CATALYSTS

专利摘要:
patent summary: "catalysts". the present invention relates to a racemic complex of formula (i), where m is zirconium or hafnium; each x is a sigma ligand; l is a divalent bridge selected from -r'2c-, -r'2c-cr'2-, -r'2si-, -r'2si-sir'2-, -r'2ge-, where each r ' it is independently a hydrogen atom, c1-20-hydrocarbyl, tri (c1-20-alkyl) silyl, c6-20-aryl, c7-20-arylalkyl or c7-20-alkylaryl; r2 and r2 'are each independently a c1-20 hydrocarbyl radical optionally containing one or more heteroatoms of groups 14-16; r5 'is a c1-20 hydrocarbyl group optionally containing one or more heteroatoms of groups 14-16 and optionally substituted by one or more halo atoms.
公开号:BR112014000465B1
申请号:R112014000465-0
申请日:2012-07-06
公开日:2020-03-31
发明作者:Norbert Hafner；Pascal Castro；Pavel Sergeevich Kulyabin；Vyatcheslav Izmer；Alexander Voskoboynikov；Luigi Resconi；Dmitry Kononovich；Ville Virkkunen；Dmitry Uborsky
申请人:Borealis Ag；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for CATALYSTS.
The present invention relates to asymmetric bisindenyl linkers, complexes thereof and catalysts comprising such complexes. The invention also relates to the use of new bisindenyl metallocene catalysts for the production of high molecular weight polypropylene at good levels of activity.
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.
The present invention provides new metallocenes, which provide high molecular weight capacity, especially in the case of copolymerization between ethylene and propylene and other alpha olefins. In the case of existing catalysts, the molecular weight of the copolymer is often greatly reduced by incorporating ethylene or higher molecular weights are obtained at the expense of catalyst activity. In addition, the overall productivity of existing catalysts still needs to be improved.
The present inventors found a new class of bisindenyl bridged metallocenes, anti, racemic, chiral, asymmetric, which are simple to synthesize despite their asymmetry and which are readily separable from their syn (meso type) isomers. The two indenyl ligands are different from each other, that is, each indenyl ligand carries a set of substituents that are either chemically different or located in different positions with respect to the other indenyl ligand. For the purpose of the present invention, anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-methyl-cyclopentadienyl plane, while syn means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl-metal- plane cyclopentadienyl.
They have high catalyst productivity and perfect performance.
2/131 made in the production of high molecular weight polypropylene homopolymers, especially those of MFR ₂ <1 and in the production of propylene copolymers. During the manufacture of the copolymer, the metallocenes of the invention have reduced chain transfer to ethylene, allowing the production of random high molecular weight and heterophasic copolymers.
Symmetric C ₂ metallocenes similar to those claimed below are disclosed, for example, in WO2007 / 116034. This document reports the synthesis and characterization of the metallocene rac-Me2Si (2-Me-4-Ph-5-OMe-6tBuInd) ₂ ZrCl ₂ and the use of it as a polymerization catalyst after activation with MAO for the homopolymerization of propylene and copolymerization of propylene with ethylene and superior alpha-olefins in solution polymerization. This metallocene is symmetrical and the synthesis of this metallocene provides a final yield of 35% and requires a tedious purification procedure.
WO2007 / 107448 describes the performance of MAO activated metallocene polymerization rac-Me ₂ Si (2-Me-4- (p-tBu-Ph) -6tBuInd) ₂ ZrCl ₂ in solution. Again, this is a symmetrical metallocene and the synthesis of this metallocene requires a tedious purification procedure and provides a very low final yield (<5%).
WO1998 / 040331 refers to a process for the preparation of substituted indanones, but mentions rac-Me ₂ Si (2-Me-4- (p- / Bu-Ph) Ind) ₂ ZrCl2.
These metallocenes are shown below:
Me ₂ Si ZrCI ₂ Me ₂ Si ZrCI ₂ Me ₂ Si ZrCI ₂ rac-Me ₂ Si (2-Me-4- (p- / Bu-Ph) -6-iBuInd) 2ZrCl2 rac-Me2Si (2-Me-4-Ph-5-OMe-6-íBuInd) 2ZrCl2 rac-Me ₂ Si (2-Me-4- (p-ZBu-Ph) Ind) 2ZrCl2 WO 2007/107448 WO 2007/116034 WO 1998/040331
Asymmetric metallocenes capable of producing isotactic polypropylene have been described in the literature, such as, for example, in Spaleck and or
3/131 tros, Journal of Molecular catalysis A, 1998, vol. 128, p. 279 or Miyake et al., Macromolecules 1995, vol. 28, p. 3074. The performance of these metallocenes was, however, far from satisfactory. Asymmetric metallocenes have now been described in patent and scientific literature, for example, EP-A-0834519, WO2001 / 048034, WO2003 / 045551, EP-A-1074577 and Elder et al., Kin. 2006, Vol. 47 (2), p. 192. Here too, the synthesis of the binders is very complicated and the performance of the catalysts is not entirely satisfactory, especially with respect to either the molecular weight or catalyst activity.
The applicant's invention relates to the use of asymmetric metallocenes, especially their anti-isomers, carrying two indenyls as ligands II that are different in their substitution pattern while still being relatively simple to synthesize, in particular where the 5 position of a linker carries a hydrogen atom and position 5 of the other ring is replaced by a non-hydrogen group. These metallocenes have surprisingly been found to have greater activities than the asymmetric catalysts previously reported, as well as greater activities compared to their symmetric analogues.
Summary of the Invention
Thus, seen from one aspect, the invention provides a racemic complex of formula (I)
on what
M is zirconium or hafnium;
each X is a sigma ligand;
L is a divalent bridge selected from -R ' ₂ C-, -R' ₂ C-CR ' ₂ -, -R' ₂ Si-, -R ' ₂ Si-SiR' ₂ -, -R ' ₂ Ge-, where each R 'is independently an á
4/131 hydrogen atom, C ₂₀ -hidrocarbila, tri (Ci-C ₂₀ alkyl) silyl, C _6-20 -aryl, C ₇ -C ₂₀ -arilalquila or C ₇ -C ₂₀ -alquilarila;
R ² and R ² 'are each independently a C 1 -C ₂₀ hydrocarbyl moiety optionally containing one or more heteroatoms of groups 14-16;
R ⁵ 'is a C _1-20 hydrocarbyl group optionally containing one or more heteroatoms of groups 14-16 and optionally substituted by one or more halo atoms;
R ⁶ and R ^{6 '} are each independently hydrogen or a C _1-20 hydrocarbyl group optionally containing one or more hetero atoms of groups 14-16;
R ⁷ and R ⁷ 'are each independently hydrogen or C _1-20 hydrocarbyl group optionally containing one or more hetero atoms of groups 14-16;
Ar is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more R ¹ groups;
Ar 'is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more R ¹ groups;
each R ¹ is a C _1-20 hydrocarbyl group or two R ¹ groups on adjacent adjacent carbon atoms can form a 5- or 6-membered non-aromatic ring fused to the Ar group, said ring being itself optionally substituted with one or more R ⁴ groups; and each R ⁴ is a C _1-20 hydrocarbyl group.
Seen from another aspect, the invention provides a catalyst comprising a complex of formula (I)
on what
5/131
M is zirconium or hafnium;
each X is a sigma ligand;
L is a divalent bridge selected from -R ' ₂ C-, -R' ₂ C-CR ' ₂ -, R' ₂ Si-, -R ' ₂ Si-SiR' ₂ -, -R ' ₂ Ge-, in that each R 'is independently a hydrogen atom, C1- _C20- hydrocarbyl tri (C1-C ₂₀ -alkyl) silyl, C6-C ₂₀ -aryl, C7C ₂₀ -arylalkyl or C7-C ₂₀ -alkylaryl;
R ² and R ² 'are each independently a C 1 -C ₂₀ hydrocarbyl radical optionally containing one or more hetero atoms of groups 14-16;
R ^{5 '} is a C1-20 hydrocarbyl group containing one or more hetero atoms of groups 14-16 optionally substituted by one or more halo atoms;
R ⁶ and R ^{6 '} are each independently hydrogen or a C1-20 hydrocarbyl group optionally containing one or more heteroatoms of groups 14-16;
R ⁷ and R ^{7 '} are each independently hydrogen or C 1-20 hydrocarbyl group optionally containing one or more hetero atoms of groups 14-16;
Ar is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more R ¹ groups;
Ar 'is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more R ¹ groups;
each R ¹ is a C _1-20 hydrocarbyl group or two R ¹ groups on adjacent adjacent carbon atoms can form a 5- or 6-membered non-aromatic ring fused to the Ar group, said ring being itself optionally substituted with one or more R ⁴ groups;
each R ⁴ is a C _1-20 hydrocarbyl group;
and (ii) a cocatalyst comprising a metal group 13 compound, for example, Al or boron.
The catalyst of the invention can be used in unsupported or solid form. The catalyst of the invention can be used as a homogeneous catalyst or heterogeneous catalyst.
6/131
The catalyst of the invention in solid form, preferably in solid particle form, can either be supported on an external carrier material, such as silica or alumina, or, in a particularly preferred embodiment, it is free of an external carrier, yet still in use. solid shape. For example, the solid catalyst is obtainable through a process in which (a) a liquid / liquid emulsion system is formed, said liquid / liquid emulsion system comprising a solution of the catalyst components (i) and (ii) dispersed in a solvent to form dispersed droplets; and (b) solid particles are formed by solidifying said dispersed droplets.
Seen from another aspect, the invention provides a process for the manufacture of a catalyst as defined hereinbefore comprising obtaining a complex of formula (I) and a cocatalyst as described hereinbefore;
forming a liquid / liquid emulsion system, which comprises a solution of the catalyst components (i) and (ii) dispersed in a solvent, and solidifying said dispersed droplets to form solid particles.
Seen from another aspect, the invention provides for the use in olefin polymerization of a catalyst as defined hereinbefore, especially for the formation of a polyolefin, especially a polyethylene or polypropylene, such as a polypropylene homopolymer or copolymer.
Seen from another aspect, the invention provides a process for the polymerization of at least one olefin comprising reacting said at least one olefin with a catalyst as described above, especially for the formation of polypropylene.
Definitions
Throughout the report the definitions that follow are used.
By exempt from an external vehicle it means that the catalyst
7/131 does not contain an external support, such as an inorganic support, for example, silica or alumina, or an organic polymeric support material.
The term C _1-20 hydrocarbyl group then includes C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _3-20 cycloalkyl, C _3-20 cycloalkenyl, C _6-20 aryl groups, C ₇ groups _-20 alkylaryl or C _7-20 arylalkyl groups or mixtures of such groups such as cycloalkyl substituted by alkyl. Linear and branched hydrocarbyl groups cannot contain cyclic units. Aliphatic hydrocarbyl groups cannot contain aryl rings.
Unless otherwise stated, preferred C _1-20 hydrocarbyl groups are C _1-20 alkyl, C _4-20 cycloalkyl, C _5-20 cycloalkyl-alkyl groups, C _7-20 alkylaryl groups, C _7-20 arylalkyl groups or C _6-20 aryl groups, especially C _1-10 alkyl groups, C _6-10 aryl groups or C ₇ groups. ₁₂ arylalkyl, for example, C _1-8 alkyl groups. Most especially preferred hydrocarbyl groups are methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, C _5-6- cycloalkyl, cyclohexylmethyl, phenyl or benzyl.
The term halo includes fluorine, chlorine, bromine and iodine groups, especially chlorine groups, when it comes to the definition of the complex.
The oxidation state of the metal ion is governed primarily by the nature of the metal ion in question and the stability of the individual oxidation states of each metal ion.
It will be understood that in the complexes of the invention the metal ion M is coordinated by ligands X in order to satisfy the valence of the metal ion and fill its available coordination sites. The nature of these σ ligands can vary widely.
Catalyst activity is defined in the present application as the amount of polymer produced / g of catalyst / h. The metal activity of the catalyst is defined here to be the quantity of the polymer produced / g Metal / h. The term productivity is also sometimes used to indicate the activity of the catalyst, although here it designates the amount of polymer produced per unit weight of the catalyst.
Detailed Description of the Invention
The complexes of the invention are asymmetric. That means yes
8/131 The two indenyl linkers that form the metallocene are different, that is, each indenyl linker carries a set of substituents that are either chemically different or located in different positions with respect to the other indenyl linker. More precisely, they are racemic, chiral bisindenyl metallocenes bridged. Although the complexes of the invention may ideally be in their syn configuration, they are in their anti configuration. For the purpose of the present invention, racemic anti means that the two indenyl ligands are oriented in opposite directions with respect to the cyclopentadienyl-metal-cyclopentadienyl plane, while racemic syn means that the two indenyl ligands are oriented in the same direction with respect to the cyclopentadienyl- metal-cyclopentadienyl, as shown in the Figure below.
Racemic Anti
Racemic Syn
Formula (I) is intended to comprise both syn and anti, preferably anti, configurations. It is also necessary that the group R ⁵ 'is not hydrogen in which position 5 in the other linker carries a hydrogen.
In reality, the metallocenes of the invention are C1 symmetrical, but they maintain a C ₂ pseudo-symmetry since they maintain C ₂ symmetry in close proximity to the metal center, although not at the periphery of the ligand. As will be seen, the use of two different indenyl binders as described in the present invention allows for a much better structural variation, in this way a more precise adjustment of the performance of the catalyst, compared with typical symmetric C ₂ catalysts. Due to the nature of their chemistry, both anti and syn enantiomer pairs are formed during complex synthesis. However, when using the binders of this
9/131 invention, separation of anti-preferred isomers from syn isomers is straightforward.
It is preferred that the metallocenes of the invention are employed as the rac anti isomer. Ideally, then, at least 95 mol%, as well as at least 98 mol%, especially at least 99 mol%, of the metallocene are in the racemic isomeric anti form.
In the catalysts of the invention:
M is preferably Zr.
Each X, which can be the same or different, is preferably a hydrogen atom, a halogen atom, an R, OR, OSO2CF3, OCOR, SR, NR ₂ or PR _{2 group} where R is a C ₁ radical. ₂₀ alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _7-20 alkylaryl or C _7-20 linear or branched arylalkyl, cyclic or acyclic; optionally containing heteroatoms belonging to groups 14-16. R is preferably a Ci _-6 alkyl group, phenyl or benzyl.
Most preferably, each X is independently a hydrogen atom, a halogen atom, a C _1-6 alkoxy group or an R group, for example, preferably a C _1-6 alkyl, phenyl or benzyl group. Most preferably, X is chlorine or a methyl radical. Preferably both groups are the same.
L is preferably an alkylene linker or a bridge comprising a heteroatom, such as silicon or germanium, for example, -SiR ⁸ 2, wherein each R ⁸ is independently C1-20 alkyl, C3-10 cycloalkyl, C6-20 aryl or tri (C1-20 alkyl) silyl, such as trimethylsilyl. More preferably, R ⁸ is C 1-6 alkyl, especially methyl or C _3-7 cycloalkyl, such as cyclohexyl. Most preferably, L is a dimethylsilyl or methylcyclohexylsilyl bridge (i.e., Me-Si-cyclohexyl). It can also be an ethylene bridge.
R ² and R ² 'may be different, but they are preferably the same. R ² and R ² 'are preferably a C _1-10 hydrocarbyl group, such as a C _1-6 hydrocarbyl group. More preferably, it is a straight or branched C _1-10 alkyl group. More preferably, it is a C _1-6 linear or branched alkyl, particularly linear C _1-6 alkyl group such as methyl or ethyl.
The groups R ² and R ^{2 '} can be interrupted by one or more hetero atoms, such as 1 or 2 hetero atoms, for example, a hetero atom,
10/131 selected from groups 14 to 16 of the periodic table. Such a heteroatom is preferably O, N or S, especially O. More preferably, however, the groups R ² and R ² 'are free of hetero atoms. Especially especially, R ² and R ² 'are methyl, especially both methyl.
The two groups Ar, Ar and Ar ', can be the same or different. It is preferred, however, that the Ar groups are different. The Ar 'group may be unsubstituted. Ar 'is preferably a phenyl based group optionally substituted by R ¹ groups, especially a substituted phenyl group.
The Ar group is preferably a C6-20 aryl group such as a phenyl group or a naphthyl group. Although the Ar group may be a heteroaryl group, such as carbazolyl, it is preferable that Ar is not a heteroaryl group. The Ar group can be unsubstituted or substituted by one or more R ¹ groups, more preferably by one or two R ¹ groups, especially at position 4 of the aryl ring attached to the indenyl ligand or at positions 3, 5.
In one embodiment, both Ar and Ar 'are not replaced. In another embodiment, Ar 'is unsubstituted and Ar is replaced by one or two groups R ¹ .
R ¹ is preferably a C1-20 hydrocarbyl group, such as a C1-20 alkyl group. R ¹ groups can be the same or different, preferably the same. More preferably, R ¹ is a C2-10 alkyl group, such as C _3-8 alkyl group. Highly preferred groups are tert-butyl or isopropyl groups. It is preferred that the group R ¹ is bulky, that is, branched. Branching would be alpha or beta for the ring. Branched C3-8 alkyl groups are then also favored.
In an additional embodiment, the two R ¹ groups on adjacent carbon atoms together can form a 5- or 6-membered non-aromatic ring fused to the Ar group, said ring being optionally substituted with one or more R ⁴ groups. Such a ring would form a tetrahydroindenyl group with the Ar ring or a tetrahydronaphthyl group.
If an R ⁴ group is present, there is preferably only 1 group of the type. It is preferably a C _1-10 alkyl group.
11/131
It is preferred that there are only one or two R ¹ groups present in the Ar group. Where there is an R ¹ group present, the group is preferably for the indenyl ring (position 4). Where two R ¹ groups are present they are preferably in positions 3 and 5.
R ⁵ 'is preferably a C1-20 hydrocarbyl group containing one or more hetero atoms of groups 14-16 and optionally substituted by one or more halo atoms or R ⁵ ' is a C _1-10 alkyl group, such as methyl, but above all preferably it is a Z'R ³ 'group.
R ⁶ and R ⁶ 'can be the same or different. In a preferred embodiment one of R ⁶ and R ⁶ 'is hydrogen, especially R ⁶ It is preferred if R ⁶ and R ⁶ ' are not both hydrogen. If not hydrogen, it is preferred if each R ⁶ and R ⁶ 'is preferably a C 1-20 hydrocarbyl group, such as a C 1-20 alkyl group or C 6-10 aryl group. More preferably, R ⁶ and R ⁶ 'are a C2-10 alkyl group such as C ₃ group. ₈ alkyl. Highly preferred groups are tert-butyl groups. It is preferred if R ⁶ and R ⁶ 'are bulky, that is, they are branched. Branching would be alpha or beta for the ring. Branched C _3-8 alkyl groups are also then favored.
The groups R ⁷ and R ⁷ 'can be the same or different. Each R ⁷ and R ⁷ 'group is preferably hydrogen, a C 1-6 alkyl group or is a ZR ³ group. It is preferred if R ⁷ ' is hydrogen. It is preferred if R ⁷ is hydrogen, C1-6 alkyl or ZR ³ . The combination of both R ⁷ and R ^{7 '} being hydrogen is more preferred. It is also preferred if ZR ³ represents OC1-6 alkyl, such as methoxy. It is also preferred if R ⁷ represents C 1-6 alkyl such as methyl.
Z and Z 'are O or S, preferably O.
R ³ is preferably a C1-10 hydrocarbyl group, especially a C1-10 alkyl group or aryl group optionally substituted by one or more halo groups. More especially, R ³ is a C 1-6 alkyl group, such as a C _1-6 linear alkyl group, for example, methyl or ethyl.
R ³ 'is preferably a C _1-10 hydrocarbyl group, especially a C1-10 alkyl group, or aryl group optionally substituted by one or more halo groups. Especially especially, R ^{3 '} is a C 1-6 alkyl group, such as a C 1-6 linear alkyl group, for example, methyl or ethyl or it is a
12/131 phenyl-based radical optionally substituted with one or more halo groups such as Ph or C6F ₅ .
Thus, preferred complexes of the invention are of Formula (II ') or (II)
on what
M is zirconium or hafnium each X is a sigma binder, preferably each X is independently a hydrogen atom, a halogen atom, C _1-6 alkoxy group, C _1-6 alkyl, phenyl or benzyl group;
L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, R ' ₂ Si-, -R' ₂ Si-SiR ' ₂ -, -R' ₂ Ge-, where each R 'is independently a hydrogen atom, C _1-20 alkyl, C _3-10 cycloalkyl, tri (C ₁ -C _20.) silyl, C _6-20 aryl, C _7-20 arylalkyl , or C _7-20 alkylaryl;
each R ² or R ² 'is a C _1-10 alkyl group;
R ⁵ 'is a C _1-10 alkyl group or Z'R ³ 'group;
R ⁶ is hydrogen or a C _1-10 alkyl group;
R ⁶ 'is a C _1-10 alkyl group or C _6-10 aryl group;
R ⁷ is hydrogen, a C _1-6 alkyl group or ZR ³ group;
R ⁷ 'is hydrogen or a C _1-10 alkyl group;
Z and Z 'are independently O or S;
R ³ 'is a C _1-10 alkyl group or a C _6-10 aryl group optionally substituted by one or more halo groups;
13/131
R ³ is a C _1-10 alkyl group;
each n is independently 0 to 4, for example, 0, 1 or 2;
and each R ¹ is independently a C _1-20 hydrocarbyl group, for example, C _1-10 alkyl group.
Seen from another aspect, the invention provides a complex of formula (III ') or (III):
M is zirconium or hafnium;
each X is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, a Ci _-6 alkoxy group, C _1-6 alkyl, phenyl or benzyl.
L is a divalent bridge selected from -R ' ₂ C- or -R' ₂ Si- where each R 'is independently a hydrogen atom, C _1-20 alkyl or C _3-10 cycloalkyl;
R ⁶ is hydrogen or a C _1-10 alkyl group;
R ⁶ 'is a C _1-10 alkyl group or C _6-10 aryl group;
R7 is hydrogen, C _1-6 alkyl or OC _1-6 alkyl;
Z 'is O or S;
R ³ 'is a C _1-10 alkyl group or C _6-10 aryl group optionally substituted by one or more halo groups;
n is independently 0 to 4, for example, 0, 1 or 2; and
14/131 each R ¹ is independently a C _1-10 alkyl group.
Seen from an even more preferred aspect, the invention provides a
M is zirconium or hafnium;
each X is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, a C16-alkoxy group, C _1-6 alkyl, phenyl or benzyl group;
each R 'is independently a hydrogen atom, C _1-20 alkyl or C _3-7 cycloalkyl;
R ⁶ is hydrogen or a C _1-10 alkyl group;
R ⁶ 'is a C _1-10 alkyl group or C _6-10 aryl group;
R ⁷ is hydrogen, C _1-6 alkyl or OC _1-6 alkyl;
Z 'is O or S;
R ³ 'is a C _1-10 alkyl group or C _6-10 aryl group optionally substituted by one or more halo groups;
n is independently 0, 1 to 2; and each R ¹ is independently a C _3-3 alkyl group.
Especially especially, the complex of the invention is of formula (V ') or (V):
15/131
wherein each X is a sigma ligand, preferably each X is independently a hydrogen atom, a halogen atom, a C _1-6 alkoxy group, C _1-6 alkyl, phenyl or benzyl group;
R 'is independently a C _1-6 alkyl or C _3-10 cycloalkyl;
R ¹ is independently C _3-8 alkyl;
R ⁶ is hydrogen or a C _3-8 alkyl group;
R ⁶ 'is a C _3-8 alkyl group or C _6-10 aryl group;
R ³ 'is a C _1-6 alkyl group or C _6-10 aryl group optionally substituted by one or more halo groups; and n is independently 0, 1 or 2.
Particular compounds of the invention include:
Me ₂ Si ZrCI ₂ Me ₂ Si ZrCI ₂ Me2Si Ζ1ΌΙ2 Me ₂ Si Ζ1ΌΙ2 i 2 “ rac-anti-Me ₂ Si (2- Me-4-Ph-6- / Bu-Ind) (2-Me-4-Ph-5- OMe-6-tBu- Ind) ZrCl2 rac-anti-Me ₂ Si (2Me-4- (p- / BuPh) Ind) (2-Me-4-Ph-5OMe-6-tBu- Ind) ZrCl2 rac-anti-Me ₂ Si (2-Me- 4- (3,5-di-ffiuPh) -6- / Bu-Ind) (2-Me-4-Ph- 5- OMe-6- / Bu-Ind ) ZrCl2 rac-anti-Me ₂ Si (2Me-4-Ph-6- / Bu-Ind) (2-Me-4,6-di- Ph-5-OMe- Ind) ZrCl2
16/131
Me ₂ Si ZrCI ₂ FMe ₂ Si ZrCI ₂ 'ογ-'ΧΣΓ Me ₂ Si ZrCI ₂ ° rac-anti-Me ₂ Si (2- Me-4- (p-íBuPh) Ind) (2-Me-4-Ph- 5-OC6F5) -6- / Pr- Ind) ZrCl2 rac-anti-Me (CyHex) Si (2-Me-4-Ph-6-íBu-Ind) (2-Me-4-Ph-5-OMe-6-íBu-Ind) ZrCl2 rac-anti-Me2Si (2-Me-4- (3,5-diZBuPh) -7-MeInd) (2-Me-4-Ph5-OMe-6-íBuInd) ZrCl2 rac-anti-Me2Si (2-Me-4- (3,5-diZBuPh) -7-OMeInd) (2-Me-4-Ph5-OMe-6-íBuInd) ZrCl2 Me ₂ Si ZrCI ₂ / Me ₂ Si ZrCI ₂ Me ₂ Si ZrCI ₂ /// ”/ Me2Si ΖγΟΙ ₂ rac-anti-Me2Si (2-Me-4- (p-íBuPh) -6-íBu-Ind) (2-Me4-Ph-5-OMe-6-ZBu-Ind) ZrCl2 rac-anti-Me2Si (2-Me-4- (p-íBuPh) Ind) (2-Me-4- (4ZBuPh) -5-OMe-6-ZBu-Ind) ZrCl2 rac-anti-Me2Si (2-Me-4- (p-íBuPh) -Ind) (2-Me-4- (3,5ZBu2Ph) -5-OMe6-íBu-Ind) ZrCl2 rac-anti-Me2Si (2Me-4- (p-íBuPh) Ind) (2-Me-4-Ph5-OiBu-6-íBuInd) ZrCl2
For the avoidance of doubt, any more limited definition of a substituent offered above can be combined with any other broad or more limited definition of any other substituent.
Throughout the above description, in which a more limited definition of a substituent is presented, the more limited definition is considered to be disclosed together with all the broader and more limited definitions of other substituents in the application.
Synthesis
The binder required to form the complexes and then catalysts of the invention can be synthesized by any process and the skilled organic chemist would be able to develop various synthetic protocols for the manufacture of the necessary binder materials.
For example, the following general synthetic scheme can be used:
Scheme I
Suitable reagents for this transformation are given in the Examples section. Although this scheme refers to specific compounds, the general principles shown here apply to the metallocenes of the invention. The important point to remember is that the ligands are asymmetric, a conventional reaction with SiMe ₂ CI ₂ cannot be carried out to bridge two ligands as it leads to symmetrical products. On the contrary, each ligand has to be connected to the bridge in stages with control over the reaction stoichiometry.
Of particular interest is the synthesis of compounds having an alkoxy group at position 7 of the eventual metallocene. The present inventors have developed a new process for the synthesis of the precursors necessary to produce such substituted materials.
The process starts from the middleman:
otc ^ j alkyl
Br where the alkyl is preferably methyl. This intermediary is readily
18/131 prepared and the examples offer several options for its preparation. This intermediate can then be reacted with diethyl methylmalonate and cyclized in this process:

Reduction of carbonyl and alkylation to form an alkoxide and subsequent Grignard chemistry at position 4 then introduces the Ar-type substituent group while also eliminating the alkoxide group to form a double bond at position 1-2 of the 5-membered ring:

Reaction with a bridging group precursor (! _ ') Such as SiMe ₂ Cl2 in the presence of base preferably provides the compounds in which the L group binds in position 1 with the double bond changed to position 2-3 of the ring. This intermediate can then be used in the preparation of additional metallocene as is well known. Note that the method provides an alkoxy group at position 7.

The key to the presence of the alkoxy group at position 7 is the formation of the bicyclic ring system in the presence of the alkoxy group at position 7/131 and this forms an additional aspect of the invention.
In this way, seen from another aspect the invention provides a process for the preparation of a compound of formula (VI)
wherein R ⁶ is as defined hereinbefore, preferably H, with 5 comprising cyclization of a compound
preferably in the presence of P4O10 θ MeSOsH. (Eaton's reagent).
In a further embodiment the compound of formula (VI) is reduced, for example, in the presence of sodium borohydride and reacted with an alkylating agent such as Mel to form compound (VII)
In an additional embodiment the compound of formula (VII) is converted into
20/131
where Ar is as previously defined here.
Intermediaries
Although the invention mainly refers to catalysts, it will be understood that the complexes of the invention and the binders used to form such complexes are also new. The invention then relates to complexes of formula (I) and ligands of formula (I ') from which the MX ₂ coordination has been removed and the proton has returned to indenyl.
Linkers of interest are therefore of formula (I ')
wherein the substituents are as defined hereinbefore and the dotted lines represent a double bond present between carbons 1 and 2 or 2 and 3 of the indenyl ring. It will then be understood that this molecule contains double bonded isomers. By double bonded isomers means compounds in which the double bond is positioned between atoms 2 and 3 instead of atoms 1 and 2 of the bicyclic ring. It is possible that more than one double bonded isomer is present in a sample. Li
Preferred giants are analogues of the complexes described above from which MX ₂ coordination was removed and the proton returned to indenyl. Cocatalyst
To form an active catalytic species, it is usually necessary to employ a cocatalyst as is well known in the art. Cocatalysts comprising one or more Group 13 compounds of metals, such as organoaluminium compounds or borates used to activate metallocene catalysts, are suitable for use in the present invention.
The olefin polymerization catalyst system of the invention comprises (i) a complex in which the metal ion is coordinated by a binder of the invention; and usually (ii) an alkyl aluminum compound (or other suitable cocatalyst) or its reaction product. In this way, the cocatalyst is preferably an alumoxane, such as MAO or an alumoxane other than MAO.
Borate cocatalysts can also be used. It will be understood by the converse that where boron-based cocatalysts are used, it is normal to reactivate the complex through its reaction with an alkyl aluminum compound, such as TIBA. This procedure is well known and any suitable alkyl aluminum, for example, Al (C1-6 alkyl) 3, can be used.
Boron-based cocatalysts of interest include those of formula
BY3 where Y is the same or different and is a hydrogen atom, an alkyl group of from 1 to about 20 carbon atoms, an aryl group of from 6 to about 15 carbon atoms, alkylaryl, arylalkyl , haloalkyl or haloaryl, each having from 1 to 10 carbon atoms in the alkyl radical and from 6-10 carbon atoms in the aryl or fluorine, chlorine, bromine or iodine radical. Preferred examples of Y are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl such as phenyl, tolyl, benzyl, p-fluorphenyl, 3,5-difluorphenyl, pentachlorophenyl, pentafluorphenyl, 3,4,5 -trifluorphenyl and 3,5-di (trifluoromethyl) phenyl. options
Preferred 22/131 are trifluorborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorphenyl) borane, tris (4-fluoromethylphenyl) borane, tris (2,4,6-trifluorphenyl) borane, tris (penta -fluorfenyl) borane, tris (tolyl) borane, tris (3,5-dimethyl-phenyl) borane, tris (3,5difluorfenyl) borane and / or tris (3,4,5-trifluorfenyl) borane.
Particular preference is given to tris (pentafluorfenil) borane.
It is preferred, however, that borates are used, that is, compounds containing a 3+ borate ion. Such ionic cocatalysts preferably contain a non-coordinating anion such as tetracis (pentafluorfenyl) borate and tetrafenylborate. Suitable counterions are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, dimethylammonium, N-methylanilinium, diphenylammonium, N, N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, pyridinium, pyridinium, pyridine, N-dimethylanilinium or p-nitro-N, N-dimethylanilinium.
Preferred ionic compounds that can be used according to the present invention include:
triethylammoniotetra (phenyl) borate, tributylammoniotetra (phenyl) borate, trimethylammoniotetra (tolyl) borate, tributylammoniotetra (tolyl) borate, tributylammoniotetra (pentafluorfenyl) borate, tripropylammoniotetra (dimethylphenyl) borate, tributylamonetra (4)
N, N-dimethylcyclohexylamoniotetracis (pentafluorfenyl) borate, N, N-dimethylbenzylamoniotetracis (pentafluorfenyl) borate, N, N-dimethylanilinotetra (phenyl) borate, N, N-diethylanilinotetra (phenyl) borate, phenyl) borate, borate,
N, N- di (propyl) ammoniotetracis (pentafluorfenyl) borate, di (cyclohexyl) ammoniotetracist (pentafluorfenyl) borate, triphenylphosphoniotetracis (phenyl) borate, triethylphosphoniotetracis (phenyl) borate, phenylphenethisphonetron (phenyl) phosphate phenyl) borate, tri (dimethylphenyl) phosphoniotetracis (phenyl) borate, triphenylcarbenotetracis (pentafluorfenyl) borate, or ferrocenotetracis (pentafluorfenil)
23/131 borate. Preference is given to triphenylcarbenotetracis (pentafluorfenil) borate,
N, N-dimethylcyclohexylammoniotetracis (pentafluorfenyl) borate or N, N-dimethylbenzolamoniotetracis (pentafluorfenyl) borate.
The use of B (C6F5) 3, C6H5N (CH3) 2H: B (C6F5) 4, ^ 5) 3 ^^ 5) 4 or Ni (CN) 4 [B (C6F5) 3] 4 ^2- is especially preferred.
Catalyst Manufacturing
The metallocene complex of the present invention can be used in combination with a suitable cocatalyst as a catalyst for the polymerization of olefins, for example, in a solvent such as toluene or an aliphatic hydrocarbon (i.e., for solution polymerization), as is well known in the art. Preferably, polymerization of olefins, especially propylene, takes place in the condensed phase or in the gas phase.
The catalyst of the invention can be used in supported or unsupported form. The particulate backing 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 silicaalumina. The use of a silica backing is preferred. The expert is aware of the procedures required to support a metallocene catalyst.
Especially preferably the support is a porous material so that the complex can be loaded into the pores of the support, for example, using a process analogous to that described in WO94 / 14856 (Mobil), WO95 / 12622 (Borealis) and WO2006 / 097497. The particle size is not critical, but is preferably in the range of 5 to 200 pm, more preferably 20 to 80 pm. The use of these supports is routine in the technique.
In an alternative mode, no support is used in any way. Such a catalyst can be prepared in solution, for example, in an aromatic solvent such as 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 powder medium
24/131 limerization. In a preferred embodiment, the metallocene (when X differs from alkyl or hydrogen) is pre-reacted with an alkyl aluminum, in a metal / aluminum ratio of from 1: 1 to 1:50, preferably from 1 : 1 to 1: 250, and then combined with a solution of the borane or borate cocatalyst dissolved in an aromatic solvent, or in a separate container or directly in the polymerization reactor. Preferred metal / boron ratios are between 1: 1 and 1: 100, more preferably 1: 1 to 1:10.
In a particularly preferred embodiment, no external vehicle is used, but the catalyst is still presented in the form of a solid particle. In this way, no external support material such as an inert organic or inorganic vehicle, such as, for example, silica, as described above is employed.
In order to provide the catalyst of the invention in solid form, but without using an external vehicle, it is preferred if a liquid / liquid emulsion system is used. The process involves forming dispersion of liquid components of the catalyst (i) and (ii) in a solvent and solidifying said dispersed droplets to form solid particles.
In particular, the method involves preparing a solution of one or more catalyst components; dispersing said solution in a solvent to form an emulsion in which said one or more components of the catalyst are present in the droplets of the dispersed phase; immobilizing the catalyst components in the dispersed droplets, in the absence of a porous support in an external particle, to form solid particles comprising said catalyst, and optionally recovering said particles.
This process allows the manufacture of active catalyst particles with improved morphology, for example, with a spherical shape, predetermined surface properties and particle size and without using any added external porous support material, such as an inorganic oxide, for example, silica. By the term preparation of a solution of one or more catalyst components, it means that the compounds that form the catalyst can be combined in a solution that is
25/131 dispersed in the immiscible solvent or, alternatively, at least two separate catalyst solutions for each part of the catalyst forming compounds can be prepared, which are then dispersed successively in the solvent.
In a preferred method for forming the catalyst, at least two separate solutions for each or part of said catalyst can be prepared, which are then dispersed successively in the immiscible solvent.
More preferably, a solution of the complex comprising the transition metal compound and the cocatalyst is combined with the solvent to form an emulsion in which this inert solvent forms the continuous liquid phase and the solution comprising the catalyst components forms the dispersed phase (phase discontinuous) in the form of dispersed droplets. The droplets are then solidified to form solid catalyst particles, and the solid particles are separated from the liquid and optionally washed and / or dried. The solvent that forms the continuous phase can be non-miscible in the catalyst solution at least under the conditions (for example, temperatures) used during the dispersion step.
The term non-miscible with the catalyst solution means that the solvent (continuous phase) is totally non-miscible or partially non-miscible, that is, not fully miscible with the dispersed phase solution.
Preferably said solvent is inert with respect to the compounds of the catalyst system to be produced. Full description of the required process can be found in WO03 / 051934, which is incorporated herein by reference.
The inert solvent must be chemically inert at least under the conditions (for example, temperature) used during the dispersion step. Preferably, the solvent of said continuous phase does not contain any significant amounts of catalyst forming compounds dissolved therein. In this way, the solid particles of the catalyst are formed in the droplets of the compounds that originate from the dispersed phase (that is, they are provided for the emulsion in a solution dispersed in the continuous phase).
26/131
The terms immobilization and solidification are used here interchangeably for the same purpose, that is, for the formation of free-flowing solid catalyst particles in the absence of an external porous particle vehicle, such as silica. Solidification then takes place inside the droplets. Said step can be carried out in several ways as disclosed in said WO03 / 051934. Preferably solidification is caused by any external stimulus to the emulsion system such as a change in temperature to cause solidification. In this way, in said step the component (s) of the catalyst remains fixed within the solid particles formed. It is also possible that one or more of the catalyst components can participate in the solidification / immobilization reaction.
In this way, compositionally uniform, solid particles having a predetermined particle size range can be obtained.
In addition, the particle size of the catalyst particles of the invention can be controlled by the size of the droplets in the solution, and spherical particles with a uniform particle size distribution can be obtained.
The invention is also industrially advantageous, since it allows the preparation of solid particles to be carried out as a one-pot procedure. Continuous or semi-continuous processes are also possible for producing the catalyst.
Scattered Phase
The principles for preparing two-phase emulsion systems are known in the chemical field. In this way, in order to form the two-phase liquid system, the solution of the catalyst component (s) and the solvent used as the continuous liquid phase must be essentially non-miscible at least during the dispersion step. This can be achieved in a known manner, for example, by choosing the two liquids and / or the temperature of the dispersion step / solidification step accordingly.
A solvent can be used to form the catalyst component (s) solution. Said solvent is chosen so that
27/131 it dissolves said component (s) of the catalyst. The solvent may preferably be an organic solvent as used in the field, comprising an optionally substituted hydrocarbon such as linear or branched aliphatic, alicyclic or aromatic hydrocarbon, such as a linear or cyclic alkane, an aromatic hydrocarbon and / or halogen-containing hydrocarbon.
Examples of aromatic hydrocarbons are toluene, benzene, ethylbenzene, propylbenzene, butylbenzene and xylene. Toluene is a preferred solvent. The solution can comprise one or more solvents. Such a solvent can then be used to facilitate the formation of an emulsion and is generally not part of the solidified particles, but, for example, is removed after the solidification step along with the continuous phase.
Alternatively, a solvent may form part of the solidification, for example, an inert hydrocarbon having a high melting point (waxes), such as above 40 ° C, suitably above 70 ° C, for example, above 80 ° C or 90 ° C, can be used as dispersed phase solvents to immobilize the catalyst compounds within the droplets formed.
In another embodiment, the solvent consists partially or completely of a liquid monomer, for example, liquid olefin monomer designed to be polymerized in a prepolymerization immobilization step.
Continuous phase
The solvent used to form the continuous liquid phase is a single solvent or a mixture of different solvents and may be non-miscible with the solution of the catalyst components at least under the conditions (for example, temperatures) used during the dispersion step. Preferably said solvent is inert with respect to said compounds.
The term inert with respect to said compounds here means that the solvent of the continuous phase is chemically inert, that is, it does not undergo any chemical reaction with any catalyst forming component. In this way, the solid particles of the catalyst are formed in the droplets of the compounds that originate from the dispersed phase, that is, they are provided for the emulsion in a solution dispersed in the continuous phase.
It is preferred that the components of the catalyst used to form the solid catalyst are not soluble in the solvent of the continuous liquid phase. Preferably, said components of the catalyst are essentially insoluble in said continuous phase forming solvent.
Solidification occurs essentially after the droplets are formed, that is, solidification is carried out within the droplets, for example, by causing a solidification reaction among the compounds present in the droplets. In addition, even if some solidifying agent is added to the system separately, it reacts within the droplet phase and any catalyst forming components go into the continuous phase.
The term emulsion used here comprises both bi- and multiphase systems.
In a preferred embodiment said solvent which forms the continuous phase is an inert solvent including a halogenated organic solvent or mixtures thereof, preferably fluorinated organic solvents and particularly semi, highly or perfluorinated organic solvents and functionalized derivatives thereof. Examples of the solvents mentioned above are semi, highly or perfluorinated hydrocarbons, such as alkanes, alkenes and cycloalkanes, ethers, for example, perfluorinated ethers and amines, particularly tertiary amines, and their functionalized derivatives. Preferred hydrocarbons are semi, highly or perfluorinated, particularly perfluorinated, for example, perfluoridrocarbonetos, for example, C3-C30, such as C4-Ci _0. Specific examples of suitable perfluoralkanes and perfluorocycloalkanes include perfluorhexane, -heptane, -octane and - (methylcyclohexanone). Semi-fluorinated hydrocarbons refer particularly to semi-fluorinated nalkans, such as perfluoralkylalkane.
Semi-fluorinated hydrocarbons also include hydrocarbons of the type in which blocks of -C-F and -C-H alternate. Highly fluorinated means that most -C-H units are replaced with -C-F units. Perfluored means that all -C-H units are replaced with -C-F units. See the article by A. Enders and G. Maas in Chemie in unserer
29/131
Zeit, 34 Jahrg, 2000, Nr.6 and Pierandrea Lo Nostro in Advances in Colloid and Interface Science, 56 (1995) 245-287, Elsevier Science.
Dispersion step
The emulsion can be formed by any means known in the art: by mixing, such as by stirring said solution vigorously for said solvent forming the continuous phase or by means of a mixing mill, or by means of an ultrasonic wave, or using a called a phase change method for preparing the emulsion, first forming a homogeneous system that is then transferred by changing the system temperature to a two-phase system so that the droplets will be formed.
The two-phase state is maintained during the emulsion formation step and the solidification step, for example, through appropriate stirring.
In addition, emulsifying agents / emulsion stabilizers can be used, preferably in a manner known in the art, to facilitate the formation and / or stability of the emulsion. For said purposes, for example, surfactants, a class based on hydrocarbons (including polymeric hydrocarbons with a molecular weight, for example, of up to 10,000 and optionally interrupted with a hetero atom (s)), preferably halogenated hydrocarbons, such as highly sown hydrocarbons fluorinated optionally having a functional group selected, for example, from -OH, -SH, NH ₂ , NR ₂ , -COOH, -CONH2, alkene oxides, -CR = CH ₂ , where R is hydrogen or Ci-C groups ₂₀ alkyl, C ₂ - ₂₀ alkenyl or C ₂ - ₂₀ alkynyl, oxo groups, cyclic ethers and / or any reactive derivative of these groups, such as alkoxy groups, or alkyl ester of carboxylic acid, or, preferably, semi-hydrocarbons. highly- or perfluorinated having a functionalized terminal, can be used. Surfactants can be added to the catalyst solution, which forms the dispersed phase of the emulsion, to facilitate the formation of the emulsion and stabilize the emulsion.
Alternatively, an emulsifier and / or emulsion stabilization aid can also be formed by reacting a surfactant precursor
30/131 loading at least one functional group with a compound reactive with said functional group and present in the catalyst solution or in the solvent that forms the continuous phase. The reaction product obtained acts as the emulsification aid and / or real stabilizer in the formed emulsion system.
Examples of surfactant precursors useful for forming said reaction product include, for example, known surfactants that carry at least one functional group selected from, for example, -OH, -SH, NH2, NR2, -COOH, -COONH2, oxides of alkenes, -CR = CH2, wherein R is hydrogen or Ci-C ₂₀ alkyl, , C ₂ - ₂₀ alkenyl , or , C ₂ - ₂₀ alkynyl, oxo, cyclic ethers with 3 to 5 ring atoms and / or any reactive derivative of these groups, such as alkoxy and alkyl ester of carboxylic acid; for example, semi-, highly or perfluorinated hydrocarbons carrying one or more of said functional groups. Preferably, the surfactant precursor has terminal functionality as defined above.
The compound reacting with said surfactant precursor is preferably contained in the catalyst solution and can be an additional additive or one or more of the catalyst forming compounds. Such a compound is, for example, a group 13 compound (for example, MAO and / or alkyl aluminum compound and / or transition metal compound).
If a surfactant precursor is used, it is preferably first reacted with a compound of the catalyst solution before the addition of the transition metal compound. In one embodiment, a highly fluorinated C1n alcohol (suitably C4-30 or C5-15) (eg, heptane, octanol or highly fluorinated nonanol), oxide (eg, propenoxide) or acrylate ester is reacted with a cocatalyst to form the real surfactant. Then, an additional amount of cocatalyst and the transition metal compound is added to said solution and the obtained solution is dispersed in the solvent forming the continuous phase. The actual surfactant solution can be prepared before the dispersion step or in the dispersion system. If said solution is made before the dispersion step, then the prepared real surfactant solution and the transition metal solution can be dispersed successively (for example, the surfactant solution
31/131 first) in the non-miscible solvent or be combined before the dispersion step.
Solidification
The solidification of the catalyst component (s) in the dispersed droplets can be carried out in several ways, for example, causing or accelerating the formation of said solid catalyst reaction products of the compounds present in the droplets. This can be done, depending on the compounds used and / or the desired solidification rate, with or without an external stimulus, such as a system temperature change.
In a particularly preferred embodiment, solidification is carried out after the emulsion system is formed by subjecting the system to an external stimulus, such as a change in temperature. Temperature differences of, for example, 5 to 100 ° C, such as 10 to 100 ° C or 20 to 90 ° C, such as 50 to 90 ° C.
The emulsion system can be subjected to a rapid temperature change to cause rapid solidification in the dispersed system. The dispersed phase can, for example, be subjected to an immediate temperature change (within milliseconds to a few seconds) in order to obtain rapid solidification of the component (s) within the droplets. The appropriate temperature change, that is, an increase or decrease in the temperature of an emulsion system, necessary for the desired solidification rate of the components cannot be limited to any specific range, but depends naturally on the emulsion system, that is , the compounds used and their concentrations / ratios, as well as the solvents used, and is chosen accordingly. It is also evident that any techniques can be used to provide sufficient heating or cooling effect for the dispersed system to cause the desired solidification.
In one embodiment, the heating or cooling effect is obtained by bringing the emulsion system with a certain temperature to an inert receiving medium with a significantly different temperature, for example, as stated above, so that said change of
32/131 the temperature of the emulsion system is sufficient to cause rapid droplets to solidify. The receiving medium can be gaseous, for example, air, or a liquid, preferably a solvent, or a mixture of two or more solvents, in which the component (s) of the catalyst is / are non-miscible and which is inert with respect to the catalyst component (s). For example, the receiving medium comprises the same non-miscible solvent used as the continuous phase in the first emulsion formation step.
Said solvents can be used alone or as a mixture with other solvents, such as aliphatic or aromatic hydrocarbons, such as alkanes. Preferably, a fluorinated solvent as the receiving medium is used, which can be the same as the continuous phase in the formation of the emulsion, for example, perfluorinated hydrocarbon.
Alternatively, the temperature difference can be achieved by gradually heating the emulsion system, for example, to 10 ° C per minute, preferably 0.5 to 6 ° C per minute and more preferably at 1 to 5 ° C per minute .
In the event that a melt of, for example, a hydrocarbon solvent is used to form the dispersed phase, solidification of the droplets can be carried out by cooling the system using the temperature differences mentioned above.
Preferably, changing a phase as useful for forming an emulsion can also be used to solidify the catalytically active contents within the droplets of an emulsion system by again making a temperature change in the dispersion system, so that the solvent used in the droplets it becomes miscible with the continuous phase, preferably a continuous fluorous phase as defined above, so that the droplets become depleted of the solvent and the solidification components that remain in the droplets begin to solidify. In this way, immiscibility can be adjusted with respect to solvents and conditions (temperatures) to control the solidification step.
The miscibility of, for example, organic solvents with fluorine solvents can be verified from the literature and chosen
33/131 adequately by an expert. Also, the critical temperatures required for the phase change are available from the literature or can be determined using methods known in the art, for example, Hildebrand-Scatchard-Theorie. Reference is also made to the articles by A. Enders and G. and Pierandrea Lo Nostro mentioned above.
In this way, according to the invention, all or only part of the droplet can be converted into a solid form. The size of the solidified droplet can be smaller or larger than that of the original droplet, for example, if the amount of monomer used for prepolymerization is relatively large.
The recovered solid catalyst particles can be used, after an optional washing step, in an olefin polymerization process. Alternatively, the separated and optionally washed solid particles can be dried to remove any solvent present in the particles prior to use in the polymerization step. The optional washing and separation steps can be carried out in a known manner, for example, by filtering and subsequently washing the solids with a suitable solvent.
The droplet shape of the particles can be substantially maintained. The particles formed can have an average size range of 1 to 500 pm, for example, 5 to 500 pm, advantageously 5 to 200 pm or 10 to 150 pm. Even a medium-sized range from 5 to 60 pm is possible. The size can be chosen depending on the polymerization for which the catalyst is used. Advantageously, the particles are essentially spherical in shape, they have a low porosity and a low surface area.
Solution formation can be carried out at a temperature of 0-100 ° C, for example, at 20-8013. The dispersing step can be carried out at -20 ° C-100 ° C, for example, at about -10-70 ° C, such as at -5 to 30 ° C, for example, around 0 ° C .
To the obtained dispersion an emulsifying agent as defined above can be added to improve / stabilize droplet formation. Solidification of the catalyst component in the droplets is preferable
34/131 carried out by increasing the temperature of the mixture, for example, from 0 ° C to 100 ° C, for example, up to 60-9 0 ° C, gradually. For example, in 1 to 180 minutes, for example, 1-90 or 5-30 minutes, or as a quick heat exchange. The heating time depends on the size of the reactor.
During the solidification step, which is preferably carried out at about 60 to 100 ° C, preferably at about 75 to 90 ° C, (below the boiling point of the solvent), the solvents can preferably be removed and optionally the solids are washed with a washing solution, which can be any solvent or mixture of solvents such as those defined above and / or used in the art, preferably a hydrocarbon, such as pentane, hexane or heptane, suitably heptane. The washed catalyst can be dried or it can be made into a slurry in an oil and used as a catalyst-oil slurry in the polymerization process.
All or part of the preparation steps can be done on an ongoing basis. Reference is made to WO2006 / 069733 which describes principles of such continuous or semi-continuous preparation methods of the types of solid catalyst, prepared via the emulsion / solidification method. Polymerization
The olefin polymerized using the catalyst of the invention is preferably propylene or a higher alpha-olefin. It can also be ethylene or a mixture of ethylene and α-olefin. Alternatively, it can also be an alpha olefin mixture, for example, C _2-20 olefins, for example, ethylene, propylene, 1-butene, 1-hexene-, 4-methyl-1-pentene, 1-octene, etc. The olefins polymerized in the method of the invention can include any compound that includes unsaturated polymerizable groups. In this way, for example, unsaturated compounds, such as C6-20 olefins (including cyclic and polycyclic olefins (eg, norbornene)), and polyenes, especially C4-20 dienes, can be included in a comonomer mixture with lower olefins, for example, C _2-5 α-olefins. Diolefins (ie, dienes) are suitably used to introduce long chain branching into the
35/131 resulting polymer. Examples of such dienes include linear dienes α, ω such as 1,5-hexadiene, 1,6-heptadiene, 1,8-nonadiene, 1,9-decadiene, etc.
The catalysts of the present invention are particularly suitable for use in the manufacture of polypropylene polymers or copolymers or homopolymers thereof.
As comonomers for propylene, ethylene or higher olefins, for example, C4-C12 olefins, such as 1butene, 1-hexene, 1-octene or any mixtures thereof, preferably ethylene, are preferably used. It is especially preferred if the copolymer is a propylene ethylene copolymer. This copolymer can be a random copolymer or a heterophasic copolymer. The ethylene content in such a polymer can be up to 50% by weight, for example, 0.5 to 20% by weight, depending on the desired properties of the polymer. In particular, catalysts are used to manufacture propylene homopolymers, random polypropylene copolymers or heterophasic polypropylene copolymers, preferably with ethylene as a comonomer. Heterophasic copolymers can contain a homopolymer or propylene copolymer matrix with an amorphous propylene copolymer component. Such polymers are typically made in a multistage process well known in the art.
Polymerization in the method of the invention can be carried out in one or more, for example, 1, 2 or 3, polymerization reactors, using conventional polymerization techniques, for example, gas phase, solution phase, slurry or mass polymerization.
In general, a combination of slurry (or mass) and at least one gas phase reactor is often preferred, particularly with the order of the reactor being slurry (or mass), then one or more gas phase reactors.
In case of propylene polymerization for slurry reactors, the reaction temperature will generally be in the range of 60 to 110 ° C (for example, 60-90 ° C), the reactor pressure will generally be in the range of 5 to 80 bar (for example, 20-60 bar) and the residence time will generally be in the range of 0.1 to 5 hours (for example, 0.3 to 2 hours). The monomer is generally used as a reaction medium.
For gas phase reactors, the reaction temperature used will generally be in the range of 60 to 115 ° C (for example, 70 to 110 ° C), the pressure of the reactor will generally be in the range of 10 to 25 bar and the residency will generally be 0.5 to 8 hours (for example, 0.5 to 4 hours). The gas used will be the monomer optionally as a mixture with a non-reactive gas such as nitrogen or propane. In addition to polymerization steps and actual reactors, the process may contain any additional polymerization steps, such as prepolymerization step, and any reactor handling steps as known in the art.
For solution polymerization, an aliphatic or aromatic solvent can be used to dissolve the monomer and polymer, and the polymerization temperature will generally be in the range of 80 to 200 ° C (for example, 90 to 150 ° C).
Generally the amount of catalyst used will depend on the nature of the catalyst, the types of reactor and the conditions and properties desired for the polymer product. As is well known in the art, hydrogen can be used to control the molecular weight of the polymer.
The metallocene catalysts of the invention have excellent catalyst activity and good hydrogen response. The catalysts are also capable of providing polymers of average high molecular weight Mw.
In addition, the random copolymerization behavior of metallocene catalysts of the invention shows polymerization activity and activity decline with increased ethylene feed comparable to a symmetrical analogue, but importantly the average molecular weight Mw does not show a negative correlation with increase of ethylene feed as witnessed with symmetric catalysts. This indicates a reduced tendency for chain transfer to ethylene.
Another significant difference is the superior conversion of ethylene with metallocenes of the invention.
Polymers obtained with the metallocenes of the invention have normal particle morphology37 / 131.
Heterophasic copolymers can be prepared with the catalysts of the invention and the activity of this catalyst in both liquid and gas phases is much better than that obtained with a standard symmetrical metallocene. The greater activity in volume and gas phase makes those of the invention the preferred catalyst over symmetrical ones.
In general, then, the catalyst of the invention can provide:
- high activity in volume propylene polymerization;
- very high molecular weight capacity (Mw> 900 kg / mol);
- incorporation of improved ethylene into propylene copolymers;
- high activity obtained in C2 / C3 copolymerization in gas phase;
- good polymer morphology.
It is a feature of the invention that the claimed catalysts allow the formation of high molecular weight polymers. These characteristics can be obtained at commercially interesting polymerization temperatures, for example, 60 ° C or more. It is a preferred feature of the invention that the catalysts of the invention are used to polymerize propylene at a temperature of at least 60 ° C, preferably at least 65 ° C, such as at least 70 ° C.
The Mw of the polymers made using the catalysts of the invention can exceed 200,000, preferably at least 250,000, for example, at least 350,000. Values of more than 500,000 were also obtained. Mw / Mn values are generally low, for example, less than 4, such as less than 3.5 or even less than 3.
Polypropylenes made by the metallocenes of the invention can be made with MFR21 values in the range of 0.1 to 100 g / 10 min depending on the amount of comonomer content and / or the use and amount of hydrogen used as an MFR regulating agent.
Polymers made by the catalysts of the invention are useful in all types of final articles such as tubes, films (fused, blown or BOPP films, such as, for example, BOPP for
38/131 capacitor), fibers, molded articles (for example, injection molded, blow molded, rotational molded articles), extrusion coatings and so on.
The invention will now be illustrated with reference to the following non-limiting examples.
Analytical Tests
Measurement methods:
Determination of Al and Zr (ICP method)
The elementary analysis of a catalyst was carried out by taking a solid mass sample, M, cooling on dry ice. The samples were diluted to a known volume, V, by dissolving in nitric acid (HNO ₃ , 65%, 5% V) and freshly deionized water (DI) (5% V). The solution was then added to hydrofluoric acid (HF, 40%, 3% V), diluted with DI water to the final volume, V, and allowed to stabilize for two hours.
The analysis was performed at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma - Optical Emmission Spectrometer (ICP-OES) that was calibrated using a non-active solution (a 5% HNO ₃ solution, ₃ % HF in DI water) and 6 standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of Al, with 0.5 ppm, 1 ppm, 5 ppm, 20 ppm, 50 ppm and 100 ppm of Hf and Zr in solutions of 5% HNO3, 3% HF in DI water.
Immediately before analysis, the calibration is resloped using the solution with no activity and 100 ppm Al, 50 ppm Hf, standard Zr, a quality control sample (20 ppm Al, 5 ppm Hf, Zr in a solution of 5% HNO ₃ , 3% HF in DI water) is performed to confirm the reclination. The QC sample is also performed after each sample and 5 at the end of a set of programmed analysis.
The hafnium content was monitored using the 282.022 nm and 339.980 nm lines and the zirconium content using the 339.198 nm line. The aluminum content was monitored via the 167,079 line, when the Al concentration in the ICP sample was between 0-10 ppm (calibrated only to 100 ppm) and via the 396,152 nm line for Al concentrations above 10 ppm.
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The reported values are an average of the three successive aliquots obtained from the same sample and are related back to the original catalyst by entering the original sample mass and dilution volume into the software.
DSC Analysis
The melting point (T _m ) and the crystallization temperature (T _c ) were determined on a DSC200 TA instrument by placing a 5-7 mg polymer sample in a closed DSC aluminum pan, heating the sample to -10 ° C to 210 ° C to 10 ° C / min, keeping for 5 minutes at 210 ° C, cooling from 210 ° C to -10 ° C keeping for 5 minutes at -10 ° C, heating from -10 ° C to 210 ° C at 10 ° C / min. The reported _{m m} is the maximum of the second heating sweep curve and T _c is the maximum of the cooling sweep curve.
Fusion Flow Rate
The melt flow rate (MFR) is determined according to ISO 1133 and is given in g / 10 min. The MFR is an indication of the flowability, and then processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR is determined at 230 ° C and can be determined at different loads such as 2.16 kg (MFR2) and 21.6 kg (MFR21).
Intrinsic viscosity is measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135 ° C).
GPC: Molecular weight averages, molecular weight distribution and polydispersity index (Mn, Mw, Mw / Mn)
Molecular weight averages (Mw, Mn), Molecular Weight Distribution (MWD) and its extension, described by polydispersity index, PDI = Mw / Mn (where Mn is the numerical average molecular weight and Mw is the average molecular weight) were determined using Gel Permeation Chromatography (GPC) (Gel Permeation Chromatography) according to ISO 16014-4: 2003 and ASTM D 6474-99. A Waters GPCV200 instrument, equipped with differential refractive index detector and on-line viscometer, was used with TSK 2 x gel columns
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GMHXL-HT and 1 x G7000HXL-HT from Tosoh Bioscience and 1,2,4trichlorobenzene (TCB, stabilized with 250 mg / L of 2,6-Di-tert butyl-4-methyl-phenol) as solvent at 140 ° C and in a constant flow rate of 1 mL / min. 209.5 pL of sample solution was injected by analysis. The column set was calibrated using universal calibration (according to ISO 16014-2: 2003) with at least 15 MWD polystyrene (PS) standards limited in the range of 1 kg / mol to 12 000 kg / mol. Mark Houwink constants for PS, PE and PP used are as for ASTM D 6474-99. All samples were prepared by dissolving 0.5-4.0 mg of polymer in 4 mL (at 140 ° C) of TCB (stabilized) (same as the mobile phase) and maintaining for a maximum of 3 hours at 160 ° C with maximum agitation continuous smoothness before sampling on the GPC instrument.
Determination of soluble xylene fraction (XS):
2.0 g of polymer are dissolved in 250 ml of p-xylene at 135 ° C with stirring. After 30 minutes the solution is left to cool for 15 minutes at room temperature and then left to settle for 30 minutes at 25 ° C. The solution is filtered with filter paper in two 100 ml flasks.
The solution of the first 100 ml container is evaporated in a nitrogen flow and the residue is dried under vacuum at 90 ° C until constant weight is reached.
XS% = (100mVo) / (mo'v); mo = amount of starting polymer (g); m = weight of residue (g); Vo = initial volume (ml); v = volume of sample analyzed (ml).
Ethylene content (FTIR C ₂ )
Ethylene content was measured with Fourier transform infrared spectroscopy (FTIR) calibrated for results obtained by ¹³ C NMR spectroscopy using a method that is responsible for the insertion of regio-irregular propene. When measuring the ethylene content in polypropylene, the thin film of the sample (thickness of about 0.220 to 0.250 mm) was prepared by pressing with heat at 230 ° C (preheating 5 minutes, pressing 1 minute, cooling (cold water) 5 minutes) using a Graseby Specac press. The FTIR spectra of the sample
41/131 were recorded immediately with a Nicolet Protégé 460 spectrometer from 4000 to 400 cm ^-1 , resolution 4 cm ^-1 , sweeps 64. The peak absorption area at 733 cm ^-1 (baseline from 700 cm ^-1 to 760 cm ^-1 ) and the reference peak weight at 809 cm ^-1 (baseline from 780 cm ^-1 to 880 cm ^-1 ) were evaluated. The result was calculated using the following formula:
E _tot = ax A / R + b where
A = peak absorption area at 733 cm ^-1
R = height of the reference peak at 809 cm ^-1
Etot = C2 content (% by weight) a, b are calibration constants determined by the correlation of multiple calibration standards of known ethylene content as determined by ¹³ C NMR spectroscopy for A / R.
The result was reported with an average of two measurements. DMTA
Dynamic mechanical analysis (DMTA) data are obtained according to ISO 6721-1 (General Principles) & 6721-7 (Torsional vibration Non-resonance method)
Experimental Adjustment:
An ARES rheometer from Rheometric scientific, equipped with a liquid nitrogen unit and an oven (convection and radiation heating), a standard torsion rectangular tool and a V6.5.8 software orchestrator or an Anton Paar MCR301 rheometer with a control unit TC30 temperature sensors combined with a liquid nitrogen unit and a CTD600 oven (convection and radiation heating), a standard torsion rectangular tool and RHEOPLUS / 32 v3.40 software are used.
Sample preparation
Stabilized dry pellets are molded by compression at 210 ° C (gel time 5 minutes, pressure time 25 bar / 3 min, cooling rate 25 bar / 15 K / min, release temperature 40 ° C) in a 100 * mold 100 * 1 mm. Only of the homogeneous, bubble-free plates are per
42/131 drilled for strips of 50x10x1 mm and are conditioned for at least 96 hours at room temperature.
Conduct of the experiment:
The device is cooled with the sample set to the initial temperature (standard -130 ° C). After 5 minutes of delay time, the experiment starts with a test frequency of 1 Hz, a heating rate of 2K / min and a ε strip of 0.1%. Measurements are performed under an inert atmosphere (nitrogen) and a tension force (vertically) of 50 g (+/- 20 g).
Temperature dependence of storage module G ', loss module G and tan loss angle tangent (õ) are used for evaluations.
Determinations of transition sections (for example, glass transition temperature, T _g ) are based on the tan (õ) vs. loss tangent. temperature curve (peak curve). Species number: 1. Accuracy: +/- 5%, temperature values: +/- 1.5K.
Examples
Chemical Agents
All chemical agents and chemical reactions were handled under an inert gas atmosphere using Schlenk and glove box techniques, with glassware, syringes, needles or cannulas dried in the oven.
MAO was purchased from Albermarle and used as a 30 wt% toluene solution. Perfluoralkyl ethyl acrylate ester mixture (CAS number 65605-70-1) was purchased from Cytonix Corporation, dried on activated molecular sieves (2 times) and degassed by argon bubbling before use. Hexadecafluor-1,3-dimethylcyclohexane (CAS number 335-27-3) was obtained from commercial sources and dried on activated molecular sieves (2 times) and degassed by bubbling argon before use. Triethyl aluminum was purchased from Crompton and used in pure form. Hydrogen is supplied by AGA and purified before use. Propylene is provided by Borealis and properly purified before use.
1-tert-Butyl-2-methoxybenzene was synthesized via alkylation of 2
43/131 tert-butylphenol (Acros) by dimethyl sulfate (Merck) in the presence of aqueous NaOH (Reachim, Russia) as described in [Stork, G .; White, W. N. J. Am. Chem. Soc. 1956, 78, 4604.]. 2-Methyl-4-bromo-6-tert-butylindanone-1 was obtained as described in the literature [Resconi, L .; Nifant'ev, I. E .; Ivchenko, P. V .; Bagrov, V ,; Focante, F .; Moscardi, G. Int. Pat. Appl. WO2007 / 107448 A1].
7-Bromo-5-tert-butyl-2-methyl-1H-indene was obtained from 2methyl-4-bromo-6-teri-butylindanone-1 as described in [Voskoboynikov, A. Z .; Asachenko, A. F .; Kononovich, D. S .; Nikulin M. V .; Tsarev, A. A .; Maaranen, J .; Vanne, T .; Kauhanen, J .; Mansner, E .; Kokko, E .; Saarinen, L. Int. Pat. Appl. WO2009 / 027075].
B / s chloride (2,6-diisopropylphenyl) imidazolium chloride, i.e. IPr (HCl), and (IPr) NiCl2 (PPh3) were synthesized as described in [Hintermann, L. Beilstein J. Org. Chem. 2007, 3, 1.] and [Matsubara, K .; Ueno, K .; Shibata, Y. Organometallics 2006, 25, 3422.], respectively.
4/7-Bromo-2-methyl-3 // H-indene was obtained as described in [Izmer, V.V .; Lebedev, A.Y .; Nikulin, M.V .; Ryabov, A.N .; Asachenko, A.F .; Lygin, A.V .; Sorokin, D.F .; Voskoboynikov, A.Z. Organometallics 2006, 25, 1217.].
Anisol (Acros), 3-methylanisol (Acros), tert-Butyl toluene (Aldrich), 1-Bromo-4-tert-butylbenzene (Acros), P4O10 (Reachim), Pd (P ^t Bu3) 2 (Strem), ZnCl2 1 , 0 M in THF (Aldrich), 3,5-di-tert-butylphenylmagnesium bromide in 1.0 M THF (Aldrich), hexanes (Reachim, Russia), N-bromosuccinimide (Acros), diethyl methylmalonate (Aldrich) , methyl iodide (Acros), acetone (Reachim, Russia), tetraethylammonium iodide (Acros), triphenylphosphine (Acros), CuCN (Merck), methanesulfonic acid (Aldrich), sodium tetrafenylborate (Aldrich), palladium acetate (Aldrich) ), copper cyanide (Merck), magnesium shavings (Acros), lithium aluminum hydride (Aldrich), bromobenzene (Acros), ⁿ BuLi in 2.5 M hexanes (Chemetall), ZrCL (THF) 2 (Aldrich), NaBH (Aldrich), Ni (OAc) 2 (Aldrich), silica gel 60 (40-63 pm, Merck), AlCl ₃ (Merck), bromine (Merck), benzoyl peroxide (Aldrich), iodine (Merck), NaHCO ₃ (Merck), Na2CO3 (Merck), K2CO3 (Merck), Na2SO4 (Merck), Na2SO3 (Merck), sodium metal (Merck), chloret thionyl (Merck), sodium acetate, trihydrate (Merck), tetraethylammonium iodide (Acros), triphenylphosphine (Acros), KOH (Merck),
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Na ₂ SO ₄ (Akzo Nobel), TsOH (Aldrich), HCl 12 M (Reachim, Russia), methanol (Merck), anhydrous ethanol (Merck), CDCl ₃ and DMSO-d6 (Deutero GmbH) as well as hexanes (Merck) , carbon tetrachloride (Merck), ether (Merck), ethyl acetate (Merck), toluene (Merck) and CH ₂ Cl ₂ (Merck) for extractions were used as received.
Tetrahydrofuran (Merck), ether (Merck) and dimethoxyethane (Acros) freshly distilled from cetyl benzophenone were used. Dichloromethane (Merck) for organometallic synthesis as well as CD ₂ Cl ₂ (Deutero GmbH) for NMR experiments were dried and kept in CaH ₂ . Toluene (Merck), noctane (Merck) and hexanes (Merck) for organometallic synthesis were maintained and distilled in Na / K alloy. Dichlorodimethylsilane (Merck) and methacrylic acid (Acros) were distilled before use.
Rac-methyl (cyclohexyl) silanediylbis [2-methyl-4- (4-tertbutylphenyl) indenyl] zirconium (C1) bichloride:
was purchased from a commercial source.
Rac-dimethylsilanediilbis (2-methyl-4-phenyl-5-methoxy-6tert-butylindenyl) zirconium bichloride (C2):
Me ₂ Si ZrCI ₂ was synthesized as described in WO 2007/116034.
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Preparation of metallocene complexes of the invention
Synthesis of antidimethylsilylene bichloride (2-methyl-4-phenyl-5-methoxy-6- / erc-butylindenyl) (2-methyl-4-phenyl-6- / erc-butyl-indenyl) zirconium (Metallocene E1)
6-tert-Butyl-5-methoxy-2-methylindan-1-one
CH ₂ = C (Me) CO ₂ H
P4O10-MeSO3H

To an Eaton reagent obtained from 110 g of P ₄ Oi ₀ and 560 ml of methanesulfonic acid a mixture of 65.6 g (0.399 mol) of 1-tert-butyl-2 methoxybenzene and 43.0 g (0.50 mol) of methacrylic acid was added about 1 hour at 50-55 ° C. The resulting mixture was stirred for 1 hour at this temperature, then cooled to room temperature and poured into a mixture of 1 liter of cold water and 1 kg of ice. The crude product was extracted with 3 x 500 ml of dichloromethane. The combined organic extract was washed with aqueous K ₂ CO ₃ and then evaporated to dryness. Fractional rectification of the residue provided 64.9 g of yellowish oil which crystallizes at room temperature. Under evidence of NMR spectroscopy, this product includes about 90% of the target material. In addition, this product was dissolved in 180 ml of hot hexanes. Crystals precipitated from this solution at room temperature were collected, washed with 100 ml of cold hexanes and dried under vacuum. This procedure provided 39.6 g (43%) of the analytically substituted pure indanone.
Anal. calc. for C ₁₅ H ₂₀ O ₂ : C, 77.55; H, 8.68. Found: C, 77.48; H, 8.79.
1H NMR (CDCle): δ 7.68 (s, 1H, 7-H on indanone), 6.87 (s, 1H, 4-H on indanone), 3.93 (s, 3H, OMe), 3, 32 (m, 1H, 3-H on indanone), 2.69 (m, 1H, 2-H on indanone), 2.64 (m, 1H, 3'-H on indanone), 1.37 (s, 9H, ^f Bu), 1.29 (d, J = 7.3 Hz, 3H, 2-Me in indanone). ¹³ C {1H} NMR (CDCle): δ 208.1,
164.6, 154.4, 138.8, 128.7, 122.1, 107.8, 55.2, 42.1, 35.0, 34.7, 29.6, 16.6. 6-tert-Butyl-5-methoxy-2-methylindan-1-one (second experiment)
Eaton's reagent obtained from 118 g of P ₄ O ₁₀ and 600 ml of methanesulfonic acid is a mixture of 70.3 g (0.428 mol) of 1-tert-butyl
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2-methoxybenzene and 295.0 g (3.43 mol, 8 equivalents) of methacrylic acid was added for about 1 hour at 50-55 ° C. The resulting mixture was stirred for 0.5 h at this temperature, then cooled to room temperature and poured into a mixture of 1.5 liters of cold water and 2 kg of ice. After the ice melted, the precipitated crude 6-tert-butyl-5-methoxy-2-methylindan-1-one was filtered and then washed with 2x100 ml of cold water. The crude product was dissolved in 500 ml of dichloromethane and this solution was washed with aqueous K ₂ CO ₃ , dried over anhydrous K ₂ CO ₃ and then evaporated in Rotavap. The residue was vacuum distilled to provide 70.6 g of crude 6-tert-butyl-5-methoxy-2-methylindan-1one, eg 155-165 ° C / 5 mm Hg. This product was dissolved in 200 ml of hot hexanes. The precipitated crystals of this solution at 5 ° C were collected, washed with 50 ml of cold hexanes and dried in vacuo. This procedure provided 64.1 g (65%) of the analytically pure substituted indanone.
4-Bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one
Br ₂ , AcONa, Et4NI
CH ₂ Cl ₂ -H ₂ O
To a mixture of 60.0 g (0.258 mol) of 6-tert-butyl-5-methoxy-2methylindan-1-one, 130 g of NaOAc (H ₂ O) ₃ , 1.5 g of Et ₄ NI, 220 ml of dichloromethane and 450 ml of water cooled to 5 ° C, 45.0 g (0.282 mol) of bromine were added for about 5 minutes by vigorous stirring. This mixture was stirred for 1 hour at 5 ° C and then a solution of 60.0 g of NaOAc (H2O) in 200 ml of water was added. To the resulting mixture 23.5 g (0.147 mmol) of bromine were added at 5 ° C. The resulting solution was stirred for 30 minutes and then Na2SO3 was added in small portions to remove excess bromine. The CH2Cl2 layer was separated from the upper aqueous layer and the latter was extracted with 2 x 300 ml of dichloromethane. The combined organic extract was dried over K2CO3, passed through a short layer of silica gel 60 (40-63 pm) and then evaporated until dry. The residue was dried in vacuo to provide 79.9 g (99%) of the title compound which was used further without further purification.
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Anal. calc. for Ci ₅ Hi ₉ BrO ₂ : C, 57.89; H, 6.15. Found: C, 57.70; H, 6.08.
1H NMR (CDCfe): δ 7.70 (s, 1H, 7-H in indanone), 4.03 (s, 3H, OMe), 3.31 (dd, J = 17.4 Hz, J = 7, 8 Hz, 1H, 3-H on indanone), 2.72 (m, 1H, 2-H on indanone), 2.62 (dd, J = 17.4 Hz, J = 3.8 Hz, 1H, 3 '-H in indanone), 1.40 (s, 9H, ^f Bu), 1.32 (d, J = 7.6 Hz, 3H, 2-Me in indanone). ¹³ C {1H} NMR (CDCle): δ 208.0, 162.8, 154.0, 145.5, 132.7, 121.5, 116.7, 61.7, 42.2, 36.1 , 35.7, 30.6, 16.4.
6-tero-Butyl-5-methoxy-2-methyl-4-phenylindan-1-one
NaBPh4, Na2CO3
Pd (OAc) 2 / PPh3, DME-H2O
To a mixture of 46.7 g (0.150 mol) of 4-bromo-6-tert-butyl-5methoxy-2-methylindan-1-one, 44.0 g (0.415 mol) of Na ₂ CO ₃ , 25.7 g (0.075 mol) of NaBPh4, 600 ml of DME and 240 ml of water 1.01 g (4.50 mmol) of Pd (OAc) ₂ and 2.36 g (9.00 mmol) of PPh ₃ were added. The resulting mixture was refluxed for 12 hours, cooled to room temperature and then evaporated to dryness. To the residue, 1 liter of cold water was added and the crude product was extracted with 3 x 300 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 pm; eluent: hexanes-dichloromethane-ether = 20: 10: 1, vol.). Yield 46.0 g (99%) of yellowish crystalline solid.
Anal. calc. for C ₂₁ H ₂₄ O ₂ : C, 81.78; H, 7.84. Found: C, 81.90; H, 7.93.
1H NMR (CDCle): δ 7.76 (s, 1H, 7-H in indanone), 7.47 (m, 2H,
3.5-H in Ph), 7.42 (m, 2H, 2.6-H in Ph), 7.39 (m, 1H, 4-H in Ph), 3.29 (s, 3H, OMe ), 3.13 (dd, J = 17.4 Hz, J = 7.8 Hz, 1H, 3-H on indanone), 2.63 (m, 1H, 2-H on indanone), 2.47 ( dd, J = 17.4 Hz, J = 3.8 Hz, 1H, 3'-H on indanone), 1.43 (s, 9H, ^f Bu), 1.25 (d, J = 7.3 Hz , 3H, 2 Me in indanone). ¹³ C {1H}
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NMR (CDCh): 5 208.7, 163.5, 152.7, 143.5, 136.4, 132.5, 131.0, 129.5,
128.7, 127.5, 121.6, 60.5, 42.2, 35.4, 34.3, 30.5, 16.4.
6-tert-Butyl-5-methoxy-2-methyl-4-phenylindan-1-one (second experiment)
To a mixture of 46.7 g (0.150 mol) of 4-bromo-6-fer-butyl-5methoxy-2-methylindan-1-one, 44.5 g (0.420 mol) of Na ₂ CO ₃ , 22.0 g (0.180 mol) of PhB (OH) ₂ , 570 ml of DME and 195 ml of water 0.684 g (3.0 mmol) of Pd (OAc) ₂ and 1.58 g (6.00 mmol) of PPh ₃ were added. The resulting mixture was refluxed for 12 hours, cooled to room temperature and then DME was evaporated in Rotavap. To the residue, 1 liter of cold water was added and the crude product was extracted with 3 x 300 ml of dichloromethane. The combined organic extract was dried over K ₂ CO ₃ and then evaporated to dryness. The residue after evaporation was extracted with hot hexane (500 ml, then 3 x 250 ml) and these extracts while hot were passed through a short pad of silica gel, evaporated in Rotavap to provide 45.1 g (98%) of 6 -ferc-butyl-5-methoxy-2-methyl-4-phenylindan-1-one as a slightly yellowish crystalline solid that was used more without further purification. 5-fer-Butyl-6-methoxy-2-methyl-7-phenyl-1 / - / - indene
1. NaBH _4l THF-MeOH
2. TsOH, toluene
To a solution of 45.9 g (0.149 mmol) of 6-ferc-butyl-5-methoxy2-methyl-4-phenylindan-1-one in 300 ml of THF cooled to 5 ° C, 8.51 g (0.225 mol ) of NaBH ₄ were added. In addition, 150 ml of methanol was added dropwise to this mixture by vigorous stirring for about 7 hours at 5 ° C. The resulting mixture was stirred overnight at room temperature and then 1 liter of cold water and HCI 12M to pH ~ 1 were added. The crude product was extracted with 3 x 200 ml of dichloromethane, the combined organic extract was dried over K ₂ CO ₃ and then evaporated to dryness. To a solution of the residue in 800 ml of toluene 1.0 g
49/131 TsOH was added, this mixture refluxed with Dean-Stark head for 10 minutes and then cooled to room temperature using a water bath. The resulting solution was washed with 10% aqueous Na ₂ CO ₃ , the organic layer was separated, the aqueous layer was extracted with 2 x 50 ml of dichloromethane. The combined organic solution was dried over K2CO3 and then passed through a short layer of silica gel 60 (40-63 pm). The silica layer was further washed with 100 ml of dichloromethane. The combined organic eluate was evaporated to dryness. This procedure provided 43.1 g (99%) of yellowish oil which was used more without additional purification.
Anal. calc. for C ₂ iH ₂₄ O: C, 86.26; H, 8.27. Found: C, 86.39; H, 8.37.
¹ H NMR (CDCle): δ 7.47-7.49 (m, 2H, 2.6-H in Ph), 7.43 (m, 2H,
3.5-H in Ph), 7.34 (m, 1H, 4-H in Ph), 7.22 (s, 1H, 4-H in indene), 6.44 (m, 1H, 3-H in indeno), 3.22 (s, 3H, OMe), 3.12 (s, 2H, 1,1'-H in indeno), 2.06 (s, 3H, 2-Me in indeno), 1, 44 (s, 9H, ^f Bu). ¹³ C { ¹ H} NMR (CDCle): δ
154.3, 145.3, 141.7, 141.0, 138.5, 131.6, 129.5, 128.3, 126.9, 126.8, 117.2,
60.7, 42.8, 35.2, 31.0, 16.6.
5-tert-Butyl-6-methoxy-2-methyl-7-phenyl-1 H-indene (second experiment)
To a solution of 44.3 g (0.144 mmol) of 6-tert-butyl-5-methoxy2-methyl-4-phenylindan-1-one in 150 ml of cooled THF to 5 ° C 2.72 g (71.9 mmol) of NaBH ₄ were added. In addition, 75 ml of methanol was added dropwise to this mixture by vigorous stirring for 1 hour at 5 ° C. The resulting mixture was further stirred 1 hour at 5 ° C, then 0.5 hour at room temperature and then added to 1 liter of cold water and 30 ml of 12 M HCl in a separatory funnel. The crude product was subsequently extracted with 250, 100 and 50 ml of dichloromethane and the combined organic extract was evaporated to dryness. To the solution of the residue in 500 ml of toluene 1.0 g of TsOH was added, this mixture was refluxed with Dean-Stark head for 10 minutes and then cooled to room temperature using a water bath. The resulting solution was washed with aqueous K ₂ CO ₃ (20 g of K ₂ CO ₃ in 200 ml of H ₂ O), the organic layer was separated, the aqueous layer was extracted with 2 x 50 ml of dichloromethane. The solution
The combined organic 50/131 was dried over K2CO3 and then passed through a short layer of silica gel 60 (40-63 µm, ca. 10 g). The silica gel layer was further washed with 50 ml of dichloromethane. The combined organic eluate was evaporated to dryness. This procedure provided 42.0 g (~ 100%) of yellowish oil which was used further without further purification.
(6-tert-Butyl-5-methoxy-2-methyl-4-phenyl-1/7-inden-1-yl) (chlorine) dimethylsilane
ⁿ BuLi, toluene-THF-hexanes
2. M62SCI2
To a solution of 16.2 g (55.4 mmol) of 5-tert-butyl-6-methoxy-2methyl-7-phenyl-1/7-indene in 300 ml of toluene, 22.2 ml (55.5 mmol) of 2.5 M BuLi in hexanes were added at room temperature. The resulting viscous solution was stirred for 2 hours and then 15 ml of THF was added. The suspension formed was stirred for 12 hours at room temperature, about 2 hours at 60 ° C, then cooled to -20 ° C, and 35.8 g (277 mmol) of dichlorodimethylsilane was added in one portion. The resulting solution was heated to 60 ° C and stirred for 1 hour at this temperature. The resulting mixture was evaporated to about% of its volume, then filtered through glass frit (G3). The precipitate was additionally washed with 20 ml of toluene. The combined filtrate was evaporated to dryness to provide 21.2 g (99%) of viscous yellowish oil.
Anal. calc. for C23H29CIOSI: C, 71.75; H, 7.59. Found: C, 71.92; H, 7.80.
¹ H NMR (CDCl 3): 0 7.52-7.54 (m, 2H, 2.6-H in Ph), 7.48 (m, 2H,
3.5-H in Ph), 7.45 (s, 1H, 7-H in indenyl), 7.38 (m, 1H, 4-H in Ph), 6.49 (m, 1H, 3-H in indenyl), 3.59 (m, 1H, 1-H in indenyl), 3.27 (s, 3H, OMe), 2.23 (m, 3H, 2-Me in indenyl), 1.48 (s , 9H, ^f Bu), 0.47 (s, 3H, Si / WeMe '), 0.22 (s, 3H, SiMe / We'). ¹³ C { ¹ H} NMR (CDCI3): δ 155.8, 146.2, 143.7, 138.2,
137.6, 137.0, 130.2, 128.3, 127.4, 126.7, 126.5, 121.1.60.5, 50.1, 35.2, 31.2,
17.6, 1.1, -0.6.
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5-tert-Butyl-2-methyl-7-phenyl-1H-indene
Br
I PhMgBr
Ni (OAc) ₂ , IPr (HCl), THF

IPr
To a solution of PhMgBr obtained from 89.0 g (567 mmol) of bromobenzene, 15.8 g (650 mmol) of magnesium chips and 450 ml of THF, 1.60 g (3.76 mmol) of chloride bis (2,6-diisopropylphenyl) imidazolium, i.e., IPr (HCl), and 0.66 g (3.76 mmol) of Ni (OAc) 2 were added. In addition, a solution of 50.0 g (189 mmol) of 7-bromo-5-tert-butyl-2-methyl-1H-indene in 50 ml of THF was added. The resulting mixture was stirred for 2 hours at room temperature, refluxed for 1 hour, cooled to room temperature and then 200 ml of water were added in drops. Finally, 100 ml of 12 M HCl was added in drops. The product was extracted with 300 ml of ether. The organic layer was separated and the aqueous layer was further extracted with 2 x 150 ml of dichloromethane. The combined organic extract was dried over K2CO3, passed through a short layer of silica gel 60 (40-63 pm) and then evaporated to dryness. Fractional rectification of the residue provided 34.7 g (70%) of viscous yellow oil, e.g. 180-210 ° C / 5 mm Hg. The product is a mixture of about 1 to 1 of 6-tert-butyl-2-methyl-4-phenyl1H-indene and 5-tert-butyl-2-methyl-7-phenyl-1H-indene.
Anal. calc. for C ₂₀ H ₂₂ : C, 91.55; H, 8.45. Found: C, 91.61;
H, 8.50.
¹ H NMR (CDCfe): δ 7.52 (m, 4H), 7.40-7.43 (m, 6H), 7.29-7.33 (m, 3H), 7.17 (m, 1H ), 6.62 (m, 1H), 6.50 (m, 1H), 3.32 (s, 4H), 2.10 (s, 6H),
I, 37 (s, 9H), 1.36 (s, 9H).
52/131 (6-tert-Butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl) - (6-tert-butyl-2-methyl-4-phenyl1 / - / - inden -1 -iDdimethylsilane
1. ⁿ BuLi, Et ₂ 0-hexanes

To a solution of 14.5 g (55.4 mmol) of 5-tert-butyl-2-methyl-7-phenyl-1 / - / - indene in 400 ml of water cooled to -78 ° C, 22.2 ml ( 55.5 mmol) of 2.5 M BuLi ⁿ in hexanes were added. This mixture was stirred overnight at room temperature, then cooled to -78 ° C and 200 mg (2.23 mmol) of CuCN were added. The resulting mixture was stirred for 30 minutes at -20 ° C, then cooled to -78 ° C and a solution of (6-tert-butyl-5-methoxy-2-methyl) 21.2 g (55.4 mmol) -4-phenyl-1 / - / - inden-1 yl) (chlorine) dimethylsilane in 200 ml of ether was added. This mixture was stirred overnight at room temperature, then 1 ml of water was added. The obtained mixture was passed through a short layer of silica gel 60 (40-63 pm), the eluate was evaporated until dry. The product was isolated by flash chromatography on silica gel 60 (40-63 µm, eluent: hexanes-dichloromethane = 10: 1, vol., Then 3: 1, vol.). This procedure provided 24.5 g (72%) of yellowish glassy solid.
Anal. calc. for C43H50OS: C, 84.54; H, 8.25, Found: C, 84.69; H, 8.34.
¹ H NMR (CDCI3): δ 7.35-7.62 (m), 6.81 (s), 6.75 (s), 6.63 (s), 6.45 (s), 3.73 (s), 3.71 (s), 3.70 (s), 3.30 (s), 2.23 (s), 2.22 (s), 2.15 (s), 2.08 ( s, 1.50 (s), 1.49 (s), 1.43 (s), 1.42 (s), 0.06 (s), -0.06 (s), -0.07 (s), -0.08 (s), -0.12 (s).
53/131
Anfretfimethylsilylene bichloride (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl) (2methyl-4-phenyl-6-tert-butyl-indenyl) zirconium (metallocene E1)
To a solution of 7.64 g of (12.5 mmol) of (6-tert-butyl-5methoxy-2-methyl-4-phenyl-1/7-inden-1-yl) (6-fer-butyl) -2-methyl l-4-phen i 1-1 / 7-inden-1 yl) dimethylsilane in 200 ml of ether cooled to -78 ° C, 10.0 ml (25.0 mmol) of ⁿ BuLi 2.5 M in hexanes were added. The resulting mixture was stirred overnight at room temperature, then cooled to 78 ° C and 4.72 g (12.5 mmol) of ZrCl4 (THF) ₂ were added. This mixture was stirred for 24 hours at room temperature. Under evidence of NMR spectroscopy, this mixture included anti and syn zirconocenes at a ratio equal to about 70:30. This mixture was filtered on a glass frit (G4), the filtrate was evaporated to dryness. The residue was dissolved in a mixture of 60 ml of n-octane and 15 ml of refluxed toluene. Crystals precipitated from this solution at -30 ° C were collected, washed with 2 x 10 ml of cold hexanes and vacuum dried. This procedure provided 1.97 g (20%) of pure racemic zirconocene. Additional quantity of this product was obtained in a similar way from the mother liquor. In this way, the combined yield of the product was 3.54 g (37%) as a yellowish-orange crystalline solid.
Anal. calc, for C43H ₄₈ CI ₂ OSiZr: C, 66.98; H, 6.27. Found: C, 67.09; H, 6.33.
¹ H NMR (CDCh): 0 7.28-7.70 (m, 13H, 7-H and 5.7-H in indenyls and Ph), 6.94 (s, 1H, 3-H in indenyl), 6.60 (s, 1H, 3-H in indenyl), 3.41 (s, 3H, OMe), 2.26 (s, 3H, 2-Me in indenyl), 2.23 (s, 3H, 2 Me in indenyl), 1.42 (s, 9H, ^f Bu), 1.36 (s, 3H, Si / WeMe '), 1.35 (s, 9H, ^f Bu), 1.34 (s, 3H, Si54 / 131
Me Me ’).
Synthesis of an // dimethylsilylene bichloride (2-methyl-4-phenyl-5-methoxy-6- / erc-butylindenyl) (2-methyl-4- (4- / erc-butyl-phenyl) indenyl) zirconium (Metallocene E2)
4 / 7- (4-tert-Butylphenyl) -2-methyl-3 / 1H-indene
Br

To a solution of 4-tert-butylphenylmagnesium bromide obtained from 110 g (0.518 mol) of 4-tert-butylbenzene and 12.6 g (0.518 mol) of magnesium chips in 500 ml of THF, 0.65 g (0.83 mmol) of (IPr) NiCl ₂ PPh ₃ and a solution of 77.6 g (0.371 mol) of 4/7-bromo-2-methyl-3 / 1H-indene in 50 ml of THF were added. This mixture was stirred at reflux for 30 minutes and then for 20 minutes at room temperature. Finally, 150 ml of water and then 70 ml of 4 M HCl were added. The product was extracted with 200 ml of ethanol and then 2 x 100 ml of dichloromethane. The combined organic extract was dried over K ₂ CO ₃ , passed through a short column with Slicagel 60 and evaporated until dry. Rectification of the residue, eg 163-171 ° C / 5 mm Hg, provided 93.8 g (96%) of a mixture of the isomeric titers such as yellowish viscous oil which is slowly crystallized.
Anal. calc. for C ₂₀ H ₂₂ : C, 91.55; H, 8.45. Found: C, 91.62; H, 8.52.
¹ H NMR (CDCl ₃ ): δ 7.62 (m, C ₆ H ₄ of both isomers), 7.46 (m, 5- and 6-H in 4- and 7-arylindenes), 7.40 ( m, 7- and 4-H in 4- and 7-arylindenes), 7.31 (m, 6- and 5-H in 4- and 7-arylindenes), 6.88 (m, 3-H in 4 / 7-arylindene), 6.68 (m, 3-H in 7/4-arylindene), 3.55 (m, 1-CH2 in 7/4-arylindene), 3.49 (m, 1-CH2 in 4 / 7-arylindene), 2.28 (2-Me in 4/7-arylindene), 2.27 (2-Me in 7/4
55/131 arylindene), 1.54 (s, ‘Bu in 4- and 7-arylindenes). (6-tert-Butyl-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl) [4- (4-te / 'c-butylphenyl) -2-methyl1 H-inden-1 - il] dimethylsilane
1. ⁿ BuLi, Et ₂ O- /
2.CuCN ³ qO
Λ ^M x ^] SiMe ₂ ClI
----------------------- ►SiMe / ⁷ OMe o
To a solution of 11.5 g (43.8 mmol) of 7- (4-tert-butylphenyl) -2methyl-1H-indene in 300 ml of ether, 17.0 ml (42.5 mmol) of 2.5 M BuLi in hexanes was added in one portion at -78 ° C. This mixture was stirred overnight at room temperature, then cooled to -60 ° C and 150 mg of CuCN was added. The resulting mixture was stirred for 1 hour at -20 ° C, then cooled to -70 ° C and 16.2 g of (6-tert-butyl-5-methoxy-2methyl-4-phenyl-1H-inden-1- il) (chloro) -dimethylsilane (42.08 mmol) in 150 ml of ether were added. In addition, this mixture was stirred overnight at room temperature, so 0.5 ml of water was added. This solution was filtered on a silica gel 60 pad (40-63 pm) which was further washed with dichloromethane. The combined organic eluate was evaporated to dryness and the yellowish oil obtained was purified by flash chromatography on silica gel 60 (40-63 µm; eluent: hexane-dichloromethane, 10: 1 to 3: 1, vol.). This procedure provided 23.4 g (91%) of the title compound as a yellowish glass.
Anal. Calc. for C ₄₃ H ₅₀ OSi: C, 84.54; H, 8.25%. Found: C, 84.70; H, 8.33%.
¹ H NMR (CDCle): δ 7.59-7.18 (m), 6.89 (m), 6.83 (m), 6.51 (m), 6.48 (m), 3.77 (m), 3.73 (m), 3.68-3.70 (m), 3.31 (s), 3.29 (s), 2.25 (s), 2.23 (s), 2.16 (s), 2.10 (s), 1.50 (s), 1.48 (s), 1.45 (s), 1.44 (s), 0.00 (s), - 0.09 (s), 0.11 (s), -0.12 (s).
56/131
Anti- and syn-dimethylsilylene (2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl) (2-methyl-4- (4-tert-butyl-phenyl) indenyl) zirconium bichloride
The x
1. ⁿ BuLi, Et ₂ O ',
I 2. ZrCl ₄ (THF) ₂ /
SiMe ₂ ---------------- Cl ₂ z SiM ^e 2
OMe OMe o
To a solution of 15.3 g (25.0 mmol) of (6-tert-butyl-5-methoxy-2methyl-4-phenyl-1 H-inden-1-yl) [4- (4-tert-butylphenyl) ) -2-methyl-1 H-inden-1-yl] dimethylsilane in 300 ml of ether cooled to -78 ° C, 20.0 ml (50.0 mmol) of 2.5 M BuLi ⁿ in hexanes were added in a portion. This mixture was stirred overnight at room temperature, then cooled to 60 ° C and 9.43 g (25.0 mmol) of ZrCl ₄ (THF) ₂ were added. The resulting mixture was stirred for 24 hours (a light orange solution with a significant amount of precipitate was formed), then evaporated to dryness and 350 ml of toluene was added. The resulting solution heated to 80 ° C was filtered on a glass frit (G4) to form under evidence of NMR spectroscopy a mixture of about 1 to 1 of anti and syn zirconocenes. Crystals precipitated overnight from this solution at room temperature were collected, washed with 2 x 10 ml of cold toluene and dried under vacuum. This procedure provided 3.50 g of pure syn zirconocene as a light orange microcrystalline powder. The mother liquor was evaporated to about 100 ml. Crystals precipitated overnight from this solution at room temperature were collected, washed with 10 ml of cold toluene and dried under vacuum. This procedure provided an additional amount (4.10 g) of pure syn zirconocene. In this way, the combined yield of syn zirconocene was 7.60 g (39%) as a light orange microcrystalline powder. Crystals precipitated after 3 days at room temperature were collected, washed with 10 ml of cold toluene and dried under vacuum. This I proceeded
57/131 gave 2.95 g of pure antizirconocene as a slightly orange microcrystalline powder. Additional amounts of this product were obtained in a similar way from the evaporated mother liquor to about 35 ml. Thus, the combined yield of antizirconocene was 5.65 g (29%). anti-E2
Anal. Calc. for C ₄₃ H48Cl ₂ OSiZr: C, 66.98; H, 6.27%. Found: C, 67.00; H, 6.31%.
¹ H NMR (CDCfe): δ 7.61-7.63 (m, 3H, 2.6-H in C6H4 and 5-H in I indenyl), 7.54 (s, 1H, 7-H in indenyl of 7.4), 7.46-7.48 (m, 2H, 3.5-H in C6H4 of I), 7.42 (m, 2H, 3.5-H in Ph of II), 7.37 ( d, J = 7.1 Hz, 1H, 7-H in I indenyl), 7.32 (m, 1H, 4-H in Ph of II), 7.09 (dd, J = 8.6 Hz, J = 7.1 Hz, 1H, 6-H in I indenyl), 7.02 (s, 1H, 3-H in II indenyl), 6.57 (s, 1H, 3H in I indenyl), 3.39 (s, 3H, OMe), 2.25 (s, 3H, 2-Me in I), 2.17 (s, 3H, 2-Me in II), 1.39 (s, 9H, 6 - ^t Bu in II), 1.33 (s, 9H, 4- ^t Bu in I), 1.31 (s, 6H, SiMe ₂ ); where I is 4- (4-tert-butylphenyl) -2-methyl-1H-inden-1-yl, II - 6-tert-butyl5-methoxy-2-methyl-4-phenyl-1 H-inden-1 -ila.
syn-E2
Anal. Found: C, 66.12; H, 6.35%.
¹ H NMR (CDCle): δ 7.64 (m, 1H, 5-H in I indenyl), 7.56-7.58 (m, 2H, 2.6-H in I C6H4), 7, 54 (s, 1H, 7-H in II indenyl), 7.44-7.46 (m, 2H, 3.5-H in C6H ₄ of I), 7.41 (m, 2H, 3.5 -H in Ph of II), 7.30 (m, 1H, 4H in Ph of II), 7.15 (d, J = 7.1 Hz, 1H, 7-H in I indenyl), 6.91 (s, 1H, 3-H in II indenyl), 6.87 (dd, J = 8.6 Hz, J = 7.1 Hz, 1H, 6-H in I indenyl), 6.47 (s , 1H, 3-H in I indenyl), 3.20 (s, 3H, OMe), 2.44 (s, 3H, 2-Me in I), 2.37 (s, 3H, 2-Me in II), 1.44 (s, 3H, SiMeMe '), 1.34 (s, 9H, 6- ^t Bu in II), 1.33 (s, 9H, 4- ^t Bu in I), 1.22 (s, 3H, SiMeMe) where I is 4- (4-tert-butylphenyl) -2methyl-1H-inden-1-yl, II - 6-tert-butyl-5-methoxy-2-methyl-4-phenyl -1H-inden-1-yl. Synthesis of antidimethylsilylene bichloride (2-methyl-4-phenyl-5-methoxy-6-tero-butylindenyl) (2-methyl-4- (3,5-di-tert-butyl-phenyl) -6-tert-butyl -indenyl) zirconium (Metallocene E3) 4/7-Bromo-2-methyl-6/5-tero-butyl-1H-indene
58/131
Br
4- ^t BuC ₆ H ₄ ZnCl
Pd (P'Bu ₃ ) ₂ , THF
To 81.0 ml (47.0 mmol) of 3,58-di-tert-butylphenylmagnesium bromide 0.58 M in THF, 51.0 ml (51.0 mmol) of 1.0 M ZnCl ₂ in THF were added. In addition, a solution of 11.4 g (43.0 mmol) of 7-bromo-2-methyl-5-tert-butyl-1H-indene and 438 mg of Pd (P ^f Bu ₃ ) ₂ in 100 ml of THF was added . The resulting mixture was stirred overnight at 65 ° C, then cooled to room temperature and finally poured into 200 ml of water. The organic layer was separated and the aqueous layer was extracted with 3 x 100 ml of ethyl acetate. The combined organic extract was washed with 2 x 100 ml of cold water, dried over Na ₂ SO ₄ and evaporated to dryness. The residue was vacuum distilled using a Kugelrohr apparatus. This procedure provided 12.0 g (74%) of white crystalline solid.
Anal. Calc. for C ₂₈ H ₃₈ : C, 89.78; H, 10.22%. Found: C, 89.69; H, 10.29%.
¹ H NMR (CDCfe): δ 7.42 (m), 7.38 (m), 7.35 (m), 7.30-7.32 (m), 7.19 (m), 6.59 (m, 3-H in indenyl), 6.62 (m, 3-H in indenyl), 3.36 (m, 1.1H in indenyl), 3.33 (m, 1.1-H in indenyl) , 2.13 (s, 2-Me in indenyl), 1,381.39 (s, 27H, ^t Bu). [6-te / 'c-Butyl-4- (3,5-di-te /' c-butylphenyl) -2-methyl-1H-inden-1-yl] - (6-te / 'c-butyl- 5methoxy-2-methyl-4-phenyl-1 H-inden-1-yl) dimethylsilane
OMe
To a solution of 11.1 g (29.6 mmol) of 4/7-bromo-2-methyl-6/559/131 tert-butyl-1H-indene in 250 ml of ether, 11.9 ml (29, 8 mmol) of 2.5 M ⁿ BuLi in hexanes was added in one portion at -78 ° C. This mixture was stirred overnight at room temperature, then cooled to -60 ° C and 150 mg of CuCN was added. The resulting mixture was stirred for 1 hour at -20 ° C and then a solution of 11.4 g (29.6 mmol) of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1 H -inden-1-yl) (chlorine) -dimethylsilane in
200 ml of ether was quickly added at -70 ° C. The reaction mixture was allowed to warm to room temperature and stirred overnight, then treated with 0.5 ml of water, filtered on a short pad of silica gel 60 (40-63 pm). The silica gel layer was further washed with 100 ml of dichloromethane. The combined eluate was evaporated to dryness providing a yellowish oil which was purified by flash chromatography on silica gel 60 (4-63 pm; eluent: hexanes-dichloromethane from 10: 1 to 3: 1, vol.) This procedure provided 15.2 g (71%) of the title product as a yellowish glassy solid.
Anal. Calc. for C ₅ iH ₆₆ OSi: C, 84.70; H, 9.20%. Found: C,
84.92; H, 9.34%.
1H NMR (CDCle): δ 7.42-7.70 (m), 6.85 (s), 6.57 (s), 6.53 (s), 3.84 (m), 3.80 ( m), 3.77 (m), 3.34 (s), 1.54 (s), 1.53 (s), 1.51 (s), 1.50 (s), 1.49 (s) ), 1.48 (s), -0.04 (s), -0.06 (s), -0.10 (s), -0.11 (s).
Anti- and sv ^, n-dimethylsilanodiyl [2-methyl-4- (3,5-di-tert-butylphenyl) -6-tertbutyl-inden-1-yl1 (2-methyl-4-phenyl-5-methoxy) -6-tert-butyl-1 H-inden-1 -yl) zirconium complex δχΧ
X> x '1. ⁿ BuLi, Et ₂ O -VvXX7X_ | 2. ZrCl ₄ (THF) ₂
SiMe ₂ --------------- ► Cl ₂ Ziy SiMe ₂ γΧ τ 'OMe ° Me
THE
60/131
To a solution of 15.0 g (20.7 mmol) of [6-tert-butyl-4- (3,5-ditherc-butylphenyl) -2-methyl-1H-inden-1-yl] (6-tert -butyl-5-methoxy-2-methyl-4-phenyl-1Hinden-1-yl) dimethylsilane in 200 ml of ether cooled to -78 ° C, 16.5 ml (41.3 mmol) of ⁿ BuLi 2.5 M in hexanes were added in one portion. This mixture was stirred overnight at room temperature, then cooled to -78 ° C and 7.80 g (20.7 mmol) of ZrCl ₄ (THF) ₂ were added. The resulting mixture was stirred for 24 hours (a light orange solution with a significant amount of precipitate was formed), then evaporated to dryness and 350 ml of toluene were added. The resulting mixture heated to 80 ° C was filtered through glass frit (G4). Under the evidence of NMR spectroscopy, this mixture contained anti and syn zirconocenes in a ratio of about 70:30. The filtrate was evaporated to 100 ml, heated to 80 ° C and 25 ml of n-octane were added. Crystals precipitated after 24 hours at -30 ° C were collected, washed with 2 x 10 ml of about 1 to 1 mixture of toluene and n-hexane and dried in vacuo. This procedure provided 6.62 g (36%) of pure anti zirconocene as a light orange crystalline powder. The mother liquor was evaporated to 50 ml, diluted with 100 ml of nhexane and crystallized overnight at -30 ° C. The precipitate formed was filtered on a glass frit (G3) and then dried under vacuum. This procedure provided 6.40 g of a mixture of zirconocene anti and zyn in the ratio of 3: 2. The mother liquor was evaporated to dryness and the residue was dissolved in 20 ml of hot noctane. Crystals precipitated at -30 ° C were collected, washed with 2 x 5 ml of cold n-hexane and dried under vacuum. This procedure provided an additional amount (450 mg) of pure anti zirconocene. A precipitate formed after keeping the mother liquor at room temperature for 3 days was filtered (G3) and then dried under vacuum. This procedure provided 210 mg of pure syn zirconocene.
anti-E3
Anal. Calc. for C ₅ iH ₆₄ Cl ₂ OSiZr: C, 69.35; H, 7.30%. Found: C, 69.43; H, 7.41%.
1H NMR (CDCle): δ 7,15-7,60 (m, 11H, 5,7-H in indenyl and 2,4,6H in aryl of I as well as 7-H in indenyl and Ph in II), 6 , 87 (s, 1H, 3-H in
61/131 I indenyl), 6.53 (s, 1H, 3-H in II indenyl), 3.40 (s, 3H, OMe), 2.22 (s, 3H, 2-Me in indenyl) , 2.20 (s, 3H, 2-Me in indenyl), 1.40 (s, 9H, 6- ^t Bu in I indenyl), 1.36 (s, 18H, 3.5- ^t Bu in aryl ), 1.33 (s, 9H, 6- ^t Bu in indenyl of II), 1.32 (s, 3H, SiMeMe '), 1.30 (s, 3H, SiMeMe'), where I is 6- fer-butyl-4 (3,5-di-fer-butyl-phenyl) -2-methyl-1H-inden-1-yl, II - 6-fer-butyl-5-methoxy-2-methyl4-phenyl-1 H- inden-1-il.
syn-E3
Anal. Found: C, 69.47; H, 7.40%.
¹ H NMR (CDCle): δ 7,16-7,54 (m, 11H, 5,7-H in indenyl and 2,4,6H in I aryl as well as 7-H in indenyl and Ph in II), 6.88 (s, 1H, 3-H in I indenyl), 6.53 (s, 1H, 3-H in II indenyl), 3.17 (s, 3H, OMe), 2.45 (s , 3H, 2-Me in indenyl), 2.40 (s, 3H, 2-Me in indenyl), 1.45 (s, 3H, SiMeMe '), 1.38 (s, 18H, 3.5- ^t Bu in aryl), 1.35 (s, 9H, 6- ^t Bu in indenyl of I), 1.31 (s, 9H, 6- ^t Bu in indenyl of II), 1.21 (s, 3H, SiMeMe ) where I is 6ferc-butyl-4- (3,5-di-fer-butyl-phenyl) -2-methyl-1H-inden-1-yl, II - 6-fer-butyl-5-methoxy-2-methyl-4 -phenyl-1 H-inden-1-yl.
Synthesis of an (/ dimethylsilanodiyl [2-methyl-4- (4- (erc-butylphenyl) -inden1 -yl] [2-methyl-4-phenyl-5- (pentafluorfenoxy) -6-isopropyl-inden-1 -il] zirconium (metallocene E4)
1- (Pentafluorfenoxy) -2-isopropylbenzene
HO
C ₆ F ₆ , KOH, DMSO ^C S ^F 5 ^O
A mixture of 50.0 g (0.36 mol) of 2-isopropylphenol, 137 g
62/131 (0.72 mol) of hexafluorbenzene, 50.4 g (0.90 mol) of KOH powder and 1000 ml of DMSO was stirred for 48 hours at 80 ° C. This mixture was cooled to room temperature and then poured into 3000 ml of water. The product was extracted with 4 x 500 ml of dichloromethane. The combined organic extract was dried over Na ₂ SO ₄ and then evaporated in a Rotavap. The residue was vacuum distilled, 130-140 ° C / 13 mm Hg.
Yield: 68.3 g (63%).
Anal. calc. for C ₅ HhF ₅ O: C, 59.61; H, 3.67. Found: C, 59.76; H, 3.80.
¹ H NMR (CDCfe): δ 7.42-7.38 (m, 1H, 4-H), 7.17-7.12 (m, 2H, 3.5H), 6.61 (m, 1H, 6-H), 3.61-3.53 (m, 1H, CHMe2), 1.42-1.36 (m, 6H, CHM92). 6-Isopropyl-2-methyl-5- (pentafluorfenoxy) indan-1-one
CH ₂ = C (Me) CO ₂ H ^C 6 ^F 5 ^O MeSO ₃ HP ₄ O ₁₀ C ⁶ ^ ⁰
I o
A mixture of 39.3 g (0.46 mol) of methacrylic acid and 115 g (0.38 mol) of 1- (pentafluorfenoxy) -2-isopropylbenzene was added dropwise to an Eaton reagent (prepared from 99 g of P4O10 and 500 ml of MeSO ₃ H) for 1 hour at 70 ° C. The resulting mixture was stirred at 70 ° C for 1 hour, then cooled to room temperature and poured into 1000 cm ³ of ice. The crude product was extracted with 3 x 200 ml of dichloromethane. The organic extract was washed with aqueous K ₂ CO ₄ , dried over Na ₂ SO ₄ and then evaporated to dryness. The product was purified by flash chromatography on silica gel 60 (40-63 µm; eluent: n-hexane-dichloromethane = 5: 1, vol., Then n-hexane-dichloromethane-ether = 50: 25: 1, vol .) to provide 30.1 g (20%) of the title indan. In addition, 39.4 g of 1- (pentafluorfenoxy) -2-isopropylbenzene were also isolated.
Anal. calc. for Ci ₉ Hi ₅ F ₅ O ₂ : C, 61.62; H, 4.08. Found: C, 61.85; H, 4.22.
¹ H NMR (CDCls): δ 7.76 (s, 1H, 7-H), 6.54 (s, 1H, 4-H), 3.49 (sept, J = 6.8 Hz, 1H, CHMe2 ), 3.25 (dd, J = 17.1 Hz, J = 7.7 Hz, 1H, 3-H), 2.74-2.65 (m, 1H, 2-H), 2.59 ( dd, J = 17.1 Hz, J = 3.5 Hz, 1H, 3'-H), 1.33 (d, J
63/131 = 6.8 Hz, 6H, CH / We ₂ ), 1.29 (d, J = 7.5 Hz, 3H, 2-Me).
4-Bromo-6-isopropyl-2-methyl-5- (pentafluorfenoxy) indan-1-one
Br
To a suspension of 17.5 g (131 mmol) of AICI ₃ in 28 ml of dichloromethane cooled to -20 ° C a solution of 32.4 g (87.5 mmol) of 6isopropyl-2-methyl-5- (pentafluorfenoxy ) indan-1-one in 46 ml of dichloromethane was added in drops. In addition, this solution was heated to 0 ° C and 4.80 ml (96.0 mmol) of bromine were added in drops by vigorous stirring for 0.5 hour. This mixture was stirred for 24 hours at room temperature and then poured into cold aqueous Na ₂ SO ₃ to remove excess bromine. The product was extracted with 3 x 50 ml of dichloromethane. The combined extract was evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 µm; eluent: n-hexane-dichloromethane ether = 50: 50-1, vol.). Yield 20.1 g (51%). In addition, 15.0 g of starting indanone were recovered.
¹ H NMR (CDCI ₃ ): δ 7.72 (s, 1H, 7-H), 3.38-2.28 (m, 2H, 3-H and CHMe ₂ ), 2.82-2.73 ( m, 1H, 2-H), 2.62 (dd, J = 17.5 Hz, J = 3.9 Hz, 1H, 3'-H), 1.34 (d, J = 7.5 Hz, 3H, 2-Me), 1.27 (d, J = 6.9 Hz, 6H, CH / We ₂ ). 5-lsopropyl-2-methyl-6- (pentafluorfenoxy) -7-phenyl-1 / - / - indene
A mixture of 33.4 g (74.4 mmol) of 4-bromo-5- (pentafluorfenoxy) -6-isopropyl-2-methylindanone, 25.4 g (74.4 mmol) of NaBPh ₄ , 21.8 g (206 mmol) Na ₂ CO ₃ , 1.00 g (4.46 mmol, 6 mol.%) Of Pd (OAc) ₂ , 2.34 g (8.93 mmol, 12 mol.%) Of PPh ₃ , 100 ml of water and 300 ml of DME was refluxed for 12 hours and then quenched with water. The organic solvents were evaporated using Rotavap. The residue was dissolved in 500 ml of dichloride
64/131 methane, the solution was washed with 500 ml of water. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic solution was evaporated to dryness. Crude product was isolated by flash chromatography on silica gel 60 (40-63 µm; eluent: n-hexane-dichloromethane = 2: 1, vol.). In addition, this crude product was recrystallized from n-hexane to provide 27.3 g (80%) of a yellowish solid of the respective aryl-substituted indanone. To a mixture of 14.8 g (32.0 mmol) of this aryl-substituted indanone and 1.88 g of NaBH ₄ in 100 ml of THF, 50 ml of methanol were added in drops by vigorous stirring for 1 hour at 0 ° C. ° C. This mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was dissolved in 50 ml of dichloromethane and this solution was washed with 3 x 50 ml of water and then evaporated until dry. To a solution of the residue in 250 ml of toluene, 250 ml of TsOH were added. The mixture was refluxed for 15 minutes with Dean-Stark head and then cooled to room temperature using a water bath. The resulting reddish solution was washed with 10% aqueous Na ₂ CO ₃ , the organic layer was separated and the aqueous layer was extracted with 2 x 100 ml of dichloromethane. The combined organic solution was dried over K ₂ CO ₃ and then filtered over a short pad of silica gel 60 (40-63 pm). The silica gel layer was further washed with 50 ml of dichloromethane. The combined organic eluate was evaporated to dryness to provide 14.6 g (99%) of the title product as a yellowish oil.
¹ H NMR (CDCfe): δ 7,26-7,12 (m, 5H, 2,3,4,5,6-H in Ph), 6,48 (s, 1H, 3-H in indenyl), 3.41 (sept, J = 6.9 Hz, 1H, CHMe2), 3.03 (s, 2H, 1-H in indenyl), 2.06 (s, 3H, 2-Me in indenyl), 1, 30 (d, J = 6.9 Hz, 6H, CHMe2). Chlorine [6-isopropyl-2-methyl-5- (pentafluorfenoxy) -4-phenyl-1H-inden-1-yl1dimethylsilane
O o
I 1. KH, THF |
2. Me ₂ SiCl ₂ ^C6F 5 ^O
SiMe ₂ Cl
65/131
To a solution of 8.61 g (20.0 mmol) of 5-isopropyl-2-methyl-6 (pentafluorfenoxy) -7-phenyl-1H-indene in 200 ml of THF cooled to -25 ° C, 885 mg ( 22.1 mmol) of potassium hydride were added. The resulting mixture was stirred overnight at room temperature, filtered through glass frit (G3) to remove excess KH, then cooled to -25 ° C and 13.0 g (101 mmol, 5 equivalents) of dichlorodimethylsilane were added in one portion. The resulting solution was stirred overnight at room temperature, then evaporated to dryness. The residue was dissolved in 200 ml of toluene and the suspension formed was filtered through glass frit (G3). The precipitate was further washed with 2 x 30 ml of toluene. The combined filtrate was evaporated to dryness to provide 10.5 g (99%) of the title product which was used further without further purification.
Anal. calc. for C ₂₇ H ₂₄ ClF ₅ OSi: C, 62.00; H. 4.63, Found: C, 62.53; H, 4.80.
¹ H NMR (CDCfe): δ 7.43 (s, 1H, 7-H in indenyl), 7.27-7.18 (m, 5H, 2,3,4,5,6-H in Ph), 6.31 (s, 1H, 3-H in indenyl), 3.64 (s, 1H, 1-H in indenyl), 3.43 (sept, J = 6.7 Hz, 1H, CHMe ^ 2.19 (s, 3H, 2-Me in indenyl), 1.30 (t, J = 6.7 Hz, 6H, CHMe2), 0.38 (s, 3H, SiMeMe'Cl), 0.19 (s, 3H , SiMeMeCl). [4- (4-fero-Butylphenyl) -2-methyl-1H-inden-1-yl] [6-isopropyl-2-methyl-5- (pentafluor phenoxy) -4-phenyl-1 H- inden-1-yl] dimethylsilane
1. ⁿ BuLi, Et ₂ O

To a solution of 6.39 g (24.4 mmol) of 7- (4-tert-butylphenyl) -2methyl-1H-indene in 200 ml of ether, 9.80 ml (24.5 mmol) of BuLi 2, 5 M in hexanes was added in one portion at -40 ° C. This mixture was stirred overnight at room temperature, then cooled to -40 ° C
66/131 and 150 mg of CuCn were added. The resulting mixture was stirred for 1 hour at -20 ° C, then cooled to -40 ° C and a solution of 10.5 g (20.0 mmol) of chlorine [6-isopropyl-2-methyl-5- (pentafluorfenoxy ) -4-phenyl-1 H-inden-1-yl] dimethylsilane in 200 ml of ether was added in one portion. In addition, this mixture was stirred overnight at room temperature, so 0.5 ml of water was added. This solution was filtered on a silica gel 60 pad (40-63 pm) which was then additionally washed with 2 x 75 ml of dichloromethane. The combined organic eluate was evaporated to dryness and the residue was dried in vacuo. The product was isolated by flash chromatography on silica gel 60 (40-63 µm; eluent: hexanes-dichloromethane = 10: 1, vol., Then 5: 1, vol.). This procedure provided 7.86 g (53%) of the title product (of about 90% purity as a mixture of about 1: 1 of the stereoisomers under NMR spectroscopy evidence) as a yellowish glass.
Anal. calc. for C ₄₇ H ₄₅ F ₅ OSi: C, 75.37; H, 6.06. Found: C, 75.91; H, 6.55.
¹ H NMR (CDCfe): δ 7.49 (s), 7.46 (s), 7.41-7.36 (m), 7.30-7.16 (m), 6.86 (s) , 6.79 (s), 6.32 (s), 6.26 (s), 3.76 (s), 3.71 (s), 3.70 (s), 3.68 (s), 3.46-3.38 (m), 2.21 (s), 2.18 (s), 2.13 (s), 2.02 (s), 1.39 (s), 1.29- 1.26 (m), 0.10 (s), -0.11 (s), -0.18 (s), -0.20 (s).
Anfrtfimethylsilanodiyl dichloride [2-methyl-4- (4-te / O-butylphenyl) -inden-1 -yl] [2-methyl-
4-phenyl-5- (pentafluorfenoxy) -6-isopropyl-inden-1-yl] zirconium (metallocene E4)
1. KH, THF
2. ZrCl ₄ (THF) ₂
SiMe ₂
Cl ₂ Zr SiMe ₂
To a solution of 3.93 g (5.25 mmol) of [4- (4-tert-butylphenyl) -2methyl-1 H-inden-1-yl] [6-isopropyl-2-methyl-5- (pentafluorfenoxy ) -4-phenyl-1 H-inden1-yl] dimethylsilane (obtained as described above) in 100 ml of THF cools
67/131 of to -25 ° C, 463 mg (11.5 mmol, 2.2 equivalents) of potassium hydride were added. The resulting mixture was stirred overnight at room temperature, then filtered on a glass frit (G3) to remove excess KH (the precipitate was further washed with 10 ml of THF). The combined filtrate was cooled to -25 ° C and 1.98 g (5.25 mmol) of ZrCl ₄ (THF) ₂ was added in one portion. The resulting solution was stirred overnight at room temperature, then evaporated to dryness. The residue was dissolved in 100 ml of warm toluene, the suspension formed was filtered through glass frit (G4) and the precipitate was further washed with 2 x 10 ml of toluene. The combined filtrate was evaporated to dryness, the residue was dissolved in 45 ml of n-octane. Crystals precipitated from this solution after 2 days at -30 ° C were collected, washed with 3 x 10 ml of n-hexane and discarded. The mother liquor was evaporated to dryness and 25 ml of n-hexane was added. Crystals precipitated from this solution overnight at room temperature were collected, washed with 3 ml of n-hexane and dried under vacuum. This procedure provided 0.55 g (12%) of anti zirconocene. Assignment in NMR spectra was made using the following abbreviations: L ¹ for 4- (4-tert-butylphenyl) -2-methyl-1Hinden-1-yl and L ² for 6-isopropyl-2-methyl-5- ( pentafluorfenoxy) -4-phenyl-1H-indene-yl.
Anti zirconocene.
Anal. calc. for C ₄₇ H ₄₃ Cl ₂ F ₅ OSiZr: C, 62.10; H, 4.77. Found: C, 62.29; H, 4.70.
¹ H NMR (CDCfe): δ 7.62 (s, 1H, 7-H in L ² ), 7.59 (d, J = 8.8 Hz, 1H, 7-H in L ¹ ), 7.54 (dt, J = 8.6 Hz, J = 2.1 Hz, 2H, 2.6-H in C6H4 ^t Bu), 7.45 (dt, J = 8.6 Hz, J = 2.1 Hz, 2H, 3.5-H in CeH / Bu), 7.40 (broad s, 2H, 2.6-H in Ph), 7.33 (dd, J = 7.0 Hz, J = 0.6 Hz , 1H, 5-H in L ¹ ), 7.25-7.15 (m, 3H,
3,4,5-H in Ph), 7,06 (dd, J = 8,8 Hz, J = 7,0 Hz, 1H, 6-H in L ¹ ), 7,01 (s, 1H, 3- H in L ¹ ), 6.39 (s, 1H, 3-H in L ² ), 3.40 (sept, J = 6.7 Hz, 1H, CHMe2), 2.34 (s, 3H, 2- Me in L ¹ ), 2.17 (s, 3H, 2-Me in L ₂ ), 1.36 (s, 3H, CHMeMe '), 1.34 (s, 9H, ^t Bu in CeH / Bu), 1.32 (s, 3H, CHMeMe '), 1.29 (s, 3H, SiMeMe'), 1.27 (s, 3H, SiMeMe ').
68/131
Synthesis of an // bimethylsilanodiyl dichloride (2-methyl-4-phenyl-5-methoxy-6- / erc-butyl-indenyl) [2,7-dimethyl-4- (3,5-di- / erc-butylphenyl) ) indenyl] zirconium (metallocene E5)

5-Bromo-2-methylbenzaldehyde
Br ₂ , AlCl ₃ , CH ₂ Cl ₂
To a suspension of 344 g (2.58 mol, 1.5 eq.) Of AlCl ₃ in 1100 cm ³ of dichloromethane, 206.8 g (1.72 mol) of 2-methylbenzaldehyde were added in drops by vigorous stirring. for 15 minutes at 5 ° C. The resulting mixture was stirred for 15 minutes at 5 ° C, and then 88.9 ml (276 g, 1.73 mmol) of bromine were added for 1 hour at this temperature. The final mixture was further stirred for 6 hours at room temperature and then poured into 2 kg of ice. The organic layer was separated, the aqueous layer was extracted with 2 x 200 ml of dichloromethane. The combined organic extract was washed with aqueous NaHCO3, dried over Na2SO4 and then evaporated to dryness to provide reddish liquid. This crude product was vacuum distilled, eg 100-120 ^o C / 5 mm Hg. The colorless liquid obtained (which completely crystallizes at 5 ^o C) was dissolved in 900 ml of n-hexane. Crystals precipitated from this solution for 3 days at 5 ^o C were collected and dried under vacuum. Under evidence of NMR spectroscopy this mixture consists of 5-bromo-2-methylbenzaldehyde and 3-bromo-2-methylbenzaldehyde in a ratio of about 3 to 1. This mixture was crystallized from 500 ml of hot n-hexane. The white crystals precipitated at 5 ^o C were collected, washed with 150 ml of cold n-hexane (+5 ^o C) and vacuum dried (~ 60 ^o C / 20 mm Hg) to provide colorless liquid that crystallizes at room temperature.
69/131
Yield 80.9 g (24%) of 5-bromo-2-methylbenzaldehyde including about 2% of 3-bromo-2-methylbenzaldehyde.
Anal. calc. for C ₈ H7BrO: C, 48.27; H, 3.54. Found: C, 48.05; H, 3.41.
¹ H NMR (CDCl3): δ 10.21 (s, 1H, CHO), 7.90 (d, J = 2.2 Hz, 1H,
6-H), 7.57 (dd, J = 8.2 Hz, J = 2.3 Hz, 1H, 4-H), 7.14 (d, J = 8.2 Hz, 1H, 3-H ), 2.61 (s, 3H, Me). ¹³ C { ¹ H} NMR (CDCle): δ 191.0, 139.3, 136.4, 135.5, 134.1,
133.4, 120.0, 18.85.
5-bromo-2-methylbenzyl chloride
1. NaBH ₄ , THF-MeOH 2. SOCl ₂ , CH ₂ Cl ₂ r / ^ Cl ΪBr VBr
To a mixture of 80.9 g (0.406 mol) of 5-bromo-2-methylbenzaldehyde and 7.80 g (0.206 mol) of NaBH4 in 300 ml of THF, 200 ml of methanol were added in drops by vigorous stirring for 5 hours at 0-5 ^o C. This mixture was stirred at room temperature and then added to 1 liter of cold water. The resulting mixture was acidified by 2M HCl to pH ~ 1 and the formed methanol (5-bromo-2-methylphenyl) methane was extracted with 3 x 250 ml of dichloromethane. The combined organic extract was dried over Na2SO4 and evaporated to dryness. To the residue dissolved in 450 ml of dichloromethane, 37 ml of SOCl2 were added in drops at +5 ^o C. The resulting solution was stirred overnight at room temperature, evaporated until dry, the residue was dissolved in 500 ml of CH2Cl2 and the obtained solution was washed with 500 ml of water. The organic layer was separated, the aqueous layer was further extracted with 2 x 100 ml of dichloromethane. The combined organic extract was passed through a short pad of silica gel 60 (40-63 pm), the filtrate was evaporated to dryness and the residue was vacuum dried to provide 5-bromo-2-methylbenzyl chloride as a slightly liquid yellowish which was used more without further purification.
Anal. calc. for C ₈ H ₈ BrCl: C, 43.77; H, 3.67. Found: C, 43.89; H, 3.80.
70/131 ¹ H NMR (CDCI3): δ 7.45 (d, J = 2.0 Hz, 1H, 3-H), 7.35 (dd, J =
8.2 Hz, J = 2.0 Hz, 1H, 5-H), 7.06 (d, J = 8.2 Hz, 1H, 6-H), 4.53 (s, 2H, CH ₂ Cl ), 2.36 (s, 3H, Me). ¹³ C { ¹ H} NMR (CDCfe): δ 137.5, 136.0, 132.4, 132.3, 131.7, 119.5, 43.8, 18.3.
3- (5-bromo-2-methylphenyl) -2-methylpropanoyl chloride
1. MeCH (COOEt) ₂ , EtONa, EtOH
2. KOH, H ₂ O-EtOH
3. ΗβΟ ⁺
4. Δ
5. SOCl ₂
Br
In a three-necked round bottom flask, 9.50 g (0.413 mol) of sodium metal was dissolved in 260 ml of dry ethanol. To the resulting solution, 72.0 g (0.413 mol) of diethyl methylmalonate were added. This mixture was stirred for 15 minutes, then 5-bromo-2-methylbenzyl chloride prepared above was added by vigorously stirring at such a rate in order to maintain smooth reflux. This mixture was refluxed for another 2 hours and then cooled to room temperature. A solution of 85 g of KOH in 250 ml of water was added. The resulting mixture was refluxed for 4 hours to saponify the ester formed. Ethanol and water were distilled until the temperature reached 95 ^o C, and 1000 ml of water and then 12 M HCl (for pH 1) were added to the residue. The precipitated substituted methylmalonic acid was filtered, washed with 3 x 100 ml of water and then decarboxylated at 180 ^o C to provide 3- (5-bromo-2-methylphenyl) -2-methylpropanoic. A mixture of this acid and 105 ml of SOCl2 was stirred at room temperature for 24 hours. After evaporation of an excess of thionyl chloride, the residue was vacuum distilled to provide 85.3 g (75% 5-bromo-2-methylbenzaldehyde chloride) 3- (5bromo-2-methylphenyl) -2-methylpropanoyl, eg 115 ^o / 1 mm Hg.
Anal. calc. for C ₁₁ H ₁₂ BrClO: C, 47.94; H, 4.39. Found: C, 48.12; H, 4.45.
¹ H NMR (CDCle): δ 7.28-7.26 (m, 2H, 6.4-H in Ph), 7.03 (d, J = 7.7 Hz, 1H, 3-H in Ph) , 3.18 (dd, J = 13.8 Hz, J = 5.9 Hz, 1H, ArCHH '), 3.10
71/131 (m, 1H, CHCOCl), 2.65 (dd, J = 13.8 Hz, J = 8.1 Hz, 1H, ArCHH '), 2.28 (s, 3H, Ar Me), 1 , 29 (d, J = 6.7 Hz, 3H, CHMe). ¹³ C { ¹ H} NMR (CDCfe): δ 176.9, 138.1, 135.2, 132.4, 132.2, 130.0, 119.5, 51.8, 36.1, 19, 0, 16.6.
7-Bromo-2,4-dimethylindan-1-one
Br
AlCl ₃ , CH ₂ Cl ₂
To a stirred suspension of 49.5 g (0.371 mol, 1.2 equivalent) of AlCl ₃ in 300 ml of dichloromethane a solution of 85.3 g (0.310 mol) of 3- (5-bromo-2-methylphenyl chloride) ) -2-methylpropanoyl in 50 ml of dichloromethane was added in drops. This mixture was stirred overnight at room temperature and then poured into 500 g of ice. The organic layer was separated and the aqueous layer was further extracted with 3 x 75 ml of dichloromethane. The combined organic extract was washed with aqueous K2CO3, dried over K2CO3, passed through a short pad of silica gel and then evaporated until dry. This procedure provided 74.0 g (> 99%) of 7-bromo-2,4-dimethylindan-1-one as a light orange liquid, solidified at room temperature, which was used more without further purification.
Anal. calc. for C ₁₁ H ₁₁ BrO: C, 55.25; H, 4.64. Found: C, 55.40; H, 4.81.
¹ H NMR (CDCfe): δ 7.41 (d, J = 8.0 Hz, 1H, 6-H in indan-1-one), 7.21 (d, J = 8.0 Hz, 1H, 5 -H in indan-1-one), 3.24 (dd, J = 17.3 Hz, J = 7.9 Hz, 3-H in indan-1-one), 2.73 (m, 1H, 2 -H in indan-1-one), 2.54 (dd, J = 17.3 Hz, J = 4.1 Hz, 1H, 3'-H in indan-1-one), 2.29 (s, 3H, 4-Me in indan1-one), 1.33 (d, J = 7.3 Hz, 3H, 2-Me in indan-1-one). ¹³ C {1H} NMR (CDCfe): δ 207.0, 155.0, 135.6, 134.8, 133.1, 132.3, 116.5, 42.4, 33.0, 17.4 , 16.4.
7-Bromo-1-methoxy-2,4-dimethylindane
1. NaBH ₄ , THF-MeOH
2. MeI, KOH, DMSO
72/131
To a mixture of 74.0 g (0.310 mol) of 7-bromo-2,4-dimethylindan-1-one and 5.86 g (0.155 mol) of NaBH ₄ in 310 ml of THF, 155 ml of methanol were added in drops through vigorous stirring for 5 hours at 0-5 ^o C. This mixture was stirred overnight at room temperature and then 1 liter of cold water was added. The resulting mixture was acidified by 2M HCl to pH ~ 5, and then it was extracted with 3 x 250 ml of dichloromethane. The combined organic extract was dried over Na2SO4 and evaporated. The resulting orange oil was dissolved in 600 ml of DMSO, then 70 g (1.25 mol) of KOH and 88 g (0.62 mol) of MeI were added to the resulting solution. This mixture was stirred for 3 hours at room temperature. In addition, the solution was decanted from an excess of KOH, the latter was washed with 2 x 200 ml of dichloromethane and 2000 cm ³ of water were added to the combined solution. The organic layer was separated and the aqueous layer was further extracted with 2 x 100 ml of dichloromethane. The combined organic extract was additionally washed with 5 x 1500 ml of water, dried over Na2SO4 and evaporated to dryness. Fractional distillation of the vacuum residue provided 72.3 g (92%) of 7-bromo-1-methoxy-2,4-dimethylindane, eg 107-112 ^o C / 5 mm Hg.
Anal. calc. for C ₁₂ H ₁₅ BrO: C, 56.49; H, 5.93. Found: C, 56.43; H, 6.02.
¹ H NMR (CDCls): δ 7.25 (t, J = 8.57 Hz, 2H, 6-H of syn and anti isomers), 6.93 (t, J = 8.57 Hz, 2H, 5H of syn and anti isomers), 4.57 (d, J = 5.5 Hz, 1H, syn-isomer 1-H), 4.42 (s, 1H, anti-isomer 1-H), 3.53 (s , 3H, syn isomer OMe), 3.45 (s, 3H, anti isomer OMe), 3.27 (dd, J = 16.6 Hz, J = 7.3 Hz, 1H, 3-H isomer anti), 2.87 (dd, J = 15.7 Hz, J = 7.5 Hz, 1H, syn-isomer 3-H), 2.68 (dd, J = 15.7 Hz, J = 9, 8 Hz, 1H, 3'-H syn isomer), 2.57 (m, 1H, 2-H anti isomer), 2.44 (m, 1H, 2-H syn isomer), 2.39 ( dd, J = 16.6 Hz, J = 1.4 Hz, 3'-H of anti isomer), 2.18 (s, 6H, 4Me of syn and anti isomers), 1.26 (d, J = 6 , 9 Hz, 3H, 2-Me of syn isomer), 1.05 (d, J = 7.3 Hz, 2-Me of anti isomer).
73/131
4- (3,5-Di-tert-butylphenyl) -2,7-dimethyl-1/7-indene
NiCI ₂ (PPh ₃ ) IPr, THF
2. TsOH, toluene
1. SS-di'BuCgHsMgBr
To a solution of 3,5-di-fer-butylphenylmagnesium bromide obtained from 59.0 g (0.219 mol) of 1-bromo-3,5-di-tert-butylbenzene and 9.31 g (0.383 mol) , 1.75 equivalent) of magnesium chips in 550 ml of THF, 1.0 g (1.28 mmol, 0.71% mmol) of NiCl2 (PPh ₃ ) IPr and a solution of 46.1 g (0.181 mol) ) of 7-bromo-1-methoxy-2,4-dimethylindane in 50 ml of THF were added. A moderate reflux occurs approximately after one minute, which stops after the next 30 seconds. This mixture was further refluxed for 1 hour. Finally, 50 ml of water was added and the main part of THF was distilled in a rotary evaporator. In addition, 500 ml of dichloromethane and 500 ml of 2M HCI were added to the residue. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to provide a yellowish oil. To a solution of this oil in 700 ml of toluene 0.8 g of TsOH was added. The resulting mixture was refluxed using Dean-Stark heads for 20 minutes, a further portion (0.8 g) of TsOH was added and the mixture was refluxed for another 20 minutes. The resulting mixture cooled to room temperature was washed with 200 ml of 10% aqueous NaHCO ₃ . The organic layer was separated, the aqueous layer was further extracted with 2 x 100 ml of dichloromethane. The combined organic extract was evaporated to dryness, a solution of the residue in 500 ml of dichloromethane was passed through a short pad of silica gel 60 (40-63 pm) and then evaporated to dryness to provide yellowish crystalline material. This crude product was recrystallized from 200 ml of hot nhexane. Crystals precipitated from this solution at 5 ° C were collected and dried under vacuum. This procedure provided 49.8 g of white microcrystalline product. The mother liquor was evaporated to dryness and the
74/131 of 1,3-di-tert-butylbenzene was distilled at high temperature in the rotary evaporator. The residue was then recrystallized from 80 ml of nhexane at -30 ° C overnight. This provided another 6.21 g of the product. In this way, the total yield of 4- (3,5-di-tert-butylphenyl) -2,7-dimethyl1 H-indene was 56.0 g (93%).
Anal. calc, for C25H32: C, 90.30; H, 9.70. Found: C, 90.44; H, 9.89.
¹ H NMR (CDCI3): ó (t, J = 1.8 Hz, 1H, 4-H in C6H3 ^f Bu2), 7.33 (d, J = 1.8 Hz, 2H, 2.6-H in C ₆ H ₃ ^f Bu2), 7.24 (d, J = 7.7 Hz, 1H, 5-H in indenyl), 7.01 (d, J = 7.7 Hz, 1H, 6-H in indenyl ), 6.67 (m, 1H, 3-H in indenyl), 3.27 (s, 2H, 1-H in indenyl), 2.37 (s, 3H, 7-Me in indenyl), 2.16 (s, 3H, 2Me in indenyl), 1.37 (s, 18H, * Bu). ¹³ C { ¹ H} NMR (CDCl3): δ 150.5, 146.0, 143.1, 142.4, 140.2, 133.0, 131.3, 127.2, 126.7, 125, 2, 123.3, 120.4, 42.0, 34.9, 31.5, 18.5, 17.0.
A mixture of (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-1 / - / - inden-1iI) [2,7-dimethi 1-4- (3,5-di-tert- butiIphenyl) -1 H-inden-1-yl] dimethylIsilane and (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-1 H-inden-1-yl) [2,4-dimethyl-7- ( 3,5-di-tert-butylphenyl) 1 H-inden-1-yl] dimethyl silane ether
To a solution of 11.4 g (34.3 mmol) of 4- (3,5-di-tert-butylphenyl) 2,7-dimethyl-1 H-indene in 200 ml of ether, 13.7 ml (34 , 3 mmol) of 2.5 M nBuLi in hexanes was added in one portion at -40 ° C. This mixture was stirred overnight at room temperature, then cooled to -40 ° C and 200 mg of CuCN was added. The resulting mixture was stirred for 1 hour at -20 ° C, then cooled to -40 ° C and a solution of 13.2
75/131 g (34.3 mmol) of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1 / - / - inden-1-yl) (chlorine) dimethylsilane in 150 ml of ether was added in one portion. In addition, this mixture was stirred overnight at room temperature, and then 0.5 ml of water was added. The formed mixture was filtered on a silica gel 60 pad (40-63 pm) which was further washed with dichloromethane. The combined organic eluate was evaporated to dryness and the residue was dried in vacuo. This procedure provided 24.2 g of a about 1 to 1 mixture of (6-fer-butyl-5-methoxy-2-methyl-4-phenyl-1 / - / - inden-1-yl) [4- ( 3,5-di-fercbutilfeni I) -2,7-dimethyl 1-1 / - / - inden-1-yl] dimethylisane and (6-tert-butyl-5-methoxy-2methyl l-4- pheni 1-1 / - / - inden-1 -i I) [7- (3,5-di-fer-butyl Ifen il) -2,4-di methyl 1-1 / - / - inden-1 il] dimethylsilane (> 90% purity under the evidence of NMR spectroscopy) which was used most without further purification.
Anal. calc, for C48H ₆ oOSi: C, 84.65; H, 8.88, Found: C, 84.82; H, 9.15.
¹ H NMR (CDCh): δ 7.55-7.28 (m), 7.21-6.93 (m), 6.76 (s), 6.73 (s), 6.71 (s) , 6.68 (s), 6.44 (s), 6.41 (s), 6.20 (s), 6.18 (s), 4.42 (s), 4.15 (s),
4.01 (s), 3.79 (s), 3.67 (s), 3.65 (s), 3.24 (s), 3.22 (s), 3.18 (s), 3 , 16 (s), 2.45 (s), 2.44 (s), 2.36 (s), 2.29 (s), 2.25 (s), 2.23 (s), 2, 21 (s), 2.20 (s), 2.12 (s),
2.06 (s), 1.80 (s), 1.61 (s), 1.46 (s), 1.43 (s), 1.39 (s), 1.38 (s), 1 , 38 (s), 1.33 (s), 1.31 (s), -0.15 (s), -0.18 (s), -0.24 (s), -0.30 (s) ), -0.37 (s), -0.64 (s), -0.67 (s), -0.71 (s).
Anf / c dichloride (/ methylsilanediyl (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl) [2,7-dimethyl-4- (3,5-di-tert-butylphenyl) indenillzirconium (metallocene E5)
76/131
To a solution of 24.2 g (ca. 34.3 mmol,> 90% purity) of a mixture of (6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1 H-inden-1 -yl) [4- (3,5-di-tertbutylphenyl) -2,7-dimethyl-1 H-inden-1-yl] dimethylsilane and (6-tert-butyl-5-methoxy-2methyl-4-phenyl- 1 H-inden-1-yl) [7- (3,5-di-tert-butylphenyl) -2,4-dimethyl-1 H-inden-1-yl] dimethylsilane in 250 ml of ether, 28.4 ml (71.0 mmol) of 2.5 M ⁿ BuLi in hexanes was added in a portion of -30 ^o C. This mixture was stirred overnight at room temperature, then cooled to -40 ^o C and 13 ° C, 4 g (35.5 mmol) of ZrCl ₄ (THF) ₂ was added. The resulting mixture was stirred for 24 hours, then the orange precipitate was filtered from a red solution through glass frit (G4), the precipitate was washed with 30 ml of ether. Under evidence of NMR spectroscopy, this precipitate includes the desired anti-zirconocene (isomer A), although isomeric complexes A, B and C in a ratio equal to 1: 2: 2 are in the infiltrate. This precipitate was dissolved in 100 ml of hot toluene and the solution formed was filtered through glass frit (G4) to remove LiCl. The filtrate was evaporated to dryness and the residue was recrystallized from 40 ml of hot n-octane. Crystals precipitated at room temperature were collected, washed with 15 ml of n-hexane and vacuum dried to provide 5.72 g of anti-complex. To the mother liquor 5 ml of hexanes were added, the solution formed was heated to reflux. Crystals precipitated from this solution at room temperature were collected and dried under vacuum to provide 0.42 g of anti complex. Crystals precipitated after one week from the filtrate described above including complexes A, B and C in a ratio equal to 1: 2: 2 were collected and dried under vacuum to provide 4.40 g of red-orange crystalline solid as a about mixture from 2 to 5 of the isomeric complexes A and B. The mother liquor was evaporated to dryness, the residue was dissolved in 50 ml of hot toluene, then 50 ml of hot toluene, then 50 ml of n-hexane was added. Crystals precipitated from this solution at room temperature were collected and dried in vacuo to provide 2.70 g of a about 2 to 3 mixture of isomeric complexes A and B. Again, the mother liquor was evaporated until dry, the residue was recrystallized from 45 ml of n-hexane-toluene (2: 1, vol.). This procedure provided 0.95 g of a mixture about 1
77/131 for 1.2 of isomeric complexes A and B. Thus, the overall loop zirconocene yield was 14.2 g (49%). Assignment in NMR spectra was made using the following abbreviations: L ¹ for 4- (3,5-di-tert-butylphenyl) 2,7-dimethyl-1H-inden-1-yl and L ² for 6-tert- butyl-5-methoxy-2-methyl-4-phenyl-1Hinden-1-yl. Anti zirconocene.
Anal. calc. for C ₄₈ H ₅₈ Cl ₂ OSiZr: C, 68.54; H, 6.95. Found: C, 68.48; H, 7.11.
¹ H NMR (CDCfe): δ 7.61-7.57 (m, 2H, 2.6-H in Ph), 7.55 (s, 1H, 7-H in L ² ), 7.50 (d , 2-H, 2,6-H in C6H3 ^f Bu2), 7.44-7.40 (m, 3H, 3.5-H in Ph and 4-H in C6H3 ^f Bu2), 7.32 (m , 1H, 4-H in Ph), 7.30 (d, J = 7.1 Hz, 1H, 5-H in L ¹ ), 7.05 (s, 1H, 3-H in L ¹ ), 6 , 98 (d, J = 7.1 Hz, 6-H in L ¹ ), 6.58 (s, 1H,
3-H in L ² ), 3.39 (s, 3H, OMe), 2.65 (s, 3H, 7-Me in L ¹ ), 2.31 (s, 3H, 2-Me in L ¹ ) , 2.07 (s, 3H, 2-Me in L ² ), 1.40 (s, 9H, 6- ^f Bu in L ² ), 1.35 (s, 3H, SiMeMe '), 1.34 ( s, 18H, ^f Bu in C6H3 ⁽ Bu2), 1.27 (s, 3H, SiMeMe ').
Synthesis of amphid dichloride / methylsilanediyl (2-methyl-4-phenyl-5-methoxy-6-tertbutyl-indenyl) (2-methyl-4- (3,5-di-te / 'c-butylphenyl) -7- methoxy-inden-1-yl) zirconium (metallocene E6)
1-Bromo-2- (bromomethyl) -4-methoxybenzene
Method 1
OMe
OMe
Br
- (Bromomethyl) -3-methoxybenzene
To a solution of 122 g (1.0 mol) of 1-methoxy-3-methylbenzene in 900 ml of CCl ₄ , 178 g (1.0 mol) of NBS and 1.0 g of (PhCO ₂ ) ₂ were added. / 131

at room temperature. This mixture was refluxed for 3 hours, cooled to room temperature and the succinimide formed was filtered. The succinimide was additionally washed with 2 x 150 ml of CCl4. The combined filtrate was evaporated to dryness and the residue was vacuum distilled, eg 112-125 ^o C / 8 mm Hg. This procedure provided 152.5 g of 1 (bromomethyl) -3-methoxybenzene contaminated with about 25% of the isomeric product, i.e., 1-bromo-4-methoxy-2-methylbenzene.
Anal. calc. for C ₈ H9BrO: C, 47.79; H, 4.51. Found: C, 47.93; H, 4.65.
¹ H NMR (CDCfe): δ 7.26 (m, 1H, 5-H), 6.98 (m, 1H, 6-H), 6.94 (m, 1H, 2-H), 6.85 (m, 1H, 4-H), 4.47 (s, 2H, CH2Br), 3.81 (s, 3H, OMe). 1-Bromo-2- (bromomethyl) -4-methoxybenzene
OMe OMe
Br ₂ , CHCl ₃
Br
Br
To a solution of the crude 1- (bromomethyl) -3-methoxybenzene described above (152.5 g) in 1 L of chloroform a solution of 134 g (0.841 mol) of bromine in 200 ml of chloroform was added dropwise by stirring vigorous at room temperature. The reaction mixture was stirred overnight at room temperature and then evaporated to dryness. The residue was triturated with 1000 ml of n-hexane and the precipitate was filtered, washed with 100 ml of n-hexane and then vacuum dried. An additional amount of the product was obtained by evaporating the mother liquor followed by treatment of the residue with 200 ml of n-hexane. In total, this procedure provided 153 g (55% general yield for two stages) of 1-bromo-2 (bromomethyl) -4-methoxybenzene. (average of two rounds).
Anal. calc. for C ₈ H ₈ Br ₂ O: C, 34.32; H, 2.88. Found: C, 34.30; H, 3.01.
¹ H NMR (CDCfe): δ 4.48 (d, J = 8.8 Hz, 1H, 6-H), 7.02 (d, J = 3.0 Hz, 1H, 3-H), 6, 76 (dd, J = 8.8 Hz, J = 3.0 Hz, 1H, 5-H), 4.58 (s, 2H, CH2BO, 3.83 (s, 3H, OMe).
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Method 2
-Bromo-4-methoxy-2-methylbenzene
OMe
NBS, MeCN

To a solution of 122 g (1.0 mol) of 1-methoxy-3-methylbenzene in 1 L of acetonitrile, 178 g (1.0 mol) of NBS was added in small portions by vigorously stirring for 1 hour at 10 ^o C. The reaction mixture was stirred at room temperature overnight and then evaporated to dryness. The residue was dissolved in 1 L of n-hexane and filtered through glass frit (G2). The precipitate was further washed with 2 x 150 ml of n-hexane. The combined filtrate was evaporated to dryness to provide 173 g (86%) of 1-bromo-4-methoxy-2-methylbenzene.
Anal. calc. for C ₈ H ₉ BrO: C, 47.79; H, 4.51. Found: C, 47.83; H, 4.69.
¹ H NMR (CDCfe): δ 7.43 (d, J = 8.8 Hz, 1H, 6-H), 6.82 (d, J = 2.9 Hz, 1H, 3-H), 6, 64 (dd, J = 8.8 Hz, J = 2.9 Hz, 1H, 5-H), 3.80 (s, 3H, OMe), 2.40 (s, 3-H, 2-Me) .
1-Bromo-2- (bromomethyl) -4-methoxybenzene
OMe OMe
NBS, CCl ₄
Br Br
To a solution of 173 g (0.86 mol) of 1-bromo-4-methoxy-2 methylbenzene in 850 ml of CCl ₄ 153 g (0.86 mol) of NBS and 1.0 g of (PhCOO) 2 were added at room temperature. This mixture was refluxed for 16 hours, cooled to room temperature and then filtered through glass frit (G2). The precipitate was further washed with 2 x 150 ml of CCl4. The combined filtrate was evaporated to dryness and the residue was triturated with 600 ml of n-hexane. The precipitate was filtered (glass frit G3), washed with 50 ml of n-hexane and dried in vacuo. This procedure provided

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121 g of the title product. Additional quantity of the product was obtained by evaporation of a mother liquor followed by recrystallization of the residue from 200 ml of n-hexane at -25 ^o C. In total, 157 g (65%; or 56% of general yield for two stages) of 1-bromo-2- (bromomethyl) -4-methoxybenzene were isolated.
Anal. calc. for C ₈ H ₈ Br ₂ O: C, 34.32; H, 2.88. Found: C, 34.44; H, 2.95.
Method 3
1-Bromo-2- (bromomethyl) -4-methoxybenzene
OMe
NBS, CCl ₄
N-Bromosuccinimide (45.9 g) was added to a solution of 15.1 g (123 mmol) of 3-methylanisole in 240 ml of tetrachloromethane. The mixture was refluxed for 14 hours with 0.3 g of benzoyl peroxide. The resulting mixture was filtered on glass frit (G3), to the filtrate 100 ml of dichloromethane and 300 ml of cold water were added. The organic layer was separated, dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was recrystallized from hot hexanes to provide 16.0 of the title compound. The mother liquor was evaporated to dryness and the residue was recrystallized from hexanes to provide 6.1 g of the title material. Total yield 22.1 g (64%) of a white crystalline solid.
Anal. calc. for C8H8Br2O: C, 34.32; H, 2.88. Found: C,
34.47; H, 3.02.
3- (2-bromo-5-methoxyphenyl) -2-methylpropanoic acid
1. MeCH (CO ₂ Et) ₂ , EtONa, EtOH
2. KOH, H ₂ O
3. H3O ⁺
4. Δ
Br
OMe
To a solution of sodium ethoxide obtained from 15.2 g
81/131 (0.661 mol) of sodium and 540 ml of dry ethanol, 115 g (0.658 mol) of diethyl methylmalonate were added. This mixture was stirred for 15 minutes; then 184 g (0.659 mol) of 1-bromo-2- (bromomethyl) -4-methoxybenzene were added with vigorous stirring of such a rate in order to maintain smooth reflux. This mixture was refluxed for another 2 hours and then cooled to room temperature. A solution of 130 g of KOH in 400 ml of water was added. The resulting mixture was refluxed for 4 hours to saponify the ester formed. Ethanol and water were distilled until the steam temperature reached 95 ^o C. To the residue cooled to room temperature 1500 ml of water and then HCl 12 M (for pH 1) were added. The precipitate formed from (2-bromo-5-methoxybenzyl) (methyl) malonic acid was filtered, washed with 2 x 200 ml of cold water and air-dried. Decarboxylation of substituted methylmalonic acid at 180 ^o C provided 152 g (84%) of the title product.
Anal. calc. for CnHi ₃ BrO ₃ : C, 48.37; H, 4.80. Found: C, 48.21; H, 4.92.
1H NMR (CDCl3): δ 7.45 (d, J = 8.8 Hz, 1H, 3-H in aryl), 6.82 (d, J = 3.0 Hz, 1H, 6-H in aryl) , 6.69 (dd, J = 8.8 Hz, J = 3.0 Hz, 1H, 4-H in aryl), 3.79 (s, 3H, OMe), 3.17 (dd, J = 13 , 6 Hz, J = 7.1 Hz, 1H, CHHCH), 2.94 (m, 1H, CHMe), 2.82 (dd, J = 13.6 Hz, J = 7.5 Hz, 1H, CHH (CH), 1.26 (d, J = 7.1 Hz, 3H, CHMe).
4-Bromo-7-methoxy-2-methylindan-1-one
Br Br
P ₄ O ₁₀ -MeSO ₃ H
LJ Co ₂ h 'LJL
OMe OMe ^O
Eaton's reagent obtained from 153 g of P4O10 and 780 ml of MeSO ₃ H, 149 g (0.544 mol) of 3- (2-bromo-5-methoxyphenyl) -2methylpropanoic acid were added by vigorous stirring for 50 minutes at 60-62 ^o C. The resulting mixture was further stirred for 30 minutes at the same temperature and then poured into a mixture of 2 kg of ice and 2000 cm ³ of cold water. The crude product was extracted with 800 ml of dichloromethane, the aqueous layer was then further extracted with 2 x
82/131
200 ml of dichloromethane for each 2 L of aqueous phase. The combined organic extract was washed with aqueous K ₂ CO ₃ , dried over K ₂ CO ₃ and then evaporated to dryness. The resulting red oil was vacuum distilled at 155170 ^o C / 5 mm Hg to provide 104 g (75%) of 4-bromo-7-methoxy-2methylindan-1-one as a yellow oil which slowly crystallizes at room temperature.
Anal. calc. for CnHnBrO ₂ : C, 51.79; H, 4.35. Found: C, 51.84; H, 4.40.
¹ H NMR (CDCls): δ 7.64 (d, J = 8.6 Hz, 1H, 5-H), 6.73 (d, J = 8.6 Hz, 1H, 6-H), 3, 94 (s, 3H, OMe), 3.27 (dd, J = 17.7 Hz, J = 8.1 Hz, 1H, CHH'CH), 2.70 (m, 1H, CHMe), 2.59 (dd, J = 17.7 Hz, J = 3.9 Hz, 1H, CHH'CH), 1.31 (d, J = 7.5 Hz, 3H, 2-Me).
4-Bromo-1,7-dimethoxy-2-methylindane
Br Br
T 1. NaBH ₄ , THF-MeOH T
YvA 2. MeI, KOH, DMSO
------------- OMe ^O OMe ^OMe
To a mixture of 104 g (0.407 mmol) of 4-bromo-7-methoxy-2methylindan-1-one and 15.0 g (0.397 mmol) of NaBH4 in a mixture of 410 ml in THF, 205 ml of methanol in drops with vigorous stirring for 4 hours at +5 ^o C. This mixture was stirred overnight at room temperature and then added to 1 liter of cold water. The resulting mixture was carefully acidified by 2 M HCl to pH 5.0 and the formed indan-ol was extracted with 500 ml of dichloromethane. The aqueous layer was further extracted with 2 x 200 ml of dichloromethane. The combined organic extract was evaporated to dryness. To the yellowish liquid resulting from crude 4-bromo-7-methoxy-2-methylindan-1-ol, 800 ml of DMSO, 92.0 g (1.64 mol, 4.0 equivalent) of KOH and 116 g (0.817 mol , 2.0 equivalents) of MeI were added. This mixture was stirred for 3 hours at room temperature and then added to 3L of cold water. The crude product was extracted with dichloromethane (500 ml, then 3 x 250 ml). The combined organic extract was washed 5 times with 1 liter of water and then evaporated to dryness. The pro
83/131 duct was isolated by flash chromatography on silica gel 60 (40-63 pm; eluent: hexanes-dichloromethane = 2: 1, then 1: 2 and finally 1: 5, vol.) Followed by vacuum rectification, 149-154 ° C / 8 mm Hg. Yield 96.0 g (87%) of a mixture of about 1 to 2 of two diastereomers.
Anal. calc, for Ci ₂ Hi ₅ BrO ₂ : C, 53.15; H, 5.58. Found: C, 53.08; H, 5.65.
¹ H NMR (CDCI3), greater diastereomer: δ 7.36 (d, J = 8.6 Hz, 1H,
5-H), 6.62 (d, J = 8.6 Hz, 1H, 6-H), 4.68 (d, J = 1.3 Hz, 1H, CHOMe), 3.82 (s, 3H , 7-OMe), 3.38 (s, 3H, 1-OMe), 3.27 (dd, J = 16.7 Hz, J = 7.3 Hz, 1H, 3-H), 2.54 ( m, 1H, 2-H), 2.41 (dd, J = 16.7 Hz, J = 2.0 Hz, 1H, 3'-H), 1.03 (d, J =
7.3 Hz, 3H, 2-Me); minor disastereomer: δ 7.33 (d, J = 8.6 Hz, 1H, 5-H), 6.61 (d, J = 8.6 Hz, 1H, 6-H), 4.69 (d, J = 5.6 Hz, 1H, CHOMe), 3.81 (s, 3H, 7-OMe), 3.38 (s, 3H, 1-OMe), 3.27 (dd, J = 16.0 Hz , J = 7.8 Hz, 1H, 3-H), 2.41 (dd, J = 16.0 Hz, J = 9.6 Hz, 1H, 3'-H), 2.54 (m, 1H , 2-H), 1.22 (d, J = 6.9 Hz, 3H, 2-Me).
2-Methyl-4-methoxy-7- (3,5-di-tert-butylphenyl) -1H-indene
To a solution of 3,5-di-tert-butylphenylmagnesium bromide obtained from 59.3 g (0.220 mol) of 1-bromo-3,5-di-tert-butylbenzene and 7.60 g (0.313 mol, 1.42 equivalent) of magnesium chips in 450 ml of THF, 1.00 g (1.28 mmol, 0.65 mol%) of NiCI ₂ (PPh ₃ ) IPr and a solution of 53.4 g (0.197 mol) of 4-bromo-1,7-dimethoxy-2-methylindane in 50 ml of THF was added. A vigorous reflux occurs approximately after about 30 seconds and stopped after the next 30 seconds. This mixture was stirred for 30 minutes at room temperature. Finally, 1000 ml of water and then 50 ml of 12 M HCI were added. The product was extracted with 500 ml of dichloromethane, the organic layer was separated, the aqueous layer was
84/131 additionally extracted with 200 ml of dichloromethane. The combined organic extract was dried over K ₂ CO ₃ , passed through a short column with silica gel 60 (40-63 pm), and then evaporated to dryness. To the residue dissolved in 700 ml of toluene, 1.4 g of TsOH was added. This solution was refluxed using Dean-Stark head for 20 minutes, cooled to room temperature, washed with 200 ml of 10% aqueous NaHCO ₃ . The organic layer was separated and the aqueous layer was extracted with 2 x 100 ml of dichloromethane. The combined organic solution was evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 pm; eluent: hexane-dichloromethane = 10: 1, then 1: 1, vol.). This procedure provided 67.6 g (99%) of 2-methyl-4-methoxy-7- (3,5-di-tert-butylphenyl) -1H-indene as a yellowish crystalline powder. The latter can be recrystallized from nhexane with marginal weight loss.
Anal. calc. for C ₂₅ H ₃₂ O: C, 86.15; H, 9.25. Found: C, 86.09; H, 9.23.
¹ H NMR (CDCle): δ 7.40 (m, 1H, 4-H in! Bu2C6H3), 7.35 (m, 2H,
2,6-H in! Bu2C6H3), 7.15 (d, J = 8.4 Hz, 1H, 6-H in indenyl), 6.88 (d, J =
8.4 Hz, 1H, 5-H in indenyl), 6.70 (m, 1H, 3-H in indenyl), 3.92 (s, 3H, OMe), 3.41 (m, 2H, 2, 2'-H in indenyl), 2.15 (s, 3H, 2-Me in indenyl), 1.38 (s, 18H, iBu). Chlorine [4- (3,5-di-tero-butylphenyl) -7-methoxy-2-methyl-1H-inden-1-yl] dimethylsilane

To a solution of 13.1 g (37.5 mmol) of 7- (3,5-di-tert-butylphenyl) 4-methoxy-2-methyl-1H-indene in 200 ml of toluene, 15.0 ml ( 37.5 mmol) of
2.5 M BuLi in hexanes were added at room temperature. The resulting viscous solution was stirred for 2 hours and then 10 ml of THF was added. The suspension formed was stirred for 12 hours at room temperature, about 2 hours at 60 ^o C, cooled to 20 ^o C and 24.0 g (0.186
85/131 mol, 5 equivalents) of dichlorodimethylsilane were added in one portion. The resulting solution was warmed to room temperature, stirred for 2 hours at this temperature, evaporated to about ½ of its volume and then filtered through glass frit (G3). The precipitate was further washed with 2 x 30 ml of toluene. The combined filtrate was evaporated to dryness to provide a viscous yellow oil which contained about 90% chlorine [4- (3,5-di-tert-butylphenyl) -7-methoxy-2-methyl-1 H-inden-1 -yl] dimethylsilane. This product was used more without further purification.
Anal. calc. for C ₂₇ H ₃₇ ClOSi: C, 73.51; H, 8.45. Found: C, 73.70; H, 8.57.
¹ H NMR (CDCle): δ 7.41 (m, 1H, 4-H in ^f Bu2C6H3), 7.34 (m, 2H,
2,6-H in ^f Bu2C6H3), 7.29 (d, J = 8.5 Hz, 1H, 6-H in indenyl), 6.76 (m, 1H,
3-H in indenyl), 6.74 (d, J = 8.5 Hz, 1H, 5-H in indenyl), 3.89 (s, 3H, OMe), 3.84 (s, 1H, 1- H in indenyl), 2.31 (s, 3H, 2-Me in indenyl), 1.40 (s, 18H, ^f Bu), 0.64 (s, 3H, SiMeMe'Cl), 0.01 (s , 3H, SiMeMe'Cl). [2-Methyl-4-phenyl-5-methoxy-6-fer-butyl-1H-inden-1-yl] - [2-methyl-4- (3,5-di-fer butylphenyl) -7-methoxy- 1 H-inden-1-yl] dimethylsilane
1. ⁿ BuLi, Et ₂ O
2. CuCN
3.
^SiMe 2 ^Cl MeO
SiMe ₂
OMe
MeO

To a solution of 12.3 g (35.3 mmol) of 7- (3,5-di-tert-butylphenyl) -
4-methoxy-2-methyl-1H-indene in 200 ml of ether, 14.2 ml (35.5 mmol) of nBuLi
2.5 M in hexanes was added in one portion at -50 ^o C. This mixture was stirred overnight at room temperature, then cooled to -40 ^o C and 150 mg of CuCN were added. The resulting mixture was stirred for 1 hour at -20 ^o C, then cooled to -40 ^o C and a solution of 13.6
86/131 g (35.3 mmol) of (2-methyl-4-phenyl-5-methoxy-6-tert-butyl-1 / - / - inden-1-yl) (chlorine) dimethylsilane in 200 ml of ether was added in one portion. In addition, this mixture was stirred overnight at room temperature, so 0.5 ml of water was added. This solution was filtered on a silica gel 60 pad (40-63 pm) which was further washed with dichloromethane. The combined organic eluate was evaporated to dryness and dried under vacuum. This procedure provided 24.9 g of a yellowish glass. This product of about 90% purity was used most without further purification.
Anal. calc. for C48H60O2Si: C, 82.70; H, 8.68. Found: C, 83.07; H, 8.80.
¹ H NMR (CDCI3): δ 7.70 (s), 7.29-7.55 (m), 6.72-6.81 (m), 6.49 (m), 6.43 (m) , 4.07 (s), 3.95 (s), 3.94 (s), 3.89 (s), 3.88 (s), 3.95 (s), 3.84 (s), 3.28 (s), 3.26 (s), 2.33 (s), 2.20 (s), 2.12 (s), 1.99 (s), 1.49 (s), 1 , 45 (s), 1.43 (s), 1.42 (s), -0.13 (s), -0.15 (s), -0.23 (s), -0.31 (s) ).
Anf / c dichloride // methylsilanediyl (2-methyl-4- (3,5-di-tert-butylphenyl) -7-methoxyinden-1-yl) (2-methyl-4-phenyl-5-methoxy-6- tert-butyl-inden-1-yl) zirconium (Metallocene E6)
To a solution of 24.9 g (ca. 35.3 mmol, ca. 90% purity) of [6-tert-butyl-5-methoxy-2-methyl-4-phenyl-1 / - / - indent 1 -yl] [4- (3,5-di-tert-butylphenyl) -7methoxy-2-methyl-1 / - / - inden-1-yl] dimethylsilane in 300 ml of toluene, 28.3 ml (70, 8 mmol) of 2.5 M nBuLi in hexanes was added in one portion at room temperature. This mixture was stirred overnight at room temperature, then cooled to -25 ° C and 13.3 g (35.3 mmol)
87/131 of ZrCl4 (THF) 2 was added. The resulting mixture was stirred for 24 hours, then 20 ml of THF was added and the reaction mixture was stirred for 2 hours at 60 ^o C. After evaporating about 50 ml of the solvents, the resulting solution heated to 80 ^o C was filtered through glass frit (G4) to provide a 1 to 1 mixing solution of anti and syn zirconocenes. This solution was evaporated to dryness. The residue was dissolved in a mixture of 60 ml of toluene and 10 ml of refluxing n-octane. Orange crystals precipitated from this solution at room temperature were filtered (G3), washed with 3 x 10 ml of cold toluene (This led to a noticeable decrease in the amount of precipitate in the filter), 3 x 10 ml of cold nhexane and dried at vacuum. This procedure provided 6.12 g (20%) of anti-pure zirconocene. Red crystals precipitated from the combined mother liquor at room temperature after resting this solution for one week were filtered, washed with 3 x 10 ml of cold toluene, 3 x 10 ml of cold nhexane and dried under vacuum. This procedure provided 2.72 g of syn zirconocene. The mother liquor was diluted with a little n-hexane. Crystals precipitated from this solution were collected and treated as described above. This procedure was repeated three times in total to provide an additional amount of pure syn zirconocene. In this way, 8.32 g (28%) of pure syn zirconocene were isolated in total.
Anti Complex:
Anal. calc. for C ₄₈ H ₅₈ Cl ₂ O ₂ SiZr: C, 67.26; H, 6.82. Found: C, 67.40; H, 6.93.
¹ H NMR (CDCfe): δ 7.59 (broad s, 2H, 2.6-H in Ph), 7.57 (s, 1H, 7-H in 2-methyl-4-phenyl-5-methoxy- 6-tert-butylindenyl), 7.47 (d, J = 1.8 Hz, 2H,
2,6-H in 3,5-tBu2C6H3), 7.43 (m, 2H, 3,5-H in Ph), 7.88 (t, J = 1.8 Hz, 1H, 4-H in 3 , 5-tBu2C6H3), 7.33 (d, J = 7.8 Hz, 1H, 5-H in 2-methyl-4-aryl-7methoxyindenyl), 7.32 (m, 1H, 4-H in Ph) , 6.97 (s, 1-H, 3-H in 2-methyl-4-aryl-7-methoxy-indenyl), 6.55 (s, 1-H, 3-H in 2-methyl-4-phenyl- 5-methoxy-6-tertbutylindenyl), 6.39 (d, J = 7.8 Hz, 1H, 6-H in 2-methyl-4-aryl-7-methoxyindenyl), 3.88 (s, 3H, OMe in 2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl), 3.39 (s, 3H, OMe in 2-methyl-4-aryl-7-methoxy-indenyl), 2.26 (s , 3H, 2 Me in
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2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl), 2.04 (s, 3H, 2-Me in 2-methyl-4aryl-7-methoxy-indenyl), 1.40 (s, 9H, tBu in 2-methyl-4-phenyl-5-methoxy-6-tertbutylindenyl), 1.35 (s, 18H, tBu in 3.5- / Bu2C6H3), 1.30 (s, 3H, SiMeMe ') ,
1.18 (s, 3H, SiMeMe)
Syn Complex:
Found: C, 67.33; H, 6.90.
¹ H NMR (CDCls): δ 7.70 (s, 1H, 7-H in 2-methyl-4-phenyl-5-methoxy6-tert-butylindenyl), 7.59 (broad s, 2H, 2.6- H in Ph), 7.50 (d, J = 1.8 Hz, 2H, 2.6-H in 3.5-tBu2C6H3), 7.43 (m, 2H, 3.5-H in Ph), 7.36 (t, J = 1.8 Hz, 1H, 4-H in 3,5-tBu2C6H3), 7.32 (m, 1H, 4-H in Ph), 7.17 (d, J = 7 , 8 Hz, 1H,
5-H in 2-methyl-4-aryl-7-methoxy-indenyl), 6.94 (s, 1-H, 3-H in 2-methyl-4-aryl-7-methoxy-indenyl), 6.54 ( s, 1-H, 3-H in 2-methyl-4-phenyl-5-methoxy-6-tertbutylindenyl), 6.33 (d, J = 7.8 Hz, 1H, 6-H in 2-methyl- 4-aryl-7-methoxyindenyl), 3.99 (s, 3H, OMe in 2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl),
3.19 (s, 3H, OMe in 2-methyl-4-aryl-7-methoxy-indenyl), 2.44 (s, 3H, 2-Me in 2-methyl-4-phenyl-5-methoxy-6-tert -butylindenyl), 2.41 (s, 3H, 2-Me in 2-methyl-4aryl-7-methoxy-indenyl), 1.35 (s, 18H, tBu in 3,5-tBu2C6H3), 1.32 ( s, 3H, SiMeMe '), 1.30 (s, 9H, tBu in 2-methyl-4-phenyl-5-methoxy-6-tert-butylindenyl),
1.20 (s, 3H, SiMeMe)
Synthesis of ant / tf / methylsilanodiyl dichloride [2-methyl-4- (4-tert-butylphenyl) -inden1 -yl] [2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-terc -butyl-inden-1-yl] zirconium (metallocene E7)
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6-tert-Butyl-4- (4-tert-butylphenyl) -5-methoxy-2-methylindan-1-one
4- ^í BuC ₆ H ₄ B (OH) ₂
Na ₂ CO ₃ , Pd (OAc) ₂ / PPh ₃
DME-H ₂ O
A mixture of 31.1g (100 mmol) of 4-bromo-6-tert-butyl-5-methoxy-2-methylindanone, 25.0 g (140 mmol) of 4-ferc-butylphenylboronic acid, 29.4 g (280 mmol ) Na ₂ CO ₃ , 1.35 g (6.00 mmol, 6 mol.%) of Pd (OAc) ₂ and 3.15 g (12.0 mmol, 12 mol.%) of PPh ₃ in 130 ml of water and 380 ml of DME was refluxed for 6 hours in an argon atmosphere. The formed mixture was evaporated to dryness. To the residue, 500 ml of dichloromethane and 500 ml of water were added. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was dried over Na ₂ SO4, evaporated to dryness and the crude product was isolated using flash chromatography on silica gel 60 (40-63 pm; eluent: hexanes-dichloromethane = 2: 1, vol.). This crude product was recrystallized from n-hexane to provide 29.1 g (81%) of a white solid.
Anal. calc. for C ₂ 5H ₃₂ O _2: C, 82.37; H, 8.85. Found: C, 82.26; H, 8.81.
¹ H NMR (CDCl3): δ 7.74 (s, 1H, 7-H in indenyl), 7.48 (d, J = 8.0 Hz, 2H, 2.6-H in C6H4 ^f Bu), 7 , 33 (d, J = 8.0 Hz, 2H, 3.5-H in C6H ₄ ^f Bu), 3.27 (s, 3H, OMe), 3.15 (dd, J = 17.3 Hz, J = 7.7 Hz, 1H, 3-H on indan-1-one), 2.67-2.59 (m, 1H, 2-H on indan-1-one), 2.48 (dd, J = 17.3 Hz, J = 3.7 Hz, 3'H in indan-1-one), 1.42 (s, 9H, ^f Bu in CeH / Bu), 1.38 (s, 9H, 6- ^f Bu in indan-1-one), 1.25 (d, J = 7.3 Hz, 3H, 2-Me in indan-1-one). 5-tert-Butyl-7- (4-te / 'c-butylphenyl) -6-methoxy-2-methyl-1/7-indene
The
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To a solution of 28.9 g (79.2 mmol) of 6-fer-butyl-4- (4-ferbutylphenyl) -5-methoxy-2-methylindan-1-one in 400 ml of THF cooled to 5 ^o C , 5.00 g (132 mmol) of NaBH ₄ were added. In addition, 100 ml of methanol was added in drops to this mixture by vigorous stirring for about 7 hours at 5 ^o C. The resulting mixture was evaporated to dryness and the residue was divided between 500 ml of dichloromethane and 1000 ml of HCl 0 , 5 M. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to provide a colorless oil. To a solution of this oil in 500 ml of toluene, 1.0 g of TsOH was added. The formed mixture was refluxed with Dean-Stark head for 15 minutes and then cooled to room temperature using a water bath. The resulting reddish solution was washed with 10% aqueous Na2CO3, the organic layer was separated, the aqueous layer was extracted with 2 x 100 ml of dichloromethane. The combined organic extract was dried over K2CO3 and then passed through a short pad of silica gel 60 (40-63 pm). The silica gel pad was additionally washed with 50 ml of dichloromethane. The combined organic eluate was evaporated to dryness to provide a yellowish crystalline mass. The product was isolated by recrystallizing this mass from 150 ml of hot n-hexane. The precipitated crystals at 5 ° C were dry collected vacuo. This procedure provided 23.8 g of white 5-tert-butyl-7- (4-te / 'c-butylphenyl) -6-methoxy-2methyl-1H-indene. The mother liquor was evaporated to dryness and the residue was recrystallized from 20 ml of n-hexane in the same way. This procedure provided an additional 2.28 g of the product. In this way, the total yield of the title product was 26.1 g (95%).
Anal. calc. for C ₂₅ H ₃₂ O: C, 86.15; H, 9.25. Found: C, 86.24; H, 9.40.
¹ H NMR (CDCle): δ 7.44 (d, J = 8.5 Hz, 2H, 2.6-H in C6H4 ^f Bu), 7.40 (d, J = 8.5 Hz, 2H, 3 , 5-H in C ₆ H ₄ ^f Bu), 7.21 (s, 1H, 4-H in indenyl), 6.43 (m, 1H, 3-H in indenyl), 3.20 (s, 3H , OMe), 3.15 (s, 2H, 1-H in indenyl), 2.05 (s, 3H, 2-Me in indenyl), 1.43 (s, 9H, 5- ^f Bu in indenyl), 1.37 (s, 9H, ^f Bu in C6H4 ^f Bu).
91/131 [6-tert-Butyl-4- (4-tert-butylphenyl) -5-methoxy-2-methyl-1H-inden-1-ill (chloro) dimethylsilane
1. ⁿ BuLi, toluene e-THF
2. Μ © 2 ^ 1CI2
To a solution of 10.5 g (30.0 mmol) of 5-ferc-butyl-7- (4-fercbutylphenyl) -6-methoxy-2-methyl-1 / - / - indene in 200 ml of toluene, 12 , 0 ml (30.0 mmol) of 2.5 M BuLi in hexanes was added at room temperature. The resulting viscous solution was stirred for 10 hours and then 10 ml of THF was added. The formed mixture was stirred for 2 hours at 60Ό, then cooled to -20 ° C and 19.4 g (150 mmol, 5 equivalents) of dichlorodimethylsilane were added in one portion. The resulting solution was warmed to room temperature, refluxed for 1 hour and then filtered through glass frit (G3). The precipitate was further washed with 2 x 10 ml of toluene. The combined filtrate was evaporated to dryness to provide 13.2 g (99%) of the title product with a yellowish oil which was used further without further purification.
Anal. calc. for C27H37CIOSI: C, 73.51; H, 8.45. Found: C, 73.38; H, 8.50.
¹ H NMR (CDCl 3): δ 7.45 (d, J = 8.5 Hz, 2H, 2.6-H in C6H4 ^f Bu), 7.41-7.38 (m, 3H, 3.5- H in C6H ₄ ^f Bu and 7-H in indenyl), 6.48 (s, 1H, 3-H in indenyl), 3.54 (s, 1H, 1-H in indenyl), 3.20 (s, 3H, OMe), 2.19 (s, 3H, 2-Me in indenyl), 1.43 (s, 9H, 6- ^f Bu in indenyl), 1.38 (s, 9H, ^f Bu in C ₆ H ₄ ^f Bu), 0.43 (s, 3H, Si / WeMe'CI), 0.16 (s, 3H, SiMe / We'CI).
92/131 [6- / efc-Butyl-4- (4- / erc-butylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl] [4- (4- / ercbutylphenyl) -2- methyl-1 H-inden-1-yl] dimethylsilane
1. ⁿ BuLi, Et ₂ O

To a solution of 7.88 g (30.0 mmol) of 7- (4-tert-butylphenyl) -2methyl-1H-indene in 200 ml of ether, 12.0 ml (30.0 mmol) of ⁿ BuLi 2 , 5 M in hexanes was added in one portion at -40 ^o C. This mixture was stirred overnight at room temperature, then cooled to -40 ^o C and 215 mg of CuCN were added. The resulting mixture was stirred for 1 hour at -20 ^o C, then cooled to -40 ^o C and a solution of 13.2 g (30.0 mmol) of [6-tefc-butyl-4- (4-tefc- butylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl] (chlorine) dimethylsilane (prepared as described above) in 150 ml of ether was added in one portion. In addition, the mixture was stirred overnight at room temperature, so 0.5 ml of water was added. This solution was filtered on a silica gel 60 pad (40-63 pm) which was further washed with 2 x 75 ml of dichloromethane. The combined organic eluate was evaporated to dryness and the residue was dried in vacuo. This procedure provided 20.1 g of the title product (under the evidence of NMR spectroscopy, it is about 90% pure and is about 1: 1 mixture of diastereomers) as yellowish glass which was used additionally without further purification .
Anal. calc. for C ₄₇ H ₅₈ OSi: C, 84.63; H, 8.76. Found: C,
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84.31; Η, 8.57.
¹ Η NMR (CDCI ₃ ): δ 7.51-7.40 (m), 7.34 (s), 7.33 (s), 7.28-7.21 (m), 7.16-7 , 10 (m), 6.83 (s), 6.82 (s), 6.50 (s), 3.71 (s), 3.68 (s), 3.66 (s), 3, 23 (s), 3.22 (s), 2.19 (s), 2.17 (s), 2.16 (s), 2.11 (s), 1.44 (s), 1.42 (s), 1.39 (s), 1.39 (s), 1.38 (s), -0.12 (s), -0.18 (s), -0.22 (s).
Anti- and syn-dimethylsilanodiyl dichloride [2-methyl-4- (4-tert-butylphenyl) -inden-1-ill [2-methyl-4- (4-tert-butylphenyl) -5-methoxy-6-tert -butil-inden-1-illzirconium (metallocene E7)

To a solution of 20.1 g (ca. 30.0 mmol) of [6-ferc-butyl-4- (4tert-butylphenyl) -5-methoxy-2-methyl-1 Hidenen-1-yl] [4 - (4-fer-butylphenyl) -2-methyl 1-1Hinden-1 -yl] dimethyl-silane (of ca. 90% purity as described above) in 250 ml of ether cooled to -30 ° C, 24.0 ml (60.0 mmol) of 2.5 M nBuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature. The resulting red solution was cooled to -30 ° C and 7.00 g (30.0 mmol) of ZrCl ₄ were added. The reaction mixture was stirred for 24 hours resulting in a solution with a large amount of light orange precipitate. The same 55/45 antí / syn ratio was found both in solution and precipitated by NMR spectroscopy. The reaction mixture was evaporated to dryness, the residue was treated with 450 ml of hot toluene and the resulting hot suspension was filtered hot on glass frit (G4). Crystals precipitated from the filtrate at room temperature were collected and dried under vacuum. This one
The procedure 94/131 provided about 10 g of a mixture of about 4: 1 syn and anti zirconocenes. Crystallization of this mixture from 125 ml of hot toluene gave 6.20 g (25%) of pure syn zircononcene. The mother liquor was evaporated to dryness and the residue was recrystallized from 45 ml of toluene to provide 2.53 g (10%) of anti zirconocene as a slightly orange powder. Again, the mother liquors were evaporated to dryness and then 100 ml of n-hexane was added. The suspension was filtered through glass frit (G3) and the precipitate was dried in vacuo. This procedure provided 9.20 g of a mixture of about 70:30 of anti and syn zirconocenes. Thus, the total yield of the isolated zirconocenes loop was 17.9 g (72%). Designation on NMR spectra was made using the following abbreviations: L ¹ for 4- (4-tert-butylphenyl) -2-methyl-1H-inden-1-yl and L ² for 6-tert-butyl4- (4- tert-butylpenyl) -5-methoxy-2-methyl-1H-inden-1-yl.
Anti zirconocene.
Anal. calc. for C ₄₇ H ₅₆ Cl ₂ OSiZr: C, 68.25; H, 6.82. Found: C, 68.43; H, 7.01.
¹ H NMR (CDCle): δ 7.63-7.61 (m, 3H, 2.6-H in Ce ^ 'Bu in L ¹ and 7-H in L ¹ ), 7.53-7.51 ( m, 3H, 2,6-H in C6H4 ^t Bu in L ² and 7-H in L ² ), 7,477.42 (m, 4H, 3,5-H in Ce ^ 'Bu in L ¹ and 3,5 -H in Ce ^ 'Bu in L ² ), 7.37 (d, J = 7.0 Hz, 1H, 5-H in L ¹ ), 7.08 (dd, J = 8.5 Hz, J = 7.0 Hz, 1H, 6-H in L ¹ ), 7.01 (s, 1H, 3-H in L ¹ ), 6.62 (s, 1H, 3-H in L ² ), 3.36 (s, 3H, OMe), 2.24 (s, 3H, 2-Me in L ¹ ), 2.17 (s, 3H, 2-Me in L ² ), 1.39 (s, 9H, ^t Bu in Ce ^ 'Bu in L ¹ ), 1.33-1.31 (m, 24H, ^t Bu in Ce ^' Bu in L ² , 6- ^t Bu in L ² , SiMeMe 'and SiMeMe').
Zirconocene syn.
Anal. calc. for C ₄₇ H ₅₆ Cl ₂ OSiZr: C, 68.25; H, 6.82. Found: C, 68.33; H, 6.98.
¹ H NMR (CDCl ₃ ): δ 7.64 (d, J = 8.6 Hz, 1H, 7-H in L ¹ ), 7.57 (d, J = 7.7 Hz, 2H, 2.6 -H in Ce ^ 'Bu in L ¹ ), 7.52-7.41 (m, 7H, 2.6-H in Ce ^' Bu in L ² , 7-H in L ² , 3.5-H in Ce ^ 'Bu in L ¹ and 3,5-H in C6H4B in L ² ), 7,177.14 (m, 1H, 5-H in L ¹ ), 6.91 (s, 1H, 3-H in L ¹ ), 7.08 (t, J = 7.6 Hz, 1H, 6-H in L ¹ ), 6.51 (s, 1H, 3-H in L ² ), 3.18 (s, 3H, OMe), 2.43 (s, 3H, 2-Me in L ¹ ),
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2.37 (s, 3H, 2-Me in L ² ), 1.44 (s, 3H, SiMeMe '), 1.33 (m, 27H, ^f Bu in CeH4 ^f Bu in L ¹ , ^f Bu in CeH / Bu in L ² , 6- ^f Bu in L ² ), 1.22 (s, 3H, SiMeMe '). Synthesis of ant / d / methylsilanediyl dichloride [2-methyl-4- (4-tert-butylphenyl) -inden1 -ill [2-methyl-4- (3,5-di-te / 'c-butylphenyl) -5 -methoxy-6-te / 'c-butyl-inden-1 -illzirconium (metallocene E8)

6-tert-Butyl-4- (3,5-di-te / 'c-butylphenyl) -5-methoxy-2-methylindan-1-one
3,5- ⁱ Bu ₂ C ₆ H ₃ B (OH) ₂
Na ₂ CO ₃ , Pd (OAc) ₂ , PPh ₃
H2O-DME
A mixture of 30.7 g (98.6 mmol) of 4-bromo-6-tert-butyl-5methoxy-2-methylindanone, 30.6 g (128 mmol) of 3,5-di-tert-butylphenylboronic acid, 29.7 g (280 mmol) of Na ₂ CO ₃ , 1.35 g (5.92 mmol; 6 mol.%) Of Pd (OAc) ₂ , 3.15 g (11.8 mmol; 12 mol.% ) of PPh ₃ , 130 ml of water and 380 ml of 1,2-dimethoxyethane was refluxed for 12 hours. In addition, the reaction mixture was quenched with water, solvents were evaporated. The residue was dissolved in 500 ml of dichloromethane and this solution was washed with 500 ml of water. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was dried over Na ₂ SO ₄ , then evaporated to dryness. The crude product isolated from the residue using flash chromatography on silica gel 60 (40-63 pm, hexanes-dichloromethane = 2: 1, vol.) Was then recrystallized from n-hexane to provide 18.5 g (43%) of a white solid.
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Anal. calc, for C29H40O2: C, 82.81; H, 9.59. Found: C, 83.04; H, 9.75.
¹ H NMR (CDCl 3): 5 7.74 (s, 1H, 7-H in indan-1-one), 7.41 (t, J = 1.6 Hz, 1H, 4-H in C6H3 ^f Bu2) , 7.24 (d, J = 1.6 Hz, 2.6-H in C ₆ H3 ^f Bu2), 3.24 (s, 3H, OMe), 3.17 (dd, J = 17.3 Hz , J = 8.0 Hz, 1H, 3-H on indan-1-one), 2.64 (m, 1H, 2-H on indan-1-one), 2.47 (dd, J = 17, 3 Hz, J = 3.7 Hz, 1H, 3-H 'in indan-1-one), 1.43 (s, 9H, 6-'Bu in indan-1-one), 1.36 (s, 18H, ^f Bu in C6H3 ^f Bu ₂ ), 1.25 (d, J = 7.3 Hz, 3H, 2-Me in indan-1-one). 5-tert-Butyl-7- (3,5-di-tert-butylphenyl) -6-methoxy-2-methyl-1 / - / - indene

To a solution of 16.3 g (38.8 mmol) of 6-tert-butyl-4- (3,5-ditherc-butylphenyl) -5-methoxy-2-methylindan-1-one in 200 ml of cooled THF to 5 ° C, 1.47 g (38.9 mmol) of NaBH ₄ was added. In addition, 80 ml of methanol was added dropwise to this mixture by vigorous stirring for about 7 hours at 5 ° C. The resulting mixture was evaporated to dryness and the residue was treated with 300 ml of dichloromethane and 300 ml of 2M HCI. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to provide a colorless oil. To a solution of this oil in 250 ml of toluene, 0.1 g of TsOH was added, this mixture was refluxed with Dean-Stark head for 15 minutes and then cooled to room temperature using a water bath. The resulting solution was washed with 10% aqueous Na ₂ CO ₃ . The organic layer was separated and the aqueous layer was extracted with 2 x 50 ml of dichloromethane. The combined organic extract was dried over K ₂ CO ₃ and then passed through a short layer of silica gel 60 (40-63 pm). The silica gel layer was further washed with 100 ml of dichloromethane. The combined organic eluate was evaporated to dryness to provide 15.7 g (99%) of a mild crystalline product which was used further without further purification.
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Anal. calc, for C29H40O: C, 86.08; H, 9.96. Found: C, 86.26; H, 10.21.
¹ H NMR (CDCI3): δ 7.36 (t, J = 1.8 Hz, 1H, 4H in C6H3 ^f Bu2), 7.33 (d, J = 1.8 Hz, 2H, 2.6-H in C ₆ H ₃ ^f Bu2), 7.21 (s, 1H, 4-H in indenyl), 6.44 (m, 1H, 3-H in indenyl), 3.17 (s, 3H, OMe), 3.14 (s, 2H, 1-H in indenyl), 2.06 (s, 3H, 2-Me in indenyl), 1.44 (s, 9H, 5- ^f Bu in indenyl), 1.35 ( s, 18H, ^f Bu in C6H ₃ ^f Bu ₂ ). ¹³ C { ¹ H} NMR (CDCI3): δ 150.4, 145.2 (two resonances), 141.7, 140.9, 140.6, 137.3, 132.5, 126.9, 124, 0, 120.1, 116.9, 60.2, 43.0, 35.2, 34.9, 31.5, 31.0, 16.7.
[6-tert-Butyl-4- (3,5-di-tert-butylphenyl) -5-methoxy-2-methyl-1 / - / - inden-1-ill (chloro) dimethylsilane
1. ^ BuLi.toluene-THF
2. MG2SÍCI2
To a solution of 15.7 g (38.8 mmol) of 5-tert-butyl-7- (3,5-diferc-butylphenyl) -6-methoxy-2-methyl-1 / - / - indene in 200 ml of toluene, 16.0 ml (40.0 mmol) of 2.5 M BuLi in hexanes were added at room temperature. The resulting viscous solution was stirred for 10 hours and then 10 ml of THF was added. This mixture was stirred for 2 hours at 60 ° C, then cooled to -20 ° C and 25.0 g (194 mmol, 5 equivalents) of dichlorodimethylsilane were added in one portion. The resulting solution was refluxed for 2 hours, then evaporated to about% of its volume and filtered through glass frit (G3). The precipitate was further washed with 2 x 30 ml of toluene. The combined filtrate was evaporated to dryness to provide 19.2 g (99%) of white solid which was used without further purification.
Anal. calc. for C31H45CIOSI: C, 74.88; H, 9.12. Found: C, 75.12; H, 9.37.
¹ H NMR (CDCl3): 5 7.38 (s, 1H, 7-H in indenyl), 7.36 (t, J = 1.6 Hz, 1H, 4-H in C6H3 ^f Bu2), 7.33 (d, J = 1.6 Hz, 2H, 2.6-H in C ₆ H ₃ ^f Bu ₂ ), 6.49 (m, 1H, 3-H in indenyl), 3.54 (s, 1H, 1-H in indenyl), 3.17 (s, 3H, OMe),
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2.19 (s, 3H, 2-Me in indenyl), 1.44 (s, 9H, 6- ^f Bu in indenyl), 1.36 (s, 18H, ^f Bu in C6H3 ^f Bu2), 0.45 (s, 3H, SiMeMe '), 0.18 (s, 3H, SiMeMe').
[6-te / 'c-Butyl-4- (3,5-di-te /' c-butylphenyl) -5-methoxy-2-methyl-1H-inden-1-yl] [4- (4-te / '(butylphenyl) -2-methyl-1 H-inden-1-yl] dimethylsilane

To a solution of 5.54 g (21.1 mmol) of 7- (4-tert-butylphenyl) -2methyl-1H-indene in 150 ml of ether, 8.50 ml (21.3 mmol) of BuLi 2, 5 M in hexanes was added in one portion at -40 ^o C. This mixture was stirred overnight at room temperature, then cooled to -40 ^o C and 190 mg of CuCN were added. The resulting mixture was stirred for 1 hour at -20 ^o C, then cooled to -40 ^o C and a solution of 10.5 g (21.1 mmol) of [6-tert-butyl-4- (3,5- di-te / 'c-butylphenyl) -5-methoxy-2-methyl-1 H-inden-1-yl] (chlorine) dimethyl silane in 150 ml of ether was added in one portion. In addition, this mixture was stirred overnight at room temperature, so 0.5 ml of water was added. This solution was filtered on a silica gel 60 pad (40-63 pm), which was further washed with 2 x 75 ml of dichloromethane. The combined eluate was evaporated to dryness and the residue was triturated with 70 ml of n-hexane. The obtained suspension was filtered through glass frit, the precipitate was washed with 30 ml of n-hexane and dried under vacuum to provide a white powder. In addition, the mother liquor was evaporated to a small volume. The suspension formed was filtered through glass frit (G3) and the precipitate was washed with 2 x 15 ml of n-hexane and then dried under vacuum. Again, the mother liquor was evaporated to provide a yellowish oil that was recrystallized at -30 ^o C for two months. Crystals precipitated from this solution
99/131 were collected and dried under vacuum. In this way, 12.2 g (80%) of the title product were isolated. Designation on NMR spectra was made using the abbreviations that follow:
L ¹ for 4- (4-tert-butylphenyl) -2-methyl-1 / - / - inden-1-yl and L ² for 6terc-butyl-4- (3,5-di-tert-butylphenyl) -5 -methoxy-2-methyl-1 / - / - inden-1-yl.
Anal. calc, for C ₅ iH ₆ 6OSi: C, 84.70; H, 9.20. Found: C, 84.91; H, 9.35.
¹ H NMR (CDCl3): δ 7.48-7.46 (s, 5H, 2.6-H in C6H4 ^f Bu and 2.4.6-H in C6H ₃ ^f Bu2), 7.38 (s, 3H, 3,5-H in C6H4 ^f Bu and 7-H in L ² ), 7.34 (d, J = 7.5 Hz, 1H, 7-H in L ¹ ), 7.24 (d, J = 7.5 Hz, 1H, 5-H in L ¹ ), 7.14 (t, J = 7.5 Hz, 1H, 6-H in L ¹ ), 6.80 (s, 1H, 3-H in L ¹ ), 6.51 (s, 1H, 3-H in L ² ), 3.71 (s, 1H, 1-H in L ¹ ), 3.68 (s, 1H, 1-H in L ² ), 3.20 (s, 3H, OMe), 2.18 (s, 3H, 2-Me in L ¹ ), 2.13 (s, 3H, 2-Me in L ² ), 1.44 ( s, 9H, 6- ^f Bu in L ² ), 1.39 (s, 9H, ^f Bu in C6H ₄ ^f Bu), 1.38 (s, 18H, ^f Bu in C6H3 ^f Bu2), -0.13 (s, 3H, SiMeMe '), -0.21 (s, 3H, SiMeMe').
Anti- and sv77-dimethylsilanodiyl [2-methyl-4- (4-tert-butylphenyl) -inden-1-ill [2-methyl-4- (3,5-di-tert-butylphenyl) -5-methoxy -6-tert-butyl-inden-1-illzirconium (metallocene E8)

To a solution of 10.3 g (14.2 mmol) of [6-tert-butyl-4- (3,5-diterc-butylphenyl) -5-methoxy-2-methyl-1 / - / - inden-1 -il] [4- (4-fer-buti Ifeni I) -2-methyl 1-1Hinden-1 -yl] dimethylsilane in 200 ml of toluene (slightly warm solution was used because of the low solubility of the formation binder starting bridge), 11.4 ml (28.5 mmol) of 2.5M BuLi ⁿ in hexanes were added
100/131 in one serving. This mixture was stirred overnight at room temperature, then for 2 hours at 80 ^o C. The resulting mixture was cooled to -20 ^o C and 5.37 g (14.2 mmol) of ZrCl ₄ (THF) _{2 have} been added. This mixture was stirred for 24 hours, then 20 ml of THF was added. The formed mixture was stirred for 3 hours at 80 ^o C and then evaporated to about 150 ml. The resulting mixture was filtered on glass frit (G4) at 80 ^o C to provide under the evidence of NMR spectroscopy a solution about 1 to 1 of anti and syn zirconocene. This filtrate was then evaporated to about 10 ml and then 100 ml of n-hexane was added. The orange precipitate formed was immediately filtered on a glass frit (G4), washed with 2 x 10 ml of n-hexane and dried under vacuum. This procedure provided 2.10 g of zirconocene syn contaminated with 2% anti isomer. The filtrate was evaporated to dryness and the residue was recrystallized from n-hexane. Crystals precipitated from this solution were collected and dried under vacuum to provide 3.52 g of a about 1: 1 mixture of syn and anti zirconocenes. In addition, 1.46 g of a 1:10 mixture of syn and anti zirconocenes precipitated after one week of the filtrate at room temperature. The last product was recrystallized from 25 ml of n-octane. Crystals precipitated at room temperature were collected and dried under vacuum to provide 0.75 g of anti-pure zirconocene. The mother liquor was evaporated to 7 ml, then the residue was heated to dissolve the precipitate formed. Crystals precipitated from this solution at room temperature were collected and dried under vacuum to provide 490 mg of anti-contaminated zirconocene with 8% syn isomer. Designation on NMR spectra was made using the abbreviations that follow:
L ¹ for 4- (4-tert-butylphenyl) -2-methyl-1H-inden-1-yl and L ² for 6tert-butyl-4- (3,5-di-tert-butylphenyl) -5-methoxy 2-methyl-1H-inden-1-yl. Anti zirconocene.
Anal. calc. for C ₅₁ H ₆₄ Cl ₂ OSiZr: C, 69.35; H, 7.30. Found: C, 69.54; H, 7.49.
¹ H NMR (CDCls): δ 7.63-7.61 (m, 3H, 7-H in L ¹ and 2.6-H in C6H4 ^t Bu), 7.51 (s, 1H, 7-H in L ² ), 7.47 (d, J = 8.5 Hz, 2H, 3.5-H in
101/131
CeH / Bu), 7.44 (broad s, 2H, 2.6-H in ΟθΗ ^ Βι ^), 7.37 (d, J = 6.8 Hz, 1H, 5H in L ¹ ), 7.34 (t, J = 1.6 Hz, 1H, 4-H in C6H3 ^f Bu2), 7.07 (dd, J = 8.5 Hz, J = 6.9 Hz, 1H, 6-H in L ¹ ) , 7.01 (s, 1H, 3-H in L ¹ ), 6.62 (s, 1H, 3-H in L ² ), 3.35 (s, 3H, OMe), 2.25 (s, 3H, 2-Me in L ² ), 2.19 (s, 3H, 2-Me in L ¹ ), 1.40 (s, 9H, 6- ^f Bu in L ² ), 1.34 (s, 9H , ^f Bu in C6H4 ^f Bu), 1.33-1.23 (m, ^f Bu in C6H3 ^f Bu2, SiMeMe 'and SiMeMe').
Zirconocene syn.
Anal. calc. for C ₅₁ H ₆₄ Cl ₂ OSiZr: C, 69.35; H, 7.30. Found: C, 69.33; H, 7.58.
¹ H NMR (CDCl3): δ 7.65 (d, 1H, J = 8.6 Hz, 7-H in L ¹ ), 7.57 (d, J = 8.5 Hz, 2H, 2.6- H in CeH / Bu), 7.52 (s, 1H, 7-H in L ² ), 7.47 (d, J = 8.5 Hz, 2H, 3.5-H in CeH / Bu), 7 , 44 (broad s, 2H, 2,6-H in C6H3 ^f Bu2), 7.33 (t, J = 1.6 Hz, 1H, 4-H in C6H ₃ ^f Bu2), 7.13 (d, J = 6.8 Hz, 1H, 5-H in L ¹ ), 6.90 (s, 1H, 3-H in L ¹ ), 6.85 (dd, J = 8.6 Hz, J = 6, 8 Hz, 1H, 6-H in L ¹ ), 6.50 (s, 1H,
3-H in L ² ), 3.14 (s, 3H, OMe), 2.44 (s, 3H, 2-Me in L ² ), 2.38 (s, 3H, 2-Me in L ¹ ) , 1.44 (s, 3H, SiMeMe '), 1.35-1.33 (m, 36H, 6- ^f Bu in L ² , ^f Bu in C6H4 ^f Bu and ^f Bu in C6H ₃ ^f Bu2), 1 , 22 (s, 3H, SiMeMe ').
Synthesis of amphetf / methylsilanodiyl dichloride [2-methyl-4- (4-te / O-butylphenyl) -inden1 -yl] (2-methyl-4-phenyl-5-isobutoxy-6-te / O-butyl-inden -1 -yl) zirconium (metallocene E9)
Me ₂ Si ZrCI ₂
-tert-Butyl-2-isobutoxybenzene
HO
To a solution of 60.1 g (0.40 mol) of 2-tert-butylphenol in 600
102/131 ml of DMSO, 89.6 g (1.60 mol) of KOH and 147 g (0.80 mol) of isobutyl iodide were added. This mixture was stirred for 2 hours at room temperature, then 73.6 g (0.40 mol) of isobutyl iodide were added. The resulting mixture was stirred for 1 hour and again, then 73.6 g (0.40 mol) of isobutyl iodide were added. The mixture formed was stirred overnight at room temperature. The upper layer was separated. To the lower layer 5 liters of water were added and a little product was extracted with 2 x 250 ml of dichloromethane. The combined organic extract (including the separated top layer) was washed with 5 x 1 liter of water, dried over Na ₂ SO ₄ and evaporated to dryness. The crude product (free of 2-tert-butylphenol) was obtained from the residue by flash chromatography on silica gel 60 (40-63 pm; eluent: hexanes). In addition, this crude product was distilled to provide 1-tert-butyl-2-isobutoxybenzene, eg 85-95 ^o C / 4 mm Hg. This procedure provided 44.9 g (54%) of the title product.
Anal. calc. for C ₁₄ H ₂₂ O: C, 81.50; H, 10.75. Found: C, 81.45; H, 10.84.
¹ H NMR (CDCl3): δ 7.35 (dd, J = 7.7 Hz, J = 1.6 Hz, 1H, 6-H), 7.22 (td, J = 7.7 Hz, J = 1.6 Hz, 1H, 5-H), 6.96-6.90 (m, 2H, 3.4-H), 3.82 (d, J = 6.3 Hz, 2H, OCH2CHMe2), 2 , 23 (m, 1H, OCH2CHMe2), 1.47 (s, 9H, ^f Bu), 1.15 (d, J = 6.7 Hz, 6H, OCXCH2). 5-Isobutoxy-6-tero-butyl-2-methylindanone
CH ₂ = C (Me) CO ₂ H MeSO3H-P4O _w
THE
A mixture of 75.1 g (0.872 mol) of methacrylic acid and 90.0 g (0.436 mol) of 1-tert-butyl-2-isobutoxybenzene was added dropwise to Eaton's reagent (prepared from 119 g of P4O10 and 600 ml of MeSO3H) for 2 hours at 50 ^o C. The resulting mixture was stirred at 50 ^o C for 30 minutes, then cooled to room temperature and poured into 1 liter of cold water. The crude product was extracted with 3 x 200 ml of dichloromethane. The organic extract was washed with aqueous K ₂ CO ₃ , dried over Na ₂ SO ₄ and then

103/131 passed through a silica gel pad (40-63 pm). The silica gel pad was additionally washed with 100 ml of dichloromethane. The combined eluate was evaporated to dryness. The residue was vacuum distilled, e.g. 155170 ° C / 5 mm Hg. The product was purified by flash chromatography on silica gel 60 (40-63 pm; eluent: n-hexane-dichloromethane-ether = 25: 25: 1, vol.) To provide 91.9 g (76%) of the indanone title.
Anal. calc. for C ₁₈ H ₂₆ O ₂ : C, 78.79; H, 9.55. Found: C, 78.94; H, 9.70.
¹ H NMR (CDCl ₃ ): δ 7.69 (s, 1H, 7-H on indan-1-one), 6.87 (s, 1H, 4-H on indan-1-one), 3.86 (d, J = 6.3 Hz, 2H, OCH2CHMe2), 3.30 (dd, J = 16.5 Hz, J = 7.1 Hz, 1H, 3-H in indan-1-one), 2, 69-2.59 (m, 2H, 2,3'-H on indan-1-one), 2.22 (m, 1H, OCH2CHMe2), 1.41 (s, 9H, ^f Bu), 1.28 (d, J = 7.3 Hz, 3H, 2-Me in indan-1-one), 1.11 (d, J = 6.7 Hz, 6H, OC ^ CH ^).
4-Bromo-5-isobutoxy-6-tero-butyl-2-methylindanone
Br ₂ , NaOAc
Et ₄ NI, H ₂ O-CH ₂ Cl ₂
To a mixture of 91.9 g (335 mmol) of 5-isobutoxy-6-tert-butyl2-methylindanone, 82.5 g (1.0 mol) of NaOAc, 1.70 g (7.0 mmol) of iodide of tetraethylammonium, 500 ml of water and 170 ml of dichloromethane, 17.2 ml (335 mmol) of bromine were added by vigorously stirring for 1 hour at 0 ^o C. The resulting mixture was stirred for 1 hour at this temperature and then 41 , 3 g (0.5 mol) of NaOAc were added. To the obtained mixture, 9.0 ml (175 mmol) of bromine were added in drops for 0.5 hour at 0 ^o C. The mixture formed was stirred for 2 hours at 0 ^o C, then Na ₂ SO ₃ was added to remove an excess of bromine. The organic layer was separated, dried over Na ₂ SO ₄ and then evaporated to dryness. This procedure provided 116 g (98%) of the title product which was used further without further purification.
Anal. calc. for C ₈ H ₂₅ BrO ₂ : C, 61.19; H, 7.13. Found: C, 61.36; H, 7.33.
1H NMR (CDCle): δ 7.71 (s, 1H, 7-H in indan-1-one), 3.93 (m,
104/131
2H, OCH2CHMe2), 3.29 (dd, J = 17.5 Hz, J = 7.7 Hz, 1H, 3-H in indan-1ona), 2.76-2.67 (m, 1H, 2- H in indan-1-one), 2.60 (dd, J = 17.5 Hz, J = 3.8 Hz, 1H, 3'-H in indan-1-one), 2.34 (m, 1H , OCH2CHMe2), 1.41 (s, 9H, 6- ^f Bu in indan-1-one), 1.31 (d, J = 7.3 Hz, 3H, 2-Me in indan-1-one), 1.10 (d, J = 6.7 Hz, 6H, OCH2 CHM02).
6-tert-Butyl-5-isobutoxy-2-methyl-4-phenylindan-1-one
PhB (OH) ₂ , Na ₂ CO ₃
Pd (OAc) ₂ / PPh ₃ , H2O-DME
A mixture of 48.4 g (137 mmol) of 4-bromo-5-isobutoxy-6terc-butyl-2-methylindanone, 25.0 g (205 mmol) of phenylboronic acid, 40.5 g (382 mmol) of Na ₂ CO ₃ , 1.90 g (8.22 mmol, 6 mol%) of Pd (OAc) ₂ , 4.30 g (16.4 mmol, 12 mol%) of PPh ₃ , 180 ml of water and 520 ml of DME was refluxed for 6 hours. Then, this reaction mixture was quenched with water, the solvents were evaporated. The residue was dissolved in 500 ml of dichloromethane, this solution was washed with 500 ml of water. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness, the crude product was obtained from the residue by flash chromatography on silica gel 60 (40-63 pm; eluent: hexanes-dichloromethane = 2: 1, vol.). This crude product was recrystallized from n-hexane to provide 40.3 g (84%) as a white solid.
Anal. calc. for C ₂₄ H ₃₀ O ₂ : C, 82.24; H, 8.63. Found: C, 82.02; H, 8.49.
¹ H NMR (CDCl ₃ ): δ 7.77 (s, 1H, 7-H in indan-1-one), 7.47-7.36 (m, 5H, 2,3,4,5,6- H in Ph), 3.25 (d, J = 6.7 Hz, 2H, OCH2CHMe2), 3.11 (dd, J = 17.3 Hz, J = 7.7 Hz, 1H, 3-H in indan -1-one), 2.62 (m, 1H, 2-H in indan-1-one), 2.44 (dd, J = 17.3 Hz, J = 3.8 Hz, 1H, 3'- H in indan-1-one), 1.65 (m, 1H, OCH2CHMe2), 1.44 (s, 9H, 6- ^f Bu in indan-1-one), 1.25 (d, J = 7, 3 Hz, 3H, 2-Me in indan-1-one), 0.66 (d, J = 6.7 Hz, 6H, OCH2CHMe2).
105/131
5-tert-Butyl-6-isobutoxy-2-methyl-7-phenyl-1/7-indene
1. NaBH ₄₁ THF-MeOH
2. TsOH, toluene
To a solution of 34.0 g (97.0 mmol) of 6-tert-butyl-5-isobutoxy
2-methyl-4-phenylindan-1-one in 300 ml of THF cooled to 5 ° C, 5.00 g (132 mmol) of NaBH ₄ were added. In addition, 150 ml of methanol was added dropwise to this mixture by vigorous stirring for about 7 hours at 5 ° C. The resulting mixture was evaporated to dryness and the residue was partitioned between 500 ml of dichloromethane and 500 ml of 1M HCI. The organic layer was separated, the aqueous layer was further extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to provide a colorless oil. To a solution of this oil in 500 ml of toluene, 1 g of TsOH was added and this mixture was refluxed with Dean-Stark head for 15 minutes and then cooled to room temperature using a water bath. The resulting solution was washed with 10% aqueous Na ₂ SO ₄ . The organic layer was separated, the aqueous layer was extracted with 2 x 100 ml of dichloromethane. The combined organic solution was dried over K ₂ CO ₄ and then passed through a short pad of silica gel 60 (40-63 pm). The silica gel pad was additionally washed with 100 ml of dichloromethane. The combined organic eluate was evaporated to dryness. This procedure provided 32.4 g (99%) of 5-tert-butyl-6-isobutoxy-2-methyl-7-phenyl-1/7-indene which was used without further purification.
Anal. calc, for C ₂₄ H ₃₀ O: C, 86.18; H, 9.04. Found: C, 86.01; H, 9.20.
¹ H NMR (CDCI ₃ ): δ 7.45 (d, J = 7.7 Hz, 2H, 2.6-H in Ph), 7,417.37 (m, 2H, 3.5-H in Ph), 7.30 (t, J = 7.2 Hz, 1H, 4-H in Ph), 7.22 (s, 1H, 4-H in indenyl), 6.43 (m, 1H, 3-H in indenyl) ), 3.18 (d, J = 6.5 Hz, 2H, OC / 7 ₂ CHMe ₂ ), 3.10 (s, 2H, 1-H in indenyl), 2.04 (s, 3H, 2- Me in indenyl), 1.61 (m, 1H, OCH ₂ C / 7Me ₂ ), 1.44 (s, 9H, 5- ^f Bu in indenyl), 0.64 (d, J = 6.7
106/131
Hz, 6H, OCH ₂ CHMe ₂ ).
(6-tert-Butyl-5-isobutoxy-2-methyl-4-phenyl-1H-inden-1-yl) (chlorine) dimethylsilane

To a solution of 16.8 g (50.2 mmol) of 5-tert-butyl-6-isobutoxy2-methyl-7-phenyl-1/7-indene in 200 ml of toluene, 20.1 ml (50.5 mmol) of 2.5 M BuLi in hexanes were added at room temperature. The viscous solution formed was stirred for 10 hours and then 10 ml of THF was added. The resulting mixture was stirred for 1 hour at 65 ° C, then cooled to -20 ° C and 32.5 g (252 mmol, 5 equivalents) of dichlorodimethylsilane was added in one portion. This mixture was warmed to room temperature, refluxed for 0.5 hour and then filtered through glass frit (G3). The precipitate was further washed with 2 x 30 ml of toluene. The combined filtrate was evaporated to dryness to provide 21.5 g (99%) of (6tert-butyl-5-isobutoxy-2-methyl-4-phenyl-1/7-inden-1-yl) (chlorine) dimethylsilane which more was used without further purification.
Anal. calc, for C ₂₆ H3 ₅ CIOSi: C, 73.12; H, 8.26. Found: C, 73.49; H, 8.52.
¹ H NMR (CDCl 3): 5 7.55-7.45 (m, 5H, 2,3,5,6-H in Ph and 7-H in indenyl), 7.38 (t, J = 7.1 Hz, 1H, 4-H in Ph), 6.49 (s, 1H, 3-H in indenyl), 3.61 (s, 1H, 1-H in indenyl), 3.22 (m, 2H, OCH2CHMe2 ), 2.24 (s, 3H, 2-Me in indenyl), 1.73 (m, 1H, OCH2C / 7Me2), 1.51 (s, 9H, 6- ^f Bu in indenyl), 0.73 ( dd, J = 13.3 Hz, J = 6.6 Hz, 6H, OCH2CHMe ₂ ), 0.49 (s, 3H, SiMeMe'CI), 0.23 (s, 3H, SiMeMe'CI).
107/131 (6-tert-Butyl-5-isobutoxy-2-methyl-4-phenyl-1H-inden-1-yl) [4- (4-tert-butylphenyl) -2methyl-1 H-inden-1 - il] dimethylsilane
1. ⁿ BuLi, Et ₂ O
To a solution of 13.2 g (50.3 mmol) of 7- (4-tert-butylphenyl) -2methyl-1 H-indene in 200 ml of ether, 20.1 ml (50.3 mmol) of ⁿ BuLi 2.5 M in hexanes was added in one portion at -40 ^o C. This mixture was stirred overnight at room temperature, then cooled to -40 ^o C and 200 mg of CuCN were added. The resulting mixture was stirred for 1 hour at -20 ^o C, then cooled to -40 ^o C and a solution of 21.5 g (50.2 mmol) of (6-tert-butyl-5-isobutoxy-2-methyl -4-phenyl-1 H-inden-1-yl) (chlorine) dimethylsilane in 200 ml of ether was added in one portion. In addition, this mixture was stirred overnight at room temperature, so 0.5 ml of water was added. This solution was filtered on a silica gel 60 pad (40-63 pm) which was further washed with 2 x 75 ml of dichloromethane. The combined eluate was evaporated to dryness under vacuum. The residue was recrystallized from 250 ml of hot n-hexane. Crystals precipitated at room temperature were collected, washed with 2 x 50 ml of n-hexane and dried under vacuum. This procedure provided 11.4 g (35%) of anti- (6-tert-butyl-5-isobutoxy-2-methyl-4-phenyl-1H-inden-1-yl) [4- (4-tert-butylphenyl) ) -2methyl-1H-inden-1-yl] dimethylsilane. The mother liquor was evaporated to dryness and the products were isolated by flash chromatography on silica gel 60 (40-63 pm; eluent: hexanes: dichloromethane = 10: 1, vol., Then 3: 1, vol.). This procedure provided 11.6 g (35%) of (6-tert-butyl-5-isobutoxy-2-methyl-4-phenyl-1H-inden-1-yl) [4- (4-tert
108/131 butylphenyl) -2-methyl-1H-inden-1-yl] dimethylsilane as a mixture of about 2: 1 of syn and anti isomers. In this way, the overall yield of the title product was 70%. Designation on NMR spectra was made using the following abbreviations: L ¹ for 4- (4-tert-butylphenyl) -2-methyl-1H-inden-1-yl and L ² for 6-tert-butyl-5-isobutoxy -2-methyl-4-phenyl-1 H-inden-1-yl.
Anal. calc. for C ₄₆ H ₅₆ OSi: C, 84.61; H, 8.64. Found: C, 84.94; H, 8.73.
rac compound ¹ H NMR (CDCl3): δ 7.51-7.46 (m, 6H, 2,3,5,6-H in Ph and 2,6-H in C6H4 ^t Bu), 7,42-7 , 39 (m, 2H, 7-H in L ¹ and 7-H in L ² ), 7,357.29 (m, 3H, 4-H in Ph, 3,5-H in C6H4 ^t Bu), 7,26 (d, J = 7.5 Hz, 1H, 5-H in L ¹ ), 7.14 (t, J = 7.5 Hz, 1H, 6-H in L ¹ ), 6.83 (s, 1H , 3-H in L ¹ ), 6.44 (s, 1H,
3-H in L ² ), 3.71 (s, 1H, 1-H in L ¹ ), 3.67 (s, 1H, 1-H in L ² ), 3.16 (m, 2H, OCH2CHMe2) , 2.19 (s, 3H, 2-Me in L ¹ ), 2.16 (s, 3H, 2-Me in L ² ), 1.67 (sept, J = 6.6 Hz, 1H, OCH2CHMe2) , 1.43 (s, 9H, 6- ^t Bu in L ² ), 1.38 (s, 9H, ^t Bu in C6H4 ^t Bu), 0.69 (d, J = 6.8 Hz, 3H, OCXCHMeMe '), 0.65 (d, J = 6.8 Hz, 3H, OCH2CHMeMe'), -0.18 (s, 6H, SiMe2).
Anti- and syn-dimethylsilanodiyl dichloride [2-methyl-4- (4-tert-butylphenyl) -inden-1yl] (2-methyl-4-phenyl-5-isobutoxy-6-tert-butyl-inden-1 - il) zirconium (metallocene E9)
O 'BuO jD Z χ
1 · ⁿ BuLi, Et ₂ O r;
I 2. ZrCl ₄
SiMe ₂ -------------- * Cl ₂ Zr SiMe ₂ mT)
VJ O'Bu
To a solution of 11.6 g (17.8 mmol) of (6-tert-butyl-5-isobutoxy2-methyl-4-phenyl-1 H-inden-1-yl) [4- (4-tert-butylphenyl) ) -2-methyl-1 H-inden-1 yl] dimethylsilane in 200 ml of ether cooled to -30 ^o C, 14.5 ml (36.3 mmol) of 2.5M BuLi ⁿ in hexanes were added in one portion . This mixture was stirred overnight at room temperature, then cooled to -40 ^o C and 4.14 g (17.8 mmol) of ZrCl ₄ were added. The mixture of
109/131 reaction was stirred for 24 hours, then evaporated to dryness. The residue was dissolved in 300 ml of warm toluene and the suspension formed was filtered through glass frit (G4) to provide a solution that includes under the evidence of NMR spectroscopy a mixture about 1: 1 of anti and syn zircononcenes. The filtrate was evaporated to 125 mol. Crystals precipitated at room temperature were collected, washed with 10 ml of toluene, 10 ml of n-hexane and then dried under vacuum. This procedure provided 1.97 g (14%) of syn zirconocene. The mother liquor was evaporated to dryness and the residue was recrystallized from 80 ml of toluene. This procedure provided precipitate A and mother liquor. Under evidence of NMR spectroscopy, this precipitate A consists of an anti-contaminated complex with about 15% syn metallocene. The mother liquor was evaporated to dryness and the residue was recrystallized from 50 ml of toluene. This procedure provided a little precipitate (consisting of syn complex contaminated with various percentages of anti isomer) and mother liquor. This precipitate was recrystallized from 25 ml of toluene to provide 1.34 g of pure syn complex and the mother liquor was evaporated to dryness and the residue was recrystallized from 30 ml of toluene. The last procedure provided a precipitate consisting of an anti-contaminated complex with about 10% syn isomer. A mixture of this precipitate and precipitate A was recrystallized from 50 ml of a mixture of about 1 to 1 toluene and n-hexane to provide 2.64 g of anti-pure complex. In this way, syn and anti metallocenes were isolated at 24 and 19% of total yields, respectively. Designation on NMR spectra was made using the abbreviations that follow:
L ¹ for 4- (4-tert-butylphenyl) -2-methyl-1H-inden-1-yl and L ² for 6terc-butyl-5-isobutoxy-2-methyl-4-phenyl-1 H-inden-1 -ila.
Anti zirconocene.
Anal. calc. for C ₄₆ H ₅₄ Cl ₂ OSiZr: C, 67.95; H, 6.69. Found: C, 68.09; H, 6.57.
¹ H NMR (CDCls): δ 7.63-7.52 (m, 6H, 2.6-H in Ph, 2.6-H in C6H4 ^t Bu, 7-H in L ¹ and 7-H in L ² ), 7.46 (d, J = 8.1 Hz, 2H, 3.5-H in
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CeH / Bu), 7.40-7.36 (m, 3H, 3.5-H in Ph and 5-H in L ¹ ), 7.30 (m, 1H, 4-H in Ph), 7, 10-7.06 (m, 1H, 6-H in L ¹ ), 7.01 (s, 1H, 3-H in L ¹ ), 6.56 (s, 1H, 3-H in L ² ), 3.40 (m, 1H, CHH'CHMe2), 3.28-3.24 (m, 1H, CHH'CHMe2), 2.24 (s, 3H, 2-Me in L ¹ ), 2.17 ( s, 3H, 2-Me in L ² ), 1.77-1.67 (m, 1H, CH2CHMe2), 1.40 (s, 9H, ^f Bu in C6H4 ^f Bu), 1.33-1.30 (m, 15H, 6- ^f Bu in L ² , SiMeMe 'and SiMeMe'), 0.70 (d, J = 6.6 Hz, 3H, C ^ CHMeMe '), 0.65 (d, J = 6 , 6 Hz, 3H, CH2CHMeMe ').
Zirconocene syn.
Anal. calc. for C ₄₆ H ₅₄ Cl ₂ OSiZr: C, 67.95; H, 6.69. Found: C, 68.21; H, 6.90.
¹ H NMR (CDCI3): δ 7.64 (d, J = 8.6 Hz, 1H, 7-H in L ¹ ), 7.58 (d, J = 8.2 Hz, 2H, 2.6- H in C6H4 ^f Bu), 7.55 (s, 1H, 7-H in L ² ), 7.50 (broad s, 2H, 2.6-H in Ph), 7.46 (d, J = 8 , 2 Hz, 2H, 3,5-H in C6H ₄ Bu), 7.38 (wide s, 2H,
3.5-H in Ph), 7.30-2.27 (m, 1H, 4-H in Ph), 7.15 (d, J = 7.0 Hz, 1H, 5-H in L ¹ ) , 6.91 (s, 1H, 3-H in L ¹ ), 6.86 (dd, J = 8.6 Hz, J = 7.0 Hz, 1H, 6-H in L ¹ ), 6.45 (s, 1H, 3-H in L ² ), 3.11 (d, J = 6.9 Hz, 2H, CH2CHMe2), 2.43 (s, 3H, 2Me in L ¹ ), 2.37 (s , 3H, 2-Me in L ² ), 1.63-1.52 (m, 1H, CH2CHMe2), 1.44 (s, 3H, SiMeMe '), 1.35 (s, 9H, ^f Bu in C6H4 ^f Bu), 1.33 (s, 9H, 6- ^f Bu in L ² ), 1.22 (s, 3H, SiMeMe '), 0.61 (d, J = 6.7 Hz, 3H, C ^ CHMeMe '), 0.55 (d, J = 6.7 Hz, 3H, CH2CHMeMe').
Preparation of Solid Catalysts
Catalyst E1:
Inside the glove box, 80 µl of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a septum flask with 2 mL of a 30 wt% solution of MAO in toluene and allowed to react overnight. . The following day, 58.9 mg of metallocene E1 of the invention (rac-anti-Me ₂ Si (2-Me-4-Ph-6- / Bu-Ind) (2-Me-4Ph-5-OMe-6- (Bu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, 4 ml of the MAOmetalocene solution and 1 ml of the perfluoralkylethyl acrylate ester mixture in MAO solution were successively added to a glass reactor.
111/131 50 ml emulsification containing 40 ml of hexadecafluor-1,3-dimethylcyclohexane kept at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ^o C / 600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ^o C and stirred at 600 rpm until the transfer was complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3-dimethylcyclohexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ^o C in an argon flow. 0.62 g (catalyst E1) of a free flowing red powder was obtained.
Catalyst E2:
Inside a glove box, 80 µl of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a septum flask with 2 ml of 30 wt% MAO solution in toluene and allowed to react overnight. The next day, 58.7 mg of the metallocene E2 of the invention (rac-anti-Me ₂ Si (2-Me-4- (p- / BuPh) -Ind) (2-Me-4-Ph-5-OMe- 6ZBu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 min, the 4 ml of the MAOmetalocene solution and 1 ml of perfluoralkyl ether acrylate mixture in the MAO solution were successively added to a 50 ml emulsifying glass reactor containing 40 ml of hexadecafluor-1,3- dimethylcyclohexane kept at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ^o C / 600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ^o C and stirred at 600 rpm until the transfer was complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the
112/131 oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3-dimethylcyclohexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C under an argon stream. 0.52 g (E2 catalyst) of a free flowing red powder was obtained.
Catalyst E3:
Inside the glove box, 80 µl of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a septum flask with 2 ml of 30 wt% MAO solution in toluene and allowed to react overnight. The following day, 67.1 mg of the metallocene E3 of the invention (rac-anti-Me ₂ Si (2-Me-4- (3,5-di- / BuPh) -64Bu-Ind) (2-Me-
4-Ph-5-OMe-6-iBu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, the 4 ml of MAOmetalocene solution and 1 ml of the perfluoralkylethyl acrylate ester mixture in MAO solution were successively added to a 50 ml emulsifying glass reactor containing 40 ml of hexadecafluor-1,3- dimethylcyclohexane maintained at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ^o C / 600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ^o C and stirred at 600 rpm until the transfer was complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3-dimethylcyclohexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C under an argon stream. 0.67 g (catalyst E3) of a red free fluid powder was obtained.
Catalyst E5:
Inside the glove box, 80 pL of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a
113/131 septum flask with 2 mL of a 30 wt% solution of MAO in toluene and allowed to react overnight. The next day, 63.9 mg of metallocene E5 of the invention (rac-anti-Me ₂ Si (2-Me-4- (3,5- / Bu2Ph) -7-MeInd) (2-Me-4-Ph- 5-OMe-6-iBu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoralkylethyl acrylate ester mixture in the MAO solution were successively added to a 50 mL emulsifying glass reactor containing 40 mL of hexadecafluor-1, 3-dimethylcyclohexane kept at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ^o C / 600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ^o C and stirred at 600 rpm until the transfer was complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle over hexadecafluor-1,3-dimethylcyclohexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C in an argon stream. 0.38 g (catalyst E5) of a free flowing red powder was obtained.
Catalyst E6:
Inside the glove box, 80 µl of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a septum flask with 2 mL of a 30 wt% solution of MAO in toluene and allowed to react overnight. . The next day, 65.2 mg of the metallocene E6 of the invention (rac-anti-Me ₂ Si (2-Me-4- (3,5- / Bu2Ph) -7-OMeInd) (2-Me-4-Ph- 5-OMe-6-iBu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoralkyl ethyl acrylate ester mixture in the MAO solution were successively added to a
114/131 50 ml glass emulsification reactor containing 40 ml of hexadecafluor-1,3dimethylcyclohexane maintained at -10 ^o C and equipped with a suspended stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ° C / 600rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ^o C and stirred at 600 rpm until the transfer is complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3dimethylcyclohexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C under an argon stream. 0.39 g (E6 catalyst) of a red free fluid powder was obtained.
Catalyst E7:
Inside the glove box, 80 µl of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a septum flask with 2 mL of a 30 wt% solution of MAO in toluene and allowed to react overnight. . The following day, 66.3 mg of the metallocene E7 of the invention (rac-anti-Me ₂ Si (2-Me-4- (p- / BuPh) -Ind) (2-Me-4 (p- / BuPh) - 5-OMe-6- / Bu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoralkylethyl acrylate ester mixture in the MAO solution were successively added to a 50 mL emulsifying glass reactor containing 40 mL of hexadecafluor-1, 3dimethylcyclohexane kept at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ° C / 600rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ^o C and stirred at 600 rpm until the transfer is complete. The speed was reduced to 300 rpm. After 15 minutes
115/131 stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3-dimethylcycliexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C under an argon stream. 0.31 g (E7 catalyst) of a free flowing red powder was obtained.
Catalyst E8:
Inside the glove box, 80 µl of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a septum flask with 2 mL of a 30 wt% solution of MAO in toluene and allowed to react overnight. . The following day, 67.1 mg of the metallocene E8 of the invention (rac-anti-Me ₂ Si (2-Me-4- (p- / BuPh) -Ind) (2-Me-4 (3,5-íBu2Ph) -5-OMe-6-iBu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, the 4 mL of the MAO-metallocene solution and 1 mL of the perfluoralkylethyl acrylate ester mixture in the MAO solution were successively added to a 50 mL emulsifying glass reactor containing 40 mL of hexadecafluor-1, 3-dimethylcyclohexane kept at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ° C / 600rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot hexadecafluor-1,3-dimethylcyclohexane heated to 90 ° C and stirred at 600 rp m until the transfer is complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3dimethylcycliexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C under an argon stream. 0.49 g (catalyst E8) of a free flowing red powder was obtained. Catalyst E9:
Inside the glove box, 80 pL of a dry, degassed mixture of perfluoralkyl ethyl acrylate ester was mixed in a
116/131 flask with septum with 2 mL of a 30 wt% solution of MAO in toluene and allowed to react overnight. The following day, 61.7 mg of the metallocene E9 of the invention (rac-anti-Me ₂ Si (2-Me-4- (p- / BuPh) -Ind) (2-Me-4Ph-5-OiBu-6- (Bu-Ind) ZrCl ₂ ) (0.076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another bottle with septum and allowed to shake inside the glove box. After 60 minutes, the 4 mL of the MAOmetalocene solution and 1 mL of the perfluoralkylethyl acrylate ester mixture in the MAO solution were successively added to a 50 mL emulsifying glass reactor containing 40 mL of maintained hexadecafluor-1,3dimethylcyclohexane at -10 ^o C and equipped with an overhead stirrer (stirring speed = 600 rpm). The total amount of MAO is 5 mL (300 equivalents). A red emulsion formed immediately and was stirred for 15 minutes at 0 ° C / 600rpm. Then the emulsion was transfected erida via a Teflon tube to 2/4 hexadecafluor 100 ml hot-1,3-dimethylcyclohexane heated to 90 ° C and stirred at 600 rpm until the transfer is complete. The speed was reduced to 300 rpm. After 15 minutes of stirring, the oil bath was removed and the stirrer turned off. The catalyst was allowed to settle on top of hexadecafluor-1,3-dimethylcyclohexane and after 35 minutes the solvent was sucked out. The remaining red catalyst was dried for 2 hours at 50 ° C under an argon stream. 0.33 g (catalyst E9) of a free flowing red powder was obtained.
Comparative Catalyst C1:
The C1 catalyst of the comparative example was synthesized according to the recipe described above with 78.2 g of racmethyl (cyclohexyl) silanediilbis [2-methyl-4- (4-tert-butylphenyl) indenyl] zirconium dichloride as the metallocene .
Comparative Catalyst C2:
The C2 catalyst of the comparative example was synthesized according to the recipe described above with 60.6 mg of rac-Me ₂ Si (2-Me-4-Ph-5OMe-6-tBu-Ind) ₂ ZrCl ₂ as the metallocene.
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Table 1. Composition of catalyst as determined by ICP
Cat. Al (%) Zr (%) Al / Zr (molar) E1 26.20 0.31 285 E2 18.90 0.24 266 E3 26.10 0.32 276 E5 26.70 0.35 258 E6 23.50 0.28 283 E7 30.20 0.35 291 E8 28.30 0.34 281 E9 28.30 0.35 273 C1 31.00 0.37 283 C2 23.5 0.22 248
E1P, E2P, E3P and C1P: offline prepolymerization of E1, E2, E3 and C1 catalysts
The catalysts of the invention E1, E2 and E3, as well as the comparative catalyst C1, were prepolymerized according to the following procedure: offline prepolymerization experiments were carried out in a 125 ml pressure reactor equipped with lines gas supply and a suspended stirrer. Dry and degassed hexadecafluor-1,3-dimethylcyclohexane (15 mL) and the desired amount of the red catalyst to be prepolymerized were loaded into the reactor inside a glove box and the reactor was sealed. The reactor was then removed from the glove box and placed in a cold water bath. The suspended stirrer and the feed lines were then connected. The supply line was pressurized with hydrogen and the experiment was started by opening the valve between the H ₂ supply line and the reactor. At the same time, propylene feed was initiated through the same H ₂ feed line to ensure that all hydrogen was fed to the reactor. The propylene supply was left open and the monomer consumption was compensated by keeping the total pressure in the reactor constant (about 5 barg). The experiment was continued until the polymerization time was sufficient to provide the desired degree of polymerization. The reactor was then taken back to the glove box before opening and the contents were poured into a container
118/131 glass. Hexadecafluor-1,3-dimethylcyclohexane was evaporated until a constant weight was obtained to provide a prepolymerized pink catalyst. The degree of polymerization was determined gravimetrically and / or by analyzing the ash and / or aluminum content of the catalyst to be 3.5 for E1P, 4.6 for E2P, 2.9 for E3P and 3.1 for C1P.
Polymerizations:
Homopolymerization of propylene with catalysts E1 to E3 and random copolymerization C ₂ / C ₃ with catalysts E1 to E3 and E7
The polymerizations were carried out in a 5L reactor. 200 pl of triethyl aluminum were fed as a sequester in 5 ml of dry and degassed pentane. The desired amount of hydrogen was then charged (measured in mmol) and 1100 g of liquid propylene were added to the reactor. The desired amount of ethylene was fed to the reactor (random copolymerizations). The temperature was adjusted to 30 ^o C. The desired amount of catalyst in 5 ml of hexadecafluor-1,3-dimethylcyclohexane was flowed into the reactor with an overexpression of nitrogen. The temperature was then raised to 70 C over a period of 15 minutes. Polymerization was stopped after 30 minutes by reactor ventilation and nitrogen flow before the polymer was collected. The catalyst activity was calculated based on the 30 minute period.
Homopolymerization of propylene with E5 to E9 catalysts
The polymerizations were carried out in a 5 L. reactor. 200 pl of triethyl aluminum were fed as a sequestrant in 5 ml of dry and degassed pentane. The desired amount of hydrogen was then charged (measured in mmol) and 1100 g of liquid propylene was fed to the reactor. The temperature was adjusted to 20 ^o C. The desired amount of catalyst in 5 ml of hexadecafluor-1,3-dimethylcyclohexane was flowed into the reactor with a nitrogen overpressure. After 5 minutes (prepolymerization) the temperature was then increased to 70 ° C over a period of 15 minutes. The polymerization was stopped after 60 minutes by venting the reactor and flowing with nitrogen before the polymer was collected. The catalyst activity was calculated based on the 60 minute period.
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The catalyst activity for catalysts E1-E3 and E5-E9 was determined according to:
Activity kg / g (cat) / h = amount of polymer produced in kg / (catalyst load in grams x polymerization time in hours)
Details and results of polymerization are revealed in Table 2 (Ex. 1-26 and c-1 - c-10) and Table 3 (Ex. 27-34 and c-11 - c-13) Hypophasic ethylene-propylene copolymerization with catalyst E1P
Heterophasic copolymer was prepared with E1P catalyst in a sequential volume / gas phase process as follows: A 21.2 L autoclave with a double propeller agitator containing ~ 0.4 barg propylene was filled with another 5.18 kg of propylene. After adding 0.2 NL of H2 and 0.97 mmol of triethyl aluminum (1 molar solution in hexane) using a stream of 248 g of propylene, the solution was stirred at 250 rpm. After 20 minutes, the reactor temperature was increased to 40 ^o C and 298 mg of the solid prepolymerized E1P catalyst were contacted with 5 ml of
1,3-dimethylcyclohexane under N ₂ pressure (0.003 mol at ~ 10 barg) in a stainless steel flask connected to the autoclave for 60 seconds and flowed into the reactor with 494 g of propylene. Thereafter the stirring speed was increased to 350 rpm and the temperature in the reactor increased to 70 ^o C for ~ 13 minutes. This temperature was maintained for 30 minutes after reaching 68 ° C. After that, the pressure was reduced to 1 bar-a via flashing. To obtain target conditions for the gas phase of 15 bar-g at 60 ° C, ethylene and propylene are dosed in a ratio of C3 / C2 = 1.26 g / g in the reactor to a total amount of 429 g over 8 minutes. 60 ^o C (temperature decreased during rapiding due to enthalpy of vaporization) reached 16 minutes after the start of the pressure increase and the total pressure was constantly maintained at 15 bar-g via ethylene and propylene dosing at a ratio of C3 / C2 = 1.83 g / g. Polymerization was stopped 67 minutes after the start of the pressure increase to 15 barg via flashing and cooling. The residence time used to calculate catalyst activity in the gas phase was 55.5 minutes (start after reaching a polymerization temperature of 58 ^o C in the gas phase).
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After overflowing the reactor with N ₂ with a vacuum / N2 cycle, the product was taken and dried overnight in a chapel and another 2 hours in a vacuum drying oven at 60 ^o C.
Copolymerization of heterophasic ethylene-propylene with E2P catalyst
Heterophasic copolymer was prepared with E2P catalyst in a sequential mass / gas phase process as follows: a 21.2 L autoclave with double helix stirrer containing ~ 0.5 barg of propylene was filled with an additional 3.97 kg of propylene . After adding 0.2 NL of hydrogen and 0.73 mmol of triethyl aluminum (1 molar solution in hexane) using a stream of 246 g of propylene the solution was stirred at 250 rpm. After 20 minutes, the reactor temperature was increased to 40 ° C and 253 mg of prepolymerized, solid E2P catalyst (degree of polymerization 4.6), were contacted with 5 ml of perfluor-1,3-dimethylcyclohexane under nitrogen pressure (0.003 mol at ~ 10 bar-g) for 60 seconds and overflowed in the reactor with 243 g of propylene. Thereafter the agitaçãof hi speed increased to 350 rpm and the reactor temperature increased to 70 ° C for ~ 17 minutes. This temperature was maintained for 30 minutes after reaching 68 ^o C. After that the pressure was reduced to 1.1 barg via flashing. To obtain target conditions for ~ 15 barg gas phase at 60 ^o C, ethylene and propylene are dosed in a ratio of C3 / C2 = 1.23 g / g in the reactor to a total amount of 406 g over 8 minutes. 60 ^o C (temperature decreased during flashing due to enthalpy of vaporization) was reached 14 minutes after the start of pressure increase and the total pressure was constantly maintained at 15 barg via ethylene and propylene dosing at a ratio of C3 / C2 = 1 , 83 g / g. The polymerization was stopped 41.5 minutes after the start of the pressure increase to 15 barg via flashing and cooling. The residence time used to calculate the catalyst activity in the gas phase was 27.5 minutes (beginning after reaching the polymerization temperature of 58 ^o C in the gas phase).
After overflowing the reactor with nitrogen and a vacuum / nitrogen cycle the product is picked up and dried overnight in a chapel and another 2 hours in a vacuum drying oven at 60 ^o C.
This polymerization was repeated using a different amount of
121/131 catalyst and C3 / C2 feeds.
Copolymerization of heterophasic ethylene-propylene with E3P catalyst
Heterophasic copolymer was prepared with E3P catalyst in a sequential volume / gas phase process as follows: a 21.2 L autoclave with double helix stirrer containing ~ 0.5 barg of propylene was filled with an additional 3.96 kg of propylene . After adding 0.2 NL of hydrogen and 0.73 mmol of triethyl aluminum (1 molar solution in hexane) using a stream of 247 g propylene the solution was stirred at 250 rpm. After 20 minutes, the reactor temperature was increased to 40 ^o C and 212 mg of the prepolymerized, solid E3P catalyst (degree of polymerization 2.9), were contacted with 5 ml of perfluor-1,3-dimethylcyclohexane under nitrogen pressure (0.003 mol at ~ 10 bar-g) for 60 seconds and overflowed in the reactor with 242 g of propylene. Thereafter, the stirrer speed was increased to 350 rpm and the reactor temperature increased to 70 ° C for ~ 15 minutes. This temperature was maintained for 30 minutes after reaching 68 ^o C. After that the pressure was reduced to 0.9 bara via flashing. To achieve target conditions for ~ 15 barg gas phase at 60 ^o C, ethylene and propylene are dosed in a ratio of C3 / C2 = 0.4 g / g in the reactor to a total amount of 351 g over 8 minutes. 60 ^o C (the temperature decreased during flashing due to the enthalpy of vaporization) was reached 18 minutes after the start of the pressure increase and the total pressure was constantly maintained at 15 barg via the dosage of ethylene and propylene in a ratio of C3 / C2 = 1 g / g. Polymerization was stopped 93 minutes after starting to increase the pressure to 15 barg via flashing and cooling. The residence time used to calculate the activity of the catalyst in the gas phase was 82 minutes (beginning after reaching polymerization temperatures of 58 ^o C in the gas phase).
After 3 times overflow of the reactor with nitrogen and a vacuum / nitrogen cycle the product is taken and dried overnight in a chapel and another 2 hours in a vacuum drying oven at 60 ^o C. Ethylene copolymerization -heterophasic propylene with C1P (comparative)
Batch production of a heterophasic ethylene copolymer with prepolymerized comparison catalyst C1P in phase process
122/131 volume / gas: a stirred autoclave (double helix shaker) with a volume of 21.2 dm ³ containing 0.5 barg of propylene was filled with another 5.18 kg of propylene. After adding 0.2 ln of hydrogen and 0.97 mmol of triethyl aluminum (1 molar solution in hexane) using a stream of 244 g of propylene the solution was stirred at 250 rpm. After 20 minutes, the reactor temperature was increased to 40 ^o C and 494 mg of the solid prepolymerized C1P catalyst were contacted with 5 ml of perfluor-1,3-dimeithylcyclohexane under nitrogen pressure (0.003 mol at ~ 10 barg) by 60 seconds and overflowed in the reactor with 491 g of propylene. Thereafter the stirring speed was increased to 350 rpm and the temperature in the reactor increased to 70 ^o C for ~ 17 minutes. This temperature was maintained for 30 minutes after reaching 68 ^o C. After that the pressure is reduced to 1.1 barg via flashing. To achieve target conditions for the 15 barg gas phase at 60 ° C, ethylene and propylene are dosed in a ratio of C3 / C2 = 1.23 g / g in the reactor to a total amount of 401 g over 8 minutes. 60 ^o C (the temperature decreased during flashing due to the enthalpy of vaporization) was reached 19 minutes after the start of the pressure increase and the total pressure was constantly maintained at 15 barg via dosage of ethylene and propylene in a ratio of C3 / C2 = 1.83 g / g. Polymerization was stopped 103 minutes after the start of pressure increase to 15 barg via flashing and cooling. The residence time used to calculate the activity of catalyst in the gas phase was 90 minutes (beginning after reaching the polymerization temperature of 58 ^o C in the gas phase).
After overflowing the reactor with nitrogen and a vacuum / nitrogen cycle, the product was picked up and dried overnight in a chapel and an additional 2 hours in a vacuum drying oven at 60 ^o C.
The catalyst activity for E1P and E2P and E3P was determined according to:
Activity kg / g (cat) / h = {amount of polymer produced in kg / [(prepolymerized catalyst load in grams) x polymerization time in hours]} x (degree of prepolymerization + 1).
The results of the heterophasic polymerizations are summarized in Tables 4 and 5. (Ex. 35-42, c-14 and c-15).
Table 2. Propylene homopolymerization
Cat. Ex Catalyst (mg) H ₂ (mmol) PolPol Weather. (min) Polymer (g) Activity ⁽¹⁾ (kg / g / h) E1 1 11.7 1.0 30 126.0 21.62 4.6 6.0 30 113.0 49.33 8.7 15.0 30 245.0 56.24 6.6 25.0 30 198.0 60.0 E2 5 20.3 1.0 30 191 18.86 4.9 6.0 30 127 51.87 12.1 15.0 30 414 68.48 6.8 25.0 30 250 73.5 E3 9 13.6 1.0 30 123 18.010 10.3 6.0 30 253 49.211 7.3 15.0 30 235 64.5 E5 12 9.7 1.0 60 211 21.813 10.9 6.0 60 452 41.414 9.3 15.0 60 481 51.8 E6 15 16.3 1.0 60 188 11.616 8.2 6.0 60 210 25.617 6.5 15.0 60 183 28.1 E7 18 9.8 1.0 60 239 24.4
123/131
Cat. Ex Catalyst (mg) H ₂ (mmol) PolPol Weather. (min) Polymer (g) Activity ⁽¹⁾ (kg / g / h)19 9.8 6.0 60 479 48.820 6.1 15.0 60 394 64.6 E8 21 12.7 1.0 60 209 16.422 10.0 6.0 60 309 30.923 10.0 15.0 60 410 41.0 E9 24 9.7 1.0 60 189 19.525 9.8 6.0 60 384 39.226 9.7 15.0 60 425 43.8 C1 c-1 28.8 0.0 30 113 7.8c-2 27.4 1.0 30 193 14.1c-3 30.2 6.0 30 337 22.3c-4 28.6 15.0 30 407 28.5c-5 32.1 25.0 30 531 33.1c-6 14.4 1.0 60 133 9.2c-7 15.8 6.0 60 254 16.1c-8 14.5 15.0 60 273 18.8 C2 c-9 19.0 6.0 30 428 45.1c-10 17.4 15.0 30 365 42.0
124/131
Table 2 - continued-
Cat. Ex Activity ⁽²⁾ (kg / gzr / h) MFR2 (g / 10 min) MFR21 (g / 10 min) M _w (kg / mol) Mw / Mn Tm (° C) E1 1 6970 - 2.6 957 2.1 142.22 15891 - 56.0 424 2.3 144.03 18139 6.9 - 244 2.2 143.54 19345 36.0 - 154 2.6 142.9 E2 5 7820 - 1.6 994 2.4 148.26 21582 - 19.0 549 2.4 147.57 28512 2.4 - 305 2.5 149.18 30637 14.0 - 188 3.1 148.2 E3 9 5630 - 3.4 853 2.6 144.910 15376 - 78.0 404 2.7 146.911 20146 13.0 - 204 3.0 146.9 E5 12 6221 - 10.0 545 2.2 147.413 11843 - 95.0 321 2.4 148.214 14786 9.0 - 221 2.3 148.2 E6 15 4126 - 21.0 508 2.7 148.516 9151 - 110.0 337 2.5 151.217 10027 14.0 - 199 2.6 150.2 E7 18 6980 - 3.0 817 2.2 148.019 13956 - 28.0 472 2.2 149.4
125/131
Cat. Ex Activity ⁽²⁾ (kg / gzr / h) MFR2 (g / 10 min) MFR21 (g / 10 min) M _w (kg / mol) Mw / Mn Tm (° C)20 18454 3.6 - 274 2.2 150.3 E8 21 4838 - 5.4 711 2.7 151.522 9088 - 43.0 418 2.7 151.623 12068 5.0 - 270 2.6 152.3 E9 24 5561 - 2.5 791 2.3 147.125 11198 - 27.0 485 2.1 147.226 12521 3.4 - 279 2.4 148.2 C1 c-1 2121 - 5.9 757 2.3 149.2c-2 3807 - 12.5 665 2.5 149.4c-3 6032 1.3 - 416 2.1 150.6c-4 7692 12.3 - 222 2.4 151.0c-5 8942 32.8 - 168 2.3 150.9c-6 3173 - 10 560 2.7 -c-7 5541 1.8 - 312 2.5 -c-8 6495 15.0 - 202 2.5 - C2 c-9 14079 0.33 - 524 2.6 143.3c-10 13111 3.9 - 275 3.3 144.4
126/131 (1) Activity in kg of polymer per gram of catalyst per hour (2) Activity in kg of polymer per gram of zirconium per hour
Table 3. - C ₂ / C ₃ random copolymerization
Cat Ex Catalyst (mg) H ₂ (mmol) C2 (g) Polymer (g) Activity (kg / g / h) Activity (kg / g _Zr / h) E1 27 5.4 6.0 7.1 129.0 47.8 1542428 5.2 6.0 19.9 113.0 43.5 14032 E2 29 5.1 6.0 19.9 149.0 58.5 2437930 10.0 6.0 40.2 193.0 38.6 1609231 15.0 6.0 49.9 236.0 31.4 13094 E3 32 8.7 6.0 20.2 324.0 74.4 2324033 8.9 6.0 30.0 261.0 58.7 18343 E7 34 8.3 6.0 20.0 329.0 79.3 22657 C1 c-11 5.3 6.0 20.0 112.5 42.5 12129c-12 6.5 6.0 39.9 73.0 22.5 6418c-13 8.0 6.0 50.3 72.8 18.2 5200
127/131
Table 3 -continuation-
Cat Ex MFR2 (g / 10 min) MFR21 (g / 10 min) M _w (kg / mol) M _w / M _n FTIR C ₂ (% by weight) Tm (° C) E1 27 - 44.0 450 2.3 1.2 139.028 - 65.0 422 2.2 2.2 131.6 E2 29 - 18.0 538 2.4 2.0 135.230 - 19.0 516 2.4 3.1 124.231 - 21.0 504 2.6 3.9 119.3 E3 32 - 66.0 395 2.5 1.9 133.733 - 67.0 409 2.5 3.3 127.2 E7 34 - 24.0 482 2.2 1.4 136.5 C1 c-11 2.50 - 324 2.2 1.4 138.4c-12 3.40 - 288 2.1 3.0 128.6c-13 3.80 - 276 2.2 4.0 122.4
128/131
Table 4. Hypophasic ethylene-propylene copolymerizations
Ex Cat. Quantity of prepolymerized catalyst (mg) Total polymer yield (g) Polymer yield by volume (g) Volume activity kgPP / (g cat * h) c-14 C1P 494 915 601 10.0 35 E1P 298 1301 787 23.8 36 E2P 257 680 483 21.0 37 E2P 253 692 428 18.9 38 E3P 212 1100 762 28.0
Table 4. -continuation-
Ex Cat. C3 / C2 in feed (transition gas phase) (g / g) C3 / C2 in feeding (gas phase) (g / g) Residence time (gas phase) (min) Yield of polymer in gas phase (g) (g) Gas phase activity kg / g (cat) * h c-14 C1P 1.23 1.83 90 314 1.74 35 E1P 1.26 1.83 55.5 514 8.39 36 E2P 0.40 1.00 22.5 197 11.45 37 E2P 1.23 1.83 27.5 264 12.75 38 E3P 0.4 1.00 82 338 4.6
(1) Activity in kg of polymer per gram of catalyst per hour
129/131
Table 5. Hypophasic ethylene-propylene copolymerizations - polymer properties
Ex Cat. MFR2 C2 in XS XS IV (XS) G'23 * C Tg (EPR) M _w at the max MWD curve of the C2C3 copolymer Mw (XS) (g / 10min) (IR)% by weight % by weight dL / g Mpakg / mol kg / mol c-14 C1P 2.43 23.3 34.3 0.58 228 -38.6 47 41 35 E1P 0.47 23 38 1.15 185 -38 94 94 36 E2P 0.07 43.3 28.6 1.26 311 -54 140 101 37 E2P 0.15 22.3 35 1.24 222 -36 129 111 38 E3P 0.35 39.9 35.2 1.55 271 -52 146 125
130/131
131/131
comments
The polymerization behavior of catalysts E1 to E3 and E5 to E9 was evaluated against reference catalysts C1 and C2 prepared similarly to catalysts E1-E3 and E5-E9 (see Table 1). The propylene polymerization experiments carried out with the new metallocene catalysts clearly show that the catalysts of the invention E1 to E3 outperformed the catalysts C1 and C2 in catalytic activity and the catalysts of the invention E5 to E9 outperformed the catalyst C1 in polymerization activity ( see Table 2). Importantly, in the range of MFR (higher molecular weight), catalysts E1 to E3 and E5 to E9 provide significantly higher activities than catalyst C1, while in the range of high MFR (lower molecular weight), catalysts E1, E2 and E3 provide significantly greater activities than both catalysts C1 and C2 and catalysts E5 to E9 significantly greater activities than catalyst C1.
The second set of polymerization experiments focused on investigating the ethylene response and molecular weight capacity of catalysts E1 to E3 in random copolymerization. The random copolymerization behavior of catalysts E1, E2 and E3 was evaluated against catalyst C1 (Table 3). For incorporation of similar ethylene, the catalysts of the invention show greater polymerization activity compared to catalyst C1. Importantly, the average molecular weight Mw does not show a strong negative correlation with high ethylene feed with catalysts E1, E2 and E3 as witnessed with catalyst C1. This indicates a reduced tendency for ethylene chain transfer. Another significant difference is the superior conversion of ethylene with E1, E2 and E3 catalysts. For the same ethylene content, catalyst E7 shows better C2 randomization, as deduced by the lower melting point (compare c-11 to Ex. 34).
In gas phase copolymerization the applicant obtained much higher activities and higher molecular weight of copolymer with the catalysts of the invention compared to the catalyst known in the art.

权利要求:
Claims (15)
[1]
1. Racemic complex, characterized by the fact that it presents formula (I)

[2]
2/7 carbon atoms optionally substituted by one or more R ¹ groups;
each R ¹ is a C1-20 hydrocarbyl group or two adjacent R ¹ groups on adjacent carbon atoms that can form a 5- or 6-membered non-aromatic ring fused to the Ar group, said ring being itself optionally substituted with one or more R ⁴ groups; and each R ⁴ is a C1-20 hydrocarbyl group.
2. Complex according to claim 1, characterized by the fact that it is an anti racemic isomer.
[3]
3. Complex according to claim 1 or 2, characterized by the fact that R ⁷ and R ⁷ 'are hydrogen and R ² and R ² ' are the same.
[4]
4. Complex according to any of claims 1 to 4, characterized by the fact that Ar and Ar 'are different.
[5]
5. Complex, according to any of claims 1 to 4, characterized by the fact that it has the formula (II ') or (II);

[6]
6. Complex according to any one of claims 1 to 5, characterized by the fact that it has the formula (III ') or (III):

[7]
7. Complex according to any one of claims 1 to 6, characterized by the fact that it has the formula (IV ') or (IV)

[8]
8. Complex according to any one of claims 1 to 7, characterized by the fact that it has the formula (V) or (V ')

[9]
9. Catalyst, characterized by the fact that it comprises a complex of formula (I), as defined in any preceding claim and (ii) a cocatalyst comprising a compound of a metal group 13, for example, Al or boron.
[10]
10. Catalyst according to claim 9, characterized by the fact that it is an unsupported solid particulate.
[11]
11. Process for the manufacture of a catalyst, as defined in claim 9 or 10, characterized by the fact that it comprises
Petition 870190100182, of 10/07/2019, p. 8/14
Obtaining a complex of formula (I) and a cocatalyst, as defined in any one of claims 1 to 8;
forming a liquid / liquid emulsion system, which comprises a solution of catalyst components (i) and (ii) dispersed in a solvent and solidifying said dispersed droplets to form solid particles.
[12]
12. Use of a catalyst, as defined in claim 9 or 10, characterized by the fact that it is for the formation of a polypropylene homopolymer or a propylene ethylene copolymer.
[13]
13. Process for the preparation of a polypropylene homopolymer or a propylene ethylene copolymer, characterized in that it comprises the polymerization of propylene and optionally ethylene with a catalyst as defined in claim 9 or 10.
that presents the formula (I ')
[14]
14. Ligand, characterized by the fact

[15]
15. Process for the preparation of a compound of formula (VI)
Petition 870190100182, of 10/07/2019, p. 9/14
7/7

where R ⁶ is as previously defined, preferably H, characterized by the fact that it comprises cyclization of a compound

preferably in the presence of P4O10 and MeSOsH (Eaton's reagent).

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法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-02-04| B09A| Decision: intention to grant|

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2020-03-31| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP11173344.0|2011-07-08|

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EP11173344|2011-07-08|

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PCT/EP2012/063288|WO2013007650A1|2011-07-08|2012-07-06|Catalysts|

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