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WO2025016565A1 - Catalyseurs pour polymérisation d'oléfines - Google Patents

Catalyseurs pour polymérisation d'oléfines Download PDF

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Publication number
WO2025016565A1
WO2025016565A1 PCT/EP2024/057071 EP2024057071W WO2025016565A1 WO 2025016565 A1 WO2025016565 A1 WO 2025016565A1 EP 2024057071 W EP2024057071 W EP 2024057071W WO 2025016565 A1 WO2025016565 A1 WO 2025016565A1
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Prior art keywords
hydrocarbyl
branched
independently
alkyl
same
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Inventor
Luigi Maria Cristoforo RESCONI
Dmitry S. Kononovich
Alexander Z. Voskoboynikov
Soile LUSTIG
Martin NEUHEIMER
Vyatcheslav V. Izmer
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Borealis GmbH
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Borealis GmbH
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Priority to PCT/EP2024/069910 priority Critical patent/WO2025016933A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom

Definitions

  • the present disclosure relates to new indenyl and indacenyl ligands, bisindenyl ligands comprising said indenyl and/or indacenyl ligands, complexes thereof, and catalysts comprising those complexes.
  • the present disclosure also relates to the use of the new bisindenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers, especially with ethylene, in particular heterophasic polypropylene (hPP), with high activity levels, high molecular weight, and hence low MFR, and with ideal melting points.
  • hPP heterophasic polypropylene
  • the catalysts are especially useful in the manufacture of propylene ethylene copolymers as they exhibit remarkable catalyst activity in such polymerizations.
  • 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.
  • WO2001048034 describes C1-symmetric bisindenyl complexes bearing one 2-isopropyl substituent.
  • Such catalysts produce relatively high melting hPP (156 - 159 °C), but the catalysts have very low activities.
  • 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.
  • 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.
  • WO2005058916 describes a series of C1-symmetric bisindenyl complexes combining one 2-iso-propyl-4-aryl-indenyl ligand and one 2-methyl-4-aryl-indacenyl ligand. While T m of hPP is somewhat high varying from 152 to 160°C, catalyst activities are invariably low.
  • WO0202576 describes the C 2 -symmetric rac-Me 2 Si(2-iPr-4-(3,5-Me 2 Ph)-ind) 2 ZrCl 2 . This complex provides a catalyst of very low activity and hPP of relatively low T m of 152 to 154°C). The teaching from this patent is that iPr groups lower catalyst activity without increasing hPP T m .
  • the present inventors thus sought new metallocenes, which are able to provide high activity, 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.
  • 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.
  • An object of the present disclosure is to provide new ligands, metallocene complexes, and hence catalysts that overcome the problems of the catalysts of the prior art.
  • the object of the disclosure is achieved by 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.
  • 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-C20-alkyl, C4-C20-cycloalkyl, C5-C20-cycloalkyl-alkyl groups, C7-C20-alkylaryl groups, C7-C20-arylalkyl groups, and C6-C20- 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-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.
  • Sensitivity Internal C 1 -C 6 -alkyl groups. Most especially preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C 5 -C 6 -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 sometimes used to indicate the catalyst activity although herein it designates the amount of polymer produced per unit weight of catalyst.
  • metallocene catalyst complexes are asymmetrical. Asymmetrical means simply that the two ligands forming the metallocene are different, that is, each ligand bears a set of substituents that are chemically different.
  • the metallocene complexes of the invention are preferably chiral, racemic, bridged bisindenyl C1-symmetric metallocenes in their anti-configuration.
  • Sensitivity Internal of the invention are formally C 1 -symmetric, the complexes ideally retain a pseudo-C 2 - symmetry since they maintain C 2 -symmetry in close proximity of the metal center although not at the ligand periphery. By nature of their chemistry both anti and syn enantiomer pairs (in case of C 1 -symmetric complexes) are formed during the synthesis of the complexes.
  • racemic-anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane
  • racemic-syn means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, as shown in the scheme below.
  • Racemic Anti Racemic Syn Preferred metallocene catalyst complexes are in the anti-configuration. The metallocene complexes of the invention are preferably employed as the racemic-anti- isomers.
  • the metallocene catalyst complex requires the combination of three distinctive features of the ligand framework: 1: an indacenyl ligand with 4,8-diaryl substitution, 2: a 5-alkoxy indene, preferably methoxy indene, with 6-tertiary hydrocarbyl, preferably tertiary alkyl, substituent, and 3: at least one alpha-branched alkyl substituent on one of the 2-positions of the ligand, preferably on the 2-position of the alkoxy indenyl ligand.
  • 1 an indacenyl ligand with 4,8-diaryl substitution
  • 2 a 5-alkoxy indene, preferably methoxy indene, with 6-tertiary hydrocarbyl, preferably tertiary alkyl, substituent
  • 3 at least one alpha-branched alkyl substituent on one of the 2-positions of the ligand, preferably on the 2-position of the alkoxy indenyl ligand.
  • the present invention accordingly relates to metallocene complexes of formula (I) wherein Mt is Zr or Hf; X is a sigma ligand; R 1 are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C4-C8-ring; R 2 and R 2 ’ are each independently a C -C -hydrocarbyl, pro 2 1 10 vided that at least one of R and R 2 ’ is an alpha-branched C3-C10-hydrocarbyl; n are each independently, same or different from each other, an integer from 1 to 5;
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, -OR 31 , SR 31 , or N(R 31 ) 2 , with R31 being C 1 -C 10 -hydrocarbyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H;
  • R 5 and R 6 are each independently, same or different from each other, H or C 1 -C 10 - hydrocarbyl, or may form together with the C atoms they are attached to a C 5 -C 7 - carbocycle;
  • R 51 ’ is C 1 -C 10 -hydrocarbyl; and
  • R 6 ’ is C(R 61 ) 3 , with R 61 being linear or branched C 1 -C 6 -al
  • each X is a sigma ligand.
  • each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R ⁇ group, with R ⁇ being C1-C6-alkyl, phenyl, or benzyl.
  • 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 and R 2 ’ are each independently, same of different from each other, alpha- branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or a C6-C9-aryl, provided that at least one of R 2 and R 2 ’ is alpha- branched C3-C9-hydrocarbyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,
  • Sensitivity Internal being H or linear or branched C 1 -C 3 -alkyl, provided that at least one of R 2 and R 2 ’ is alpha- branched C 3 -C 6 -alkyl.
  • R 2 and R 2 ’ are different and one, preferably R 2 ’, is alpha-branched C 3 -C 10 - hydrocarbyl; more preferably alpha-branched C 3 -C 6 -alkyl, even more preferably CH(CH 3 ) 2 , and the other, preferably R 2 , is a CH 2 -R 21 -group, with R 21 being H or C 1 -C 6 -alkyl, more preferably H or linear C 1- C 3 -alkyl, most preferably methyl.
  • R 2 is CH 2 -R 21 , with R 21 being H or linear C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, n-butyl, more preferably R 21 being H or linear C 1 -C 3 -alkyl, even more preferably, R2 is methyl or ethyl, most preferably methyl.
  • R 2’ is alpha-branched C 3 -C 10 -hydrocarbyl; more preferably R 2’ is alpha- branched C 3 -C 6 -alkyl, even more preferably R 2’ is CH(CH 3 ) 2 .
  • R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl; more preferably, R2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl, most preferably R 2 is methyl and R 2’ is CH(CH3)2.
  • each n is independently, same or different from each other, an integer from 1 to 3, such as 1, 2 or 3.
  • the R 3 and R 4 substituents of the respective phenyl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring. It is for example possible that the phenyl ring is substituted in the para position i.e.
  • n 1, the only R 3 and/or R 4 group, respectively, is preferably in the para position. If n is 2, then the two R 3 and/or R 4 groups, respectively are preferably in the meta positions.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, or C6-C20-aryl, more preferably H, linear or branched C1-C4-alkyl, or –OR 31 , with R 31 being C1-C4-hydrocarbyl, even more preferably, each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially hydrogen, methyl, or tert-butyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H.
  • R 5 and R 6 form together (R 56 ) m , wherein each (R 56 ) m is independently -CH 2 -, - CHR*-, or -C(R*) 2 - group, with R* being C 1 -C 2 -alkyl, preferably methyl, and m being 3 to 5, preferably 3 to 4; more preferably each (R 56 ) m is -CH 2 -, with m being and integer from 3 to 5, preferably 3 or 4, most preferably 3.
  • R 51 ’ is C 1 -C 10 -hydrocarbyl, for example, linear or branched C 1 -C 10 - hydrocarbyl.
  • R 51 ’ is linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C 7 -C 10 -arylalkyl, C 7 -C 10 -alkylaryl, or C 6 -C 10 -aryl, more preferably 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 6 ’ is C(R 61 ) 3 , with R 61’ being linear C 1 -C 3 -alkyl; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (I-a) wherein Mt is Zr or Hf; X is a sigma ligand; R 1 are each independently, same or different from each other, C1-C20-hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form, together with the Si atom they are attached to, a C4-C8-ring; R 2 and R 2 ’ are each independently a C 1 -C 10 -hydrocarbyl, provided that at least one of R2 and R 2 ’ is an alpha-branched C3-C10-hydrocarbyl;
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, -OR 31 , SR 31 , or N(R 31 ) 2 , with R31 being C 1 -C 10 -hydrocarbyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H;
  • R 5 and R 6 are each independently, same or different from each other, H or C 1 -C 10 - hydrocarbyl, or may form together with the C atoms they are attached to a C 5 -C 7 - carbocycle;
  • R 51 ’ is C 1 -C 10 -hydrocarbyl; and
  • R 6 ’ is C(R 61 ) 3 , with R 61 being linear or branched C 1 -C 6 -al
  • each X is a sigma ligand.
  • each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R ⁇ , with R ⁇ being C1-C6-alkyl, phenyl, or benzyl.
  • 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 and R 2 ’ are each independently, same of different from each other, alpha- branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or a C6-C9-aryl, provided that at least one of R 2 and R 2 ’ is alpha- branched C3-C9-hydrocarbyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,
  • R 2 and R 2 ’ are different and one, preferably R 2 ’, is alpha-branched C 3 -C 10 - hydrocarbyl; more preferably alpha-branched C 3 -C 6 -alkyl, even more preferably CH(CH 3 ) 2 , and the other, preferably R 2 , is CH 2 -R 21 , with R 21 being H or C 1 -C 6 -alkyl, more preferably H or linear C 1 -C 3 -alkyl, most preferably methyl.
  • R 2 is CH 2 -R 21 , with R 21 being H, linear C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, n-butyl, more preferably R 21 being H or linear C 1 -C 3 -alkyl, even more preferably, R2 is methyl or ethyl, most preferably methyl.
  • R 2’ is alpha-branched C 3 -C 10 -hydrocarbyl; more preferably R 2’ is alpha- branched C 3 -C 6 -alkyl, even more preferably R 2’ is CH(CH 3 ) 2 .
  • R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl; more preferably, R2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl, most preferably R 2 is methyl and R 2’ is CH(CH3)2.
  • 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, more preferably H, a linear or branched C1-C4- alkyl, or -OR 31 , with R 31 being a C1-C4-hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially hydrogen, methyl, or tert-butyl, whereby at least one R 3 per phenyl group 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.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 three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups is H.
  • R 3 and/or R 4 groups are H then the remaining R 3 and/or R 4 group, respectively, is preferably in the para position. If one R 3 and/or R 4 group is H then the remaining R 3 and/or R 4 groups are preferably in the meta positions.
  • one or two R 3 per phenyl group are not H, more preferably on both phenyl groups the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl for both phenyl groups.
  • Sensitivity Internal for 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 5 and R 6 form together (R 56 ) m , wherein each (R 56 ) m is independently -CH 2 -, - CHR*-, or -C(R*) 2 -, with R* being C 1 -C 2 -alkyl, preferably methyl, and m being 3 to 5, preferably 3 to 4; more preferably each (R 56 ) m is -CH 2 -, with m is 3 to 5, preferably 3 to 4, most preferably 3.
  • R 51 ’ is C 1 -C 10 -hydrocarbyl, for example, linear or branched C 1 -C 10 - hydrocarbyl.
  • R 51 ’ is linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C 7 -C 10 -arylalkyl, C 7 -C 10 -alkylaryl, or C 6 -C 10 -aryl, more preferably 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 6 ’ is C(R 61 )3, with R 61’ being linear C1-C3-alkyl; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • the invention provides a metallocene catalyst complex of formula (l-b) 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;
  • Internal R 2 and R 2 ’ are each independently a C 1 -C 10 -hydrocarbyl, provided that at least one of R2 and R 2 ’ is an alpha-branched C 3 -C 10 -hydrocarbyl;
  • R 3 and R 4 are each independently, same or different from each
  • 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 ⁇ , with R ⁇ being C 1- C 6 -alkyl, phenyl, or benzyl.
  • 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 and R 2 ’ are each independently, same of different from each other, alpha- branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or a C6-C9-aryl, provided that at least one of R 2 and R 2 ’ is alpha- branched C3-C9-hydrocarbyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,
  • R 2 and R 2 ’ are different and one, preferably R 2 ’, is alpha-branched C 3 -C 10 - hydrocarbyl; more preferably alpha-branched C 3 -C 6 -alkyl, even more preferably CH(CH 3 ) 2 , and the other, preferably R 2 , is CH 2 -R 21 -, with R 21 being H or C 1 -C 6 -alkyl, more preferably H or linear C 1 -C 3 -alkyl, most preferably methyl.
  • R 2 is CH 2 -R 21 , with R 21 being H, linear C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, n-butyl, more preferably R 21 being H or linear C 1 -C 3 -alkyl, even more preferably, R2 is methyl or ethyl, most preferably methyl.
  • R 2’ is alpha-branched C 3 -C 10 -hydrocarbyl; more preferably R 2’ is alpha- branched C 3 -C 6 -alkyl, even more preferably R 2’ is CH(CH 3 ) 2 .
  • R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl; more preferably, R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl, most preferably R 2 is methyl and R 2’ is CH(CH 3 ) 2 .
  • 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, more preferably H, a linear or branched C1-C4- alkyl, or -OR 31 , with R 31 being a C1-C 4-hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H.
  • each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups per phenyl group 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 per phenyl group are not H, more preferably on both phenyl groups the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl for both phenyl groups.
  • 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 5 and R 6 form together (R 56 )m, wherein each (R 56 )m is independently -CH2-, - CHR*-, or -C(R*)2-, with R* being C1-C2-alkyl, preferably methyl, and m being 3 to 5, preferably 3 to 4; more preferably each (R 56 )m is -CH2-, with m is 3 to 5, preferably 3 to 4, most preferably 3.
  • the invention provides a metallocene catalyst complex of formula (I-c) (I-c) wherein Mt is Zr or Hf; X is a sigma ligand; R 1 are each independently, same or different from each other, C 1 -C 20 -hydrocarbyl, optionally containing up to two heteroatoms of Group 14-16 of the Periodic Table, or form together with the Si atom they are attached to a C 4 -C 8 ring; R 2 and R 2 ’ are each independently a C 1 -C 10 -hydrocarbyl, provided that at least one of R 2 and R 2 ’ is an alpha-branched C 3 -C 10 -hydrocarbyl; R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C
  • each X is a sigma ligand.
  • each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R ⁇ , with R ⁇ being C1-C6-alkyl, phenyl, or benzyl.
  • each X is independently, same or different from each other, Cl, benzyl, or Sensitivity: Internal methyl. It is preferred that both X groups are the same.
  • both X are Cl, methyl, or benzyl, especially Cl.
  • R 1 are each independently, same or different from each other, C 1- C 10 - hydrocarbyl, more preferably C 1 -C 10- alkyl, C 4 -C 10- cycloalkyl, C 5 -C 10- cycloalkyl-alkyl, C 7 - C 10 -arylalkyl, C 6- C 10 -aryl, or C 7 -C 10- alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert- butyl, isobutyl, C 3 -C 8 -cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C 1- C 6 -alkyl, C 5 -C 6- cycloalkyl, or C 6 -aryl.
  • each R 1 is independently, same or different from each other, C 1 -C 10 -alkyl, optionally substituted with C 1 -C 10 -alkoxy. It is preferred that both R 1 groups are the same. Most preferably, both R 1 are methyl.
  • R 2 and R 2 ’ are each independently, same of different from each other, alpha- branched C 3 -C 10 -hydrocarbyl or CH 2 -R 21 , with R 21 being H, linear or branched C 1 -C 6 -alkyl, a C 3- C 8 -cycloalkyl, or a C 6- C 9 -aryl, provided that at least one of R 2 and R 2 ’ is alpha- branched C3-C9-hydrocarbyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, i
  • R 2 and R 2 ’ are different and one, preferably R 2 ’, is alpha-branched C3-C10- hydrocarbyl; more preferably alpha-branched C3-C6-alkyl, even more preferably CH(CH3)2, and the other, preferably R 2 , is a CH2-R 21 , with R 21 being H or C1-C6-alkyl, more preferably H or linear C1-C3-alkyl, most preferably methyl.
  • R 2 is CH2-R 21 , with R 21 being H, linear C1-C6-alkyl, such as methyl, ethyl, n- propyl, n-butyl, more preferably R 21 being H or linear C1-C3-alkyl, even more preferably, R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is alpha-branched C3-C10-hydrocarbyl; more preferably R 2’ is alpha- branched C3-C6-alkyl, even more preferably R 2’ is CH(CH3)2.
  • R 2 is methyl and R 2’ is alpha-branched C 2 3-C6-alkyl; more preferably, R is methyl and R 2’ is alpha-branched C3-C6-alkyl, most preferably R 2 is methyl and R 2’ is CH(CH3)2.
  • 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, more preferably H, a linear or branched C1-C4-alkyl, or -OR 31 , with R 31 being a C 1 -C 4 -hydrocarbyl.
  • each R 3 and R 4 are Sensitivity: Internal each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially hydrogen, methyl, or tert-butyl, whereby at least one R 3 per phenyl group and at least one R 4 is not H.
  • 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 three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups is H.
  • R 3 and/or R 4 groups are H then the remaining R 3 and/or R 4 group, respectively, is preferably in the para position. If one R 3 and/or R 4 group is H then the remaining R 3 and/or R 4 groups are preferably in the meta positions.
  • one or two R 3 per phenyl group are not H, more preferably on both phenyl groups the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl for both phenyl groups.
  • R 4 on the phenyl group are not H, more preferably two R 4 are not H, and most preferably these two R 4 are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl.
  • R 51 ’ is C1-C10-hydrocarbyl, for example, linear or branched C1-C10- hydrocarbyl.
  • R 51 ’ is linear or branched C1-C6-alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C7-C10-arylalkyl, C7-C10-alkylaryl, or 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, C7-C10-arylalkyl, C
  • R 6 ’ is C(R 61 )3, with R 61’ being linear C1-C3-alkyl; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • each X is a sigma ligand.
  • each X is independently, same or different from each other, H, halogen, C1-C6-alkoxy, or R ⁇ , with R ⁇ being C1-C6-alkyl, phenyl, or benzyl.
  • each X is independently, same or different from each other, Cl, benzyl, or methyl. It is preferred that both X groups are the same.
  • R 1 are each independently, same or different from each other, C 1- C 10 - hydrocarbyl, more preferably C 1 -C 10- alkyl, C 4 -C 10- cycloalkyl, C 5 -C 10- cycloalkyl-alkyl, C 7 - C 10 -arylalkyl, C 6- C 10 -aryl, or C 7 -C 10- alkylaryl, such as methyl, ethyl, propyl, isopropyl, tert- butyl, isobutyl, C 3 -C 8 -cycloalkyl, cyclohexylmethyl, phenyl, or benzyl, even more preferably both are C 1- C 6 -alkyl, C 5 -C 6- cycloalkyl, or C 6 -aryl.
  • each R 1 is independently, same or different from each other, C 1 -C 10 -alkyl, optionally substituted with C 1 -C 10 -alkoxy. It is preferred that both R 1 groups are the same. Most preferably, both R 1 are methyl.
  • R 2 and R 2 ’ are each independently, same of different from each other, alpha- branched C 3 -C 10 -hydrocarbyl or CH 2 -R 21 , with R 21 being H, linear or branched C 1 -C 6 -alkyl, a C 3- C 8 -cycloalkyl, or a C 6- C 9 -aryl, provided that at least one of R 2 and R 2 ’ is alpha- branched C 3 -C 9 -hydrocarbyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C 3 -C 6 -alkyl or CH 2 -R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl,
  • R 2 and R 2 ’ are different and one, preferably R 2 ’, is alpha-branched C3-C10- hydrocarbyl; more preferably alpha-branched C3-C6-alkyl, even more preferably CH(CH3)2, and the other, preferably R 2 , is a CH2-R 21 , with R 21 being H or C1-C6-alkyl, more preferably H or linear C1-C3-alkyl, most preferably methyl.
  • R 2 is CH2-R 21 , with R 21 being H, linear C1-C6-alkyl, such as methyl, ethyl, n- propyl, n-butyl, more preferably R 21 being H or linear C -C -alky 2 1 3 l, even more preferably, R is methyl or ethyl, most preferably methyl.
  • R 2’ is alpha-branched C3-C10-hydrocarbyl; more preferably R 2’ is alpha- branched C3-C6-alkyl, even more preferably R 2’ is CH(CH3)2.
  • R 2 is methyl and R 2’ is alpha-branched C 2 3-C6-alkyl; more preferably, R is methyl and R 2’ is alpha-branched C3-C6-alkyl, most preferably R 2 is methyl and R 2’ is CH(CH3)2.
  • 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, more preferably H, linear or branched C1-C4-alkyl, or -OR 31 , with R 31 being a C1-C4-hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially hydrogen, methyl, or tert-butyl.
  • the R 3 and R 4 substituents of the respective phenyl ring are in the 3-, 4-, and/or 5-position of the ring, whereby the 1-position is attached to the indenyl ring.
  • 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 three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups is H.
  • R 3 and/or R 4 groups are H then the remaining R 3 and/or R 4 group, respectively, is preferably in the para position. If one R 3 and/or R 4 group is H then the remaining R 3 and/or R 4 groups are preferably in the meta positions.
  • one or two R 3 per phenyl group are not H, more preferably on both phenyl groups the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl for both phenyl groups.
  • 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.
  • the invention provides a metallocene catalyst complex of formula (I-e) wherein Mt is Zr or Hf; X is a sigma ligand; Sensitivity: Internal 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 an alpha-branched C 3 -C 10 -hydrocarbyl; R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, or -OR 31 , with R 31 being C 1 -C 10 - hydrocarbyl, whereby at least one R 3 per
  • 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 ⁇ , with R ⁇ being C 1- C 6 -alkyl, phenyl, or benzyl.
  • 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 alpha-branched C3-C10-hydrocarbyl; more preferably alpha-branched C3- C6-alkyl, even more preferably CH(CH3)2.
  • 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, more preferably H, linear or branched C1-C4-alkyl, or -OR 31 , with R 31 being a C1-C4-hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert- butyl, or methoxy, especially hydrogen, methyl, or tert-butyl, whereby at least one R 3 per phenyl group 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 three phenyl rings have different substitution patterns. It is therefore preferred if one or two R 3 and/or R 4 groups is H. If two R 3 and/or R 4 groups are H then the remaining R 3 and/or R 4 group, respectively, is preferably in the para position. 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 per phenyl group are not H, more preferably on both phenyl groups the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl for both phenyl groups.
  • 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.
  • the invention provides a metallocene catalyst complex of formula (I-f) 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; Sensitivity: Internal R 2 and R 2 ’ are each independently a C 1 -C 10 -hydrocarbyl, provided that at least one of R2 and R 2 ’ is an alpha-branched C 3 -C 10 -hydrocarbyl; R 3 and R 4 are each independently, same or different from each other, linear or branched C 1 -C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, or
  • 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 ⁇ , with R ⁇ being 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 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 and R 2 ’ are each independently, same of different from each other, alpha- branched C3-C10-hydrocarbyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or a C6-C9-aryl, provided that at least one of R 2 and R 2 ’ is alpha- branched C3-C9-hydrocarbyl; more preferably R 2 and R 2’ are each independently, same or different from each other, alpha-branched C3-C6-alkyl or CH2-R 21 , with R 21 being H, linear or branched C1-C6-alkyl, a C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,
  • R 2 and R 2 ’ are different and one, preferably R 2 ’, is alpha-branched C3-C10- hydrocarbyl; more preferably alpha-branched C3-C6-alkyl, even more preferably CH(CH3)2, and the other, preferably R 2 , is a CH2-R 21 , with R 21 being H or C1-C6-alkyl, more preferably H or linear C1-3-alkyl, most preferably methyl.
  • R 2 is CH 2 -R 21 , with R 21 being H, linear C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, n-butyl, more preferably R 21 being H or linear C 1 -C 3 -alkyl group, even more preferably, R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is alpha-branched C 3 -C 10 -hydrocarbyl; more preferably R 2’ is alpha- branched C 3 -C 6 -alkyl, even more preferably R 2’ is CH(CH 3 ) 2 .
  • R 2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl; more preferably, R2 is methyl and R 2’ is alpha-branched C 3 -C 6 -alkyl, most preferably R 2 is methyl and R 2’ is CH(CH 3 ) 2 .
  • R 3 and R 4 are each independently, same or different from each other, linear or branched C 1 -C 6 -alkyl, or C 6 -C 20 -aryl, more preferably a linear or branched C 1 -C 4- alkyl, or - OR 31 , with R 31 being a C 1 -C 4 -hydrocarbyl.
  • each R 3 and R 4 are each independently, same or different from each other, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially hydrogen, methyl, or tert-butyl.
  • each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns.
  • the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl for both phenyl groups.
  • the two R 4 are the same like 3 ⁇ ,5 ⁇ -di-methyl or 3 ⁇ ,5 ⁇ - di-tert-butyl.
  • the novel ligands of the present invention bear the combination of the distinctive features of the metallocene ligand framework: 1: an indacenyl ligand with 4,8-diaryl substitution and an alpha-branched alkyl substituent on the 2-position of the ligand; and 2: a 5-alkoxy indene, preferably methoxy indene, with 6-tertiary hydrocarbyl, preferably tertiary alkyl, substituent, and an alpha-branched alkyl substituent on the 2-position of the ligand.
  • 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 an alpha-branched C3-C10-hydrocarbyl;
  • R 4 are each independently, same or different from each other, H, linear or branched C 1 - C 6 -alkyl, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, or -OR 31 , with R 31 being C 1 -C 10 - hydrocarbyl, whereby at least one R 4 is not H;
  • R 51 ’ is C 1 -C 10 -hydrocarbyl;
  • R 6 ’ is C(R 61 ) 3 , with R 61 being linear or branched C 1 -C 6 -alkyl.
  • R 2 ’ is alpha-branched C 3 -C 10 -hydrocarbyl; more preferably alpha-branched C 3 -C 6 -alkyl, even more preferably CH(CH 3 ) 2 .
  • 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 , more preferably H, a linear or branched C 1 -C 4- alkyl, or -OR 31 , with R 31 being a C 1 -C 4 -hydrocarbyl.
  • each R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl. It is preferred that one or two R 4 groups is H. If two R 4 groups are H then the remaining R 4 group is preferably in the para position. If one R 4 group is H then the remaining R 4 groups are preferably in the meta positions. Preferably two R 4 are not H, and most preferably these two R 4 are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl.
  • R 51 ’ is C 1 -C 10 -hydrocarbyl, for example, linear or branched C 1 -C 10 - hydrocarbyl.
  • R 51 ’ is linear or branched C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or tert-butyl, C 7 -C 10 -arylalkyl, C 7 -C 10 -alkylaryl, or C 6 -C 10 -aryl, more preferably 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.
  • 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.
  • the present invention accordingly further relates to indenes of formula (III) 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 an alpha-branched C 3 -C 10 -hydrocarbyl; R 3 are each independently, same or different from each other, H, linear or branched C1- C6-alkyl, C7-C20-arylalkyl, C7-C20-alkylaryl, C6-C20-aryl, or -OR 31 , with R 31 being C1-C10- hydrocarbyl, whereby at least one R 3 per phenyl group is not H.
  • R 2 is alpha-branched C3-C10-hydrocarbyl; more preferably alpha-branched C3-C6-alkyl, even more preferably CH(CH3)2.
  • R 3 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, or C 6 -C 20 -aryl, more preferably H, a linear or branched C 1 -C 4- alkyl, or -OR 31 , with R 31 being a C 1 -C 4 -hydrocarbyl.
  • R 3 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl. Furthermore, it is possible that each of the phenyl rings have the same substitution pattern or that the two phenyl rings have different substitution patterns. It is preferred that one or two R 3 per phenyl group is H. If two R 3 groups per phenyl groups are H then the remaining R 3 group is preferably in the para position. If one R 3 per phenyl ring is H then the remaining R 3 groups are preferably in the meta positions.
  • two R 3 per phenyl group are not H, more preferably on both phenyl groups the R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl for both phenyl groups.
  • the ligand of the metallocenes include two different indenes, one alkoxyindene and one indacene with 4,8-diaryl substitution.
  • the ligands required to form the complexes and hence catalysts of the invention can be synthesized by any process and the skilled organic chemist would be able to devise various synthetic protocols for the manufacture of the necessary ligand materials. For example, WO 2007/116034 discloses the necessary chemistry.
  • Synthetic protocols can also generally be found in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052, WO2011/076780, WO2015/158790, WO2018/122134, WO2019/179959, and WO2012/058740.
  • the examples section also provides the skilled person with sufficient direction. It is appreciated that the metallocenes that are obtained can exist as both anti- or syn- isomers. It is however preferred that the metallocene of the invention is the anti-isomer.
  • 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 a group 13 element; and (iii) optionally a support.
  • the metallocene complex as described above is used in combination with a suitable cocatalyst combination as described below.
  • the metallocene catalysts can be used in supported or unsupported form.
  • the particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica- alumina.
  • 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. using a process analogous to those described in WO94/14856 (Mobil), WO95/12622 (Borealis) and WO2006/097497.
  • the particle size is not critical but is preferably in the range 5 to 200 ⁇ m, more preferably 20 to 80 ⁇ m.
  • the use of these supports is routine in the art. Especially preferred procedures for producing such supported catalysts are those described in EP1828266, WO 2020/239598, and WO 2020/239603. Alternatively, no support is used at all.
  • Such a catalyst can be prepared in solution, for example in an aromatic solvent like toluene, by contacting the metallocene (as a solid or as a solution) with the cocatalyst, for example methylaluminoxane or a borane or a borate salt previously dissolved in an aromatic solvent, or can be prepared by sequentially adding the dissolved catalyst components to the polymerization medium.
  • no external carrier is used but the catalyst is still presented in solid particulate form.
  • no external support material such as inert organic or inorganic carrier, for example silica as described above is employed, but the solid catalyst is prepared using an emulsion-solidification method.
  • Such catalysts can be prepared as described for example in WO 2003/051934, WO 2014/060540, and WO 2019/179959.
  • the catalyst system of the invention is preferably used in supported form.
  • the particulate support material used is an inorganic porous support such as a silica, alumina or a mixed oxide such as silica-alumina, in particular silica. The use of a silica support is preferred.
  • the complex may be loaded into the pores of the particulate support, e.g. using a process analogous to those described in W094/14856, W095/12622, W02006/097497, and EP18282666.
  • Sensitivity Internal
  • the average particle size of the support such as silica support can be typically from 10 to 100 ⁇ m. However, it has turned out that special advantages can be obtained, if the support has an average particle size from 15 to 80 ⁇ m, preferably from 18 to 50 ⁇ m.
  • the average pore size of the inorganic porous support such as silica support can be in the range from 10 to 100 nm and the pore volume from 1 to 3 mL/g.
  • the pore diameter of the inorganic porous support such as silica support can be in the range from 20 to 40 nm.
  • the surface area of the inorganic porous support such as silica support can be typically in the range from 100 to 400 m 2 /g.
  • suitable support materials are, for instance, ES757 produced and marketed by PQ Corporation, Sylopol 948 produced and marketed by Grace or SUNSPERA DM-L- 303 silica produced by AGC Si-Tech Co.
  • Supports can be optionally calcined prior to the use in catalyst preparation in order to reach optimal silanol group content. The use of these supports is routine in the art.
  • the catalyst can contain from 5 to 500 ⁇ mol, such as 10 to 100 ⁇ mol of transition metal of the metallocene per gram of support such as silica, and 3 to 15 mmol of Al per gram of support such as silica.
  • a metallocene 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, optionally adding a second portion of the aluminoxane cocatalyst in the hydrocarbon solvent and optionally the boron containing cocatalyst, wherein the amount of the first portion of the aluminoxane cocatalyst added in step
  • 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, Sensitivity: Internal 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
  • Aluminoxane cocatalyst can be one of formula (A): where n is usually from 6 to 20 and R has the meaning below.
  • Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR 3 , AlR 2 Y and Al 2 R 3 Y 3 where R can be, for example, C 1 - Sensitivity: Internal C 10 -alkyl, preferably C 1 -C 5 -alkyl, or C 3 -C 10 -cycloalkyl, C 7 -C 12 -arylalkyl or -alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C 1 -C 10 -alkoxy, preferably methoxy or ethoxy.
  • the resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (A).
  • the preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content. Boron containing cocatalyst According to the present invention, the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst.
  • aluminium alkyl compound such as TIBA.
  • TIBA aluminium alkyl compound
  • any suitable aluminium alkyl e.g. Al(C1-C6 alkyl)3 can be used.
  • Preferred aluminium alkyl compounds are triethylaluminium, tri-isobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium.
  • the metallocene complex is in its alkylated version, that is for example a dimethyl or dibenzyl metallocene complex can be used.
  • Boron containing cocatalysts of interest include those of formula (B) BY3 (B) wherein Y is the same or different and is a hydrogen atom, C1-10-haloalkyl, or C6-C20- haloaryl, or fluorine, chlorine, bromine or iodine.
  • Y are fluorine, trifluoromethyl, unsaturated groups such as haloaryl like p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5-di(trifluoromethyl)phenyl.
  • Y are fluorine, trifluoromethyl, aromatic fluorinated groups such as p- fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5- di(trifluoromethyl)phenyl.
  • Preferred boron containing cocatalysts of formula (B) are trifluoroborane, tris(4- fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, and/or tris(3,4,5-trifluorophenyl)borane.
  • Sensitivity Internal Particular preference is given to tris(pentafluorophenyl)borane.
  • borates are used, i.e. compounds containing a borate anion.
  • Z 4 B –- W + (C) wherein Z is a substituted phenyl derivative, said substituent being halo-C 1- C 6 -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 Z 4 B – is preferably a weakly-coordinating anion such as tetrakis(pentafluorophenyl)borate.
  • Suitable cationic counterions W + are triarylcarbenium such as triphenylcarbenium or protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n- butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N- dimethylanilinium or p-nitro-N,N-dimethylanilinium.
  • triarylcarbenium such as triphenylcarbenium or protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, trieth
  • Preferred ionic compounds which can be used according to the present invention include: tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenyl
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate Especially preferred are triphenylcarbeniumtetrakis(pentafluorophenyl) borate, Sensitivity: Internal 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; Sensitivity: Internal (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
  • Polymerization in the method of the invention may be effected in one or more, e.g.1, 2, or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization, or combinations thereof, like a combination of a slurry and at least one gas phase reactor.
  • the process may also involve an in-line pre-polymerization step.
  • This pre-polymerization step is a conventional step used routinely in polyolefin production plants and can be carried out in a continuously stirred tank reactor (CSTR) or a loop reactor, from which the prepolymerized catalyst is then transferred together with the liquid monomer(s) into the main loop reactor.
  • CSTR continuously stirred tank reactor
  • loop reactor from which the prepolymerized catalyst is then transferred together with the liquid monomer(s) into the main loop reactor.
  • Prepolymerization can be carried out at temperatures between -10 °C and 50 °C, preferably between 10 °C and 40 °C.
  • the reaction temperature will generally be in the range 60 to 110 °C (e.g. 60 to 90 °C)
  • the reactor pressure will generally be in the range 5 to 80 bar-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.
  • Sensitivity Internal 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 M w /M n .
  • 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 propylene polymers with high molecular weight. These features can be achieved at commercially interesting polymerization temperatures, e.g.60 °C or more, such as from 60 °C to 90 °C.
  • the polydispersity index (Mw/Mn) of the polymers depends 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 high melting points.
  • the propylene homopolymer formed by the process of the invention has a melting point of more than 155 °C, preferably more than 157 °C. Propylene homopolymers having melting points up to 158 °C, or even up to 160 °C, are possible.
  • Propylene copolymers with ethylene or with C4-C10 alpha olefin comonomers made by the metallocenes of the invention can be made with high productivity and low solubles.
  • the polymers made by the catalysts of the description are useful in all kinds of end articles such as pipes, films (cast, blown or BOPP films, such as for example BOPP for capacitor film), fibers, moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on.
  • end articles such as pipes, films (cast, blown or BOPP films, such as for example BOPP for capacitor film), fibers, moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on.
  • the digested sample was allowed to cool down for at least 4 h and then was transferred into a glass volumetric glass flask of 100 mL volume. 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 % HNO3) 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 % HNO3 distilled water. However, not every calibration point was used for each wavelength. 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. Immediately before analysis the calibration was verified and adjusted (instrument reslope function) using the blank and a 10 mg/L Al, B, Hf, Mg, Ti and Zr standard which had 4 mg/L Y and Rh.
  • a quality control sample (QC: 1 mg/L Al, Au, Be, Hg & Se; 2 mg/L Hf & Zr, 2.5 mg/L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn & V; 4 mg/L Rh & Y; 5 mg/L Ca, K, Mg, Mn, Na & Ti; 10 mg/L Cu, Pb and Zn; 25 mg/L Fe and 37.5 mg/L Ca in a solution of 5 % HNO3 in distilled water) was run to confirm the reslope for Al, B, Hf, Mg, Ti and Zr. 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.
  • Sensitivity Internal The content for B was monitored using B 249 nm line.
  • GPC Molecular weight averages, molecular weight distribution, and polydispersity index (Mn, Mw, Mw/Mn)
  • 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) was determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the molecular weight of the polymer. The MFR was determined at 230°C and may be determined at different loadings such as 2.16 kg (MFR2) or 21.6 kg (MFR 21 ).
  • Sensitivity Internal NMR Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity and content of regio-defects of the polypropylene homopolymers.
  • the tacticity distribution was quantified through integration of the methyl region between 23.6 and 19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci.26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromolecules 30 (1997) 6251).
  • the pentad isotacticity was determined through direct integration of the methyl region and reported as either the mole fraction or percentage of isotactic pentad mmmm with respect to all steric pentads i.e.
  • [mmmm] mmmm / sum of all steric pentads.
  • Characteristic signals corresponding to regio irregular propene insertion were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).
  • 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.
  • the crystalline (CF) and soluble fractions (SF) of the heterophasic propylene resins as well as the comonomer content and intrinsic viscosities of the respective fractions were analysed by the Crystex method.
  • the crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160°C, crystallization at 40°C and re- dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160°C.
  • Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an infrared detector (IR4) and an online 2-capillary viscometer is used for determination of the intrinsic viscosity (iV).
  • 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 Sensitivity: Internal 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).
  • SF Soluble fraction
  • CF Crystalline Fraction
  • 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.
  • CM1 CM1 was prepared as described in WO2019179959, MC-2.
  • Synthesis of CM2 CM2 was prepared as described in WO2005058916, metallocene example 1.
  • Sensitivity Internal Synthesis of IM1 Isopropylmalonic acid A solution of 125 g of potassium hydroxide in 1000 cm 3 of water was added to a solution of 110.0 g (544 mmol) of diethyl isopropylmalonate in 500 ml of methanol.
  • the crude product was extracted with 3 ⁇ 600 ml of dichloromethane.
  • the combined organic phase was washed by aqueous K2CO3, dried over K2CO3, filtered through a short pad of silica gel 60 (40-63 ⁇ m) and then evaporated to dryness.
  • the residue was purified by vacuum distillation to give 193.8 g (93.0 %, ca.95% purity) of 6- tert-butyl-5-methoxy-2-isopropylindan-1-one as a yellowish oil (bp 150-190 o C /4 mm Hg).
  • 6-tert-Butyl-2-isopropyl-5-methoxy-4-(3,5-dimethylphenyl)-indan-1-one A mixture of 124.84 g (368.0 mmol) of 4-bromo-6-tert-butyl-2-isopropyl-5-methoxyindan- 1-one, 69.7 g (464.7 mmol, 1.26 equiv.) of 3,5-Me2C6H3B(OH)2, 1.9 g (3.72 mmol, 1 mol. %) of Pd(P t Bu3)2, 118.3 g of Na2CO3, 600 ml of 2-methyltetrahydrofurane and 540 ml of water was refluxed for 6 h.
  • reaction mixture was quickly cooled to room temperature using an ice-water bath.
  • the formed solution was washed with 10% Na 2 CO 3 , the organic layer was separated, the aqueous layer was extracted with 250 ml of dichloromethane.
  • the combined organic extract was dried over K2CO3 and then evaporated to dryness.
  • the resulting filtrate included only anti-dimethylsilanediyl[2-isopropyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s- indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride contaminated with some polymeric by-products.
  • This extract was evaporated to ca.30 ml, and 30 ml of hexane was added.
  • Catalyst synthesis used chemicals MAO Axion CA133030 wt% solution in toluene was purchased from Chemtura/Lanxess and used as received and stored at –20 °C for not longer than 6 months. All the chemicals and chemical reactions were handled under an inert gas atmosphere using Schlenk and glovebox techniques, with oven-dried glassware, syringes, needles or cannulas. All catalysts have been prepared using silica Sunspera AGC DM-L-303, calcined at 600 °C. 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. Only in case the metallocene is not enough soluble in toluene (metallocene MC-CE2), a second aliquot of MAO is added to the metallocene/toluene slurry in order to promote the full dissolution of the metallocene.
  • Preparation of SiO2/MAO activated carrier A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen. 10 kg of SiO2 carrier was first added from a feeding drum into the reactor, followed by careful pressurizing and depressurizing with nitrogen.
  • toluene (43.5 kg) was added.
  • the SiO2/toluene slurry was stirred for 25 min at 22 °C.
  • 18 kg of 30 wt% MAO in toluene (Axion CA 1330) was added slowly (140 min) through a 12 mm line on the top of the reactor keeping the temperature around 22 °C.
  • MAO addition the reactor temperature was quickly increased to 90 °C and the mixture was stirred at this temperature for 120 min.
  • the hot toluene was filtered out and the solid cake was washed twice with hot toluene while stirring (43.5 kg, 90 °C, 30 min, 40 rpm). Each time the hot toluene was filtered out.
  • Table 2 Catalysts tested and their metallocene content Catalyst MC Al MC in catalyst * wt% wt% CE1 MC-CE1 13.2 1.56 CE2 MC-CE2 13.2 1.28 IE1 MC-IE1 13.8 1.43 IE2 MC-IE2 13.1 1.40 * metallocene content in the dry catalyst calculated from mass balance Polymerization examples Monomers and gases Hydrogen (quality 6.0) was supplied by Air Liquide and used as received.
  • Propylene, quality 2.3, and ethylene have been purified by passing through columns filled with PolyMax301 T-4427B (60°C; Cu/CuO), Molecular sieve MS13X-APG 1/16 and Selexsorb COS 1/8.
  • Propylene polymerization procedure (bulk, 5-L reactor) A stainless-steel reactor equipped with a ribbon stirrer, with a total volume of 5.3 dm3 was filled with 800 g propylene.
  • Triethylaluminium 0.3 ml of 0.62 molar solution in n-heptane
  • H2 see Tables
  • the reactor temperature was stabilized at 25 °C (HB-Therm) and the solution was stirred and 250 rpm for at least 20 min. Then the catalyst was injected as described in the following. The desired amount of solid catalyst was loaded into a 5 ml stainless steel vial and then flushed into the reactor with 150 g propane. Stirring speed was kept at 250 rpm and pre- polymerization was run for 10 minutes at 25 °C. Then the polymerization temperature was increased to the set value. The second aliquot of H2 was added at 30 °C in between 1 and 6 min. The reactor temperature was kept constant throughout the polymerization. The polymerization time was measured starting when the temperature was 2 °C below the set polymerization temperature.
  • the Sensitivity Internal reaction was stopped by cooling the reactor and simultaneously flashing the volatile components. After purging the reactor 3 times with N2 and one vacuum/N2 cycle, the reactor was opened, the polymer powder was taken out and dried overnight in a fume hood. 50 g of the polymer was additivated with 0.5 wt% Irganox B225 (dissolved in acetone) and then dried overnight in a fume hood and additionally one hour in a vacuum drying oven at 60 °C.
  • Propylene homopolymerization procedure (bulk, 20 L BSR) 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 3.95 kg propylene. Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) was added using a stream of 250 g propylene, then 0.5 NL of H2 was added via mass flow controller in one minute. The reactor temperature was stabilized at 25 °C (HB-Therm) and the solution was stirred and 250 rpm for at least 20 min. Then 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. Stirring speed was kept at 250 rpm and pre- polymerization was run for 10 minutes at 25 °C or 30 °C. The second aliquot of H2 was added over 1 min at the end of the prepolymerization step at 30 °C. Then the polymerization temperature was increased to 70 °C. The reactor temperature was kept constant throughout the polymerization. The polymerization time was measured starting when the temperature was 2 °C below the set polymerization temperature.
  • the reaction was stopped by injecting 5 ml ethanol, cooling the reactor and simultaneously flashing the volatile components. After purging the reactor 3 times with N2 and one vacuum/N2 cycle, the reactor was opened, the polymer powder is taken out and dried overnight in a fume hood.100 g of the polymer was additivated with 0.5 wt% Irganox B225 (dissolved in acetone) and then dried overnight in a fume hood and additionally one hour in a vacuum drying oven at 60 °C.
  • 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.
  • Step 2 After the bulk homopolymerization step was completed, 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. Then the reactor pressure was increased to 20 bar-g by feeding a defined C3/C2 gas mixture (see tables).
  • 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 0.40The temperature was held constant by thermostat and the pressure was kept constant by feeding via mass flow controller a C3/C2 gas mixture of composition corresponding to the target polymer composition and by thermostat, until the set time for this step had expired. Sensitivity: Internal Then the reactor was cooled down (to about 30 °C) and the volatile components flashed out.

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Abstract

L'invention concerne un complexe métallocène de formule (I) dans laquelle Mt représente Zr ou Hf ; X est un ligand sigma ; R1 sont chacun indépendamment, identiques ou différents les uns des autres, hydrocarbyle en C1-C20, contenant éventuellement jusqu'à deux hétéroatomes du groupe 14-16 du tableau périodique, ou forment conjointement avec l'atome de Si auquel ils sont liés un cycle en C4-C8 ; R2 et R2' sont chacun indépendamment hydrocarbyle en C1-C10, à condition qu'au moins l'un de R2 et R2' soit hydrocarbyle en C3-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, identiques ou différents les uns des autres, H, alkyle en C1-C6, aryalkyle en C7-C20, alkylaryle en C7-C20, aryle en C6-C20, -OR31, SR31, ou N(R31)2 linéaire ou ramifié, R31 étant hydrocarbyle en C1-C10, au moins un R3 par groupe phényle et au moins un R4 n'étant pas H ; R5 et R6 sont chacun indépendamment, identiques ou différents l'un de l'autre, H ou hydrocarbyle en C1-C10, ou peuvent former conjointement avec les atomes de C auxquels ils sont liés un carbocycle en C5-C7 ; R51' est hydrocarbyle en C1-C10 ; et R6' est C(R61)3, R61 étant alkyle en C1-C6 linéaire ou ramifié.
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