C5-C6-cycloalkyl or C6-aryl group.
  • C1-C10- hydrocarbyl more preferably C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl, C7
  • each R 1 is independently, same or different from each other, C1-C10-alkyl, optionally substituted with C1-C10-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, C1-C10-hydrocarbyl, for example, linear or branched C1-C10-hydrocarbyl.
  • R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-C10 aryl, such as R 21 being methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2- R 21 , with R 21 being H, linear or branched C1-6-alkyl, preferably R 21 being H or linear or branched C1-C3-alkyl.
  • R 2 is CH 2 -R 21 , with R 21 being H, linear or branched C 1 -C 6 -alkyl, C 3- C 8 cycloalkyl, or C 6-10 aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21 being H or linear or branched C 1 -C 3 - alkyl group, even more preferably, R 2 is methyl or ethyl.
  • R 2’ is alpha-branched C 3 -C 10 -hydrocarbyl or CH 2 -R 21 , with R 21 being H, a linear or branched C 1 -C 6 -alkyl, a C 3 -C 8 cycloalkyl, or a C 6-10 aryl; more preferably R 2’ is alpha- branched C 3 -C 6 -alkyl or CH 2 -R 21 , with R 21 being H, linear or branched C 1-6 -alkyl, preferably R 21 being H or linear or branched C 1 -C 3 -alkyl, even more preferably R 2’ is C(CH 3 ) 2 , methyl, ethyl or n-propyl; It is preferred that R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl or CH 2 -R 21 , with R 21 being H or linear or branched C 1 -C 6 -alkyl
  • R 2 is methyl and R 2’ is either methyl, ethyl or propyl (e.g. iso-propyl or n-propyl). It is preferred that each n is independently, same or different from each other, an integer from 1 to 3, such as 1, 2 or 3.
  • the R 3 and R 4 substituents of the respective phenyl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring. It is for example possible that the phenyl ring is substituted in the para position i.e.
  • n 1, the only R 3 and/or R 4 group, respectively, is preferably in the para position. If n is 2, then the two R 3 and/or R 4 groups, respectively are preferably in the meta positions.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-10 aryl group, more preferably H, a linear or branched C1-C4-alkyl, or -OR31, wherein R31 is a C1-4 hydrocarbyl, even more preferably, each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially hydrogen, methyl, or tert-butyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H.
  • R 51 ’ is C1-C10-hydrocarbyl, for example, linear or branched C1-C10- hydrocarbyl.
  • R 51 ’ is linear or branched C1-C6-alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C 7 -C 10 -arylalkyl, C 7 -C 10 -alkylaryl, or C 6 -C 10 -aryl, more preferably a linear or branched C 1 -C 6 alkyl or C 6 -aryl, even more preferably linear C 1 -C 4 alkyl, yet even more preferably methyl or ethyl, and most preferably methyl.
  • R 6 ’ is C(R 61 ) 3 , with R 61 being a linear C 1 -C 3 alkyl group; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-a) wherein Mt is Zr or Hf; each X is independently 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, C1-C10- hydrocarbyl; R 3 and R 4 are each independently H, C1-C10 hydrocarbyl group, or a –OR 31 , -SR 31 or -N R 31 2 group in which R 31 is a C1-C
  • the substituents on the phenyl rings R 3 and R 4 may be H or C 1 -C 10 hydrocarbyl. whereby at least on R 3 per phenyl group and at least one R 4 is not hydrogen.
  • R 3 per phenyl group and at least one R 4 is not hydrogen.
  • R 4 is not hydrogen.
  • 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, C 1 -C 6 alkoxy, or R ⁇ group, where R ⁇ is a C 1- C 6 alkyl, phenyl, or benzyl group. More preferably, each X is independently, same or different from each other, chlorine, benzyl, or a methyl group. It is preferred that both X groups are the same. Most preferably 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 - 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 C 1 1-C6-alkyl, C5-C6-cycloalkyl or C6-aryl group.
  • C 1- C 10 - hydrocarbyl more preferably C 1 -C 10- alkyl, C 4 -C 10- cycloalkyl, C 5 -C 10- cycloalkyl-al
  • each R is independently, same or different from each other, C1-C10-alkyl, optionally substituted with C1-C10-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, C1-C10-hydrocarbyl, for example, linear or branched C1-C10-hydrocarbyl.
  • R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-C10 aryl, such as R 21 being methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2- R 21 , with R 21 being H, linear or branched C1-6-alkyl, preferably R 21 being H or linear or branched C1-C3-alkyl.
  • R 2 is CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-10 aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21 being H or linear or branched C1-C3- alkyl group, even more preferably, R 2 is methyl or ethyl.
  • R 21 being H, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-10 aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl,
  • R 2’ is alpha-branched C 3 -C 10 -hydrocarbyl or CH 2 -R 21 , with R 21 being H, a linear or branched C 1 -C 6 -alkyl, a C 3 -C 8 cycloalkyl, or a C 6-10 aryl; more preferably R 2’ is alpha- branched C 3 -C 6 -alkyl or CH 2 -R 21 , with R 21 being H, linear or branched C 1-6 -alkyl, preferably R 21 being H or linear or branched C 1 -C 3 -alkyl, even more preferably R 2’ is C(CH 3 ) 2 , methyl, ethyl or n-propyl; It is preferred that R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl or CH 2 -R 21 , with R 21 being H or linear or branched C 1 -C 6 -alkyl
  • R 2 is methyl and R 2’ is either methyl, ethyl or propyl (e.g. iso-propyl or n-propyl).
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, or C 6-10 aryl group, more preferably H, a linear or branched C 1 -C 4- alkyl, or -OR 31 , wherein R 31 is a C 1-4 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 hydrogen, methyl, or tert-butyl.
  • the R 3 and R 4 substituents of the respective phenyl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring. It is for example possible that the phenyl ring substituted in the para position i.e.
  • each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups is H. If two 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.
  • 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 on the phenyl group are not H, more preferably R 3 on both phenyl rings are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • R 4 on the phenyl group are not H, more preferably two R 4 are not H, and most preferably these two R 4 are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl.
  • R 51 ’ is C1-C10-hydrocarbyl, for example, linear or branched C1-C10- hydrocarbyl.
  • R 51 ’ is linear or branched C1-C6-alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C7-C10-arylalkyl, C7-C10-alkylaryl, or C 6 -C 10 -aryl, more preferably a linear or branched C 1 -C 6 alkyl or C 6 -aryl, even more preferably linear C 1 -C 4 alkyl, yet even more preferably methyl or ethyl, and most preferably methyl.
  • R 6 ’ is C(R 61 ) 3 , with R 61 being a linear C 1 -C 3 alkyl group; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-b) wherein Mt is Zr or Hf; each X is independently a sigma ligand; 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’ is a C1-C10-hydrocarbyl, preferably a linear or branched C1-C10-hydrocarbyl; R 3 and R 4 are each independently H, C1-C10 hydrocarbyl group, or a –OR 31 , -SR 31 or -N R 31
  • 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 a C 1- C 6 alkyl, phenyl, or benzyl group. More preferably, each X is independently, same or different from each other, chlorine, benzyl, or a methyl group. 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 C 1- C 6 -alkyl, C 5 -C 6- cycloalkyl or C 6 -aryl group.
  • 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’ is alpha-branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-C10 aryl, such as R 21 being methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably R 2’ is alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-6-alkyl, preferably R 21 being H or linear or branched C1-C3-alkyl; even more preferably R 2’ is C(CH3)2, methyl, ethyl or n-propyl;
  • R 3 and R 4 are each independently, same or different
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially hydrogen, methyl, or tert-butyl.
  • the R 3 and R 4 substituents of the respective phenyl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring. It is for example possible that the phenyl ring substituted in the para position i.e.
  • each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups is H. If two 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.
  • 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 on the phenyl group are not H, more preferably R 3 on both phenyl groups are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • R 4 on the phenyl group are not H, more preferably two R 4 are not H, and most preferably these two R 4 are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl .
  • R 51 ’ is C 1 -C 10 -hydrocarbyl, for example, linear or branched C 1 -C 10 - hydrocarbyl.
  • R 51 ’ is linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C 7 -C 10 -arylalkyl, C 7 -C 10 -alkylaryl, or C 6 -C 10 -aryl, more preferably a linear or branched C 1 -C 6 alkyl or C 6 -aryl, even more preferably linear C 1 -C 4 alkyl, yet even more preferably methyl or ethyl, and most preferably methyl.
  • R 6 ’ is C(R 61 )3, with R 61 being a linear C1-C3 alkyl group; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-c) (I-c) wherein Mt is Zr or Hf; each X is independently a sigma ligand; 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’ is a C 1 -C 10 -hydrocarbyl, preferably a linear or branched C 1 -C 10 -hydrocarbyl; R 3 and R 4 are each independently H, C 1 -C 10 hydrocarbyl group, or a –OR 31 , -SR
  • 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 a C 1- C 6 alkyl, phenyl, or benzyl group. More preferably, each X is independently, same or different from each other, chlorine, benzyl, or a methyl group. 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 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 C 1 1-C6-alkyl, C5-C6-cycloalkyl or C6-aryl group.
  • each R is independently, same or different from each other, C1-C10-alkyl, optionally substituted with C1-C10-alkoxy. It is preferred that both R 1 groups are the same. Most preferably, both R 1 are methyl.
  • R 2’ is alpha-branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-C10 aryl, such as R 21 being methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl; more preferably R 2’ is alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-6-alkyl, preferably R
  • R 2’ is alpha-branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, a linear or branched C1-C6-alkyl, a C3-C8 cycloalkyl, or a C6-10 aryl; more preferably R 2’ is alpha- branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-6-alkyl, preferably R 21 being H or linear or branched C1-C3-alkyl, even more preferably R 2’ is C(CH3)2, methyl, ethyl or n-propyl; It is preferred that R 2’ is alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H or linear or branched C1-C6-alkyl, more preferably, R 2 is methyl and R 2’ is CH2-R 21 , with R 21 being H or linear or branched C
  • R 2’ is either methyl, ethyl or propyl (e.g. n-propyl or iso-propyl).
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, or C 6-10 aryl group, more preferably H, a linear or branched C 1 -C 4- alkyl, or -OR 31 , wherein R 31 is a C 1-4 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 hydrogen, methyl, or tert-butyl.
  • each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns.
  • R 3 on both rings are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • two R 4 on the phenyl ring are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl .
  • the ligands required to form the complexes and hence catalysts of the invention can be synthesized 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.
  • Polymerization catalyst Viewed from a further aspect the invention provides a polymerization catalyst comprising (i) a metallocene complex of formula (I); (ii) a cocatalyst comprising a group 13 element; and (iii) optionally a support.
  • the metallocene complex as described above is used in combination with a suitable cocatalyst combination as described below.
  • 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.
  • the use of 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.
  • the particle size is not critical but is preferably in the range 5 to 200 ⁇ m, more preferably 20 to 80 ⁇ m.
  • the use of these supports is routine in the art. Especially preferred procedures for producing such supported catalysts are those described in EP1828266, WO 2020/239598 and WO 2020/239603. Alternatively, 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 metallocene (as a solid or as a solution) with the cocatalyst, for example methylaluminoxane 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 polymerization medium.
  • the cocatalyst for example methylaluminoxane 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.
  • Such catalysts can be prepared as described for example in WO 2003/051934, WO 2014/060540 and WO 2019/179959.
  • the catalyst system of the invention is preferably used in supported form.
  • the particulate support material used is an inorganic porous support such as a silica, alumina or a mixed oxide such as silica-alumina, in particular silica.
  • the use of a silica support is preferred.
  • 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.
  • 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 WO2020239603 or WO2020239598.
  • the process for the manufacture of the present polymerization catalyst includes P1-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; P-1b) optionally combining the metallocene complex with aluminoxane cocatalyst in a hydrocarbon solvent, wherein the amount of aluminoxane cocatalyst added in step a) is 75.0 to 97.0 wt% of the total amount of aluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is 3.0 to 25.0 wt% of the total amount of aluminoxane cocatalyst; P1-c) adding the boron containing cocatalyst to the solution obtained in step a
  • the said process comprises P2- a) treating a porous inorganic support with aluminoxane cocatalyst in a hydrocarbon solvent, optionally followed by thermal treatment of the aluminoxane treated support; P2-b) combining a metallocene complex with a boron containing cocatalyst and optionally with an aluminoxane cocatalyst in a hydrocarbon solvent; P2-c) loading the solution of step b) onto the treated support of step a); wherein the amount of aluminoxane cocatalyst added in step a) is 75.0 to 100.0 wt% of the total amount of aluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is 0.0 to 25.0 wt% of the total amount of aluminoxane cocatalyst.
  • the components can be mixed in any order.
  • the boron containing cocatalyst can be mixed with the metallocene complex followed by addition of a hydrocarbon and the optional aluminoxane, or the metallocene complex 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 a) is loaded only in one step with the metallocene.
  • the said process comprises P3-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; P3-b) adding the metallocene in a hydrocarbon solvent to the aluminoxane cocatalyst treated support obtained in step a) and optionally P3-c) drying the so obtained supported catalyst system.
  • 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 above defined ratios (boron/M, Al/M, Al/SiO 2 , M/SiO 2 ).
  • Cocatalyst To form an 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.
  • cocatalysts comprising aluminium, like organoaluminium compounds used to activate metallocene catalysts, are utilized in this invention.
  • a cocatalyst system comprising a boron containing cocatalyst and/or an aluminoxane cocatalyst is advantageously used in combination with the above defined metallocene catalyst complex.
  • a cocatalyst system comprising 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 suitable for use in this invention.
  • 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 feed amounts 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, also a boron containing cocatalyst can be used instead of the aluminoxane cocatalyst or the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst.
  • MAO methylaluminoxane
  • aluminium alkyl compound such as TIBA.
  • TIBA aluminium alkyl compound
  • any suitable aluminium alkyl e.g. Al(C 1 -C 6 alkyl) 3 can be used.
  • 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) BY 3 (B) wherein Y is the same or different and is a hydrogen atom, C 1-10 -haloalkyl, or C 6 -C 20 - 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 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, trieth
  • 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.
  • the catalysts according to the invention are suitable for the production of propylene homopolymers, propylene-ethylene copolymers or propylene C4-C10 alpha olefin copolymers.
  • the process comprises polymerizing propylene, propylene and ethylene or propylene and a C4-C10 alpha olefin.
  • the ethylene content in such a propylene-ethylene polymer may vary depending on the desired properties of the polymer. Typically, ethylene content will range from 0.1 to 10 mol%.
  • the catalysts of the present invention are used to manufacture propylene homopolymers or propylene copolymers with ethylene as comonomer and propylene copolymers with butene as a comonomer.
  • the present disclosure relates in a further aspect to a process for producing a propylene homopolymer, a propylene random copolymer or a heterophasic propylene copolymer using the specific catalyst system, as defined before.
  • Polymerization in the method of the invention may be effected in one or more, e.g.1, 2, or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization, or combinations thereof, like a combination of a slurry and at least one gas phase reactor.
  • the process may also involve an in-line pre-polymerization step.
  • This pre-polymerization step is a conventional step used routinely in polyolefin production plants and can be carried out in a CSTR or a loop reactor, from which the prepolymerized catalyst is then transferred together with the liquid monomer(s) into the main loop reactor.
  • Prepolymerization can be carried out at temperatures between -10 °C and 50 °C, preferably between 10 °C and 40 °C.
  • the reaction temperature will generally be in the range 60 to 110 °C (e.g.60 to 90 °C)
  • the reactor pressure will generally be in the range 5 to 80 bar (e.g.
  • the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours).
  • the liquefied monomer is usually used as reaction medium. It is a particular feature of the invention that polymerization takes place at temperatures of at least 60 °C.
  • the reaction temperature used will generally be in the range 60 to 115 °C (e.g.70 to 110 °C)
  • the reactor pressure will generally be in the range 10 to 30 bar-g (e.g.15 to 25 bar-g)
  • the residence time will generally be 0,5 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.
  • the process can contain any additional polymerization steps, like a pre- polymerization step, and any further after reactor handling steps as known in the art.
  • an aliphatic or aromatic solvent can be used to dissolve the monomer and the polymer, and the polymerization temperature will generally be in the range 80 to 200 °C (e.g.90 to 150 °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.
  • hydrogen can be used for controlling the molecular weight of the polymer.
  • the metallocene catalysts of the invention possess excellent catalyst activity and good comonomer response.
  • the catalysts are also able to provide polymers of high weight average molecular weight Mw and narrow polydispersity Mw/Mn. Moreover, the random copolymerization behavior of metallocene catalysts of the invention shows a reduced tendency of chain transfer to ethylene. Polymers It is a feature of the invention that the claimed catalysts enable the formation of propylene polymers with high molecular weight. These features can be achieved at commercially interesting polymerization temperatures, e.g.60 °C or more, such as from 60 °C to 90 °C.
  • 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.
  • Mw/Mn polydispersity index
  • Propylene homopolymers Propylene homopolymers made by catalyst system comprising the metallocenes of the invention can be made with Mw (weight average molecular weight) values in the range of 40 to 2000 kg/mol, preferably in the range of 50 to 1500 kg/mol depending on the use and amount of hydrogen used as Mw regulating agent.
  • the catalysts of the invention enable the formation of polypropylene homopolymers with high melting points.
  • the propylene homopolymer formed by the process of the invention has a melting point of more than 155 °C, preferably more than 157 °C.
  • Propylene copolymers Propylene copolymers with ethylene or with C4-C10 alpha olefin comonomers made by the metallocenes of the invention can be made with high productivity and low solubles.
  • 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, 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, moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on.
  • Standard solutions containing 1000 mg/L Y and Rh (0.4 mL) were added.
  • the flask was then filled up with distilled water and shaken well.
  • the solution was filtered through 0.45 ⁇ m Nylon syringe filters and then subjected to analysis using Thermo iCAP 6300 ICP-OES and iTEVA software.
  • the instrument was calibrated for Al, B, Hf, Mg, Ti and Zr using a blank (a solution of 5 % HNO 3 ) and six standards of 0.005 mg/L, 0.01 mg/L, 0.1 mg/L, 1 mg/L, 10 mg/L and 100 mg/L of Al, B, Hf, Mg, Ti and Zr in solutions of 5 % HNO 3 distilled water.
  • Each calibration solution contained 4 mg/L of Y and Rh standards.
  • Al 394.401 nm was calibrated using the following calibration points: blank, 0.1 mg/L, 1 mg/L, 10 mg/L and 100 mg/L.
  • Al 167.079 nm was calibrated as Al 394.401 nm excluding 100 mg/L and Zr 339.198 nm using the standards of blank, 0.01 mg/L, 0.1 mg/L, 1 mg/L, 10 mg/L and 100 mg/L. Curvilinear fitting and 1/concentration weighting was used for the calibration curves.
  • the QC sample was also run at the end of a scheduled analysis set.
  • the content for Zr was monitored using Zr 339.198 nm ⁇ 99 ⁇ line.
  • the content of aluminium was monitored via the 167.079 nm ⁇ 502 ⁇ line, when Al concentration in test portion was under 2 wt% and via the 394.401 nm ⁇ 85 ⁇ line for Al concentrations above 2 wt%.
  • Y 371.030 nm ⁇ 91 ⁇ was used as internal standard for Zr 339.198 nm and Al 394.401 nm and Y 224.306 nm ⁇ 450 ⁇ for Al 167.079 nm.
  • the content for B was monitored using B 249 nm line.
  • GPC Molecular weight averages, molecular weight distribution, and polydispersity index (Mn, Mw, Mw/Mn) The MWD and the corresponded molecular weight averages M n , M w , M v and M z of the polymer sample were determined by using Gel Permeation Chromatography (GPC) at 160°C.
  • GPC Gel Permeation Chromatography
  • w 25 polymer weight
  • V 25 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 11 500 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.
  • the reported Tm values are those of the peak of the endothermic heat flow determined from the second heating scan.
  • Melt Flow Rate The melt flow rate (MFR) was determined according to ISO 1133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the molecular weight of the polymer.
  • the MFR is determined at 230 °C and may be determined at different loadings such as 2.16 kg (MFR2) or 21.6 kg (MFR 21 ).
  • Metallocene synthesis Synthesis of comparative metallocene CM1 Synthesis of this metallocene has been carried out as described in WO2019179959, MC- 2.
  • reaction mixture was stirred for 10 min at this temperature, then 0.35 g of iron powder was added. Further on, 20.3 ml (63.0 g, 394.0 mmol, 2.03 equiv) of bromine was added dropwise over 0.5 h. The resulting mixture was stirred overnight at room temperature and then poured onto 500 cm 3 of crushed ice. The organic layer was separated, and the aqueous layer was extracted with 2 ⁇ 250 ml of dichloromethane. The combined organic extract was washed with aqueous K 2 CO 3 , dried over K 2 CO 3 , passed through a short pad of silica gel 60 (40-63 ⁇ m), and then evaporated to dryness.
  • the so obtained mixture was evaporated to dryness, 700 ml of dichloromethane and 700 ml water were added to the residue, and the so obtained mixture was acidified with 2 M HCl to pH ⁇ 6.5.
  • the organic layer was separated, the aqueous layer was additionally extracted with 2 ⁇ 300 ml of dichloromethane.
  • the combined organic extract was passed through a pad ( ⁇ 30 ml) of silica gel 60 (40-63 ⁇ m; eluent: dichloromethane) to get rid of most of the palladium black.
  • the obtained elute was evaporated to dryness to give a grey solid mass. TsOH (0.5 g) was added to a solution of this solid in 500 ml of toluene.
  • the obtained solution was added dropwise for 1 h to a suspension of 47.0 g (0.35 mol) of AlCl 3 in 470 ml of dichloromethane at 0 °C.
  • the formed mixture was refluxed for 3 h, cooled to ambient temperature, and then poured onto 1000 cm 3 of ice.
  • the organic layer was separated.
  • the aqueous layer was extracted with 3x200 ml of dichloromethane.
  • the combined organic extract was dried over K 2 CO 3 and evaporated to dryness.
  • the crude product was extracted with 3x400 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K2CO3, dried over K2CO3, 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.
  • the combined organic elute was evaporated to dryness.
  • the combined organic elute was evaporated to dryness, and the residue was dried under vacuum at elevated temperature to give 13.8 g (18.92 mmol, yield ca.91.1%, purity ca.98%) of the title product (as a ca 40:60 mixture of the stereoisomers) as a slightly yellowish glassy solid.
  • 6-tert-Butyl-2-isopropyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 124.84 g (368.0 mmol) of 4-bromo-6-tert-butyl-2-isopropyl-5-methoxyindan- 1-one, 69.7 g (464.7 mmol, 1.26 equiv.) of 3,5-Me2C6H3B(OH)2, 1.9 g (3.72 mmol, 1 mol. %) of Pd(P t Bu3)2, 118.3 g of Na2CO3, 600 ml of 2-methyltetrahydrofurane and 540 ml of water was refluxed for 6 h.
  • n BuLi in hexanes (2.5 M, 8.0 ml, 20.0 mmol) was added in one portion to a solution of 5- tert-butyl-7-(3,5-dimethylphenyl)-2-isopropyl-6-methoxy-1H-indene (6.97 g, 20.0 mmol) in 200 ml of ether cooled to –50 °C. This mixture was stirred overnight at room temperature, then the resulting yellow suspension was cooled to –50 °C, then dichlorodimethylsilane (12.1 ml, 12.95 g, 100.3 mmol, 5.02 equiv.) was added in one portion followed by 5 ml of THF.
  • Anti-dimethylsilanediyl[2-methyl-4,7-bis(3,5-dimethylphenyl)-inden-1-yl][2-iso-propyl-4- n BuLi in hexanes (2.5 M, 3.64 ml, 34.1 mmol) was added in one portion to a solution of [4,7-bis(3,5-dimethylphenyl)-2-methyl-1H-inden-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)- 2-isopropyl-5-methoxy-1H-inden-1-yl]dimethylsilane (12.67 g, 17.05 mmol) in 100 ml of di-n-butyl ether at room temperature.
  • 6-tert-Butyl-2-n-propyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 16.6 g (48.9 mmol) of 4-bromo-6-tert-butyl-2-n-propyl-5-methoxyindan-1- one, 9.45 g (63.0 mmol, 1.28 equiv.) of 3,5-Me2C6H3B(OH)2, 0.26 g (0.5 mmol, 1 mol.%) of Pd(P t Bu3)2, 15.8 g of Na2CO3, 80 ml of 2-methyltetrahydrofurane, and 75 ml of water was refluxed for 6 h.
  • Catalyst synthesis used chemicals All catalysts have been prepared using silica Sunspera AGC DM-L-303, calcined at 600 °C. MAO Axion CA1330 was used as received and stored at –20 °C for not longer than 6 months. Catalyst preparations The catalysts were prepared by following a two-step preparation method.
  • First step is the preparation of SiO 2 /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 (metallocene C), a second aliquot of MAO is added to the metallocene/toluene slurry in order to promote the full dissolution of the metallocene.
  • Preparation of SiO 2 /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.
  • Polymerization examples Propylene homopolymerization procedure (bulk, 20-L reactor) A stainless-steel reactor equipped with a ribbon stirrer, with a total volume of 20.9 dm3 containing 0.2 bar-g propylene, was filled with additional 3.95 kg propylene.
  • Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) was added using a stream of 250 g propylene, then 0.5 NL of H2 was added via mass flow controller in one minute.
  • the reactor temperature was stabilized at 25 °C (HB-Therm) and the solution was stirred and 250 rpm for at least 20 min.
  • the catalyst was injected as described in the following.
  • the desired amount of solid catalyst was loaded into a 5 ml stainless steel vial. This feeder system was mounted on a port on the lid of the autoclave. Then the catalyst was flushed into the reactor with 350 g propylene.

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  • Organic Chemistry (AREA)

Abstract

L'invention concerne un complexe métallocène de formule (I) dans laquelle Mt représente Zr ou Hf : X est un ligand sigma; R1 sont chacun indépendamment, identiques ou différents les uns des autres, hydrocarbyle en C1-C20, contenant éventuellement jusqu'à deux hétéroatomes du groupe 14-16 du tableau périodique, ou forment conjointement avec l'atome de Si auquel ils sont liés un cycle C4-C8; R2 et R2' sont chacun indépendamment, identiques ou différents les uns des autres, hydrocarbyle en C1-C10; n sont chacun indépendamment un nombre entier de 1 à 5; R3 et R4 sont chacun indépendamment H, groupe hydrocarbyle en C1-C10, ou –OR31, -SR31 ou groupe -N R31 2, R31 étant hydrocarbyle en C1-C10, au moins un R3 par groupe phényle et au moins un R4 n'étant pas hydrogène; R51' est hydrocarbyle en C1-C10; et R6' est C(R61)3, R61 étant alkyle en C1-C6 linéaire ou ramifié.
PCT/EP2024/057076 2023-07-14 2024-03-15 Métallocènes pour fabrication de polypropylène Pending WO2025016568A1 (fr)

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