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WO2025016569A1 - Métallocènes pour fabrication de polypropylène - Google Patents

Métallocènes pour fabrication de polypropylène Download PDF

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Publication number
WO2025016569A1
WO2025016569A1 PCT/EP2024/057077 EP2024057077W WO2025016569A1 WO 2025016569 A1 WO2025016569 A1 WO 2025016569A1 EP 2024057077 W EP2024057077 W EP 2024057077W WO 2025016569 A1 WO2025016569 A1 WO 2025016569A1
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hydrocarbyl
independently
alkyl
same
aryl
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Inventor
Luigi Maria Cristoforo RESCONI
Dmitry S. Kononovich
Alexander Z. Voskoboynikov
Simon Schwarzenberger
Soile LUSTIG
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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    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C43/00—Ethers; Compounds having groups, groups or groups
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F110/06—Propene
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0288—Sterically demanding or shielding ligands
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
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    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/30—Non-coordinating groups comprising sulfur
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • 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
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    • 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
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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 indenyl ligands, bisindenyl ligands comprising said indenyl 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 with very high melting points or propylene copolymers, especially with ethylene, in particular heterophasic polypropylene, with high molecular weight, and hence low MFR.
  • 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. Metallocenes are now used industrially and polyethylenes and polypropylenes in particular are often produced using cyclopentadienyl based catalyst systems with different substitution patterns. WO2007116034 describes C2-symmetric complexes bearing 5-methoxy substituents and 6-tert-butyl substituents and linear 2-substituents. Such catalysts produce relatively low melting hPP of 148 to 150 °C.
  • WO2018091684 describes C2-symmetric rac-Me2Si(2-Me-4-(3,5-Me2Ph)-5-OMe-6-tBu- Ind)2ZrCl2 complex, that produces hPP with low Tm of 150-151 °C.
  • US6995279 discloses C1-symmetric complexes including one 2-[2-(5- methylthienyl)]indenyl ligand and one 2-methylindenyl ligand.
  • the present inventors thus sought new metallocenes, which are able to provide high isoselectivity without compromising productivity, especially in the case of the homopolymerization of propylene or in the case of copolymerization between propylene and ethylene.
  • the desired catalysts should also have improved performance in the production of high melting temperature and high molecular weight polypropylene homopolymers (hPP).
  • the desired catalysts should also have improved performance in the production of propylene-ethylene copolymers, for instance having high activity for high Mw copolymer products.
  • the desired catalysts should also provide propylene-ethylene copolymers having high molecular weight.
  • the desired catalysts should also be able to produce hPP with T m at least 157 °C.
  • An object of the present disclosure is to provide new ligands, metallocene complexes, and hence catalysts that overcome the above problems.
  • the object of the disclosure is achieved by ligands of formula (II), 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.
  • the identified metallocene complexes when included in a polymerization catalyst, preferably supported catalyst system, composed of the said specific class of metallocene complexes in particular in combination with an aluminium containing cocatalyst have improved polymerization behavior, higher catalyst productivity, improved performance in the production of propylene homopolymers, propylene random copolymers and heterophasic propylene copolymers compared to systems known in the art, enabling the production of propylene-ethylene copolymers of high Mw, thus being ideal for the production of propylene random copolymers, especially propylene-ethylene random copolymers, and also suitably heterophasic propylene copolymers.
  • 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 6-20- aryl groups, especially C1-C10 alkyl groups, C6-C10-aryl groups, and C7-C12-arylalkyl groups, e.g. C1-C8 alkyl groups.
  • hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C5-C6-cycloalkyl, cyclohexylmethyl, phenyl, and benzyl.
  • C1-C20-hydrocarbyl includes C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C20- cycloalkyl, C3-C20-cycloalkenyl, C6-C20-aryl, C7-C20-alkylaryl, and C7-C20-arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl.
  • preferred C1-C20-hydrocarbyl groups are C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-cycloalkyl-alkyl groups, C7-C10-alkylaryl groups, C7-C10-arylalkyl groups, and C6-C20- 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.
  • C1-C10-hydrocarbyl includes C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C3-C10- 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 C1-C10-hydrocarbyl groups are C1-C10-alkyl, C4-C10-cycloalkyl, C5-C10-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. 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.
  • C 4 -C 8 -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 valence 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 known to be used to indicate the catalyst activity although herein it designates the amount of polymer produced per unit weight of catalyst.
  • heteroaryl refers to an aromatic monocyclic or bicyclic, preferably monocyclic, radical of 5 to 10 ring members in which one or more, preferably one, ring members are heteroatoms belong to groups 14-16 of the Periodic Table, preferably O, S or N, the remaining ring atoms being carbon.
  • the heteroaryl may optionally be substituted with 1 to 3 C1-C10-hydrocarbyls as defined in the description.
  • the present invention relates to a series of new ligands, metallocene complexes and hence catalysts that are ideal for the polymerization of olefins, in particular propylene.
  • Metallocene catalyst complexes The complexes of the invention can be asymmetrical or symmetrical, preferably asymmetrical.
  • Asymmetrical means simply that the two indenyl ligands forming the metallocene are different, that is, each indenyl ligand bears a set of substituents that are either chemically different, or located in different positions with respect to the other indenyl ligand.
  • Symmetrical complexes are based on two identical indenyl ligands.
  • the complexes of the invention are chiral, racemic, bridged bisindenyl metallocenes.
  • the metallocenes of the invention are either C 2 -symmetric or C 1 -symmetric, preferably C 2 - symmetric. When they are C 1 -symmetric, they still maintain a pseudo-C2-symmetry since they maintain C 2 -symmetry in close proximity of the metal center although not at the ligand periphery.
  • a meso form and a racemic enantiomer pair (in case of C 2 -symmetric complexes) or anti and syn enantiomer pairs (in case of C 1 - symmetric complexes) are formed during the synthesis of the complexes.
  • racemic-anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane
  • racemic-syn means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the scheme below.
  • Racemic Anti Racemic Syn Preferred metallocene catalyst complexes are in the anti-configuration. The metallocene complexes are preferably employed as the racemic-anti-isomers.
  • the numbering scheme of the indenyl ligands is the following: It will be appreciated that in the complexes of the invention, the metal ion Mt is coordinated by ligands X so as to satisfy the valency of the metal ion and to fill its available coordination sites. The nature of these ⁇ -ligands can vary greatly.
  • the present invention accordingly relates to metallocene complexes of formula (I) wherein Mt is Zr or Hf; L is O or S; 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 is heteroaryl, C 6 -C 10 -aryl, or linear or branched C 1 -C 10 -hydrocarbyl, whereby said C 6 - C 10 -aryl and heteroaryl are optionally substituted with 1 to 3 R 21’ ; with R 21’ being C 1 -C 10 - hydrocarbyl; R 2 ’ is heteroaryl or C 6 -C 10 -aryl, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C 1
  • 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, 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.
  • 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 is C6-aryl, heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C3-alkyl, and whereby said C6-aryl and heteroaryl are optionally substituted with 1 to 3 R 21 ’, with R 21 ’ being C1-C6-alkyl, preferably C1-C3-alkyl.
  • R 2 is phenyl, heteroaryl of 5 ring members in which one ring member is O or S, or CH2-R 21 , with R 21 being H or linear C1-C3-alkyl, such as methyl, ethyl, or n-propyl, preferably R 21 being H or methyl, and whereby said phenyl and heteroaryl are optionally, yet preferably, substituted with 1 or 2 R 21 ’, with R 21 ’ being C 1 -C 6 -alkyl, preferably R 21’ being C 1 -C 3 -alkyl.
  • R 2 is phenyl, furyl, thienyl, or CH 2 -R 21 , with R 21 being H or C 1 -C 3 - alkyl, such as methyl, preferably R 21 being H, and whereby said phenyl, furyl, and thienyl are optionally, yet preferably, substituted with 1 or 2 R 21 ’; with R 21 ’ being methyl.
  • R 2 is phenyl substituted with 1 or 2 C 1 -C 3 -alkyl, methylfuryl, methylthienyl, such as 5-methyl-2-furyl or 5-methyl-2-thienyl, or CH 2 -R 21 , with R 21 being H or methyl, preferably R 21 being H.
  • R 2 is CH 2 -R 21 , with R 21 being H, linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C 1 -C 3 -alkyl, even more preferably H or linear C 1-3 -alkyl, such as methyl, ethyl, or n-propyl, yet more preferably H or methyl, most preferably H.
  • R 21 being H, linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C 1
  • R 2 ’ is C 6 -aryl or heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C1-C10- hydrocarbyl, preferably C1-C6-alkyl; more preferably R 2 ’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being optionally, yet preferably, substituted with 1 or 2 R 21 ’, with R 21 ’ being C1-C6-alkyl, preferably C1-C3-alkyl; more preferably R 2 ’ is phenyl or thienyl, R 2’ being optionally substituted with 1 or 2 R 21 ’, with R 21 ’ being methyl.
  • R 2’ and/or R 2 aryl and heteroaryl are substituted.
  • the R 21’ substituents of the respective R 2 and/or R 2’ aryl ring are in the 3-, 4-, and/or 5- position of the ring, whereby the 1-position is attached to the indenyl ring.
  • the R 21’ substituents of the respective R 2 and/or R 2’ heteroaryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 2-position is attached to the indenyl ring.
  • the phenyl ring has the same substitution pattern as the phenyl rings in the 4-position of the indenyl rings or that the phenyl rings on the 2- and 4-position have different substitution patterns.
  • the heteroaryl is substituted at the position next to the heteroatom.
  • R 2’ and/or R 2 is phenyl, and the phenyl is substituted with one R 21 ’; the only R 21 ’ group is preferably in the para position. If the R 2’ or R 2 phenyl is substituted with two R 21 ’; then the two R 21 ’ groups are preferably in the meta positions. It is further preferred that when R 2’ and/or R 2 is a heteroaryl of 5 ring members, and is substituted with one R 21 ’; the only R 21 ’ group is preferably in 5 ⁇ position, whereby the 2 ⁇ - position is attached to the indenyl ring.
  • R 2 is methyl and R 2’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being substituted with 1 or 2 R 21 ’, with R 21 ’ being C 1 -C 6 - alkyl, preferably C 1 -C 3 -alkyl; preferably R 2 ’ is phenyl or thienyl, R 2’ being substituted with one or two R 21 ’. Most preferably R 2 is methyl and R 2’ is 5-methylthienyl or dimethyl phenyl. 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.
  • the phenyl ring is substituted in the para position i.e. 4 position only, like 4-tert-butyl phenyl, or di-substituted in the meta positions, i.e.3 and 5 position, like 3,5-dimethylphenyl or 3,5-ditert-butylphenyl.
  • each of the phenyl rings have the same substitution pattern or that the two phenyl rings carrying the R 3 and R 4 substituents have different substitution patterns.
  • 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, H or C1-C20-hydrocarbyl (e.g. C1-C10- hydrocarbyl) or –OR 31 , wherein R 31 is C1-C10-hydrocarbyl, whereby at least one R 3 and at least one R 4 is not hydrogen.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C10-arylalkyl, C7-C10- alkylaryl, or C6-C20-aryl (e.g. C6-C10-aryl), or –OR 31 , wherein R 31 is C1-C10-hydrocarbyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H; more preferably R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20-aryl (e.g.
  • 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, in particular methyl, whereby at least one R 3 and at least one R 4 is not H.
  • L is preferably O.
  • R 51 and R 51 ’ are each independently, same or different from each other, 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 linear C 1 -C 6 - alkyl, branched C 3 -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.
  • C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
  • R 51 and R 51 ’ are the same. Most preferably, both R 51 and R 51 ’ are methyl.
  • R 6 and R 6 ’ are each independently, same or different from each other, C(R 61 ) 3 , with R 61’ being linear C 1 -C 3 -alkyl; more preferably methyl. It is preferred that R 6 and R 6 ’ are the same.
  • both R 6 and R 6 ’ are tert-butyl.
  • the invention provides 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 C 4 -C 8 -ring; R 2 is heteroaryl, C 6 -C 10 -aryl or linear or branched C 1 -C 10 -hydrocarbyl, whereby said C 6 - C 10 -aryl and heteroaryl are optionally substituted with 1 to 3 R 21’ ; with R 21’ being C 1 -C 10 - hydrocarbyl; R 2 ’ is heteroaryl or C 6 -C 10 -aryl, R 2’ being optionally substituted with one to three R 21 ’; with R 21 ’ being C 1 -C
  • 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, 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.
  • 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 is C6-aryl, heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C3-alkyl, and whereby said C6-aryl and heteroaryl are optionally substituted with 1 to 3 R 21 ’, with R 21 ’ being C1-C6-alkyl, preferably C1-C3-alkyl.
  • R 2 is phenyl, heteroaryl of 5 ring members in which one ring member is O or S, or CH 2 -R 21 , with R 21 being H or linear C 1 -C 3 -alkyl, such as methyl, ethyl, or n-propyl, preferably R 21 being H or methyl, and whereby said phenyl and heteroaryl are optionally, yet preferably, substituted with 1 or 2 R 21 ’, with R 21 ’ being C 1 -C 6 -alkyl, preferably R 21’ being C 1 -C 3 -alkyl.
  • R 2 is phenyl, furyl, thienyl, or CH 2 -R 21 , with R 21 being H or C 1 -C 3 - alkyl, such as methyl, preferably R 21 being H, and whereby said phenyl, furyl, and thienyl are optionally, yet preferably, substituted with 1 or 2 R 21 ’; with R 21 ’ being methyl.
  • R 2 is phenyl substituted with 1 or 2 C 1 -C 3 -alkyl, methylfuryl, methylthienyl, such as 5-methyl-2-furyl or 5-methyl-2-thienyl, or CH 2 -R 21 , with R 21 being H or methyl, preferably R 21 being H.
  • R 2 is CH 2 -R 21 , with R 21 being H, linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C3-alkyl, even more preferably H or linear C1-C3-alkyl, such as methyl, ethyl, or n-propyl, yet more preferably H or methyl, most preferably H.
  • R 21 being H, linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C
  • R 2 ’ is C6-aryl or heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C1-C10- hydrocarbyl, preferably C1-C6-alkyl; more preferably R 2 ’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being optionally, yet preferably, substituted with 1 or 2 R 21 ’, with R 21 ’ being C1-C6-alkyl, preferably C1-C3-alkyl; more preferably R 2 ’ is phenyl or thienyl, R 2’ being optionally substituted with 1 or 2 R 21 ’, with R 21 ’ being methyl.
  • R 2’ and/or R 2 aryl and heteroaryl are substituted.
  • the R 21’ substituents of the respective R 2 and/or R 2’ aryl ring are in the 3-, 4-, and/or 5- position of the ring, whereby the 1-position is attached to the indenyl ring.
  • the R 21’ substituents of the respective R 2 and/or R 2’ heteroaryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 2-position is attached to the indenyl ring.
  • the phenyl ring has the same substitution pattern as the phenyl rings in the 4-position of the indenyl rings or that the phenyl rings on the 2- and 4-position have different substitution patterns.
  • the heteroaryl is substituted at the position next to the heteroatom.
  • R 2’ and/or R 2 is phenyl, and the phenyl is substituted with one R 21 ’; the only R 21 ’ group is preferably in the para position. If the R 2’ or R 2 phenyl is substituted with two R 21 ’; then the two R 21 ’ groups are preferably in the meta positions. It is further preferred that when R 2’ and/or R 2 is heteroaryl of 5 ring members, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in 5 ⁇ position, whereby the 2 ⁇ - position is attached to the indenyl ring.
  • R 2 is methyl and R 2’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being substituted with 1 or 2 R 21 ’, with R 21 ’ being C 1 -C 6 - alkyl, preferably C 1 -C 3 -alkyl; preferably R 2 ’ is phenyl or thienyl, R 2’ being substituted with one or two R 21 ’. Most preferably R 2 is methyl and R 2’ is 5-methylthienyl or dimethyl phenyl. 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.
  • the phenyl ring substituted in the para position i.e.4 position only like 4-tert-butyl phenyl, or di-substituted in the meta positions, i.e.3 and 5 position, like 3,5-dimethylphenyl or 3,5-ditert-butylphenyl.
  • each of the phenyl rings have the same substitution pattern or that the two phenyl rings carrying the R 3 and R 4 substituents have different substitution patterns.
  • 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, H or C1-C20-hydrocarbyl (e.g. C1-C10- hydrocarbyl) or –OR 31 , wherein R 31 is C1-C10-hydrocarbyl, whereby at least one R 3 and at least one R 4 is not hydrogen.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C10-arylalkyl, C7-C10- alkylaryl, or C6-C20-aryl (e.g. C6-C10-aryl), or –OR 31 , wherein R 31 is C1-C10-hydrocarbyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H; more preferably 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 -C 20 -aryl (e.g.
  • 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, in particular methyl, whereby at least one R 3 and at least one R 4 is not H.
  • R 51 and R 51 ’ are each independently, same or different from each other, 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 linear C 1 -C 6 - alkyl, branched C 3 -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.
  • C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl
  • R 51 and R 51 ’ are the same. Most preferably, both R 51 and R 51 ’ are methyl.
  • R 6 and R 6 ’ are each independently, same or different from each other, C(R 61 ) 3 , with R 61’ being linear C 1 -C 3 -alkyl; more preferably methyl. It is preferred that R 6 and R 6 ’ are the same.
  • both R 6 and R 6 ’ are tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-b) 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 is linear or branched C1-C10-hydrocarbyl; R 2 ’ is heteroaryl or C 6 -C 10 -aryl, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C 1 -C 10 -hydrocarbyl; R 3 and R 4 are each independently, H, C 1 -C 20 -hydrocarbyl, or –OR 31 , wherein R 31 is C 1 -C 10 - hydrocarbyl, whereby at least one R 3 and at least one R 4 is
  • 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.
  • 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 is CH2-R 21 , with R 21 being H, linear or branched C1-6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C3-alkyl, even more preferably H or linear C1-C3-alkyl, such as methyl, ethyl, or n-propyl, yet more preferably H or methyl, most preferably H.
  • R 21 being H, linear or branched C1-6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C3-alkyl, even more preferably H or
  • R 2 ’ is C6-aryl or heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C1-C10- hydrocarbyl, preferably C1-C6-alkyl; more preferably R 2 ’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being optionally, yet preferably, substituted with 1 or 2 R 21 ’, with R 21 ’ being C1-C6-alkyl, preferably C1-C3-alkyl; more preferably R 2 ’ is phenyl or thienyl, R 2’ being optionally substituted with 1 or 2 R 21 ’, with R 21 ’ being methyl.
  • R 2’ aryl and heteroaryl groups are substituted.
  • the R 21’ substituents of the R 2’ aryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring.
  • the R 21’ substituents of the respective R 2’ heteroaryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 2-position is attached to the indenyl ring.
  • a phenyl ring substituted in the para position i.e.4 ⁇ position only like 4 ⁇ -tert-butyl phenyl, or di-substituted in the meta positions, i.e.3 ⁇ and 5 ⁇ position, like 3,5 ⁇ -dimethylphenyl or 3 ⁇ ,5 ⁇ -ditert-butylphenyl.
  • the phenyl ring has the same substitution pattern as the phenyl rings in the 4-position of the indenyl rings or that the phenyl rings on the 2- and 4-position have different substitution patterns.
  • the heteroaryl is substituted at the position next to the heteroatom.
  • R 2’ is phenyl, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in the para position. If the R 2’ phenyl is substituted with two R 21 ’; then the two R 21 ’ groups are preferably in the meta positions. It is further preferred that when R 2’ is heteroaryl of 5 ring members, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in 5 ⁇ position, whereby the 2 ⁇ -position is attached to the indenyl ring.
  • R 2 is methyl and R 2’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being substituted with 1 or 2 R 21 ’, with R 21 ’ being C1-C6- alkyl, preferably C1-C3-alkyl; preferably R 2 ’ is phenyl or thienyl, R 2’ being substituted with one or two R 21 ’, Most preferably R 2 is methyl and R 2’ is 5-methylthienyl or dimethyl phenyl.
  • R 3 and R 4 are each independently, H or C1-C20-hydrocarbyl (e.g.
  • R 31 is C1-C10-hydrocarbyl, whereby at least one R 3 and at least one R 4 is not hydrogen.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C10-arylalkyl, C7-C10- alkylaryl, or C6-C20-aryl (e.g.
  • R 31 is C1-C10-hydrocarbyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H; more preferably R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20-aryl (e.g.
  • 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, in particular methyl, whereby at least one R 3 and at least one R 4 is not H.
  • 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.
  • each of the phenyl rings have the same substitution pattern or that the two phenyl rings carrying the R 3 and R 4 substituents have different substitution patterns.
  • 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. 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 are not H, more preferably the R 3 are the same, like 3,5-di- methyl or 4- tert-butyl.
  • one or two 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 and R 51 ’ are each independently, same or different from each other, 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 C6-C10-aryl, more preferably linear C1-C6- alkyl, branched C3-C6-alkyl, or C6-aryl, even more preferably linear C1-C4 alkyl, yet even more preferably methyl or ethyl, and most preferably methyl.
  • C1-C6-alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl,
  • R 51 and R 51 ’ are the same. Most preferably, both R 51 and R 51 ’ are methyl.
  • R 6 and R 6 ’ are each independently, same or different from each other, C(R 61 )3, with R 61’ being linear C1-C3-alkyl; more preferably methyl. It is preferred that R 6 and R 6 ’ are the same.
  • both R 6 and R 6 ’ are tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-c) 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 is linear or branched C 1 -C 10 -hydrocarbyl; R 2 ’ is heteroaryl or C 6 -C 10 -aryl, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C 1 -C 10 -hydrocarbyl; R 3 and R 4 are each independently C 1 -C 20 -hydrocarbyl, preferably C 1 -C 10 -hydrocarbyl; R 51 and R 51 ’ are each independently, same or different from each other, C 1
  • 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 is CH 2 -R 21 , with R 21 being H, linear or branched C 1-6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C 1 -C 3 -alkyl, even more preferably H or linear C 1-3 -alkyl, such as methyl, ethyl, or n-propyl, yet more preferably H or methyl, most preferably H.
  • R 21 being H, linear or branched C 1-6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C 1 -C 3 -al
  • R 2 ’ is C6-aryl or heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, R 2’ being optionally substituted with 1 to 3 R 21 ’; with R 21 ’ being C1-C10- hydrocarbyl, preferably C1-C6-alkyl; more preferably R 2 ’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being optionally, yet preferably, substituted with 1 or 2 R 21 ’, with R 21 ’ being C1-C6-alkyl, preferably C1-C3-alkyl; more preferably R 2 ’ is phenyl or thienyl, R 2’ being optionally substituted with 1 or 2 R 21 ’, with R 21 ’ being methyl.
  • R 2’ aryl and heteroaryl groups are substituted.
  • the R 21’ substituents of the R 2’ aryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring.
  • the R 21’ substituents of the respective R 2’ heteroaryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 2-position is attached to the indenyl ring.
  • the phenyl ring has the same substitution pattern as the phenyl rings in the 4-position of the indenyl rings or that the phenyl rings on the 2- and 4-position have different substitution patterns.
  • the heteroaryl is substituted at the position next to the heteroatom.
  • R 2’ is phenyl, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in the para position. If the R 2’ phenyl is substituted with two R 21 ’; then the two R 21 ’ groups are preferably in the meta positions. It is further preferred that when R 2’ is heteroaryl of 5 ring members, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in 5 ⁇ position, whereby the 2 ⁇ -position is attached to the indenyl ring.
  • R 2 is methyl and R 2’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being substituted with 1 or 2 R 21 ’; with R 21 ’ being C 1 -C 6 - alkyl, preferably C 1 -C 3 -alkyl; preferably R 2 ’ is phenyl or thienyl, R 2’ being substituted with one or two R 21 ’. Most preferably R 2 is methyl and R 2’ 5-methylthienyl or dimethyl phenyl.
  • R 3 and R 4 are each independently, H or C 1 -C 20 -hydrocarbyl (e.g.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-C10-arylalkyl, C7-C10- alkylaryl, or C6-C20-aryl (e.g.
  • R 3 per phenyl group and at least one R 4 is not H; more preferably R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20-aryl group (e.g.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, or tert-butyl, especially hydrogen, methyl, or tert-butyl, in particular methyl, whereby at least one R 3 and at least one R 4 is not H.
  • 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.
  • the phenyl ring substituted in the para position i.e.3- position only, like 4-tert.-butyl phenyl, or di-substituted in the meta positions, i.e.3- and 5-position, like 3,5-dimethylphenyl or 3,5-ditert.-butylphenyl.
  • each of the phenyl rings have the same substitution pattern or that the two phenyl rings carrying the R 3 and R 4 substituents 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 are not H, more preferably the R 3 are the same, like 3,5-di- methyl or 4- tert-butyl.
  • one or two 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 and R 51 ’ are each independently, same or different from each other, 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 linear C 1 -C 6 - alkyl, branched C 3 -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.
  • C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
  • R 51 and R 51 ’ are the same. Most preferably, both R 51 and R 51 ’ are methyl.
  • R 6 and R 6 ’ are each independently, same or different from each other, C(R 61 )3, with R 61’ being linear C1-C3-alkyl; more preferably methyl. It is preferred that R 6 and R 6 ’ are the same.
  • both R 6 and R 6 ’ are tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-d) (I-d) 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 is linear or branched C 1 -C 10 -hydrocarbyl; R 2 ’ is heteroaryl or C 6 -C 10 -aryl, R 2’ being optionally substituted with one to three R 21 ’; with R 21 ’ being C 1 -C 10 -hydrocarbyl; R 3 and R 4 are each independently C 1 -C 20 -hydrocarbyl, preferably C 1 -C 10 hydrocarbyl.
  • 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.
  • 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 is CH2-R 21 , with R 21 being H, linear or branched C1-6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, more preferably R 21 being H or linear or branched C1-C3-alkyl, even more preferably H or linear C1-3-alkyl, such as methyl, ethyl, or n-propyl, yet more preferably H or methyl, most preferably H;
  • R 2 ’ is C6-aryl or heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, R 2’ being optionally substituted with one to three R 21 ’; with R 21 ’ being C1-C10- hydrocarbyl, preferably C1-C6-alkyl; more preferably R 2 ’ is phenyl or heteroaryl of 5
  • R 2’ aryl and heteroaryl groups are substituted.
  • the R 21’ substituents of the R 2’ aryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring.
  • the R 21’ substituents of the respective R 2’ heteroaryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 2-position is attached to the indenyl ring.
  • the phenyl ring has the same substitution pattern as the phenyl rings in the 4-position of the indenyl rings or that the phenyl rings on the 2- and 4-position have different substitution patterns.
  • the heteroaryl of is substituted at the position next to the heteroatom.
  • R 2’ is phenyl, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in the para position. If the R 2’ phenyl is substituted with two R 21 ’; then the two R 21 ’ groups are preferably in the meta positions. It is further preferred that when R 2’ is heteroaryl of 5 ring members, and is substituted with one R 21 ’; the only R 21 ’ group is preferably in 5 ⁇ position, whereby the 2 ⁇ -position is attached to the indenyl ring.
  • R 2 is methyl and R 2’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being substituted with 1 or 2 R 21 ’; with R 21 ’ being C1-C6- alkyl, preferably C1-C3-alkyl; preferably R 2 ’ is phenyl or thienyl, R 2’ being substituted with one or two R 21 ’, Most preferably R 2 is methyl and R 2’ 5-methylthienyl or dimethyl phenyl.
  • R 3 and R 4 are each independently, same or different from each other, linear C1- C6-alkyl, branched C3-C6-alkyl, or C6-C10 aryl group, more preferably linear C1-C6-alkyl, branched C3-C4-alkyl. Even more preferably, each R 3 and R 4 are each independently, same or different from each other, methyl, ethyl, isopropyl, or tert-butyl, especially methyl, or tert-butyl, particularly methyl.
  • the R 3 are the same, like 3,5-di-methyl.
  • R 4 are the same like 3,5-di-methyl or 3,5-di-tert-butyl.
  • Intermediates Whilst the invention primarily relates to catalysts, it will be appreciated that the complexes of the invention and the ligands used to form those complexes are also new.
  • the novel indenes of the present invention bear the combination of the distinctive features of the indene framework: 1: a 5-alkoxy indene, preferably methoxy indene, with a tertiary hydrocarbyl, preferably tertiary alkyl, substituent, on position 6 and 2: an aryl or heteroaryl substituent on position 2.
  • the present invention accordingly further relates to indenes of formula (II) wherein the dotted lines represent a double bond present in between carbons 1 and 2 or 2 and 3 of the indenyl ring;
  • R 2 ’ is heteroaryl or C6-C10-aryl, R 2’ being optionally substituted with one to three R 21 ’; with R 21 ’ being C1-C10-hydrocarbyl;
  • R 4 are each independently, H, C1-C20-hydrocarbyl or –OR 31 , wherein R 31 is C1-C10- hydrocarbyl, whereby at least one R 4 is not H;
  • R 51 ’ is C1-C10-hydrocarbyl; and
  • R 6 ’ is C(R 61 )3, with R 61 being linear or branched C1-C6-alkyl.
  • R 2 ’ is C6-aryl or heteroaryl of 5 to 6 ring members in which one ring member is O, S, or N, R 2’ being optionally substituted with 1 to 3 R 21 ’, with R 21 ’ being C1-C10- hydrocarbyl, preferably C1-C6-alkyl; more preferably R 2 ’ is phenyl or heteroaryl of 5 ring members in which one ring member is O or S, R 2’ being optionally substituted with 1 or 2 R 21 ’, with R 21 ’ being C 1 -C 6 -alkyl, preferably C 1 -C 3 -alkyl; more preferably R 2 ’ is phenyl or thienyl, R 2’ being optionally substituted with 1 or 2 R 21 ’, with R 21 ’ being methyl.
  • R 2’ aryl and heteroaryl groups are substituted.
  • the R 21’ substituents of the R 2’ aryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring.
  • the R 21’ substituents of the respective R 2’ heteroaryl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 2-position is attached to the indenyl ring.
  • a phenyl ring substituted in the para position i.e.3-position only like 4-tert-butyl phenyl, or di-substituted in the meta positions, i.e.3- and 5- position, like 3,5-dimethylphenyl or 3,5-ditert-butylphenyl.
  • the phenyl ring has the same substitution pattern as the phenyl rings in the 4-position of the indenyl rings or that the phenyl rings on the 2- and 4-position have different substitution patterns.
  • the heteroaryl of is substituted at the position next to the heteroatom.
  • R 2’ is phenyl, which is substituted with one R 21 ’; the only R 21 ’ group is preferably in the para position. If the R 2’ phenyl is substituted with two R 21 ’; then the two R 21 ’ groups are preferably in the meta positions. It is further preferred that when R 2’ is heteroaryl of 5 ring members, and is substituted with one R 21 ’; the only R 21 ’ group is preferably in 5 ⁇ position, whereby the 2 ⁇ -position is attached to the indenyl ring.
  • R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C7-20-arylalkyl, C7-20-alkylaryl, C6-20 aryl, or –OR 31 , wherein R 31 is C1- C10-hydrocarbyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H; more preferably R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20 aryl group, even more preferably H, a linear or branched C1-C4-alkyl, or -OR 31 , wherein R 31 is a C1-4-hydrocarbyl; yet more preferably, R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially hydrogen, methyl, or tert-
  • the 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.
  • the phenyl ring substituted in the para position i.e.3-position only, like 4-tert.-butyl phenyl, or di-substituted in the meta positions, i.e.3- and 5-position, like 3,5-dimethylphenyl or 3,5-di-tert.-butylphenyl.
  • one or two R 4 groups is H. If two R 4 groups are H then the remaining R 4 group, respectively, is preferably in the para position.
  • R 4 group is H then the remaining R 4 groups are preferably in the meta positions.
  • the indenyl moiety preferably one or two 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 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 linear C 1 -C 6 –alkyl, branched C 3 -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.
  • C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert
  • R 51 ’ is methyl.
  • R 6 ’ is C(R 61 ) 3 , with R 61’ being linear C 1 -C 3 -alkyl; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • Polymerization catalyst Viewed from a further aspect the invention provides a polymerization catalyst comprising, preferably consists of (i) a metallocene complex of formula (I); (ii) a cocatalyst comprising aluminium; and (iii) optionally a support.
  • 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 skilled person is aware of the procedures required to support a metallocene catalyst.
  • the support is a porous material so that the complex may be loaded into the pores of the support, e.g.
  • 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 WO 2020/239598 and WO 2020/239603.
  • 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.
  • Such catalysts can be prepared as described for example in WO 2003/051934, WO 2014/060540 and WO 2019/179959
  • 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.
  • 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 a) is 75.0 to 100.0 wt% of the total amount of aluminoxane cocatalyst and the amount the second portion of the aluminoxane cocatalys
  • 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 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 a) is 75.0 to 100.0 wt% of the total amount of methylaluminoxane cocatalyst and the amount of aluminoxane cocatalyst added in step b) is
  • 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/SiO2, M/SiO2).
  • 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.
  • a cocatalyst system comprising a boron containing cocatalyst and/or an aluminoxane cocatalyst may be used in combination with the above defined metallocene catalyst complex.
  • cocatalysts comprising aluminium, like organoaluminium compounds used to activate metallocene catalysts, are utilized in this invention.
  • 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 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
  • Alumoxane cocatalyst The aluminoxane cocatalyst can be one of formula (A): where n is usually from 6 to 20 and R has the meaning below.
  • 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(C 1 -C 6 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) 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 is 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.
  • Preferred ionic compounds which can be used according to the present invention include: tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenyl
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N-dimethylaniliniumtetrakis(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 C4-10 alpha olefin copolymers, in particular heterophasic polypropylene and propylene-ethylene copolymers. Accordingly, the present disclosure relates 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.
  • 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 invention relates to a process for the polymerization of propylene, propylene and ethylene, or propylene and a C4-10 alpha olefin in the presence of a polymerization catalyst as described herein.
  • the present invention relates to a process for the preparation of a heterophasic polypropylene copolymer (hPP) comprising (I) polymerizing propylene in bulk in the presence of a polymerization catalyst as defined herein to form a polypropylene homopolymer matrix; (II) in the presence of said matrix and said polymerization catalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber.
  • hPP heterophasic polypropylene copolymer
  • the present invention relates to a process for the preparation of a heterophasic polypropylene copolymer comprising (I) polymerizing propylene in bulk in the presence of polymerization catalyst as defined herein to form a polypropylene homopolymer; (II) in the presence of said homopolymer and said polymerization catalyst and in the gas phase, polymerizing propylene to form a polypropylene homopolymer matrix; (III) in the presence said matrix and said polymerization catalyst and in the gas phase, polymerizing propylene and ethylene to form a heterophasic polypropylene copolymer comprising a homopolymer matrix and an ethylene propylene rubber (EPR).
  • EPR ethylene propylene rubber
  • 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 -g(e.g.20 to 60 bar-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.
  • the random copolymerization behavior of metallocene catalysts of the invention shows a reduced tendency of chain transfer to ethylene. It is a feature of the invention that the claimed catalysts enable the formation of polypropylene with very high melting point. 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.
  • 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 very high melting points.
  • the propylene homopolymer formed by the process of the invention has a melting point of more than 157 °C, preferably more than 158 °C. Propylene homopolymers having melting points up to 160 °C, or even up to 162 °C, are possible.
  • 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 (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 BO
  • 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.
  • xylene soluble fraction as defined and described in the present invention is determined in line with ISO 16152 as follows: 2.5 ⁇ 0.1 g of the polymer were dissolved in 250 ml o-xylene under reflux conditions and continuous stirring, under nitrogen atmosphere. After 30 minutes, the solution was allowed to cool, first for 15 minutes at ambient temperature and then maintained for 30 minutes under controlled conditions at 25 ⁇ 0.5 °C. The solution was filtered through filter paper. For determination of the xylene soluble content, an aliquot (100 ml) of the filtrate was taken. This aliquot was evaporated in nitrogen flow and the residue dried under vacuum at 100 °C until constant weight is reached.
  • m 0 designates the initial polymer amount (grams)
  • m 1 defines the weight of residue (grams)
  • v 0 defines the initial volume (milliliter)
  • v 1 defines the volume of the analyzed sample (milliliter).
  • GPC Molecular weight averages, molecular weight distribution, and polydispersity index (Mn, Mw, Mw/Mn)
  • Mn, Mw, Mw/Mn polydispersity index
  • a high temperature GPC equipped with a suitable concentration detector (like IR5 or IR4 from PolymerChar (Valencia, Spain), an online four capillary bridge viscometer (PL-BV 400-HT), and a dual light scattering detector (PL-LS 15/90 light scattering detector) with a 15° and 90° angle was used.
  • 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 T m 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) is 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 (MFR21).
  • Comonomer content by FTIR Quantitative infrared (IR) spectroscopy was used to estimate the C2 content of the copolymers through calibration to a primary method (NMR spectroscopy).
  • Standard transmission FTIR spectroscopy was employed using a spectral range of 5000-400 cm -1 , an aperture of 6 mm, a spectral resolution of 2 cm -1 , 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 32 and Norton Beer strong apodisation. Quantitative analysis was carried out by integration of (peak height) CH 2 rocking deformations at 732.5 cm -1 (A Q ) corresponding to isolated ethylene incorporation in PEP comonomer sequences (integration method K-OPUS, limits 759 and 702 cm -1 ).
  • the quantitative band was normalized to the height of the CH combination band at 4323 cm -1 (A R ) corresponding to CH structural units (integration method K, limits 4480, 3950 cm -1 ).
  • the calibration curve having previously been constructed by least square regression of the normalized absorptions and comonomer contents measured by the primary technique (NMR Spectroscopy).
  • C 1 is the slope of the calibration curve with 0.96 > C 1 > 1, and the intercept of -0.02 > C 0 > 0.06.
  • NMR Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and content of regio-defects of the polypropylene homopolymers. Quantitative 13 C ⁇ 1 H ⁇ NMR spectra recorded in the solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 10 mm selective excitation probehead at 125°C using nitrogen gas for all pneumatics.
  • TCE-d 2 1,2- tetrachloroethane-d 2
  • Standard single-pulse excitation was employed utilising the NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson.187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 11289). A total of 6144 (6k) transients were acquired per spectra using a 3 s recycle delay.
  • the presence of secondary inserted propene in the form of 2,1 erythro regio defects was indicated by the presence of the two methyl signals at 17.7 and 17.2 ppm and confirmed by the presence of other characteristic signals.
  • Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the ethylene content and the isotacticity of the copolymers. Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were recorded in the solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively.
  • the isotacticity of the copolymer was determined according to known methods, for example as described in Macromolecules 2005, vol.38, pp.3054-3059.
  • IR4 detector is multiple wavelength detector detecting IR absorbance at two different bands (CH3 and CH2) for the determination of the concentration and the ethylene content in ethylene-propylene copolymers.
  • IR4 detector is calibrated with series of EP copolymers with known ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13C- NMR).
  • Amount of Soluble fraction (SF) and Crystalline Fraction (CF) are correlated through the XS calibration to the “Xylene Soluble” (XS) quantity and respectively Xylene Insoluble (XI) fractions, determined according to standard gravimetric method as per ISO16152 (2005).
  • XS calibration is achieved by testing various EP copolymers with XS content in the range 2-31 wt%.
  • Intrinsic viscosity (iV) of the parent EP copolymer and its soluble and crystalline fractions are determined with a use of an online 2-capillary viscometer and are correlated to corresponding iV determined in decalin according to ISO 1628-3 (2010).
  • the sample is dissolved at 160°C until complete dissolution is achieved, usually for 60 min, with constant stirring of 800rpm.
  • a defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at elevated temperature, determining the iV[dl/g] and the C2[wt%] of the PP composition.
  • MC-CE1 Metallocene synthesis Synthesis of MC-CE1 Synthesis of this metallocene has been carried out as described in WO2018091684 MC- IE1. Synthesis of MC-IE1, IE2, IE3, IE4 Synthesis of the common intermediate 2-bromo-5-tert-butyl-7-(3,5-dimethylphenyl)-6- methoxy-1H-indene.
  • 6-tert-Butyl-4-(3,5-dimethylphenyl)-5-methoxyindan-1-one A mixture of 94.07 g (316.5 mmol) of 4-bromo-6-tert-butyl-5-methoxyindan-1-one, 60.0 g (400.0 mmol, 1.26 equiv.) of 3,5-dimethylphenylboronic acid, 1.7 g (3.33 mmol, 1 mol.%) of Pd(P t Bu 3 ) 2 , 102 g of Na 2 CO 3 , 525 ml of 2-methyltetrahydrofurane, and 470 ml of water was refluxed for 6 h.
  • this mixture was evaporated to dryness, 1000 ml of dichloromethane and 500 ml water were added to the residue, and thus obtained mixture was acidified with 2 M HCl to pH ⁇ 6.5.
  • the organic layer was separated, the aqueous layer was additionally extracted with 250 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 reddish oil.
  • the formed solution was washed with 10% Na 2 CO 3 , the organic layer was separated, and the aqueous layer was extracted with 200 ml of dichloromethane. The combined organic extract was dried over K 2 CO 3 and then evaporated to dryness.
  • 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 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. 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. Then, toluene (43.5 kg) was added.
  • the SiO2/toluene slurry was stirred for 25 min at 22 °C. Then, 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. After MAO addition, the reactor temperature was quickly increased to 90 °C and the mixture was stirred at this temperature for 120 min. Then 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.
  • the solution of metallocene in toluene was added dropwise by means of a syringe to the SiO 2 /MAO carrier over the course of 5 minutes with gentle mixing.
  • the resulting powder was allowed to rest for 1 hour, and then it was transferred into a Schlenk flask and dried under vacuum for 1 hour at 60 °C to yield the catalyst as a beige free-flowing powder.
  • the metallocene content in each catalyst is calculated by mass balance.
  • Table 1 catalysts tested and their metallocene content Catalyst MC Al MC in catalyst * type wt% wt% Comparative CE1 MC-CE1 13,2 1,33 1 IE1 Inventive 1 MC-IE1 12,8 1,39 IE2 Inventive 2 MC-IE2 12,3 1,54 IE3 Inventive 3 MC-IE3 12,7 1,38 IE4 Inventive 4 MC-IE4 12,7 1,53 * metallocene content in the dry catalyst calculated from mass balance Polymerization examples Propylene homopolymerization procedure in bulk (liquid propylene, 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 is 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.
  • Triethylaluminum (0.80 ml of a 0.62 mol/l solution in heptane) was injected into the reactor by additional 240 g propylene, then 0.5 NL of H2 is dosed in via mass flow controller. The solution was stirred at 25 °C 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. The feeder system is mounted on a port on the lid of the autoclave. Then the catalyst is flushed into the reactor with 350 g propylene. The prepolymerization was run for 10 min. at the temperature indicated in table 3.
  • the temperature was raised to 70 or 75 °C (see table 3) and kept constant throughout the polymerisation.
  • the reactor temperature reached 60 °C, 108 g of ethylene were added in two minutes via mass flow controller and, at the same time, an additional amount of H2 was dosed in 1 min via mass flow controller.
  • the polymerization time was measured starting when the internal reactor temperature was 2°C below the set temperature of the bulk step.
  • the reaction was stopped by injecting 5 ml ethanol from a steel cylinder filled with 5 ml ethanol and pressurized with 70 bar N2, cooling the reactor down to 30 °C and simultaneously flashing the volatile components.
  • Step 1 corresponds to the bulk experiment run at 75 °C with the H2 split between prepoly (0.5 NL) and transition to the bulk step (0.5 NL).
  • Step 2 was performed as follows.
  • the stirrer speed was reduced to 50 rpm and the pressure was reduced to 0.4 bar-g by venting the monomers.
  • the stirrer speed was set to 180 rpm and the reactor temperature was set to 70 °C.
  • the reactor pressure was increased to 20 bar-g by feeding a C3/C2 gas mixture of 0,937 g/g.
  • the C3/C2 ratio is defined by where C2/C3 is the weight ratio of the two monomers and R is their relative reactivity ratio, determined experimentally. In the present experiments, the value of R was set at 0.35.
  • the temperature was held constant by thermostat and the pressure was kept constant by feeding via mass flow controller a C2/C3 gas mixture of 0.333 g/g, a composition corresponding to the target polymer composition and by thermostat, until the set time of 120 min had expired. Then the reactor was cooled down (to about 30 °C) and the volatile components flashed out. After purging the reactor 3 times with N2 and one vacuum/N2 cycle, the product was taken out and dried overnight in a fume hood.100 g of the polymer was additivated with 0.5 wt% Irganox B225 (solution in acetone) and dried overnight in a hood followed by 2 hours in a vacuum drying oven at 60°C.

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Abstract

L'invention concerne un complexe métallocène de formule (I) dans laquelle Mt représente Zr ou Hf ; L est O ou S ; 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 en C4-C8 ; R2 est hétéroaryle, aryle en C6-C10, ou hydrocarbyle en C1-C10 linéaire ou ramifié, lesdits aryle et hétéroaryle en C6- C10 étant éventuellement substitués par 1 à 3 R21' ; R21' étant hydrocarbyle en C1-C10 ; R2' étant hétéroaryle ou aryle en C6-C10, R2' étant éventuellement substitué par 1 à 3 R21' ; R21' étant hydrocarbyle en C1-C10 ; n sont chacun indépendamment, identiques ou différents les uns des autres, un nombre entier de 1 à 5 ; R3 et R4 sont chacun indépendamment H ou hydrocarbyle en C1-C20 ou –OR31, R31 étant hydrocarbyle en C1- C10, au moins un R3 et au moins un R4 n'étant pas hydrogène ; R51 et R51' sont chacun indépendamment, identiques ou différents les uns des autres, hydrocarbyle en C1-C10 ; et R6 et R6' sont chacun indépendamment, identiques ou différents l'un de l'autre, C(R61)3, R61 étant alkyle en C1-C6 linéaire ou ramifié.
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