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WO2025016570A1 - Catalyseurs pour polymérisation d'oléfines - Google Patents

Catalyseurs pour polymérisation d'oléfines Download PDF

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Publication number
WO2025016570A1
WO2025016570A1 PCT/EP2024/057080 EP2024057080W WO2025016570A1 WO 2025016570 A1 WO2025016570 A1 WO 2025016570A1 EP 2024057080 W EP2024057080 W EP 2024057080W WO 2025016570 A1 WO2025016570 A1 WO 2025016570A1
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Prior art keywords
hydrocarbyl
independently
same
different
group
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/21—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

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 or propylene copolymers, especially with ethylene, in particular heterophasic polypropylene, with high activity levels, high molecular weight, and hence low MFR, and with ideal melting points.
  • the catalysts are especially useful in the manufacture of polypropylene homopolymer of high melting point.
  • 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. 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.
  • WO2001048034 describes C1-symmetric bisindenyl complexes having 1-methyl and 1- isopropyl as 2-substituents. Although the produced hPP can have Tm as high as 160 °C, the catalyst activity is always very low.
  • WO2005058916 describes a series of C1-symmetric bisindenyl complexes combining one 2-iso-propyl-4-aryl-indenyl ligand and one 2-methyl-4-aryl-indacenyl ligand. While Tm of hPP is somewhat high varying from 152 to 160°C, catalyst activities are invariably low.
  • 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).
  • EP1421090 describes C 2 -symmetric rac-Me 2 Si(2-iPr-4-(2-R-Ph)-Ind) 2 ZrCl 2 . These complexes provide catalysts of very low activity although hPP T m is relatively high (157- 159°C).
  • US9745390B2, US9464145B2, US9249239B2, EP3022235B1, and EP3022238B1 all describe bridged, C 1 -symmetric bisindenyl complexes having two different 2-substituents, but none of the complexes contain a methoxy group.
  • EP3572441 is also describing C 1 -symmetric bisindenyl complexes having two different 2- substituents being one methyl and one isopropyl containing a Et 2 Si bridge.
  • T m of hPP is relatively low at 155 to 156 °C. While these prior art catalysts have their advantages, they lack in isoselectivity, generating hPP with a relatively low melting and crystallisation temperature due to the formation of insertion regiodefects in the PP chains.
  • the present inventors sought new metallocenes, which 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 Tm at least 157 °C.
  • the object of the disclosure is achieved by metallocene complexes of formula (I), polymerisation catalyst comprising said metallocene complex of formula (I), and process for polymerisation of polypropylene optionally with comonomers which are characterized by what is stated in the independent claims.
  • the preferred embodiments of the disclosure are disclosed in the dependent claims. It was surprisingly found that specific modification of either C2-symmetric or C1-symmetric, preferably C2-symmetric, metallocenes incorporating alpha-branched alkyl substituent on one of the 2-positions of the ligand, in combination with specific substitution of the 4, 5 and 6 ligand positions, provide the desired properties.
  • the identified metallocene complexes when included in a polymerization catalyst, preferably supported catalyst system, composed of the said specific class of metallocene complexes 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.
  • C1-20-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 C6-20- 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-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. C 1 -C 6 -alkyl groups.
  • 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 known to be used to indicate the catalyst activity although herein it designates the amount of polymer produced per unit weight of catalyst.
  • the term “molecular weight” is used herein to refer to weight average molecular weight Mw unless otherwise stated.
  • This invention relates to a series of new ligands, metallocene complexes, and hence catalysts that are ideal for the polymerization of propylene.
  • Metallocene catalyst complexes The complexes of the invention can be asymmetrical or symmetrical. 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 metallocene complexes of the invention are preferably chiral, racemic bridged bisindenyl C 1 -symmetric metallocenes in their anti-configuration.
  • the complexes of the invention are formally C 1 -symmetric, the complexes ideally retain a pseudo-C 2 - symmetry since they maintain C 2 -symmetry in close proximity of the metal center although not at the ligand periphery.
  • 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 numbering scheme of the indenyl ligands is the following:
  • the present metallocene catalyst complexes require the combination of two distinctive features of the ligand framework: 1: specific 5, 6 substitution of the indenyl ligands, and 2: one alpha-branched substituent on the 2-position of one of the indenyl ligands.
  • the present invention accordingly relates to metallocene complexes of formula (I) wherein Mt is Zr or Hf, preferably Zr;
  • 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 C1-C20-, preferably C1-C10-hydrocarbyl;
  • R 2 ’ is alpha-branched C 3 -C 10 -hydrocarbyl or SiH(R 21’ ) 2 , with R 21’ being each independently, same or different from each other, C 1 -C 10 -hydrocarbyl;
  • n are each independently an integer from 1 to 5;
  • R 3 and R 4 are each independently, same or different from each other, H, C 1 -C 10
  • 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 CH 2 -R 21 , with R 21 being H, linear C 1 -C 6 -alkyl, such as methyl, ethyl, n- propyl, i-propyl, n-butyl, preferably R 21 being H or linear C 1 -C 3 -alkyl; more preferably R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is CH(R 21’ ) 2 or SiH(R 21’ ) 2 , with R 21’ being each independently, same of different from each other, linear or branched C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, or C 6 -C 9 -aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21’ being linear or branched C 1 -C 6 -alkyl; more preferably, R 2’ is CH(CH 3 ) 2 or SiHMe 2 , even more preferably CH(CH 3 ) 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.
  • 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 have different substitution patterns. It is therefore preferred when n is 1, the only R 3 and/or R 4 group, respectively, is preferably in the para position.
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C6-C10-aryl, 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 H, methyl, or tert-butyl, whereby at least one R 3 and at least one R 4 is not H.
  • R 51 ’ is C1-C10-hydrocarbyl, for example, a linear or branched C1-C10- hydrocarbyl.
  • R 51 and R 51 ’ are each independently, same of 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.
  • 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 or –OR 61 , with R 61 being each independently, same of different from each other, 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 or OMe, most preferably tert-butyl.
  • each R 62 is independently H or methyl, preferably H, and m is 1 to 3, such as 1, 2 or 3, preferably 2.
  • 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 C1-C20-, preferably C1-C10-hydrocarbyl
  • R 2 ’ is alpha-branched C1-C10-hydrocarbyl or SiH(R 21’ )2, with R 21’ being each independently, same or different from each other, C1-C10-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 C1-6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, preferably R 21 being H or linear C1-C3-alkyl; more preferably R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is CH(R 21’ )2 or SiH(R 21’ )2, with R 21’ being each independently, same of different from each other, linear or branched C1-C6-alkyl, C3-C8-cycloalkyl, or C6-C9-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21’ being linear or branched C1-C6-alkyl; more preferably, R 2’ is CH(CH3)2 or SiHMe2, 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, C6-C20-aryl, 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 H, methyl, or tert-butyl, 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 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 on the phenyl group are not H, when two R 3 are not H preferably these two R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • R 4 on the phenyl group are not H, more preferably two R 4 are not H, and most preferably these two R 4 are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl.
  • R 51 ’ is C1-C10-hydrocarbyl, for example, a linear or branched C1-C10- hydrocarbyl.
  • R 51 and R 51 ’ are each independently, same of 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 or –OR 61 , with R 61 being each independently, same of different from each other, 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 or OMe, most preferably tert-butyl.
  • each R 62 is independently H or methyl, preferably H, and m is 1 to 3, such as 1, 2 or 3, preferably 2.
  • 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 3 and R 4 are each independently H, C 1 -C 10 -hydrocarbyl, -OR 31 , -SR 31 , or –N(R 31 ) 2 , with R 31 being C 1 -C 10 -hydrocarbyl, whereby at least one R 3 and at least one R 4
  • 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, 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 3 and R 4 are each independently, same or different from each other, H, linear or branched C1-C6-alkyl, C6-C20-aryl, or -OR 31 , with R 31 being C1-C4-hydrocarbyl; 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 H, methyl, or tert-butyl, 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.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. 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 on the phenyl group are not H, more preferably R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • R 4 on the phenyl group are not H, more preferably two R 4 are not H, and most preferably these two R 4 are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl .
  • R 51 ’ is C 1 -C 10 -hydrocarbyl, for example, a linear or branched C 1 -C 10 - hydrocarbyl.
  • R 51 and R 51 ’ are each independently, same of 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- but
  • 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 or –OR 61 , with R 61 being each independently, same of different from each other, 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 or OMe, most preferably tert-butyl.
  • each R 62 is independently H or methyl, preferably H, and m is 1 to 3, such as 1, 2 or 3, preferably 2.
  • 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 C 1 -C 20 -, preferably C 1 -C 10 -hydrocarbyl
  • R 2 ’ is alpha-branched C 1 -C 10 -hydrocarbyl or SiH(R 21’ ) 2 , with R 21’ being each independently, same or different from each other,
  • 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 CH2-R 21 , with R 21 being H, linear C1-6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, preferably R 21 being H or linear C1-C3-alkyl; more preferably R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is CH(R 21’ ) 2 or SiH(R 21’ ) 2 , wherein R 21’ are each independently, same of different from each other, linear or branched C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, or C 6 -C 9 -aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21’ being linear or branched C 1 -C 6 -alkyl; more preferably, R 2’ is CH(CH 3 ) 2 or SiHMe 2 , even more preferably 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, C 6 -C 20 -aryl, or -OR 31 , with R 31 being C 1 -C 4 -hydrocarbyl; more preferably linear or branched C 1 -C 4- alkyl or -OR 31 , with R 31 being C 1 -C 4 -hydrocarbyl; even more preferably, each R 3 and R 4 are each independently, same or different from each other, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially 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.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 three phenyl rings have different substitution patterns.
  • one or two R 3 on the phenyl group are not H, more preferably R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • R 4 are the same like 3 ⁇ ,5 ⁇ -di-methyl or 3 ⁇ ,5 ⁇ -di- tert-butyl.
  • R 51 ’ is C1-C10-hydrocarbyl, for example, a linear or branched C1-C10- hydrocarbyl.
  • R 51 and R 51 ’ are each independently, same of 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, wherein R 61 are each independently, same of different from each other, 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) 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 C1-C20-, preferably C1-C10-hydrocarbyl; R 2 ’ is alpha-branched C1-C10-hydrocarbyl or SiH(R 21’ )2, with R 21’ being each independently, same or different from each other, C1-C10-hydrocarbyl; R 3 and R 4 are each independently, same or different from each other, C1-C10-hydrocarbyl group, -OR 31 , -SR 31 , or –N(R 31 )2, with R 31 being C1-C
  • 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, 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 C 1-6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, preferably R 21 being H or linear C 1 -C 3 -alkyl; more preferably R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is CH(R 21’ ) 2 or SiH(R 21’ ) 2 , with R 21’ being each independently, same of different from each other, linear or branched C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, or C 6 -C 9 -aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21’ being linear or branched C1-C6-alkyl; more preferably, R 2’ is CH(CH3)2 or SiHMe2, even more preferably CH(CH3)2.
  • R 3 and R 4 are each independently, same or different from each other, linear or branched C1-C6-alkyl, C6-C20-aryl, or -OR 31 , with R 31 being C1-C4-hydrocarbyl; more preferably linear or branched C1-C4-alkyl; even more preferably, each R 3 and R 4 are each independently, same or different from each other, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially methyl, or tert-butyl. Furthermore, it is possible that each of the phenyl rings have the same substitution pattern or that the three phenyl rings have different substitution patterns.
  • R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl.
  • R 4 of each phenyl ring 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 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 C4-C8-ring; R 2 is linear C1-C20- preferably C1-C10-hydrocarbyl; R 2 ’ is alpha-branched C1-C10-hydrocarbyl or SiH(R 21’ )2, with R 21’ being C1-C10-hydrocarbyl; R 3 and R 4 are each independently, same or different from each other, H, C1-C10- hydrocarbyl, -OR 31 , -SR 31 , or –N(R 31 ) 2 , with R 31 being C 1 -C 10 -hydrocarbyl, whereby at least one R 3 and at least one R 4 is not
  • R 1 are preferably 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 C1-6-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, preferably R 21 being H or linear C1-C3-alkyl; more preferably R 2 is methyl or ethyl, most preferably methyl.
  • R 2’ is CH(R 21’ ) 2 or SiH(R 21’ ) 2 , with R 21’ being each independently, same of different from each other, linear or branched C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, or C 6 -C 9 -aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21’ being linear or branched C 1 -C 6 -alkyl; more preferably, R 2’ is CH(CH 3 ) 2 or SiHMe 2 , even more preferably CH(CH 3 ) 2 .
  • R 3 and R 4 are each independently, same or different from each other, H, linear or branched C 1 -C 6 -alkyl, C 6 -C 20 -aryl, or -OR 31 , with R 31 being C 1 -C 4 -hydrocarbyl; more preferably H, linear or branched C 1 -C 4- alkyl, or -OR 31 , with R 31 being C 1 -C 4 -hydrocarbyl; even more preferably, each R 3 and R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or methoxy, especially H, methyl, or tert-butyl, whereby at least one R 3 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.
  • R 3 are the same, like 3 ⁇ ,5 ⁇ -di-methyl or 4 ⁇ - tert-butyl.
  • two R 4 of each phenyl ring are the same like 3 ⁇ ,5 ⁇ -di- methyl or 3 ⁇ ,5 ⁇ -di-tert-butyl.
  • 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 alpha-branched C1-C10-hydrocarbyl or SiH(R 21’ )2, with R 21’ being each independently, same or different from each other, C1-C10-hydrocarbyl;
  • R 4 are each independently H, C1-C10-hydrocarbyl, -OR 31 , -SR 31 or –N(R 31 )2 , with R 31 being C1-C10-hydrocarbyl, whereby at least one R 4 is not H;
  • R 51 ’ is C1-C10-hydrocarbyl;
  • R 6 ’ is C(R 61 )3, with R 61 being each independently, same of different from each other, linear or branched C1-C6-alkyl; or adjacent OR 5’ and R 6’ form
  • R 2’ is CH(R 21’ )2 or SiH(R 21’ )2, with R 21’ being each independently, same or different from each other, linear or branched C1-C6-alkyl, C3-C8 cycloalkyl, or C6-C10-aryl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, or phenyl, more preferably R 21’ being linear or branched C 1 -C 6 -alkyl; more preferably, R 2’ is CH(CH 3 ) 2 or SiHMe 2 , 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, C 7 -C 20 -arylalkyl, C 7 -C 20 -alkylaryl, C 6 -C 20 -aryl, or -OR 31 , being R 31 being C 1 -C 10 -hydrocarbyl , whereby at least one R 3 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 C 1 -C 6 -alkyl, or C 6 -C 20 -aryl, even more preferably H, linear or branched C 1 -C 4- alkyl, or -OR 31 , with R 31 being C 1 -C 4 -hydrocarbyl, yet more preferably, R 4 are each independently, same or different from each other, H, methyl, ethyl, isopropyl, tert-butyl, or meth
  • 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.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. It is therefore preferred if one or two R 4 groups is H.
  • R 4 groups are H then the remaining R 4 group, respectively, 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.
  • 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, a 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. Most preferably, R 51 ’ is methyl.
  • R 6 ’ is C(R 61 )3, with R 61 being each independently, same of different from each other, linear C1-C3-alkyl; more preferably methyl.
  • R 6 ’ is tert-butyl.
  • each R 62 is independently H or methyl, preferably H, with m being1 to 3, such as 1, 2 or 3, preferably 2.
  • 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.
  • Polymerization catalyst Viewed from a further aspect the invention provides a polymerization catalyst comprising (i) a metallocene complex of formula (I), e.g., selected from complexes of formula (I-a), (I- b), (I-c), (I-d) and (I-e); (ii) a cocatalyst comprising a group 13 element; and (iii) optionally a support.
  • a metallocene complex of formula (I) e.g., selected from complexes of formula (I-a), (I- b), (I-c), (I-d) and (I-e);
  • a cocatalyst comprising a group 13 element; and (iii) optionally a support.
  • Catalyst Manufacture 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.
  • 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 optionally the boron containing cocatalyst wherein the amount of the first portion of the aluminoxane cocatalyst added in step a)
  • 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/SiO 2 , M/SiO 2 ).
  • Cocatalyst To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art.
  • Cocatalysts comprising one or more compounds of Group 13 metals, like organoaluminium, organoboron, and/or borate compounds used to activate metallocene catalysts are suitable for use in this invention.
  • cocatalysts comprising aluminium, like organoaluminium compounds used to activate metallocene catalysts, are utilized in this invention.
  • a cocatalyst system comprising a boron containing cocatalyst and/or an aluminoxane cocatalyst is advantageously used in combination with the above defined metallocene catalyst complex.
  • a cocatalyst system comprising an aluminoxane cocatalyst is advantageously used in combination with the above defined metallocene catalyst complex.
  • no further cocatalysts comprising one or more compounds of Group 13 metals other than aluminium, like organoboron and/or borate compounds used to activate metallocene catalysts are 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.
  • Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR3, AlR2Y and Al2R3Y3 where R can be, for example, C1- C10-alkyl, preferably C1-C5-alkyl, or C3-C10-cycloalkyl, C7-C12-arylalkyl or -alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C10-alkoxy, preferably methoxy or ethoxy.
  • the resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (A).
  • the preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content. Boron containing cocatalyst According to the present invention, the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst. It will be appreciated by the person skilled in the art that where boron based cocatalysts are employed, it is normal to pre-alkylate the complex by reaction thereof with an aluminium alkyl compound, such as TIBA.
  • an aluminium alkyl compound such as TIBA.
  • aluminium alkyl e.g. Al(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.
  • Suitable cationic counterions W + are triarylcarbenium such as triphenylcarbenium or protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n- butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N- dimethylanilinium or p-nitro-N,N-dimethylanilinium.
  • triarylcarbenium such as triphenylcarbenium or protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N- methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, trieth
  • Preferred ionic compounds which can be used according to the present invention include: tributylammoniumtetra(pentafluorophenyl)borate, tributylammoniumtetra(trifluoromethylphenyl)borate, tributylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenyl
  • triphenylcarbeniumtetrakis(pentafluorophenyl) borate N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.
  • the catalysts according to the invention are suitable for the production of propylene homopolymers, propylene-ethylene copolymers or propylene C4-C10 alpha olefin copolymers.
  • the process comprises polymerizing propylene, propylene and ethylene or propylene and a C4-C10 alpha olefin.
  • the ethylene content in such a propylene-ethylene polymer may vary depending on the desired properties of the polymer. Typically, ethylene content will range from 0.1 to 10 mol%.
  • the catalysts of the present invention are used to manufacture propylene homopolymers or propylene copolymers with ethylene as comonomer and propylene copolymers with butene as a comonomer.
  • the present disclosure relates in a further aspect to a process for producing a propylene homopolymer, a propylene random copolymer or a heterophasic propylene copolymer using the specific catalyst system, as defined before.
  • Polymerization in the method of the invention may be effected in one or more, e.g.1, 2, or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization, or combinations thereof, like a combination of a slurry and at least one gas phase reactor.
  • the process may also involve an in-line pre-polymerization step.
  • This pre-polymerization step is a conventional step used routinely in polyolefin production plants and can be carried out in a 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.
  • Prepolymerisation 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.
  • the reactor pressure will generally be in the range 5 to 80 bar-g (e.g.20 to 60 bar-g), and 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.
  • 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 propylene polymers with high molecular weight.
  • 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 Propylene homopolymers Propylene homopolymers made by catalyst system comprising the metallocenes of the invention can be made with Mw (weight average molecular weight) values in the range of 40 to 2000 kg/mol, preferably in the range of 50 to 1500 kg/mol depending on the use and amount of hydrogen used as Mw regulating agent.
  • the catalysts of the invention enable the formation of polypropylene homopolymers with high melting points.
  • the propylene homopolymer formed by the process of the invention has a melting point of more than 155 °C, preferably more than 157 °C.
  • Propylene copolymers Propylene copolymers 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.
  • a sample was then subjected to a microwave-assisted digestion using MARS 6 laboratory microwave unit over 35 minutes at 150 °C.
  • 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 % 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. 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.
  • 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.
  • a third order polynomial fit was used to fit the calibration data.
  • 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 (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.
  • [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.
  • 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-CE3 Rac-dimethylsilanediyl-bis[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert- butyl-inden- l-yl]zirconium dichloride, MC-CE3, was prepared as described in WO2018091684 for MC- IE1.
  • Synthesis of MC-CE4 Rac-dimethylsilanediyl-bis[2-neopentyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert- butylinden-1–yl]zirconium dichloride, was prepared as described in WO2018091684 for MC-IE4.
  • the resulting mixture was refluxed for 5 h, then cooled to 5 °C, and 350 ml of ether and 1000 cm 3 of 2 M HCl were added. After mixing, the organic layer was separated, the aqueous layer was additionally extracted with 2 ⁇ 500 ml of ether. The combined organic phase was dried over Na2SO4 and then evaporated to dryness. The residue was purified by vacuum distillation to give 2- isopropylacrylic acid, bp 65 °C/4 mm Hg. Yield 57.0 g (95.5%) of a colorless liquid.
  • 6-tert-Butyl-5-methoxy-2-isopropylindan-1-one 114.1 g (1.0 mol) of 2-isopropylacrylic acid was added to Eaton's reagent obtained from 220 g of P4O10 and 1120 ml of MeSO3H at 50 °C. 131.2 g (0.8 mol) of 1-tert-butyl-2- methoxybenzene was added dropwise to this mixture with vigorous stirring for ca.1 h at 50-53 °C (water bath temperature). The resulting mixture was stirred for 1 h at this temperature, then cooled to room temperature, and poured on a mixture of 1.5 liter of cold water and 3 kg of ice.
  • 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-Me 2 C 6 H 3 B(OH) 2 , 1.9 g (3.72 mmol, 1 mol.
  • the resulting mixture was poured onto 2000 cm 3 of crushed ice.
  • the organic layer was separated, the aqueous layer was extracted with 300 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K 2 CO 3 , dried over K 2 CO 3 , and passed through a short pad of silica gel 60 (40-63 ⁇ m) which was additionally washed with 200 ml of dichloromethane.
  • the combined organic elute was evaporated to dryness to give 167.5 g (90.8%, purity ca. 90%) of 7-methyl-2,3,7,8- tetrahydro-6H-indeno[5,6-b][1,4]dioxin-6-one as a white solid mass which was used without further purification.
  • the obtained elute was evaporated to dryness to give a white solid mass which was dissolved in 800 ml of toluene, preheated to ca.60 °C, then TsOH (1.0 g) was added. This mixture was refluxed with Dean-Stark head for 10 min. Then, the reaction mixture was quickly cooled to room temperature using an ice-water bath. The formed solution was washed with 10% aqueous K 2 CO 3 , the organic layer was separated, the aqueous layer was extracted with 100 ml of dichloromethane. The combined organic extract was dried over K 2 CO 3 , passed through a pad of silica gel 6040-63 ⁇ m), and the so obtained elute was evaporated to dryness.
  • the organic layer was separated, the aqueous layer was extracted with 2x200 ml of dichloromethane.
  • the combined organic extract was washed with aqueous K2CO3, dried over K2CO3 and passed through a short pad of silica gel 60 (40-63 ⁇ m), which was additionally washed with 200 ml of dichloromethane.
  • the combined organic elute was evaporated to dryness.
  • the residue was washed with 300 ml of n-hexane and dried under vacuum to give 105.4 g (77.1%) of the title material as a white solid mass.
  • 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. 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. Only in case the metallocene is not enough soluble in toluene (metallocenes MC-CE1 and 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 SiO 2 /MAO activated carrier A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen.
  • Synthesis of SiO2/MAO/MC-CE1 catalyst Comparison catalyst 1
  • dry toluene (2.3 mL) and MAO (0.2 mL) were added to 20.8 mg of metallocene rac-dimethylsilandiyl[2-methyl-4-(4’-tert-butylphenyl)indenyl] [2-iso- propyl-4-(4’-tert-butylphenyl)indenyl]zirconium dichloride.
  • the mixture was stirred for 30 minutes at room temperature.
  • 2.0 g of SiO2/MAO (prepared with PQ silica ES70X, synthesis SMLP013) was placed in a septum bottle.
  • Synthesis of SiO2/MAO/MC-CE2 catalyst Comparison catalyst 2
  • dry toluene (2.5 mL) and MAO (0.1 mL) were added to 26.4 mg of metallocene rac-dimethylsilanediyl[2-methyl-4-(4’-tert-butylphenyl)-1,5,6,7- tetrahydro-s-indacen-1-yl])(2-isopropyl-4-(4’-tert-butyl-phenyl)indenyl) zirconium dichloride.
  • the mixture was stirred for 30 minutes at room temperature.
  • 2.0 g of SiO2/MAO batch V397 was placed in a septum bottle.
  • Synthesis of SiO2/MAO/MC-CE4 catalyst Comparison catalyst 4
  • dry toluene 2.5 mL was added to 29.9 mg of metallocene rac-dimethylsilanediylbis(2-neopentyl-4-(3’,5’-dimethylphenyl)-5-methoxy-6-tert- butylinden-1-yl) zirconium dichloride.
  • the solution was stirred for 30 minutes at room temperature.
  • 2.0 g of SiO2/MAO was placed in a septum bottle.
  • the solution of metallocene in toluene was added dropwise by means of a syringe to the SiO2/MAO carrier over the course of 5 minutes with gentle mixing.
  • Table 1 Catalysts tested and their metallocene content MC in Catalyst MC Al catalyst * type wt% wt% CE1 MC-CE1 13.6 1.00 CE2 MC-CE2 13.2 1.28 CE3 MC-CE3 13.2 1.33 CE4 MC-CE4 13.1 1.48 IE1 MC-IE1 13.8 1.33 IE2 MC-IE2 13.8 1.48 IE3 MC-IE3 12.4 1.23 * metallocene content in the dry catalyst calculated from mass balance Polymerization examples Reference examples 1-12 and 22-25 and Inventive Examples 13-21 and 26-30: Preparation of polypropylene homopolymers Propylene polymerisation procedure (liquid propylene, 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) was added using a stream of 150 g propylene, then the chosen amount of H2 (see Tables) was added via mass flow controller in one minute.
  • the reactor temperature was stabilized at 20 °C (HB-Therm) and the solution was stirred and 250 rpm for at least 20 min.
  • the catalyst was injected as described in the following.
  • the desired amount of solid catalyst was loaded into a 5 ml stainless steel vial and then flushed into the reactor with 150 g propane. Stirring speed was kept at 250 rpm and pre- polymerisation was run for 10 minutes at 25 °C. Then the polymerisation temperature was increased to the set value.
  • the second aliquot of H2 was added at 30 °C over 6 min.
  • the reactor temperature was kept constant throughout the polymerisation.
  • the polymerisation time was measured starting when the temperature was 2 °C below the set polymerisation temperature.
  • the reaction was stopped by injecting 5 ml ethanol, cooling the reactor and simultaneously flashing the volatile components.
  • Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) was added using a stream of 250 g propylene, then 0.5 NL of H2 was added via mass flow controller in one minute.
  • the reactor temperature was stabilized at 25 °C (HB-Therm) and the solution was stirred and 250 rpm for at least 20 min.
  • the catalyst was injected as described in the following.
  • the desired amount of solid catalyst was loaded into a 5 ml stainless steel vial. This feeder system was mounted on a port on the lid of the autoclave. Then the catalyst was flushed into the reactor with 350 g propylene.
  • Table 2A Propylene polymerisation conditions tnu e r 2 t o e r o n n Hn n e r l e p s l u y m t f l a a r e e y i b o d i o i t f i u t og i o i t a r e ma a x t t e m a s p i t d p e e e r f s 2n .
  • neopentyl in MC-CE4 do not increase hPP Tm, therefore (at least) one alpha-branched 2-substituent is necessary to achieve this high melting point.
  • MC-IE1 has a better molecular weight / activity balance than both MC-CE1 and MC-CE2, as shown in Figure 2.
  • Reference examples 30 and Inventive Examples 31-34 Preparation of heterophasic propylene copolymers Polymerization procedure 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 and propylene/ethylene 2-step polymerization procedure (20-L reactor, liquid + gas phase) Step 1: Propylene homo polymerization in bulk, 20-L reactor A stainless-steel reactor equipped with a ribbon stirrer, with a total volume of 20.9 dm3 containing 0.2 bar-g propylene, was filled with additional 4.45 kg propylene.
  • Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) was added using a stream of 250 g propylene, then the chosen amount of H2 (see Tables) was added via mass flow controller in one minute.
  • the reactor temperature was stabilized at 25 °C (HB-Therm) and the solution was stirred and 250 rpm for at least 20 min.
  • the catalyst was injected as described in the following.
  • the desired amount of solid catalyst was loaded into a 5 ml stainless steel vial; alternatively the chosen amount of a catalyst slurry in oil, after shaking for about 5 min in a glass vial, was drawn with a syringe and loaded into the 5 ml stainless steel vial.
  • the catalyst vial was mounted on a port on the lid of the reactor.
  • the catalyst was fed into the reactor by flushing 350 g propylene from the balance through the catalyst vial.
  • Stirring speed was kept at 250 rpm and pre-polymerization was run for 10 minutes at either 25 or 30 °C.
  • the polymerization temperature was increased to the set value.
  • the second aliquot of H2 was added at either 30 or 60 °C over 2 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. When the set polymerization time has lapsed, the reaction was stopped by injecting 5 ml ethanol, cooling the reactor and simultaneously flashing the volatile components.
  • Step 2 Ethylene-propylene copolymerization in gas phase, 20-L reactor Step 2 was performed as follows. 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 was defined by where C2/C3 was the weight ratio of the two monomers and R was their relative reactivity ratio, determined experimentally. In the present experiments, the value of R was set at 0.40.
  • the 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. Then the reactor was cooled down (to about 30 °C) and the volatile components flashed out.

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Abstract

La divulgation concerne un complexe métallocène de formule (I) dans laquelle Mt représente Zr ou Hf, de préférence Zr ; 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 auxquels ils sont liés un cycle en C4-C8 ; R2 est hydrocarbyle en C1-C20 linéaire ; R2' est hydrocarbyle en C3-C10 ou SiH(R21')2 alpha-ramifié, R21' étant chacun indépendamment, identiques ou différents les uns des autres, hydrocarbyle en C1-C10 ; n sont chacun indépendamment un nombre entier de 1 à 5 ; R3 et R4 sont chacun indépendamment, identiques ou différents l'un de l'autre, H, groupe hydrocarbyle en C1-C10, ou un groupe –OR31, -SR31 ou -NR31 2 dans lequel R31 est hydrocarbyle en C1-C10, au moins un R3 et au moins un R4 n'étant pas hydrogène ; L est O ou S ; R51 et R51' sont chacun indépendamment identiques 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 ou - OR61, R61 étant chacun indépendamment, identiques les uns des autres, alkyle en C1-C6 linéaire ou ramifié ; ou LR51 adjacent et R6 et/ou LR51' et R6' forment ensemble un groupe -O[C(R62)2]mO-, chaque R62 étant indépendamment, identique ou différent l'un de l'autre, H ou alkyle en C1-C6 linéaire ou ramifié, avec m valant de 1 à 3.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2025190884A1 (fr) * 2024-03-13 2025-09-18 Borealis Gmbh Métallocènes pour la fabrication de copolymères de propylène

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