Catalysts for olefin polymerization

Abstract

New bisindenyl ligand complexes and catalysts comprising those complexes. The invention is directed to improving the manufacturing of specific C1-symmetric bisindenyl complexes by modifying one of the indenyl ligands in order to improve the selectivity of the complex synthesis towards the desired anti-isomer, increase the yield and simplify the purification of the complex. The invention also relates to the use of the new bisindenyl metallocene catalysts for the production of polypropylene homopolymers or propylene copolymers.

Claims

1. A metallocene catalyst complex of formula (I): ##STR00047## wherein Mt is Hf or Zr; each X is a sigma-ligand, each R.sup.1 independently is the same or different and is a CH.sub.2—R.sup.7 group, with R.sup.7 being H, a linear or branched C.sub.1-6-alkyl group, a C.sub.3-8 cycloalkyl group, or a C.sub.6-10 aryl group, each R.sup.2 is independently a —CH.sub.2—, —CHY— or —CY.sub.2— group, wherein Y is a C.sub.1-10 hydrocarbyl group and where n is 3-6, each R.sup.3 and R.sup.4 are independently the same or different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, an OY group, a C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group, or C.sub.6-20 aryl group, wherein at least one R.sup.3 per phenyl group and at least one R.sup.4 is not hydrogen, and optionally two adjacent R.sup.3 or R.sup.4 groups form a ring including the phenyl carbons to which they are bonded, R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group, or C.sub.6-20-aryl group, R.sup.6 is a C(R.sup.8).sub.3 group, with R.sup.8 being a linear or branched C.sub.1-C.sub.6 alkyl group, and each R is independently a C.sub.1-C.sub.20-hydrocarbyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl, or C.sub.7-C.sub.20-alkylaryl.

2. The metallocene catalyst complex according to claim 1, wherein Mt is Zr, each X is independently a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group, or an R′ group, where R′ is a C.sub.1-6 alkyl, phenyl, or benzyl group, each R is independently a C.sub.1-C.sub.20-hydrocarbyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl, or C.sub.7-C.sub.20-alkylaryl, each R.sup.1 independently is the same or different and is a CH.sub.2—R.sup.7 group, with R.sup.7 being H, a linear or branched C.sub.1-6-alkyl group, or a C.sub.6-10 aryl group, each R.sup.2 is independently a —CH.sub.2—, —CHY— or —CY.sub.2— group, wherein Y is a C.sub.1-4 hydrocarbyl group and where n is 3-4, each R.sup.3 and R.sup.4 are independently the same or different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, or C.sub.6-20 aryl groups, wherein at least one R.sup.3 per phenyl group and at least one R.sup.4 is not hydrogen, R.sup.5 is a linear or branched C.sub.1-C.sub.6 alkyl group or C.sub.6-20 aryl group, and R.sup.6 is a C(R.sup.8).sub.3 group, with R.sup.8 being a linear or branched C.sub.1-C.sub.4 alkyl group.

3. The metallocene catalyst complex according to claim 1, wherein Mt is Zr, each X is independently a chloride, benzyl, or a methyl group, each R is independently a C.sub.1-C.sub.10-hydrocarbyl or C.sub.6-C.sub.10-aryl group, both R.sup.1 are the same and are a CH.sub.2—R.sup.7 group, with R.sup.7 being H or a linear or branched C.sub.1-C.sub.3-alkyl group, each R.sup.2 is independently a —CH.sub.2—, —CHY— or —CY.sub.2— group, wherein Y is a C.sub.1-4 hydrocarbyl group and where n is 3-4, each R.sup.3 and R.sup.4 are independently the same or different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, or C.sub.6-20 aryl groups, wherein at least one R.sup.3 per phenyl group and at least one R.sup.4 is not hydrogen, R.sup.5 is a linear or branched C.sub.1-C.sub.6 alkyl group or C.sub.6-20 aryl group and R.sup.6 is a C(R.sup.8).sub.3 group, R.sup.8 being the same and being a C.sub.1-C.sub.2-alkyl group.

4. The metallocene catalyst complex according to claim 1, the complex having formula (Ia) ##STR00048## wherein each R.sup.3 and R.sup.4 are independently the same or different and are hydrogen or a linear or branched C.sub.1-C.sub.6-alkyl group, wherein at least one R.sup.3 per phenyl group and at least one R.sup.4 is not hydrogen.

5. The metallocene catalyst complex according to claim 4, wherein; one or two R.sup.3 groups per phenyl group are not hydrogen and the remaining R.sup.3 groups are hydrogen, and both R.sup.3-substituted phenyl groups are identical, and for the indenyl moiety, two R.sup.4 on the phenyl group are not hydrogen and these two R.sup.4 are the same.

6. The metallocene catalyst complex according to claim 1 wherein the complex is: rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride; rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s indacen-1-yl][2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride; rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-ditert.-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride; or their corresponding zirconium dimethyl analogues.

7. A catalyst system comprising: (i) the metallocene catalyst complex according to claim 1; and (ii) a cocatalyst comprising a compound of a group 13 metal.

8. The catalyst system according to claim 7, wherein cocatalyst (ii) is selected from the group consisting of alumoxane, combinations of alumoxane with Al-alkyls, boron or borate cocatalysts, and combinations of alumoxanes with boron-based cocatalysts.

9. The catalyst system as claimed in claim 7, wherein the catalyst system is in solid form, being supported on an external carrier or being in solid particulate form free from an external carrier.

10. The catalyst system as claimed in claim 9, wherein the catalyst system is supported on silica.

11. The metallocene catalyst complex according to claim 1, wherein the ligand compound of the metallocene catalyst complex of formula (I) comprising the two (R.sup.3).sub.3-phenyl-group substituents is prepared by a process comprising steps 1) to 4): 1) a starting ketone-compound, R.sup.1-3,5,6,7-tetrahydro-s-indecen-1(2H)-one, is dibrominated electrophilically; 2) the obtained corresponding dibromo-compound from step 1, 4,8-dibromo-R.sup.1-3,5,6,7-tetrahydro-s-indecen-1(2H)-one, is reduced and followed by methylation to yield the corresponding OMe-compound; 3) the obtained corresponding OMe-compound from step 2 is Kumada coupled with (R.sup.3).sub.3-phenylmagnesium bromide; and 4) the compound from step 3 is demethoxylated; and wherein R.sup.1 and R.sup.3 are as defined in claim 1.

12. A process for the preparation of a polypropylene homopolymer, a propylene-ethylene copolymer, or a propylene-C4-10 alpha olefin copolymer comprising polymerizing propylene, propylene and ethylene, or propylene and a C4-10 alpha olefin, in the presence of the catalyst system according to claim 7.

Description

DETAILED DESCRIPTION OF INVENTION

(1) This invention relates to a series of new ligands, metallocene catalyst complexes and hence catalysts that are ideal for the polymerization of propylene. The metallocene catalyst complexes of the invention are asymmetrical. Asymmetrical means simply that the two ligands forming the metallocene are different, that is, each ligand bears a set of substituents that are chemically different.

(2) The metallocene catalyst complexes of the invention are chiral, racemic bridged bisindenyl C.sub.1-symmetric metallocenes in their anti-configuration. Although the complexes of the invention are formally C.sub.1-symmetric, the complexes ideally retain a pseudo-C.sub.2-symmetry since they maintain C.sub.2-symmetry in close proximity of the metal center although not at the ligand periphery. By nature of their chemistry both anti and syn enantiomer pairs (in case of C.sub.1-symmetric complexes) are formed during the synthesis of the complexes. For the purpose of this 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 plane, as shown in the scheme below.

(3) ##STR00010##

(4) Formula (I), and any sub formulae, are intended to cover both syn- and anti-configurations. Preferred metallocene catalyst complexes are in the anti configuration.

(5) The metallocene catalyst complexes of the invention are employed as the racemic-anti isomers. Ideally, therefore at least 95% mol, such as at least 98% mol, especially at least 99% mol of the metallocene catalyst complex is in the racemic-anti isomeric form.

(6) In the metallocene catalyst complexes of the invention the following preferences apply.

(7) Metallocene catalyst complexes according to the invention are of formula (I):

(8) ##STR00011##

(9) In a complex of formula (I) it is preferred if Mt is Zr or Hf, preferably Zr;

(10) Each X is a sigma ligand. Most preferably, each X is independently a hydrogen atom, a halogen atom, C.sub.1-6 alkoxy group or an R′ group, where R′ is a C.sub.1-6 alkyl, phenyl or benzyl group. Most preferably, X is chloride, benzyl or a methyl group. Preferably, both X groups are the same. The most preferred options are two chlorides, two methyl or two benzyl groups, especially two chlorides.

(11) In the formula —SiR.sub.2—, each R is independently a C.sub.1-C.sub.20-hydrocarbyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl or C.sub.7-C.sub.20-alkylaryl. The term C.sub.1-20 hydrocarbyl group therefore includes C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.2-20 alkynyl, C.sub.3-20 cycloalkyl, C.sub.3-20 cycloalkenyl, C.sub.6-20 aryl groups, C.sub.7-20 alkylaryl groups or C.sub.7-20 arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl. Unless otherwise stated, preferred C.sub.1-20 hydrocarbyl groups are C.sub.1-20 alkyl, C.sub.4-20 cycloalkyl, C.sub.5-20 cycloalkyl-alkyl groups, C.sub.7-20 alkylaryl groups, C.sub.7-20 arylalkyl groups or C.sub.6-20 aryl groups.

(12) Preferably, both R groups are the same. It is preferred if R is a C.sub.1-C.sub.10-hydrocarbyl or C.sub.6-C.sub.10-aryl group, such as methyl, ethyl, propyl, isopropyl, tertbutyl, isobutyl, C.sub.5-6-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, more preferably both R are a C.sub.1-C.sub.6-alkyl, C.sub.3-8 cycloalkyl or C.sub.6-aryl group, such as a C.sub.1-C.sub.4-alkyl, C5-6 cycloalkyl or C.sub.6-aryl group and most preferably both R are methyl or one is methyl and another cyclohexyl. Most preferably the bridge is —Si(CH.sub.3).sub.2—.

(13) Each R.sup.1 independently is the same or can be different and is a CH.sub.2—R.sup.7 group, with R.sup.7 being H, a linear or branched C.sub.1-6-alkyl group (like methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl and tert.-butyl), a C.sub.3-8 cycloalkyl group (e.g. cyclohexyl), or a C.sub.6-10 aryl group (preferably phenyl);

(14) Preferably, both R.sup.1 are the same and are a CH.sub.2—R.sup.7 group, with R.sup.7 being H or a linear or branched C.sub.1-C.sub.4-alkyl group, more preferably, both R.sup.1 are the same and are a CH.sub.2—R.sup.7 group, with R.sup.7 being H or a linear or branched C.sub.1-C.sub.3-alkyl group. Most preferably, both R.sup.1 are both methyl.

(15) Each R.sup.2 is independently a —CH═, —CY═, —CH.sub.2—, —CHY— or —CY.sub.2— group, wherein Y is a C.sub.1-10 hydrocarbyl group, preferably a C.sub.1-4 hydrocarbyl group and where n is 2-6, preferably 3-4.

(16) Each substituent R.sup.3 and R.sup.4 are independently the same or can be different and are hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group, an OY group, a C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group, or C.sub.6-20 aryl group, preferably hydrogen, a linear or branched C.sub.1-C.sub.6-alkyl group or C.sub.6-20 aryl groups, and optionally two adjacent R.sup.3 or R.sup.4 groups can be part of a ring including the phenyl carbons to which they are bonded. More preferably, R.sup.3 and R.sup.4 are hydrogen or a linear or branched C.sub.1-C.sub.4 alkyl group or a OY-group, wherein Y is a is a C.sub.1-4 hydrocarbyl group. Even more preferably, each R.sup.3 and R.sup.4 are independently hydrogen, methyl, ethyl, isopropyl, tert-butyl or methoxy, especially hydrogen, methyl or tert-butyl, wherein at least one R.sup.3 per phenyl group and at least one R.sup.4 is not hydrogen.

(17) Thus, preferably one or two R.sup.3 per phenyl group are not hydrogen, more preferably on both phenyl groups the R.sup.3 are the same, like 3′,5′-di-methyl or 4′-tert-butyl for both phenyl groups. For the indenyl moiety preferably one or two R.sup.4 on the phenyl group are not hydrogen, more preferably two R.sup.4 are not hydrogen and most preferably these two R.sup.4 are the same like 3′,5′-di-methyl or 3′,5′-di-tert-butyl.

(18) R.sup.5 is a linear or branched C.sub.1-C.sub.6-alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl, C.sub.7-20 arylalkyl, C.sub.7-20 alkylaryl group or C.sub.6-C.sub.20 aryl group. R.sup.5 is a preferably a linear or branched C.sub.1-C.sub.6 alkyl group or C.sub.6-20 aryl group, more preferably a linear C.sub.1-C.sub.4 alkyl group, even more preferably a C.sub.1-C.sub.2 alkyl group and most preferably methyl.

(19) R.sup.6 is a C(R.sup.8).sub.3 group, with R.sup.8 being a linear or branched C.sub.1-C.sub.6 alkyl group.

(20) Each R is independently a C.sub.1-C.sub.20-hydrocarbyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-arylalkyl or C.sub.7-C.sub.20-alkylaryl. Preferably each R.sup.8 are the same or different with R.sup.8 being a linear or branched C.sub.1-C.sub.4-alkyl group, more preferably with R.sup.8 being the same and being a C.sub.1-C.sub.2-alkyl group. Most preferably, all R.sup.8 groups are methyl.

(21) In a preferred embodiment, the invention provides a metallocene catalyst complex of formula (Ia)

(22) ##STR00012##
wherein
Mt is Zr or Hf, preferably Zr;
each R.sup.3 and R.sup.4 are independently the same or can be different and are hydrogen or a linear or branched C.sub.1-C.sub.6-alkyl group, wherein at least on R.sup.3 per phenyl group and at least one R.sup.4 is not hydrogen.

(23) Specific metallocene catalyst complexes of the invention include: rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(4′-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride (MC-1); rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s indacen-1-yl] [2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride (MC-2); rac-anti-dimethylsilanediyl[2-methyl-4,8-bis-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-ditert-butyl-phenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride (MC-3);
or their corresponding zirconium dimethyl analogues.

(24) ##STR00013##

(25) For the avoidance of doubt, any narrower definition of a substituent offered above can be combined with any other broad or narrowed definition of any other substituent.

(26) Throughout the disclosure above, where a narrower definition of a substituent is presented, that narrower definition is deemed disclosed in conjunction with all broader and narrower definitions of other substituents in the application.

(27) Synthesis

(28) The ligands required to form the catalysts of the invention can be synthesised by any process and the skilled organic chemist would be able to devise various synthetic protocols for the manufacture of the necessary ligand materials. WO2007/116034 discloses the necessary chemistry and is herein incorporated by reference. Synthetic protocols can also generally be found in WO2002/02576, WO2011/135004, WO2012/084961, WO2012/001052, WO2011/076780 and WO2015/158790. The examples section also provides the skilled person with sufficient direction.

(29) Synthesis of the Ligand of the Metallocene Catalyst Complex of Formula (I or Ia) Comprising the Two (R.sup.3).sub.3-Phenyl-Group Substituents, Preferably Indacenyl Ligand Synthesis.

(30) The ligand of the metallocenes as disclosed in WO2018/122134 include two different indenes, one methoxyindene and one indacene. The synthesis of the methoxyindene is simple and gives high yield, while the synthesis of the indacene requires several steps, as shown in scheme 1 for the case of the 4-(4-tert-butylphenyl)indacene:

(31) ##STR00014##

(32) The ligand of the metallocene catalyst complex of formula (I or Ia) comprising the two (R.sup.3).sub.3-phenyl-group substituents, preferably the indacene ligand used in the synthesis of the inventive metallocene catalyst complexes, which is the structural analogue of above structure, is obtained with one step less, as shown in scheme 2:

(33) ##STR00015##

(34) Thus, the new metallocene catalyst complexes of the present invention can be prepared in a simpler way and as is shown in the experimental part in a more efficient way, too.

(35) The present invention is therefore also related to a process for producing the ligand of the metallocene catalyst complex of formula (I or Ia) comprising the two (R.sup.3).sub.3-phenyl-group substituents, preferably the indacene ligand.

(36) This process analogous to scheme 2 comprises the steps 1. Electrophilic dibromination of the starting keton-compound, e.g. R.sup.1-3,5,6,7-tetrahydro-s-indecen-1(2H)-one 2. Reduction of the corresponding dibromo-compound, e.g. 4,8-dibromo-R.sup.1-3,5,6,7-tetrahydro-s-indecen-1(2H)-one, followed by methylation to yield the corresponding OMe-compound 3. Kumada coupling with (R.sup.3).sub.3-phenylmagnesium bromide and 4. Demethoxylation

(37) Thus, a metallocene catalyst complex according to anyone of claim 1 to 6, wherein the ligand of the metallocene catalyst complex of formula (I or Ia) comprising the two (R.sup.3).sub.3-phenyl-group substituents is prepared by a process comprising steps 1) to 4) wherein in step 1) a starting keton-compound, e.g. R.sup.1-3,5,6,7-tetrahydro-s-indecen-1(2H)-one, is dibrominated electrophilically 2) the obtained corresponding dibromo-compound from step 1, e.g. 4,8-dibromo-R.sup.1-3,5,6,7-tetrahydro-s-indecen-1(2H)-one, is reduced and followed by methylation to yield the corresponding OMe-compound 3) the obtained corresponding OMe-compound from step 2 is Kumada coupled with (R.sup.3).sub.3-phenylmagnesium bromide and 4) the compound from step 3 is demethoxylated.

(38) Step 1) is preferably done with aluminium chloride in dichlormethane at low temperature, like 2 to 10° C., e.g. around +5° C.

(39) The reduction in step 2) is preferably done by sodium borohydride in THF-MeOH medium at low temperature, like 2 to 10° C., e.g. around +5° C.

(40) The methylation is preferably performed at room temperature with Mel/KOH/DMSO.

(41) Step 3) is preferably done in the presence of NiCl.sub.2(PPh.sub.3)IPr catalyst at reflux temperature and step 4) is preferably done with a catalytic amount of TsOH in toluene at reflux temperature.

(42) The steps 1) to 4) are analogous to Scheme 2 above.

(43) Cocatalyst

(44) To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art.

(45) According to the present invention a cocatalyst system comprising a boron containing cocatalyst and/or an aluminoxane cocatalyst is used in combination with the above defined metallocene catalyst complex.

(46) The aluminoxane cocatalyst can be one of formula (X):

(47) ##STR00016##
where n is usually from 6 to 20 and R has the meaning below.

(48) Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR.sub.3, AlR.sub.2Y and Al.sub.2R.sub.3Y.sub.3 where R can be, for example, C.sub.1-C.sub.10 alkyl, preferably C.sub.1-C.sub.5 alkyl, or C.sub.3-10 cycloalkyl, C.sub.7-C.sub.12 arylalkyl or alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C.sub.1-C.sub.10 alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (X).

(49) The preferred aluminoxane is methylaluminoxane (MAO). Since the aluminoxanes used according to the invention as cocatalysts are not, owing to their mode of preparation, pure compounds, the molarity of aluminoxane solutions hereinafter is based on their aluminium content.

(50) According to the present invention, also a boron containing cocatalyst can be used instead of the aluminoxane cocatalyst or the aluminoxane cocatalyst can be used in combination with a boron containing cocatalyst.

(51) It will be appreciated by the skilled man that where boron based cocatalysts are employed, it is normal to pre-alkylate the complex by reaction thereof with an aluminium alkyl compound, such as TIBA. This procedure is well known and any suitable aluminium alkyl, e.g. Al(C.sub.1-6-alkyl).sub.3. can be used. Preferred aluminium alkyl compounds are triethylaluminium, tri-isobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium.

(52) Alternatively, when a borate cocatalyst is used, the metallocene catalyst complex is in its alkylated version, that is for example a dimethyl or dibenzyl metallocene catalyst complex can be used.

(53) Boron based cocatalysts of interest include those of formula (Z)
BY.sub.3  (Z)
wherein 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 6-20 carbon atoms in the aryl radical or fluorine, chlorine, bromine or iodine. Preferred examples for Y are methyl, propyl, isopropyl, isobutyl or trifluoromethyl, unsaturated groups such as aryl or haloaryl like phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5- difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and 3,5- di(trifluoromethyl)phenyl. Preferred options are trifluoroborane, triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethyl-phenyl)borane, tris(3,5-difluorophenyl)borane and/or tris (3,4,5-trifluorophenyl)borane.

(54) Particular preference is given to tris(pentafluorophenyl)borane.

(55) However it is preferred that borates are used, i.e. compounds containing a borate 3+ ion. Such ionic cocatalysts preferably contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate and tetraphenyborate. Suitable counterions are protonated amine or aniline derivatives such as methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, pyridinium, p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

(56) Preferred ionic compounds which can be used according to the present invention include: triethylammoniumtetra(phenyl)borate, tributylammoniumtetra(phenyl)borate, trimethylammoniumtetra(tolyl)borate, trbutylammoniumtetra(tolyl)borate, tributylammoniumtetra(pentafluorophenyl)borate, tripropylammoniumtetra(dimethylphenyl)borate, trbutylammoniumtetra(trifluoromethylphenyl)borate, trbutylammoniumtetra(4-fluorophenyl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetra(phenyl)borate, N,N-diethylaniliniumtetra(phenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(phenyl)borate, triethylphosphoniumtetrakis(phenyl)borate, diphenylphosphoniumtetrakis(phenyl)borate, tri(methylphenyl)phosphoniumtetrakis(phenyl)borate, tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate,
or ferroceniumtetrakis(pentafluorophenyl)borate.

(57) Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate or N,N-dimethybenzylammoniumtetrakis(pentafluoropheny)borate.

(58) It has been surprisingly found that certain boron cocatalysts are especially preferred. Preferred borates of use in the invention therefore comprise the trityl ion. Thus the use of N,N-dimethylammonium-tetrakispentafluorophenylborate and Ph.sub.3CB(PhF.sub.5).sub.4 and analogues therefore are especially favoured.

(59) According to the present invention, the preferred cocatalysts are alumoxanes, more preferably methylalumoxanes, combinations of alumoxanes with Al-alkyls, boron or borate cocatalysts and combinations of alumoxanes with boron-based cocatalysts.

(60) According to the most preferred embodiment of present invention, the preferred cocatalysts are alumoxanes, most preferably methylalumoxanes.

(61) Suitable amounts of cocatalyst will be well known to the skilled man.

(62) The molar ratio of boron to the metal ion of the metallocene may be in the range 0.5:1 to 10:1 mol/mol, preferably 1:1 to 10:1, especially 1:1 to 5:1 mol/mol.

(63) The molar ratio of Al in the aluminoxane to the metal ion of the metallocene may be in the range 1:1 to 2000:1 mol/mol, preferably 10:1 to 1000:1, and more preferably 50:1 to 500:1 mol/mol.

(64) Catalyst Manufacture

(65) The metallocene catalyst complex of the present invention can be used in combination with a suitable cocatalyst as a catalyst for the polymerization of propylene, e.g. in a solvent such as toluene or an aliphatic hydrocarbon, (i.e. for polymerization in solution), as it is well known in the art. Preferably, polymerization of propylene takes place in the condensed phase or in gas phase.

(66) The catalyst of the invention can be used in supported or unsupported form. The particulate support material used is preferably an organic or inorganic material, such as silica, alumina or zirconia or a mixed oxide such as silica-alumina, in particular silica, alumina or silica-alumina. The use of a silica support is preferred. The skilled man is aware of the procedures required to support a metallocene catalyst.

(67) Especially preferably the support is a porous material so that the complex may be loaded into the pores of the support, e.g. using a process analogous to those described in WO94/14856, WO95/12622 and WO2006/097497. The particle size is not critical but is preferably in the range 5 to 200 μm, more preferably 20 to 80 μm. The use of these supports is routine in the art.

(68) In an alternative embodiment, no support is used at all. Such a catalyst can be prepared in solution, for example in an aromatic solvent like toluene, by contacting the metallocene (as a solid or as a solution) with the cocatalyst, for example methylaluminoxane or a borane or a borate salt previously dissolved in an aromatic solvent, or can be prepared by sequentially adding the dissolved catalyst components to the polymerization medium.

(69) In one embodiment, no external carrier is used but the catalyst is still presented in solid particulate form. Thus, no external support material, such as inert organic or inorganic carrier, for example silica as described above is employed.

(70) In order to provide the catalyst of the invention in solid form but without using an external carrier, it is preferred if a liquid/liquid emulsion system is used. The process involves forming dispersing catalyst components (i) and (ii) in a solvent, and solidifying said dispersed droplets to form solid particles.

(71) In particular, the method involves preparing a solution of one or more catalyst components; dispersing said solution in an solvent to form an emulsion in which said one or more catalyst components are present in the droplets of the dispersed phase; immobilising the catalyst components in the dispersed droplets, in the absence of an external particulate porous support, to form solid particles comprising the said catalyst, and optionally recovering said particles.

(72) This process enables the manufacture of active catalyst particles with improved morphology, e.g. with a predetermined spherical shape, surface properties and particle size and without using any added external porous support material, such as an inorganic oxide, e.g. silica. By the term “preparing a solution of one or more catalyst components” is meant that the catalyst forming compounds may be combined in one solution, which is dispersed to the immiscible solvent, or, alternatively, at least two separate catalyst solutions for each part of the catalyst forming compounds may be prepared, which are then dispersed successively to the solvent.

(73) Full disclosure of the necessary process can be found in WO03/051934, which is herein incorporated by reference.

(74) The invention is also industrially advantageous, since it enables the preparation of the solid particles to be carried out as a one-pot procedure. Continuous or semi-continuous processes are also possible for producing the catalyst.

(75) Catalyst Off-Line Prepolymerization

(76) The use of the heterogeneous catalysts, where no external support material is used (also called “self-supported” catalysts) might have, as a drawback, a tendency to dissolve to some extent in the polymerization media, i.e. some active catalyst components might leach out of the catalyst particles during slurry polymerization, whereby the original good morphology of the catalyst might be lost. These leached catalyst components are very active possibly causing problems during polymerization. Therefore, the amount of leached components should be minimized, i.e. all catalyst components should be kept in heterogeneous form.

(77) Furthermore, the self-supported catalysts generate, due to the high amount of catalytically active species in the catalyst system, high temperatures at the beginning of the polymerization which may cause melting of the product material. Both effects, i.e. the partial dissolving of the catalyst system and the heat generation, might cause fouling, sheeting and deterioration of the polymer material morphology.

(78) In order to minimise the possible problems associated with high activity or leaching, it is possible to “off line prepolymerize” the catalyst before using it in polymerization process.

(79) It has to be noted that off line prepolymerization in this regard is part of the catalyst preparation process, being a step carried out after a solid catalyst is formed. The catalyst off line prepolymerization step is not part of the actual polymerization process configuration comprising a prepolymerization step. After the catalyst off line prepolymerization step, the solid catalyst can be used in polymerization.

(80) Catalyst “off line prepolymerization” takes place following the solidification step of the liquid-liquid emulsion process. Pre-polymerization may take place by known methods described in the art, such as that described in WO 2010/052263, WO 2010/052260 or WO 2010/052264.

(81) Preferable embodiments of this aspect of the invention are described herein.

(82) As monomers in the catalyst off-line prepolymerization step preferably alpha-olefins are used.

(83) Preferable C2-C10 olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene 1-decene, styrene and vinylcyclohexene are used. Most preferred alpha-olefins are ethylene and propylene, especially propylene.

(84) The catalyst off-line prepolymerization may be carried out in gas phase or in an inert diluent, typically oil or fluorinated hydrocarbon, preferably in fluorinated hydrocarbons or mixture of fluorinated hydrocarbons. Preferably perfluorinated hydrocarbons are used. The melting point of such (per)fluorinated hydrocarbons is typically in the range of 0 to 140° C., preferably 30 to 120° C., like 50 to 110° C.

(85) Where the catalyst off line prepolymerization is done in fluorinated hydrocarbons, the temperature for the pre-polymerization step is below 70° C., e.g. in the range of −30 to 70° C., preferably 0-65° C. and more preferably in the range 20 to 55° C. Pressure within the reaction vessel is preferably higher than atmospheric pressure to minimize the eventual leaching of air and/or moisture into the catalyst vessel. Preferably the pressure is in the range of at least 1 to 15 bar, preferably 2 to 10 bar. The reaction vessel is preferably kept in an inert atmosphere, such as under nitrogen or argon or similar atmosphere.

(86) Off line prepolymerization is continued until the desired pre-polymerization degree, defined as weight of polymer matrix/weight of solid catalyst before pre-polymerization step, is reached.

(87) The degree is below 25, preferably 0.5 to 10.0, more preferably 1.0 to 8.0, most preferably 2.0 to 6,0.

(88) Use of the off-line catalyst prepolymerization step offers the advantage of minimising leaching of catalyst components and thus local overheating.

(89) After off line prepolymerization, the catalyst can be isolated and stored.

(90) Polymerization

(91) The catalysts according to the invention are suited to the formation of propylene homopolymers, propylene-ethylene copolymers or propylene-C.sub.4-10 alpha olefin copolymers. Thus, the process comprises polymerizing propylene, propylene and ethylene, or propylene and a C.sub.4-10 alpha olefin. The ethylene content in such a propylene-ethylene polymer may vary depending on the desired properties of the polymer. Typically, ethylene content will range from 0.1 to 10 mol %. Especially, the catalysts of the present invention are used to manufacture propylene homopolymers or propylene copolymers with ethylene as comonomer and propylene copolymers with hexene as a comonomer.

(92) Polymerization in the method of the invention may be effected in one or more, e.g. 1, 2 or 3, polymerization reactors, using conventional polymerization techniques, e.g. gas phase, solution phase, slurry or bulk polymerization or combinations thereof, like a combination of a slurry and at least one gas phase reactor.

(93) In case of propylene polymerization for slurry reactors, the reaction temperature will generally be in the range 60 to 110° C. (e.g. 60-90° C.), the reactor pressure will generally be in the range 5 to 80 bar (e.g. 20-60 bar), and the residence time will generally be in the range 0.1 to 5 hours (e.g. 0.3 to 2 hours). The monomer is usually used as reaction medium.

(94) For gas phase reactors, the reaction temperature used will generally be in the range 60 to 115° C. (e.g. 70 to 110° C.), the reactor pressure will generally be in the range 10 to 25 bar, and the residence time will generally be 0,5 to 8 hours (e.g. 0.5 to 4 hours). The gas used will be the monomer optionally as mixture with a non-reactive gas such as nitrogen or propane. In addition to actual polymerization steps and reactors, the process can contain any additional polymerization steps, like prepolymerization step, and any further after reactor handling steps as known in the art.

(95) For solution polymerization, an aliphatic or aromatic solvent can be used to dissolve the monomer and the polymer, and the polymerization temperature will generally be in the range 80 to 200° C. (e.g. 90 to 150° C.)

(96) Generally the quantity of catalyst used will depend upon the nature of the catalyst, the reactor types and conditions and the properties desired for the polymer product. As is well known in the art hydrogen can be used for controlling the molecular weight of the polymer.

(97) The metallocene catalysts of the invention possess excellent catalyst activity and good comonomer response. The catalysts are also able to provide polymers of high weight average molecular weight Mw.

(98) Moreover, the random copolymerization behaviour of metallocene catalysts of the invention shows a reduced tendency of chain transfer to ethylene. Polymers obtained with the metallocenes of the invention have normal particle morphologies.

(99) Polymers

(100) It is a feature of the invention that the claimed catalysts enable the formation of polymers with high molecular weight. These features can be achieved at commercially interesting polymerization temperatures, e.g. 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. In a particular embodiment, the propylene polymers obtained using the catalysts of the invention have a polydispersity index (Mw/Mn) of 2.0 or greater, such as 2.2-6.5.

(101) Propylene Homopolymers

(102) Propylene homopolymers made by the metallocenes of the invention can be made with Mw (weight average molecular weight) values in the range of 40 to 2 000 kg/mol, preferably in the range of 50 to 1 500 kg/mol depending on the use and amount of hydrogen used as Mw regulating agent. The catalysts of the invention enable the formation of polypropylene homopolymers with high melting points. In a preferred embodiment the propylene homopolymer formed by the process of the invention has a melting point of more than 149.0° C., preferably more than 149.5° C., especially more than 150.0° C.

(103) Propylene Copolymers

(104) Propylene copolymers with ethylene or with C4-C10, especially with C6 comonomers made by the metallocenes of the invention can be made with high productivity. Further, increase in intrinsic viscosity can be seen in propylene-hexene copolymers.

(105) The invention will now be illustrated by reference to the following non-limiting examples.

(106) Analytical Tests

(107) Measurement Methods:

(108) Al and Zr determination (ICP-method) (examples IE1, CE1) The elementary analysis of a catalyst was performed by taking a solid sample of mass, M, cooling over dry ice. Samples were diluted up to a known volume, V, by dissolving in nitric acid (HNO3, 65%, 5% of V) and freshly deionised (DI) water (5% of V). The solution was then added to hydrofluoric acid (HF, 40%, 3% of V), diluted with DI water up to the final volume, V, and left to stabilise for two hours.

(109) The analysis was run at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES) which was calibrated using a blank (a solution of 5% HNO3, 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.

(110) Immediately before analysis the calibration is ‘resloped’ using the blank and 100 ppm Al, 50 ppm Hf, Zr standard, a quality control sample (20 ppm Al, 5 ppm Hf, Zr in a solution of 5% HNO3, 3% HF in DI water) is run to confirm the reslope. The QC sample is also run after every 5th sample and at the end of a scheduled analysis set.

(111) The content of hafnium was monitored using the 282.022 nm and 339.980 nm lines and the content for zirconium using 339.198 nm line. The content of aluminium was monitored via the 167.079 nm line, when Ai concentration in ICP sample was between 0-10 ppm (calibrated only to 100 ppm) and via the 396.152 nm line for Ai concentrations above 10 ppm.

(112) The reported values are an average of three successive aliquots taken from the same sample and are related back to the original catalyst by inputting the original mass of sample and the dilution volume into the software.

(113) In the case of analysing the elemental composition of prepolymerized catalysts, the polymeric portion is digested by ashing in such a way that the elements can be freely dissolved by the acids. The total content is calculated to correspond to the weight % for the prepolymerized catalyst.

(114) Al and Zr Determination (ICP-Method) (Examples IE2, CE2 and CE3)

(115) In a glovebox, an aliquot of the catalyst (ca. 40 mg) was weighted into glass weighting boat using analytical balance. The sample was then allowed to be exposed to air overnight while being placed in a steel secondary container equipped with an air intake. Then 5 mL of concentrated (65%) nitric acid was used to rinse the content of the boat into the Xpress microwave oven vessel (20 mL). A sample was then subjected to a microwave-assisted digestion using MARS 6 laboratory microwave unit over 35 minutes at 150° C. The digested sample was allowed to cool down for at least 4 h and then was transferred into a glass volumetric glass flask of 100 mL volume. Standard solutions containing 1000 mg/L Y and Rh (0.4 mL) were added. The flask was then filled up with distilled water and shaken well. The solution was filtered through 0.45 μm Nylon syringe filters and then subjected to analysis using Thermo iCAP 6300 ICP-OES and iTEVA software.

(116) The instrument was calibrated for Ai, B, Hf, Mg, Ti and Zr using a blank (a solution of 5% HNO3) and six standards of 0.005 mg/L, 0.01 mg/L, 0.1 mg/L, 1 mg/L, 10 mg/L and 100 mg/L of Ai, B, Hf, Mg, Ti and Zr in solutions of 5% HNO3 distilled water. However, not every calibration point was used for each wavelength. Each calibration solution contained 4 mg/L of Y and Rh standards. Ai 394.401 nm was calibrated using the following calibration points: blank, 0.1 mg/L, 1 mg/L, 10 mg/L and 100 mg/L. Al 167.079 nm was calibrated as Ai 394.401 nm excluding 100 mg/L and Zr 339.198 nm using the standards of blank, 0.01 mg/L, 0.1 mg/L, 1 mg/L, 10 mg/L and 100 mg/L. Curvilinear fitting and 1/concentration weighting was used for the calibration curves.

(117) Immediately before analysis the calibration was verified and adjusted (instrument reslope function) using the blank and a 10 mg/L Al, B, Hf, Mg, Ti and Zr standard which had 4 mg/L Y and Rh. A quality control sample (QC: 1 mg/L Al, Au, Be, Hg & Se; 2 mg/L Hf & Zr, 2.5 mg/L As, B, Cd, Co, Cr, Mo, Ni, P, Sb, Sn & V; 4 mg/L Rh & Y; 5 mg/L Ca, K, Mg, Mn, Na & Ti; 10 mg/L Cu, Pb and Zn; 25 mg/L Fe and 37.5 mg/L Ca in a solution of 5% HNO3 in distilled water) was run to confirm the reslope for Ai, B, Hf, Mg, Ti and Zr. The QC sample was also run at the end of a scheduled analysis set.

(118) The content for Zr was monitored using Zr 339.198 nm {99} line. The content of aluminium was monitored via the 167.079 nm {502} line, when Al concentration in test portion was under 2 wt % and via the 394.401 nm {85} line for Al concentrations above 2 wt-%. Y 371.030 nm {91} was used as internal standard for Zr 339.198 nm and Ai 394.401 nm and Y 224.306 nm {450} for Al 167.079 nm.

(119) The reported values were back calculated to the original catalyst sample using the original mass of the catalyst aliquot and the dilution volume.

(120) GPC: Molecular Weight Averages, Molecular Weight Distribution, and Polydispersity Index (Mn, Mw, Mw/Mn)

(121) Molecular weight averages (Mw and Mn), Molecular weight distribution (MWD) and its broadness, described by polydispersity index, PDI=Mw/Mn (wherein Mn is the number average molecular weight and Mw is the weight average molecular weight) were determined by Gel Permeation Chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D 6474-12.

(122) A high temperature GPC instrument, equipped with either infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain) or differential refractometer (RI) from Agilent Technologies, equipped with 3× Agilent-PLgel Olexis and 1× Agilent-PLgel Olexis Guard columns was used. As the solvent and mobile phase 1,2,4-trichlorobenzene (TCB) stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) was used. The chromatographic system was operated at 160° C. and at a constant flow rate of 1 mL/min. 200 μL of sample solution was injected per analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

(123) The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11 500 kg/mol. The PS standards were dissolved at room temperature over several hours. The conversion of the polystyrene peak molecular weight to polyolefin molecular weights is accomplished by using the Mark Houwink equation and the following Mark Houwink constants:
K.sub.PS=19×10.sup.−3 mL/g, α.sub.PS=0.655
K.sub.PE=39×10.sup.−3 mL/g, α.sub.PE=0.725
K.sub.PP=19×10.sup.−3 mL/g, α.sub.PP=0.725

(124) A third order polynomial fit was used to fit the calibration data.

(125) All samples were prepared in the concentration range of 0.5-1 mg/ml and dissolved at 160° C. for 2.5 hours for PP or 3 hour.

(126) DSC Analysis

(127) Melting temperature T.sub.m was measured on approx. 5 mg samples with a Mettler-Toledo 822e differential scanning calorimeter (DSC), according to ISO11357-3 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of +23 to +225° C. under a nitrogen flow rate of 50 ml min.sup.−1. Melting temperature was taken as the endotherm peak, respectively in the second heating step. Calibration of the instrument was performed with H.sub.20, Lead, Tin, Indium, according to ISO 11357-1.

(128) Melt Flow Rate

(129) The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR is determined at 230° C. and may be determined at different loadings such as 2.16 kg (MFR.sub.2) or 21.6 kg (MFR.sub.21).

(130) Polymer Powder Bulk Density

(131) Instruments:

(132) Electronic balance: Range from 0.1 g-11000 g Graduated glass cylinder: Volume=max.Math.250 ml Plastic spoon: Volume=125 ml Plastic funnel: D=105 mm

(133) Execution: A glass cylinder is filled up to the max. volume of 250 ml by pouring in the unstabilized polymer powder, using a plastic spoon and a plastic funnel.

(134) Calculation: Mass of polymer (g)/measured volume (ml)

(135) FT-IR

(136) The content of 1-hexene has been measured by FT-IR spectroscopy according to a based on prior calibration using 13C NMR spectroscopy. Calibration was facilitated through the use of a set of in-house non-commercial reference materials of known hexene contents determined by quantitative .sup.13C melt state NMR spectroscopy. The calibration procedure was undertaken in the conventional manner. The calibration set consisted of eight reference materials with 1-hexene contents ranging 0.8-6.3 wt % produced at pilot scale under a variety of conditions and characterised by .sup.13C melt state NMR spectroscopy. The calibration set was selected to reflect the typical variety of copolymers encountered by the final quantitative IR spectroscopy method. Quantitative IR spectra were recorded in the solid-state using a Bruker Vertex 70 FTIR spectrometer. Spectra were recorded on 25×25 mm square films of 300 um thickness prepared by compression moulding at 180-210° C. and 4-6 mPa. Standard transmission FTIR spectroscopy was employed using a spectral range of 5000-500 cm-1, an aperture of 6 mm, a spectral resolution of 2 cm-1, 16 background scans, 16 spectrum scans, an interferogram zero filling factor of 64 and Blackmann-Harris 3-term apodisation. Quantitative analysis was undertaken using the total area of the CH.sub.2 rocking deformations at around 727 cm.sup.−1 (AQ) corresponding to (CH.sub.2).sub.3 structural units in butyl branches (integration method B, limits 750 and 715 cm-1). The quantitative band was normalised to the area of the CH band at 4323 cm.sup.−1 (AR) corresponding to CH structural units (integration method B, limits 4450, 4007 cm.sup.−1). The hexene content in units of weight percent was then predicted from the normalised absorption (AQ/AR) using a quadratic calibration curve. The calibration curve having previously been constructed by ordinary least squares (OLS) regression of the normalised absorptions and primary comonomer contents measured on the calibration set.

(137) Description: Poly(Propylene-Co-Hexene)—Hexene Content—.sup.13C NMR Spectroscopy

(138) Quantitative .sup.13C{.sup.1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 7 mm magic-angle spinning (MAS) probehead at 180° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification. (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382., Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128., Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373). Standard single-pulse excitation was employed utilising the NOE at short recycle delays of 3s (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382., Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813) and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239., Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 2007 45, S1, S198). A total of 16384 (16k) transients were acquired per spectra. Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

(139) Characteristic signals corresponding to the incorporation of 1-hexene were observed and the comonomer content quantified in the following way.

(140) The amount of 1-hexene incorporated in PHP isolated sequences was quantified using the integral of the αB4 sites at 44.2 ppm accounting for the number of reporting sites per comonomer:
H=IαB4/2

(141) The amount of 1-hexene incorporated in PHHP double consecutive sequences was quantified using the integral of the αβB4 site at 41.7 ppm accounting for the number of reporting sites per comonomer:
HH=2*IααB4

(142) When double consecutive incorporation was observed the amount of 1-hexene incorporated in PHP isolated sequences needed to be compensated due to the overlap of the signals αB4 and αB4B4 at 44.4 ppm:
H=(IαB4−2*IααB4)/2

(143) The total 1-hexene content was calculated based on the sum of isolated and consecutively incorporated 1-hexene:
Htotal=H+HH

(144) When no sites indicative of consecutive incorporation observed the total 1-hexeen comonomer content was calculated solely on this quantity:
Htotal=H

(145) Characteristic signals indicative of regio 2,1-erythro defects were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253).

(146) The presence of 2,1-erythro regio defects was indicated by the presence of the Pαβ (21e8) and Pαγ (21e6) methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic signals.

(147) The total amount of secondary (2,1-erythro) inserted propene was quantified based on the αα21e9 methylene site at 42.4 ppm:
P21=Iαα21e9

(148) The total amount of primary (1,2) inserted propene was quantified based on the main Sαα methylene sites at 46.7 ppm and compensating for the relative amount of 2,1-erythro, αB4 and ααB4B4 methylene unit of propene not accounted for (note H and HH count number of hexene monomers per sequence not the number of sequences):
P12=I.sub.Sαα+2*P21+H+HH/2

(149) The total amount of propene was quantified as the sum of primary (1,2) and secondary (2,1-erythro) inserted propene:
Ptotal=P12+P21=I.sub.Sαα+3*Iαα21e9+(IαB4−2*IααB4)/2+IααB4

(150) This simplifies to:
Ptotal=I.sub.Sαα+3*Iαα21e9+0.5*IαB4

(151) The total mole fraction of 1-hexene in the polymer was then calculated as:
fH=Htotal/(Htotal+Ptotal)

(152) The full integral equation for the mole fraction of 1-hexene in the polymer was:
fH=(((IαB4−2*IααB4)/2)+(2*IααB4))/((I.sub.Sαα+3*Iαα21e9+0.5*IαB4)+((IαB4−2*IααB4)/2)+(2*IααB4))

(153) This simplifies to:
fH=(IαB4/2+IααB4)/(I.sub.Sαα+3*Iαα21e9+IαB4+IααB4)

(154) The total comonomer incorporation of 1-hexene in mole percent was calculated from the mole fraction in the usual manner:
H [mol %]=100*fH

(155) The total comonomer incorporation of 1-hexene in weight percent was calculated from the mole fraction in the standard manner:
H [wt %]=100*(fH*84.16)/((fH*84.16)+((1−fH)*42.08))

(156) Crystex

(157) Crystalline and Soluble Fractions and their Respective Properties

(158) The crystalline (CF) and soluble fractions (SF) of the polypropylene (PP) compositions as well as the comonomer content and intrinsic viscosities of the respective fractions were analyzed by the CRYSTEX QC Polymer Char (Valencia, Spain).

(159) A schematic representation of the CRYSTEX QC instrument is presented in Del Hierro, P.; Ortin, A.; Monrabal, B.; ‘Soluble Fraction Analysis in polypropylene, The Column, February 2014. Pages 18-23. The crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160° C., crystallization at 40° C. and re-dissolution in 1,2,4-trichlorobenzene (1,2,4-TCB) at 160° C. Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an infrared detector (IR4) and an online 2-capillary viscometer is used for determination of the intrinsic viscosity (IV).

(160) IR4 detector is multiple wavelength detector detecting IR absorbance at two different bands (CH3 and CH2) for the determination of the concentration determination and the Ethylene content in Ethylene-Propylene copolymers. IR4 detector is calibrated with series of EP copolymers with known Ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13C-NMR).

(161) Amount of Soluble fraction (SF) and Crystalline Fraction (CF) are correlated through the XS calibration to the “Xylene Cold Soluble” (XCS) quantity and respectively Xylene Cold Insoluble (XCI) fractions, determined according to standard gravimetric method as per ISO16152. XS calibration is achieved by testing various EP copolymers with XS content in the range 2-31 Wt %.

(162) Intrinsic viscosity (IV) of the parent EP copolymer and its soluble and crystalline fractions are determined with a use of an online 2-capillary viscometer and are correlated to corresponding IV's determined in decalin according to ISO 1628.

(163) Calibration is achieved with several commercial EP PP copolymers with IV=2-4 dL/g.

(164) A sample of the PP composition to be analyzed is weighed out in concentrations of 10 mg/ml to 20 mg/ml. After automated filling of the vial with 1,2,4-TCB containing 250 mg/I 2,6-tert-butyl-4-methylphenol (BHT) as antioxidant, the sample is dissolved at 160° C. until complete dissolution is achieved, usually for 60 min, with constant stirring of 800 rpm.

(165) A defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at high temperature, determining the IV[dl/g] and the C2[wt %] of the PP composition. During the second injection the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization cycle are determined (Wt % SF, Wt % C2, IV).

EXAMPLES

(166) Metallocene Synthesis

(167) Chemicals Used for Complex Preparation:

(168) 2,6-Dimethylaniline (Acros), 1-bromo-3,5-dimethybenzene (Acros), 1-bromo-3,5-di-tert-butybenzene (Acros), bis(2,6-diisopropylphenyl)imidazolium chloride (Aldrich), triphenylphosphine (Acros), NiCl2(DME) (Aldrich), dichlorodimethylsilane (Merck), ZrCl4 (Merck), trimethylborate (Acros), Pd(OAc)2 (Aldrich), NaBH4 (Acros), 2.5 M nBuLi in hexanes (Chemetal), CuCN (Merck), magnesium turnings (Acros), silica gel 60, 40-63 μm (Merck), bromine (Merck), 96% sulfuric acid (Reachim), sodium nitrite (Merck), copper powder (Alfa), potassium hydroxide (Merck), K2CO3 (Merck), 12 M HCl (Reachim), TsOH (Aldrich), MgSO4 (Merck), Na2CO3 (Merck), Na2SO4 (Akzo Nobel), methanol (Merck), diethyl ether (Merck), 1,2-dimethoxyethane (DME, Aldrich), 95% ethanol (Merck), dichloromethane (Merck), hexane (Merck), THF (Merck), and toluene (Merck) were used as received. Hexane, toluene and dichloromethane for organometallic synthesis were dried over molecular sieves 4A (Merck). Diethyl ether, THF, and 1,2-dimethoxyethane for organometallic synthesis were distilled over sodium benzophenoneketyl. CDCl3 (Deutero GmbH) and CD2Cl2 (Deutero GmbH) were dried over molecular sieves 4A.

(169) 4-Bromo-6-tert-butyl-5-methoxy-2-methylindan-1-one was obtained as described in WO2013/007650.

(170) 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene and 5-tert-butyl-7-(3,5-di-tert-butylphenyl)-6-methoxy-2-methyl-1H-indene were obtained as described in WO2015/158790.

(171) Synthesis of MC-1

4,8-Di(4-tert-butylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene

(172) ##STR00017##

(173) To a mixture of 4.3 g (5.51 mmol) of NiCl.sub.2(PPh.sub.3)IPr and 76.06 g (211.2 mmol) of 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene.sup.1 550 ml (550 mmol, 1.3 equiv) of 1.0 M 4-tert-butylphenylmagnesium bromide in THF was added at a such rate to maintain a gentle reflux. The resulting solution was refluxed for 3 h, then cooled to room temperature, and 1000 ml of water followed by 500 ml of 1.0 M HCl and 400 ml of ether were added. The organic layer was separated and then evaporated to dryness to give a red oil. The product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent: hexane-dichloromethane=5:1, vol., then 2:1, vol.). This procedure gave 91.5 g (93%) of a mixture of two diastereoisomers of 4,8-di(4-tert-butylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene as a white solid mass. .sup.1 In this case, 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene contaminated with ˜15% of its angular isomer, i.e. 4,5-dibromo-3-methoxy-2-methyl-1,2,3,6,7,8-hexahydro-as-indacene was used

(174) .sup.1H NMR (CDCl.sub.3), mixture of isomers: δ 7.46-7.38 (m, 5H), 7.37-7.32 (m, 1H), 7.32-7.27 (m, 2H), 4.38 (d, J=5.1 Hz) and 4.15 (s) {sum 1H}, 3.40-3.32 (m, 0.5H), 3.17 (s) and 3.07 (s) {sum 3H}, 2.99-2.65 (m, 5H), 2.56-2.48 (m, 0.5H), 2.43-2.34 (m, 0.5H), 2.31-2.22 (m, 0.5H), 2.06-1.94 (m, 1H), 1.94-1.82 (m, 1H), 1.38(s), 1.37 (2s) and 1.36 (s) {sum 18H}, 1.16 (d, J=6.9 Hz) and 0.90 (d, J=7.2 Hz) {sum 3H}. .sup.13C{.sup.1H} NMR (CDCl.sub.3), mixture of isomers: δ 149.48, 149.32, 149.28, 149.26, 143.88, 143.29, 141.93, 141.61, 141.57, 140.93, 140.76, 138.51, 137.01, 136.92, 136.78, 135.67, 135.00, 134.30, 133.75, 129.02, 128.64, 124.80, 124.69, 124.56, 90.17, 85.03, 57.85, 56.09, 40.77, 38.39, 38.03, 37.40, 34.52, 33.09, 32.98, 32.95, 32.68, 31.43, 31.41, 26.29, 26.08, 19.25, 14.18.

4,8-Di(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

(175) ##STR00018##

(176) 600 mg of TsOH was added to a solution of 91.5 g (196.06 mmol) of 4,8-di(4-tert-butylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene in 700 ml of toluene, and the resulting mixture was refluxed using Dean-Stark head for 10 min. After cooling to room temperature the reaction mixture was washed with 200 ml of 10% K.sub.2CO.sub.3. The organic layer was separated, and the aqueous layer was additionally extracted with 200 ml of dichloromethane. The combined organic extract was dried over anhydrous K.sub.2CO.sub.3, passed through a short pad of silica gel 60 (40-63 μm), and then evaporated to dryness to give a yellowish solid mass. This mass was triturated with warm n-hexane, the formed suspension was filtered off (G3), thus obtained precipitate was washed with n-hexane and dried in vacuum. This procedure gave 61.06 g (72%) of 4,8-di(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a white powder.

(177) .sup.1H NMR (CDCl.sub.3): δ 7.46-7.42 (m, 4H), 7.38-7.35 (m, 4H), 6.49 (m, 1H), 3.27 (s, 2H), 2.92 (t, J=7.2 Hz, 2H), 2.86 (t, J=7.2 Hz, 2H), 2.04 (s, 3H), 1.98 (quint, J=7.2 Hz, 2H), 1.38 (two s, sum 18H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.39, 149.19, 145.45, 143.01, 141.12, 140.63, 138.67, 137.14, 136.77, 133.13, 129.35, 129.15, 128.47, 126.40, 125.00, 124.86, 42.59, 34.56, 32.89, 32.66, 31.44, 31.43, 26.27, 16.83.

[4,8-Di(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl] chloro-dimethyl-silane

(178) ##STR00019##

(179) To a cooled to −50° C. solution of 10.87 g (25.01 mmol) of 4,8-di(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 200 ml of ether and 40 ml of THF 10.3 ml (25.03 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. The resulting mixture was stirred overnight at room temperature, then the obtained yellow suspension was cooled to −30° C., and 16.1 g (124.8 mmol, 5 eqv.) of dichlorodimethylsilane was added in one portion. The resulting mixture was stirred overnight at room temperature, then filtered through a glass frit (G3), and the filter cake was washed with 2×50 ml of toluene. The combined filtrate was evaporated to dryness to give the title product as a slightly yellowish oil which was further used without an additional purification.

(180) .sup.1H NMR (CDCl.sub.3): δ 7.49-7.40 (m, 6H), 7.38-7.32 (m, 2H), 6.58 (s, 1H), 4.13 (s, 1H), 3.29-3.17 (m, 1H), 3.00-2.81 (m, 2H), 2.70-2.59 (m, 1H), 2.24 (s, 3H), 2.13-2.01 (m, 1H), 1.94-1.79 (m, 1H), 1.39 (s, 9H), 1.38 (s, 9H), −0.22 (s, 3H), −0.23 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 150.04, 149.27, 146.26, 143.29, 140.95, 140.05, 138.54, 137.44, 136.98, 132.28, 129.65, 129.57, 129.16, 126.42, 125.11, 124.90, 49.63, 34.59, 34.57, 33.41, 32.88, 31.46, 31.39, 26.31, 18.13, 3.71, −1.58.

2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-buty-indan-1-one

(181) ##STR00020##

(182) A mixture of 49.14 g (157.9 mmol) of 2-methyl-4-bromo-5-methoxy-6-tert-butylindan-1-one, 29.6 g (197.4 mmol, 1.25 eq.) of (3,5-dimethylphenyl)boronic acid, 45.2 g (427 mmol) of Na.sub.2CO.sub.3, 1.87 g (8.3 mmol, 5 mol. %) of Pd(OAc).sub.2, 4.36 g (16.6 mmol, 10 mol. %) of PPh.sub.3, 200 ml of water, and 500 ml of 1,2-dimethoxyethane was refluxed for 6.5 h. DME was evaporated on a rotary evaporator, 600 ml of water and 700 ml of dichloromethane were added to the residue. The organic layer was separated, and the aqueous one was additionally extracted with 200 ml of dichloromethane. The combined extract was dried over K.sub.2CO.sub.3 and then evaporated to dryness to give a black oil. The crude product was purified by flash chromatography on silica gel 60 (40-63 μm, hexane-dichloromethane=1:1, vol., then, 1:3, vol.) to give 48.43 g (91%) of 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindan-1-one as a brownish oil.

(183) Anal. calc. for C.sub.23H.sub.28O.sub.2: C, 82.10; H, 8.39. Found: C, 82.39; H, 8.52.

(184) .sup.1H NMR (CDCl.sub.3): δ 7.73 (s, 1H), 7.02 (s, 3H), 7.01 (s, 3H), 3.32 (s, 3H), 3.13 (dd, J=17.5 Hz, J=7.8 Hz, 1H), 2.68-2.57 (m, 1H), 2.44 (dd, J=17.5 Hz, J=3.9 Hz), 2.36 (s, 6H), 1.42 (s, 9H), 1.25 (d, J=7.5 Hz, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 208.90, 163.50, 152.90, 143.32, 138.08, 136.26, 132.68, 130.84, 129.08, 127.18, 121.30, 60.52, 42.17, 35.37, 34.34, 30.52, 21.38, 16.40.

2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene

(185) ##STR00021##

(186) 8.2 g (217 mmol) of NaBH.sub.4 was added to a solution of 48.43 g (143.9 mmol) of 2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylindan-1-one in 300 ml of THF cooled to 5° C. Then, 150 ml of methanol was added dropwise to this mixture by vigorous stirring for ca. 7 h at 5° C. The resulting mixture was evaporated to dryness, and the residue was partitioned between 500 ml of dichloromethane and 500 ml of 2 M HCl. The organic layer was separated, the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a slightly yellowish oil. To a solution of this oil in 600 ml of toluene 400 mg of TsOH was added, this mixture was refluxed with Dean-Stark head for 10 min and then cooled to room temperature using a water bath. The formed solution was washed by 10% Na.sub.2CO.sub.3, the organic layer was separated, the aqueous layer was extracted with 150 ml of dichloromethane. The combined organic extract was dried over K.sub.2CO.sub.3 and then passed through a short layer of silica gel 60 (40-63 μm). The silica gel layer was additionally washed by 100 ml of dichloromethane. The combined organic elute was evaporated to dryness, and the resulting oil was dried in vacuum at elevated temperature. This procedure gave 45.34 g (98%) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene which was used without additional purification.

(187) Anal. calc. for C.sub.23H.sub.28O: C, 86.20; H, 8.81. Found: C, 86.29; H, 9.07.

(188) .sup.1H NMR (CDCl.sub.3): δ 7.20 (s, 1H), 7.08 (br.s, 1H), 6.98 (br.s, 1H), 6.42 (m, 1H), 3.25 (s, 3H), 3.11 (s, 2H), 2.36 (s, 6H), 2.06 (s, 3H), 1.43 (s, 9H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 154.20, 145.22, 141.78, 140.82, 140.64, 138.30, 137.64, 131.80, 128.44, 127.18, 126.85, 116.98, 60.65, 42.80, 35.12, 31.01, 21.41, 16.65.

[4,8-Di(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane

(189) ##STR00022##

(190) To a solution of 8.26 g (25.78 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-methyl-1H-indene in 200 ml of ether 10.5 ml (25.52 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion at −50° C. This mixture was stirred overnight at room temperature, then the resulting light-orange solution with a small amount of precipitate was cooled to −50° C., and 200 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of [4,8-di(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane (prepared above, 25.01 mmol) in a mixture of 150 ml of ether and 50 ml of THF was added in one portion. The obtained mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm) which was additionally washed by 2×50 ml of dichloromethane. The combined filtrate was evaporated under a reduced pressure, and the residue was dried in vacuum at elevated temperature. This procedure gave 21.36 g (ca. 100%) of [4,8-di(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-11H-inden-1-yl]dimethylsilane (˜95% purity by NMR, a ˜1:1 mixture of stereoisomers) as a white powder which was further used without an additional purification.

(191) .sup.1H NMR (CDCl.sub.3): δ 7.59-7.33 (m, 8H), 7.19, 7.07, 7.02 and 6.94 (4s, sum 4H), 6.54 (s, 1H), 6.20 and 6.15 (2s, sum 1H), 4.33 and 4.18 (2s, sum 1H), 3.21 and 3.20 (2s, sum 3H), 3.31-3.16 (m, 1H), 3.05-2.82 (m, 2H), 2.72-2.60 (m, 1H), 2.38 and 2.37 (2s, 1H), 2.35 and 2.34 (2s, sum 6H), 2.07, 2.05, 1.94 and 1.60 (4s, sum 6H), 2.16-2.02 (m, 1H), 1.99-1.88 (m, 1H), 1.44 and 1.43 (2s, sum 9H), 1.39 (s, 9H), 1.22 and 1.11 (2s, sum 9H), −0.49, −0.61, −0.64 and −0.69 (4s, sum 6H).

Anti-dimethylsilanedlyl[2-methyl-4,8-di(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

(192) ##STR00023##

(193) To a solution of 20.6 g (25.4 mmol) of [4,8-di(4-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-11H-inden-1-yl]dimethylsilane in 200 ml of ether, cooled to −50° C., 20.9 ml (50.8 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then, the resulting dark-red solution was cooled to −60° C., and 5.92 g (25.4 mmol) of ZrCl4 was added. The reaction mixture was stirred for 24 h at room temperature to give red solution with precipitate of LiCl. On the evidence of NMR spectroscopy, this solution included a ca. 3:1 mixture of anti- and syn-zirconocene dichlorides contaminated with some other impurities. This mixture was evaporated to dryness, and the residue was treated with 150 ml of warm toluene. The obtained suspension was filtered through glass frit (G4). The filtrate was evaporated to dryness, then the latter was dissolved in 60 ml of warm n-pentane. Orange powder precipitated from this mixture overnight at −30° C. was collected and dried in vacuum. This procedure gave 11.35 g (46%) of pure anti-dimethylsilanediyl[2-methyl-4,8-di(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride.

Anti-dimethylsilanediyl[2-methyl-4,8-di(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

(194) Anal. calc. for C.sub.58H.sub.68Cl.sub.2OSiZr: C, 71.71; H, 7.06. Found: C, 71.93; H, 7.30.

(195) .sup.1H NMR (CDCl.sub.3): δ 7.65-7.02 (m, 11H), 6.95 (s, 1H), 6.85 (s, 1H), 6.60 (s, 1H), 3.42 (s, 3H), 3.15-3.01 (m, 2H), 3.01-2.91 (m, 1H), 2.53-2.41 (m, 1H), 2.34 (s, 6H), 2.29 (s, 3H), 2.04 (s, 3H), 2.03-1.94 (m, 1H), 1.84-1.68 (m, 1H), 1.39 (s, 9H), 1.34 (2s, sum 18H), 1.13 (s, 3H), −0.17 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.92, 150.58, 149.72, 144.85, 144.23, 143.43, 138.59, 137.85, 136.85, 135.58, 134.74, 134.20, 131.85, 131.81, 131.74, 131.26, 130.85, 129.37, 128.93, 128.80, 127.38, 126.80, 125.96, 125.09, 124.72, 123.13, 121.92, 121.08, 82.42, 82.05, 62.64, 35.68, 34.70, 34.60, 33.77, 32.40, 31.41, 31.37, 30.37, 26.07, 21.42, 19.77, 18.64, 3.58, 1.23.

(196) Synthesis of MC-2

4,8-Di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

(197) ##STR00024##

(198) To a mixture of 2.0 g (2.56 mmol) of NiCl.sub.2(PPh.sub.3)IPr and 36.3 g (100.8 mmol) of 4,8-dibromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene 500 ml (250 mmol, 2.5 equiv) of 0.5 M 3,5-dimethylphenylmagnesium bromide in THF was added at a such rate to maintain a gentle reflux (for ca. 15 min). The resulting solution was refluxed additionally for 1 h, then cooled to room temperature, and 1200 ml of 0.5 M HCl and 500 ml of dichloromethane were added. The organic layer was separated, dried over K2CO.sub.3, passed through a short pad of silica gel 60 (40-63 μm, ca. 30 ml) and then evaporated to dryness to give the crude mixture of the diastereoisomers of 4,8-di(3,5-dimethylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene as a brownish oil. Further on, 315 mg of TsOH was added to a solution of the crude product in 420 ml of toluene, and the resulting mixture was refluxed using Dean-Stark head for 10 min. Then, one more portion of 220 mg of TsOH was added, and the obtained mixture was refluxed for 10 min. Finally, the last operation was repeated with 50 mg of TsOH. After cooling to room temperature the reaction mixture was washed with 200 ml of 10% K2CO.sub.3. The organic layer was separated, and the aqueous layer was additionally extracted with 200 ml of dichloromethane. The combined organic extract was dried over anhydrous K.sub.2CO.sub.3 (the organic layer became crimson at this stage), passed through a short pad of silica gel 60 (40-63 μm, 30 ml), and the resulting light-yellow solution was evaporated to ca. 30 ml to give a solution with a significant amount of a white precipitate. To this mixture 300 ml of n-hexane was added. The precipitated solid was filtered off (G3), washed with n-hexane, and dried in vacuum. This procedure gave 29.33 g (77.48 mmol, 76.9%) of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a white fine-crystalline solid. The mother liquor was evaporated to dryness to give a yellowish solid mass. This mass was triturated with 40 ml of warm n-hexane, cooled to room temperature, and filtered off (G3). The obtained solid was washed with n-hexane and dried in vacuum. This procedure gave additionally 4.55 g (12.02 mmol, 11.9%) of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a white powder. Thus, the total yield the title product was 33.88 g (89.5 mmol, 88.8%).

(199) .sup.1H NMR (CDCl.sub.3): δ 7.04 (s, 2H), 7.03 (s, 2H), 6.98 (s, 2H), 6.43 (m, 1H), 3.23 (s, 2H), 2.89 (t, J=7.3 Hz, 2H), 2.83 (t, J=7.3 Hz, 2H), 2.38 (s, 6H), 2.37 (s, 6H), 2.04 (s, 3H), 1.99 (quint, J=7.3 Hz, 2H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 145.38, 142.84, 140.85, 140.43, 140.21, 139.80, 138.37, 137.55, 137.39, 133.44, 129.64, 128.39, 128.19, 127.31, 126.61, 126.34, 42.49, 32.76, 32.51, 26.08, 21.43, 16.81

[4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane

(200) ##STR00025##

(201) To a suspension of 11.96 g (31.59 mmol) of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in a mixture of 250 ml of ether and 40 ml of THF, cooled to −30° C., 13.0 ml (31.59 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. The resulting mixture was stirred overnight at room temperature, then thus obtained light-orange solution with a large amount of orange precipitate was cooled to −50° C., and 19.0 ml (20.33 g, 157.5 mmol, 4.99 eqv.) of dichlorodimethylsilane was added in one portion. This mixture was stirred overnight at room temperature and then filtered through a glass frit (G3), the flask and filter cake were rinsed with 50 ml of toluene. The filtrate was evaporated to dryness to give 14.9 g (˜100%) of the title compound as a white solid mass which was further used without an additional purification.

(202) .sup.1H NMR (CDCl.sub.3): δ 7.09 (s, 2H), 7.02-6.94 (m, 4H), 6.51 (m, 1H), 4.07 (s, 1H), 3.26-3.14 (m, 1H), 2.95-2.79 (m, 2H), 2.60 (ddd, J=12.4 Hz, J=8.4 Hz, J=4.1 Hz, 1H), 2.38 and 2.37 (2s, sum 12H), 2.24 (s, 3H), 2.12-1.99 (m, 1H), 1.95-1.80 (m, 1H), −0.16 (s, 3H), −0.20 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 146.19, 143.17, 140.68, 140.29, 139.94, 139.92, 138.37, 137.59, 137.42, 132.60, 129.86, 128.52, 128.24, 127.85, 127.28, 126.32, 49.67, 33.33, 32.73, 26.15, 21.45, 21.42, 18.10, 3.92, −1.45.

[4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane

(203) ##STR00026##

(204) To a solution of 10.13 g (31.59 mmol) of 5-tert-butyl-7-(3,5-dimethylphenyl)-6-methoxy-2-methyl-1H-indene (produced as described above for MC-1) in 250 ml of ether, cooled to −30° C., 13.0 ml (31.59 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting light-orange solution with a small amount of precipitate was cooled to −45° C., and 200 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 14.9 g (31.59 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane (prepared above) in 200 ml of THF was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed by 2×50 ml of dichloromethane. The combined organic elute was evaporated to dryness, and the residue was dried in vacuum at elevated temperature to give 24.0 g (ca. 100% of ca. 90% purity) of the title product (ca. 55:45 mixture of the stereoisomers) as a slightly yellowish solid foam which was further used without an additional purification.

(205) .sup.1H NMR (CDCl.sub.3): δ 7.27 and 7.25 (2s, sum 2H), 7.04 (s, 4H), 6.98, 6.95 and 6.93 (3s, sum 3H), 6.90 and 6.85 (2s, sum 1H), 6.46 (s, 1H), 6.23 and 6.20 (2s, sum 1H), 4.41 and 4.16 (2s, sum 1H), 3.30-2.62 (m, 1H), 3.22 and 3.20 (2s, sum 3H), 3.04-2.79 (m, 2H), 2.68-2.56 (m, 1H), 2.39 (s, 6H), 2.35 (s, 9H), 2.32 (s, 3H), 2.18-1.80 (6s and 2m, sum 9H), 1.44 and 1.38 (2s, sum 9H), −0.52, −0.58, −0.62 and −0.73 (4s, sum 6H).

Anti-dimethylsilanedlyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

(206) ##STR00027##

(207) To a slightly cloudy yellowish solution of 23.06 g (30.54 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-dimethyl-phenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane in 250 ml of ether, cooled to −30° C., 25.1 ml (60.99 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred for 5.5 h at room temperature, then, the resulting red solution was cooled to −50° C., and 7.12 g (30.55 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give dark-red solution with precipitate of LiCl. On the evidence of NMR spectroscopy, this solution included a ca. 85/15 mixture of anti- and syn-zirconocene dichlorides contaminated with some other impurities. This mixture was evaporated to dryness (to the state of red foam), and the residue was treated with 100 ml of warm toluene. The obtained suspension was filtered through glass frit (G4), the filter cake was washed with 2×50 ml of warm toluene. The filtrate was evaporated to dryness, and the residue was dissolved in 70 ml of hot n-hexane. The light-orange precipitate fallen from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 7.8 g of anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, containing ca. 1.0 mol of n-hexane per mol of the complex, so the adjusted net weight of the isolated anti-complex was 7.13 g (26%). The mother liquor was evaporated to ca. 60 ml. Light-orange powder precipitated from this solution overnight at −25° C. was collected and dried in vacuum. This procedure gave 8.6 g of anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride, containing ca. 0.75 mol of n-hexane per mol of the complex (or 0.57 g of n-hexane in 8.6 g of the product), so the adjusted net weight of the isolated anti-complex was 8.03 g (29%).

Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride x 1.0 .SUP.n.hexane

(208) Anal. calc. for C.sub.54H.sub.60Cl.sub.2OSiZr x C.sub.6H.sub.14: C, 71.96; H, 7.45. Found: C, 72.30; H, 7.69.

(209) .sup.1H NMR (CDCl.sub.3): δ 7.55-6.90 (very br.s., 4H), 7.39 (s, 1H), 7.10 (s, 1H), 7.03 (s, 1H), 6.98 (s, 1H), 6.95 (s, 1H), 6.94 (s, 1H), 6.81 (s, 1H), 6.58 (s, 1H), 3.41 (s, 3H), 3.15-3.01 (m, 2H), 2.93 (ddd, J=16.0 Hz, 8.1 Hz, 3.3 Hz, 1H), 2.51-2.41 (m, 1H), 2.39 (s, 3H), 2.36 (s, 3H), 2.34 (s, 12H), 2.30 (s, 3H), 2.04 (s, 3H), 2.07-1.95 (m, 1H), 1.85-1.68 (m, 1H), 1.35 (s, 9H), 1.14 (s, 3H), −0.13 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.87, 144.73, 144.10, 143.25, 141.39, 138.39, 138.08, 137.81, 137.47, 136.90, 134.61, 134.39, 134.26, 132.05, 131.96, 131.74, 131.11, 128.96, 128.91, 128.82, 128.74, 127.74, 127.44, 127.01 (br.s), 126.76, 123.42, 123.12, 121.60, 121.08, 82.55, 81.91, 62.67, 35.68, 33.87, 32.39, 30.39, 26.04, 21.53, 21.47, 21.41, 21.24, 19.78, 18.60, 3.62, 1.70.

(210) Synthesis of MC-3

[4,8-Bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tertbutyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane

(211) ##STR00028##

(212) To a solution of 12.78 g (31.59 mmol) of 5-tert-butyl-7-(3,5-di-tert-butylphenyl)-6-methoxy-2-methyl-1H-indene in 250 ml of ether, cooled to −30° C., 13.0 ml (31.59 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting light-yellow solution with a large amount of white precipitate was cooled to −45° C., and 200 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 14.9 g (31.59 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane (prepared as described above) in 200 ml of THF was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed by 2×50 ml of dichloromethane. The combined organic elute was evaporated to dryness, and the yellowish residue was triturated with 100 ml of n-hexane. The obtained solid was filtered off (G3), washed with 2×25 ml of n-hexane and dried in vacuo to give 19.57 g of the title product as a white powder. The mother liquor was evaporated to dryness to give a yellowish solid mass. This mass was triturated with 20 ml of n-hexane, filtered off (G3), the obtained solid was washed with 10 ml of n-hexane and dried in vacuum. This procedure gave 4.87 g of the title product as a white powder. Thus, the total yield of this product (ca. 55:45 mixture of the stereoisomers) was 24.44 g (29.1 mmol, 92% of ca. 95% purity).

(213) .sup.1H NMR (CDCl.sub.3): δ 7.35-7.22 (m, 5.5H), 7.04 (s, 2H), 6.98 (s, 1H), 6.93, 6.90 and 6.87 (3s, sum 1.5H), 6.46 (s, 1H), 6.30 and 6.26 (2s, sum 1H), 4.41-4.17 (2s, sum 1H), 3.32-3.13 (m, 1H), 3.14 and 3.12 (2s, sum 3H), 3.02-2.81 (m, 2H), 2.68-2.56 (m, 1H), 2.39 (s, 6H), 2.35 (s, 3H), 2.33 (s, 3H), 2.24-1.81 (6s and 2m, sum 9H), 1.44 and 1.39 (2s, sum 9H), 1.35 and 1.34 (2s, sum 18H), −0.52, −0.59, −0.63 and −0.71 (4s, sum 6H).

Anti-dimethylsilanedlyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

(214) ##STR00029##

(215) To a slightly cloudy yellowish solution of 24.39 g (29.06 mmol) of [4,8-bis(3,5-dimethylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl][6-tert-butyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-2-methyl-1H-inden-1-yl]dimethylsilane in 250 ml of ether, cooled to −30° C., 23.9 ml (58.08 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred for 5.5 h at room temperature, then, the resulting red solution was cooled to −50° C., and 6.77 g (29.05 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give a dark-red solution with precipitate of LiCl. On the evidence of NMR spectroscopy, this solution included a ca. 90/10 mixture of anti- and syn-zirconocene dichlorides contaminated with some other impurities. This mixture was evaporated to dryness (to the state of red foam), and the residue was treated with 100 ml of warm toluene. The obtained suspension was filtered through glass frit (G4), the filter cake was washed with 2×50 ml of warm toluene. The combined filtrate was evaporated to dryness, the residue was dissolved in 60 ml of hot n-hexane, and 10 ml of n-pentane was added. The light-orange precipitate fallen from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 15.2 g of the title anti-complex containing ca. 0.7 mol of n-hexane per mol of the complex (or 0.87 g of n-hexane in 15.2 g of the complex), so the adjusted net weight of the isolated anti-complex was 14.33 g (49%). The mother liquor was evaporated to ca. 50 ml. Light-orange powder precipitated from this solution overnight at −25° C. was collected and dried in vacuum. This procedure gave 4.8 g of a mixture of anti- and syn-complexes in a ratio ca. 86/14, containing ca. 0.36 mol of n-hexane per mol of complex (or 0.14 g of n-hexane in 4.8 g of the complex), so the adjusted net weight of the isolated mixture was 4.66 g (16%).

Anti-dimethylsilanediyl[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3,5-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride

(216) Anal. calc. for C.sub.60H.sub.72Cl.sub.2OSiZr x 0.7C.sub.6H.sub.14: C, 72.76; H, 7.78. Found: C, 72.70; H, 8.05.

(217) .sup.1H NMR (CDCl.sub.3): δ 7.74-7.18 (very br.s., 3H), 7.41 (s, 1H), 7.34 (t, J=1.8 Hz, 1H), 7.17-6.81 (very br.s., 1H), 7.09 (s, 1H), 7.03 (s, 1H), 6.98 (s, 1H), 6.95 (s, 1H), 6.70 (s, 1H), 6.61 (s, 1H), 3.27 (s, 3H), 3.14-3.00 (m, 2H), 2.95 (ddd, J=16.0 Hz, J=8.1 Hz, J=3.6 Hz, 1H), 2.44 (ddd, J=16.6 Hz, J=8.3 Hz, J=3.4 Hz, 1H), 2.38 (s, 3H), 2.37 (s, 3H), 2.32 (s, 6H), 2.29 (s, 3H), 2.07-1.96 (m, 1H), 2.03 (s, 3H), 1.89-1.71 (m, 1H), 1.35 (s, 9H), 1.34 (s, 18H), 1.14 (s, 3H), −0.14 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.93, 150.62, 144.70, 143.99, 143.10, 141.41, 138.47, 138.10, 137.50, 135.90, 134.75, 134.53, 134.48, 132.04, 131.44, 131.29, 128.95, 128.82, 128.74, 127.70, 127.31, 124.44, 124.10, 123.01, 121.11, 120.89, 120.26, 82.55, 81.24, 62.28, 35.69, 34.98, 34.12, 33.84, 32.12, 31.48, 30.36, 25.93, 22.34, 21.50, 21.24, 19.67, 18.82, 14.07, 3.70, 1.65.

(218) Synthesis of Comparative Metallocene MC-C1 (According to WO/2018/122134, Synthesis of MC-IE3)

4-(4-tert-Butylphenyl)-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene

(219) ##STR00030##

(220) The precursor 4-bromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene was made according to the procedure described in WO2015/158790 A2 (pp 26-29).

(221) To a mixture of 1.5 g (1.92 mmol, 0.6 mol. %) of NiCl.sub.2(PPh.sub.3)IPr and 89.5 g (318.3 mmol) of 4-bromo-1-methoxy-2-methyl-1,2,3,5,6,7-hexahydro-s-indacene, 500 ml (500 mmol, 1.57 equiv) of 1.0 M 4-tert-butylphenylmagnesium bromide in THF was added. The resulting solution was refluxed for 3 h, then cooled to room temperature, and 1000 ml of 0.5 M HCl was added. Further on, this mixture was extracted with 1000 ml of dichloromethane, the organic layer was separated, and the aqueous layer was extracted with 250 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a greenish oil. The title product was isolated by flash-chromatography on silica gel 60 (40-63 μm; eluent:hexanes-dichloromethane=3:1, vol., then 1:3, vol.). This procedure gave 107 g (ca. 100%) of 1-methoxy-2-methyl-4-(4-tert-butylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene as a white solid mass.

(222) Anal. calc. for C.sub.24H.sub.30O: C, 86.18; H, 9.04. Found: C, 85.99; H, 9.18.

(223) .sup.1H NMR (CDCl.sub.3), syn-isomer: δ 7.42-7.37 (m, 2H), 7.25-7.20 (m, 3H), 4.48 (d, J=5.5 Hz, 1H), 3.44 (s, 3H), 2.99-2.47 (m, 7H), 2.09-1.94 (m, 2H), 1.35 (s, 9H), 1.07 (d, J=6.9 Hz, 3H); Anti-isomer: δ 7.42-7.37 (m, 2H), 7.25-7.19 (m, 3H), 4.39 (d, J=3.9 Hz, 1H), 3.49 (s, 3H), 3.09 (dd, J=15.9 Hz, J=7.5 Hz, 1H), 2.94 (t, J=7.3 Hz, 2H), 2.78 (tm, J=7.3 Hz, 2H), 2.51-2.39 (m, 1H), 2.29 (dd, J=15.9 Hz, J=5.0 Hz, 1H), 2.01 (quin, J=7.3 Hz, 2H), 1.36 (s, 9H), 1.11 (d, J=7.1 Hz, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3), syn-isomer: δ 149.31, 142.71, 142.58, 141.46, 140.03, 136.71, 135.07, 128.55, 124.77, 120.02, 86.23, 56.74, 39.41, 37.65, 34.49, 33.06, 32.45, 31.38, 25.95, 13.68; Anti-isomer: δ 149.34, 143.21, 142.90, 140.86, 139.31, 136.69, 135.11, 128.49, 124.82, 119.98, 91.53, 56.50, 40.12, 37.76, 34.50, 33.04, 32.40, 31.38, 25.97, 19.35.

4-(4-tert-Butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene

(224) ##STR00031##

(225) To a solution of 107 g 1-methoxy-2-methyl-4-(4-tert-butylphenyl)-1,2,3,5,6,7-hexahydro-s-indacene (prepared above) in 700 ml of toluene, 600 mg of TsOH was added, and the resulting solution was refluxed using Dean-Stark head for 10 min. After cooling to room temperature the reaction mixture was washed with 200 ml of 10% NaHCO.sub.3. The organic layer was separated, and the aqueous layer was additionally extracted with 2×100 ml of dichloromethane. The combined organic extract was evaporated to dryness to give a red oil. The product was purified by flash-chromatography on silica gel 60 (40-63 μm; eluent:hexanes, then hexanes-dichloromethane=5:1, vol.) followed by vacuum distillation, b.p. 210-216° C./5-6 mm Hg. This procedure gave 77.1 g (80%) of 4-(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene as a yellowish glassy material.

(226) Anal. calc. for C.sub.23H.sub.12: C, 91.34; H, 8.66. Found: C, 91.47; H, 8.50.

(227) .sup.1H NMR (CDCl.sub.3): δ 7.44-7.37 (m, 2H), 7.33-7.26 (m, 2H), 7.10 (s, 1H), 6.45 (br.s, 1H), 3.17 (s, 2H), 2.95 (t, J=7.3 Hz, 2H), 2.78 (t, J=7.3 Hz, 2H), 2.07 (s, 3H), 2.02 (quin, J=7.3 Hz, 2H), 1.37 (s, 9H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.37, 145.54, 144.79, 142.91, 139.92, 138.05, 137.15, 134.06, 128.36, 127.02, 124.96, 114.84, 42.11, 34.53, 33.25, 32.16, 31.41, 25.96, 16.77.

2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane

(228) ##STR00032##

(229) To a solution of 22.3 g (73.73 mmol) of 4-(4-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene in 300 ml of ether, cooled to −50° C., 30.4 ml (73.87 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. The resulting mixture was stirred overnight at room temperature, then the resulting suspension with a large amount of precipitate was cooled to −78° C. (wherein the precipitate was substantially dissolved to form an orange solution), and 47.6 g (369 mmol, 5 equiv.) of dichlorodimethylsilane was added in one portion. The obtained solution was stirred overnight at room temperature and then filtered through a glass frit (G4). The filtrate was evaporated to dryness to give 28.49 g (98%) of 2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane as a colorless glass which was used without further purification.

(230) .sup.1H NMR (CDCl.sub.3): δ 7-50-7.45 (m, 2H), 7.36 (s, 1H), 7.35-7.32 (m, 2H), 6.60 (s, 1H), 3.60 (s, 1H), 3.10-2.82 (m, 4H), 2.24 (s, 3H), 2.08 (quin, J=7.3 Hz, 2H), 1.42 (s, 9H), 0.48 (s, 3H), 0.22 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 149.27, 144.41, 142.15, 141.41, 139.94, 139.83, 136.85, 130.19, 129.07, 126.88, 124.86, 118.67, 49.76, 34.55, 33.27, 32.32, 31.44, 26.00, 17.6

[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

(231) ##STR00033##

(232) To a solution of 7.87 g (24.56 mmol) of 2-methyl-5-tert-butyl-6-methoxy-7-(3,5-dimethylphenyl)-1H-indene (produced as described above) in 150 ml of ether, 10.1 ml (24.54 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion at −50° C. This mixture was stirred overnight at room temperature, then the resulting yellow solution with a large amount of yellow precipitate was cooled to −50° C. (wherein the precipitate disappeared completely), and 150 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., then a solution of 9.70 g (24.55 mmol) of 2-methyl-[4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]chlorodimethylsilane in 150 ml of ether was added in one portion. This mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed with 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the residue was dried in vacuum at elevated temperature. This procedure gave 16.2 g (97%) of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (>95% purity by NMR, approx. 1:1 mixture of the stereoisomers) as a yellowish glassy solid which was further used without an additional purification.

(233) .sup.1H NMR (CDCl.sub.3): δ 7.49 (s, 0.5H), 7.47-7.42 (m, 2H), 7.37-7.32 (m, 2.5H), 7.25 (s, 0.5H), 7.22 (s, 0.5H), 7.15-7.09 (m, 2H), 7.01-6.97 (m, 1H), 6.57, 6.56 and 6.45 (3s, sum 2H), 3.70, 3.69, 3.67 and 3.65 (4s, sum 2H), 3.28 and 3.27 (2s, sum 3H), 3.01-2.79 (m, 4H), 2.38 (s, 6H), 2.19, 2.16 and 2.13 (3s, sum 6H), 2.07-2.00 (m, 2H), 1.43 and 1.41 (2s, sum 9H), 1.38 (s, 9H), −0.18, −0.19, −0.20 and −0.23 (4s, sum 6H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 155.30, 155.27, 149.14, 149.10, 147.45, 147.38, 146.01, 145.77, 143.98, 143.92, 143.73, 143.68, 142.13, 142.09, 139.51, 139.41, 139.26, 139.23, 139.19, 139.15, 138.22, 137.51, 137.08, 137.05, 136.98, 130.05, 130.01, 129.11, 128.22, 127.90, 127.48, 127.44, 126.18, 126.13, 125.97, 125.92, 124.82, 120.55, 120.49, 118.50, 118.27, 60.54, 60.50, 47.34, 47.33, 46.87, 46.72, 35.14, 34.54, 33.34, 33.28, 32.30, 31.44, 31.25, 31.20, 26.02, 26.01, 21.45, 17.95, 17.87.

Anti-dimethylsilanedlyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride

(234) ##STR00034##

(235) To a solution of 16.2 g (23.86 mmol) of [2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butyl-1H-inden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (prepared above) in 250 ml of ether, cooled to −50° C., 19.7 ml (47.87 mmol) of 2.43 M .sup.nBuLi in hexanes was added in one portion. This mixture was stirred for 4 h at room temperature, then the resulting red solution was cooled to −50° C., and 5.57 g (23.9 mmol) of ZrCl.sub.4 was added. The reaction mixture was stirred for 24 h at room temperature to give red solution with orange precipitate. This mixture was evaporated to dryness. The residue was treated with 150 ml of hot toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to 50 ml, and then 20 ml of n-hexane was added. The orange crystals precipitated from this solution overnight at room temperature were collected, washed with 10 ml of cold toluene, and dried in vacuum. This procedure gave 5.02 g (25%) of anti-zirconocene as a solvate with toluene (×0.75 toluene). The mother liquor was evaporated to ca. 30 ml, and 30 ml of n-hexane was added. The orange powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 6.89 g (34%) of a ca. 3 to 7 mixture of anti- and syn-zirconocenes. Thus, the total yield of rac-zirconocene isolated in this synthesis was 11.91 g (60%).

Anti-dimethylsilanediyl[2-methyl-4-(3,5-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl][2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]zirconium dichloride

(236) Anal. calc. for C.sub.48H.sub.56Cl.sub.2OsiZr x 0.75C.sub.7H.sub.8: C, 70.42; H, 6.88. Found: C, 70.51; H, 6.99.

(237) .sup.1H NMR (CDCl.sub.3): δ 7.63-7.03 (very br.s, 2H), 7.59-7.51 (br.m, 2H), 7.51-7.42 (m, 4H), 6.98 (s, 1H), 6.78 (s, 1H), 6.60 (s, 1H), 3.46 (s, 3H), 3.11-3.04 (m, 1H), 3.04-2.93 (m, 2H), 2.88-2.81 (m, 1H), 2.36 (s, 6H), 2.22 (s, 3H), 2.21 (s, 3H), 2.12-1.94 (m, 2H), 1.41 (s, 9H), 1.36 (s, 9H), 1.32 (s, 3H), 1.31 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 159.78, 149.90, 144.67, 144.07, 143.07, 136.75, 135.44, 135.40, 133.97, 133.51, 132.90, 132.23, 128.84, 128.76, 127.34, 127.01, 126.73, 125.28, 125.17, 122.89, 121.68, 121.59, 120.84, 117.94, 81.60, 81.26, 62.61, 35.73, 34.60, 33.20, 32.17, 31.36, 30.34, 26.56, 21.40, 18.41, 18.26, 2.65, 2.54.

(238) Synthesis of Comparative Metallocene MC-C2

(239) Metallocene MC-2 was synthetized according to WO/2018/122134, synthesis of MC-IE2.

(240) ##STR00035##

(241) rac-anti-dimethylsilanediyl [2-methyl-4-(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-dimethylphenyl)-5-methoxy-6-tert-butylinden-1-yl] zirconium dichloride

(242) Synthesis of Comparative Metallocene MC-C3

(243) Metallocene MC-3 was synthetized according to WO/2018/122134, synthesis of MC-IES.

(244) ##STR00036##

(245) rac-anti-dimethylsilanediyl[2-methyl-4-(3′,5′-dimethyl phenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl][2-methyl-4-(3′,5′-di-tert-butylphenyl)-5-methoxy-6-tert-butylinden-1-yl]zirconium dichloride.

(246) Synthesis of Comparative Metallocene MC-C4

(247) ##STR00037##

(248) rac-dimethylsilanedylbis[2-methyl-4,8-bis(3′,5′-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl] zirconium dichloride, in short rac-Me.sub.2Si[2-Me-4,8-(3′,5′-Me.sub.2Ph).sub.2-1,5,6,7-H.sub.4-indacenyl].sub.2ZrCl.sub.2

Bis[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane

(249) ##STR00038##

(250) .sup.nBuLi in hexanes (2.43 M, 18.8 ml, 45.68 mmol) was added in one portion to a suspension of 4,8-di(3,5-dimethylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene (17.28 g, 45.65 mmol) in a mixture of 350 ml of ether and 40 ml of THF cooled to −30° C. This mixture was stirred for 4 h at room temperature, then the resulting orange suspension was cooled to −40° C., and 250 mg of CuCN was added. The obtained mixture was stirred for 0.5 h at −25° C., and then dichlorodimethylsilane (2.95 g, 22.86 mmol) was added. The obtained mixture was stirred overnight at room temperature, then filtered through a pad of silica gel 60 (40-63 μm), which was additionally washed with 7×500 ml of dichloromethane. The combined organic elute was washed with 300 ml of water, dried over Na.sub.2SO.sub.4, and then evaporated to dryness. The yellowish residue was triturated with 200 ml of n-hexane. The formed suspension was filtered through glass frit (G3). The so obtained white precipitate was washed with 2×25 ml of n-hexane, and then dried in vacuum to give 14.61 g of the title product as a white powder. The mother liquor was evaporated to dryness to give a yellowish semisolid mass. This mass was triturated with 30 ml of n-hexane. The obtained suspension was filtered through glass frit (G3), the precipitate was washed with 2×30 ml of n-hexane and then dried in vacuo. This procedure gave additional 0.81 g of the title product. Thus, the total yield of bis[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (a ca. 92:8 mixture of the stereoisomers) was 15.42 g (19.0 mmol, 83% of ca. 95% purity).

(251) .sup.1H NMR (CDCl.sub.3), major isomer (rac−): δ 7.03-6.94 (m, 5H), 6.89 (s, 1H), 6.32 (s, 1H), 4.25 (s, 1H), 3.20-3.07 (m, 1H), 2.95-2.81 (m, 1H), 2.79-2.67 (m, 1H), 2.56-2.45 (m, 1H), 2.38 (s, 6H), 2.30 (s, 6H), 2.12 (s, 3H), 2.07-1.94 (m, 1H), 1.88-1.71 (m, 1H), −1.24 (s, 3H). .sup.13C{.sup.1H}NMR (CDCl.sub.3): δ 146.35, 142.86, 142.25, 140.70, 140.34, 139.70, 137.92, 137.28, 136.92, 132.42, 129.15, 128.15, 128.01, 127.38, 125.10, 47.32, 33.42, 32.80, 26.15, 21.45, 21.36, 17.95, −5.50.

Rac-dimethylsilanedlylbis[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacenyl]zirconium dichloride

(252) ##STR00039##

(253) .sup.nBuLi in hexanes (2.43 M, 6.5 ml, 15.8 mmol) was added at room temperature in one portion to a white suspension of bis[2-methyl-4,8-bis(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl]dimethylsilane (6.38 g, 7.85 mmol) in 350 ml of toluene. This mixture was refluxed for 4 h, then the resulting dark-red solution was cooled to −40° C., and then 1.28 ml (1.138 g, 15.78 mmol) of THF followed by 1.83 g (7.85 mmol) of ZrCl.sub.4 were added. The reaction mixture was stirred for 24 h at room temperature, then additionally refluxed for 3 h to give a dark-red solution with precipitate of LiCl. This mixture was evaporated to ca. 100 ml and filtered through glass frit (G4). The filtrate was evaporated to ca. 30 ml, and 20 ml of n-hexane was added. Yellow precipitate formed from this solution overnight at room temperature was collected and then dried under vacuum.

(254) This procedure gave 0.85 g (11%) of rac-dimethylsilanediylbis[2-methyl-4,8-di(3,5-dimethylphenyl)-1,5,6,7-tetrahydro-s-indacenyl]zirconium dichloride [1H NMR 1605_2_2].

(255) Anal. calc. for C.sub.60H.sub.62Cl.sub.2SiZr: C, 74.04; H, 6.42. Found: C, 74.42; H, 6.55.

(256) .sup.1H NMR (CDCl.sub.3): δ 7.50-7.01 (very br.s, 2H), 7.08 (s, 1H), 6.95 (s, 1H), 6.92 (s, 2H), 6.76 (s, 1H), 3.19-2.90 (m, 3H), 2.53-2.42 (m, 1H), 2.38 (s, 3H), 2.33 (s, 6H), 2.26 (s, 3H), 2.09 (s, 3H), 2.06-1.94 (m, 1H), 1.86-1.70 (m, 1H), −0.25 (s, 3H). .sup.13C{.sup.1H} NMR (CDCl.sub.3): δ 144.49, 143.19, 141.39, 138.53, 137.90, 137.43, 133.63, 132.42, 131.79, 131.71, 131.63, 129.01, 128.69, 128.21, 127.64, 127.17, 123.01, 83.23, 33.65, 32.21, 26.07, 21.53, 21.39, 21.07, 20.26, 2.92.

(257) In Table 1 it is shown that the inventive metallocene catalyst complexes are yielded with a higher selectivity and higher isolated yield of the anti-isomer than the comparative metallocene catalyst complexes.

(258) TABLE-US-00002 TABLE 1 0     MC-C1 MC-C2 Anti- ~50 ~50 isomer selectivity % isolated 25 46 yield, %     MC-C3 MC-C4 Anti- ~50 n.d. isomer selectivity % isolated 14 11 yield, %     MC-1 MC-2 Anti- 75 85 isomer selectivity, % isolated 46 55 yield, % MC-3 Anti- 90 isomer selectivity, % isolated 49 yield, %

(259) Catalyst Synthesis, Used Chemicals

(260) MAO was purchased from Chemtura/Lanxess and used as a 30 wt-% solution in toluene.

(261) As surfactants were used perfluoroalkylethyl acrylate esters (CAS number 65605-70-1) purchased from the Cytonix corporation, dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use (S1) or 1H,1H-Perfluoro(2-methyl-3-oxahexan-1-ol) (CAS 26537-88-2) purchased from Unimatec, dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use (S2).

(262) Hexadecafluoro-1,3-dimethylyclohexane (PFC) (CAS number 335-27-3) was obtained from commercial sources and dried over activated molecular sieves (2 times) and degassed by argon bubbling prior to use. Propylene is provided by Borealis and adequately purified before use.

(263) Triethylaluminum was purchased from Crompton and used in pure form. Hydrogen is provided by AGA and purified before use.

(264) All the chemicals and chemical reactions were handled under an inert gas atmosphere using Schlenk and glovebox techniques, with oven-dried glassware, syringes, needles or cannulas.

(265) As silica was used silica grade DM-L-303 from AGC Si-Tech Co, which was pre-calcined at 600° C.

(266) Catalyst Preparations:

(267) Comparative Catalyst 1—CE1: (Al/Zr=450 (mol/mol), Al/Surf.=167 (mol/mol)

(268) Inside the glovebox, 85.3 mg of dry and degassed surfactant S2 was mixed with 2 mL of MAO in a septum bottle and left to react overnight. The following day, 42.4 mg MC-C1 (0,076 mmol, 1 equivalent) were dissolved with 4 mL of the MAO solution in another septum bottle and left to stir inside the glovebox.

(269) After 60 minutes, 4 mL of the MAO-metallocene solution and 1 mL of the surfactant solution were successively added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). Total amount of MAO is 5 mL (450 equivalents). A red emulsion formed immediately and stirred during 15 minutes at 0° C./600 rpm. Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hot PFC at 90° C., and stirred at 600 rpm until the transfer is completed, then the speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the PFC and after 45 minutes the solvent was siphoned off. The remaining red catalyst was dried during 2 hours at 50° C. under argon flow. 0.52 g of a red free flowing powder was obtained.

(270) Inventive Catalyst 1—IE1: (Al/Zr=450 (mol/mol), Al/Surf.=250)

(271) Inside the glovebox, 29.2 mg of dry and degassed surfactant S2 dilute in 0.2 mL toluene was added dropwise to 5 mL of 30 wt.-% Chemtura MAO. The solutions were left under stirring for 10 minutes. Then, 49.2 mg of metallocene MC-1 was added to MAO/surfactant.

(272) After 60 minutes stirring, the surfactant-MAO-metallocene solution were added into a 50 mL emulsification glass reactor containing 40 mL of PFC at −10° C. and equipped with an overhead stirrer (stirring speed=600 rpm). A yellow emulsion formed immediately and stirred during 15 minutes at −10° C./600 rpm. Then the emulsion was transferred via a 2/4 Teflon tube to 100 mL of hot PFC at 90° C. and stirred at 600 rpm until the transfer is completed. Then the speed was reduced to 300 rpm. After 15 minutes stirring, the oil bath was removed and the stirrer turned off. The catalyst was left to settle up on top of the PFC and after 35 minutes the solvent was siphoned off. The remaining catalyst was dried during 2 hours at 50° C. under argon flow. 0.80 g of a yellow free flowing powder was obtained.

(273) Inventive Catalyst 2—IE2: (MC-2/Silica)

(274) Preparation of MAO-Silica Support.

(275) A steel reactor equipped with a mechanical stirrer and a filter net was flushed with nitrogen and the reactor temperature was set to 20° C. Next, pre-calcined silica grade DM-L-303 (7.4 kg) was added from a feeding drum followed by careful pressuring and depressurising with nitrogen using manual valves. Then toluene (32.2 kg) was added. The mixture was stirred (40 rpm) for 15 min. Next 30 wt % solution of MAO in toluene (17.5 kg) from Lanxess was added via 12 mm line on the top of the reactor within 70 min. The reaction mixture was then heated up to 90° C. and stirred at 90° C. for additional two hours. The slurry was allowed to settle and the mother liquor was filtered off. The catalyst was washed twice with toluene (32.2 kg) at 90° C., following by settling and filtration. The reactor was cooled off to 60° C. and the solid was washed with heptane (32.2 kg). Finally MAO treated S102 was dried at 60° C. for 2 h under nitrogen flow 2 kg/h, pressure 0.3 barg and then for 5 hours under vacuum (−0.5 barg) with stirring at 5 rpm. MAO treated support was collected as a free-flowing white powder found to contain 12% Al by weight.

(276) Catalyst Preparation

(277) In a nitrogen filled glovebox, a solution of MAO 0.2 mL (30% wt in toluene, Lanxess) in dry toluene (2.3 mL) was added to an aliquot of metallocene complex MC-2 (27 μmol). The mixture was stirred for 60 minutes at room temperature. Next, 2.0 g of MAO treated silica prepared as described above, was placed in a glass reactor equipped with a porous glass frit. A solution of MC-2 and MAO in toluene was then slowly added to the support over the course of 5 minutes with gentle mixing. The resulting mixture was shaken well and allowed to stay overnight. Then dry toluene (10 mL) was added, and the slurry was mixed well with the inert gas sparging through the filter net over 10 minutes. The solid was allowed to settle, and liquid was filtered off and discarded. The resulting cake was dried in vacuum for 1 hour to yield 2.0 g of the catalyst as pink free flowing powder.

(278) Comparative Catalyst 2—CE2: (MC-C3/Silica)

(279) Catalyst was prepared in the same manner as Catalyst of IE2, but using equivalent amount of comparative metallocene complex MC-C3 (27 μmol).

(280) Comparative Catalyst 3—CE3: (MC-C4/Silica)

(281) Catalyst was prepared in the same manner as Catalyst of IE2, but using equivalent amount of comparative metallocene complex MC-C4 (27 μmol).

(282) Inventive Catalyst 3—IE3: (MC-3/Silica)

(283) Preparation of MAO-Silica Support.

(284) A glass reactor equipped with a mechanical stirrer was charged with pre-calcines silica grade DM-L-303 (10.0 g). Then dry toluene (50 mL) was added. The mixture was then heated to 35° C. and stirred at 35° C. (40 rpm) for 15 min. Next 30 wt % solution of MAO in toluene (25 mL) from Lanxess was added via cannula over the course of 25 minutes and then stirred for 2 more hours at 35° C. The solid was allowed to settle and the mother liquor was siphoned off and discarded. Toluene (50 mL) was added and the mixture was heated to 80° C. and stirred at this temperature for 1 hour. The solids were allowed to settle, and the liquid was siphoned off and discarded. The toluene wash was repeated two more times, followed by a heptane (50 mL) wash at 60° C. Then the cake was dried under vacuum at 60° C. over for hours to yield 13.7 g of support as white powder.

(285) Catalyst Preparation

(286) In a nitrogen filled glovebox, a solution of MAO 0.25 mL (30% wt in toluene, Lanxess) in dry toluene (1 mL) was added to an aliquot of metallocene MC-3 (38 μmol). The mixture was stirred for 60 minutes at room temperature. Next, 1.0 g of MAO treated silica prepared as described above, was placed in a glass vial. The solution of metallocene and MAO in toluene was then slowly added to the support over the course of 5 minutes with gentle mixing. The resulting mixture was shaken well and allowed to stay overnight. Then dry toluene (5 mL) was added, and the slurry was mixed well at 60° C. for 30 minutes. The solid was allowed to settle, and liquid was siphoned off and discarded. The wash with 5 mL toluene was repeated twice at room temperature. The resulting cake was dried in Ar flow for 3 hours at 60° C. to yield 1.0 g of the catalyst as pink free flowing powder

(287) Inventive Catalyst 4—IE4: (MC-2/Silica)

(288) Catalyst was prepared in the same manner as Inventive Catalyst IE3, but using equivalent amount of inventive metallocene MC-2 (38 μmol, 35.4 mg).

(289) Comparative Catalyst 4—CE4: (MC-C2/Silica)

(290) Catalyst was prepared in the same manner as Inventive Catalyst of IE3, but using equivalent amount of comparative metallocene MC-C2 (38 μmol).

(291) TABLE-US-00003 TABLE 2 Catalyst analysis of examples IE2, CE2 and CE3 MC content MAO content Catalyst Al Zr Al/Zr based on Zr based on Al example MC wt % wt % Mol/mol wt % wt % IE2 MC-2 13 0.086 510 0.86 27.9 CE2 MC-C3 12 0.090 470 0.84 25.8 CE3 MC-C4 13 0.090 500 0.93 27.9

Polymerization Examples

(292) Homopolymerization of Propylene with Catalysts of Examples CE1 and IE1 (Comparative Polymerisation Example PCE1 and Inventive Polymerisation Example PIE1)

(293) The polymerizations were performed in a 5 litre jacketed stainless-steel reactor equipped with a stirrer, lines for monomer and hydrogen, an exhaust line and feeding systems for catalyst and scavenger.

(294) The catalyst feeder comprises two stainless steel cylinders in series. Inside a glovebox, desired amount of catalyst (see Table 3) was loaded into the lower steel cylinder of the feeder and the second cylinder, containing 5 ml of dry Perfluoro-1,3-dimethylcyclohexane, was attached on top. The steel cylinder of the scavenger feeder was filled with 200 μl of triethylaluminum and 5 ml of dry pentane. Outside glovebox, the feed cylinders were attached to the reactor and the connections flushed with nitrogen. Reactor temperature was controlled to 20° C. The contents of the scavenger feeder was flushed into the reactor with nitrogen over pressure. Then, desired amount of hydrogen (see Table 3), followed by 1100 g of liquid propylene, was fed into the reactor. Stirring speed was set to 400 rpm. The reactor temperature was stabilised to 20° C. and after minimum of 5 minutes, the polymerization was started by injecting the catalyst into the reactor as described in the following. The valve between the two cylinders of the catalyst feeder was opened and the catalyst was then immediately flushed into the reactor with nitrogen over pressure. The feeder was pressurised three times with nitrogen and flushed into the reactor. Total nitrogen loading to reactor was about 0.42 mol.

(295) After 5 minutes prepolymerization at 20° C., the reactor temperature was raised to 70° C. over a period of 15 minutes. The polymerization was continued at 70° C. for 60 minutes and then stopped by flushing the reactor to normal pressure. Polymer was collected after flushing the reactor with nitrogen several times, left to dry until constant mass was reached, and then weighed to record the yield.

(296) The catalyst activity was calculated based on the 60 minute period according to the following formula:

(297) $\mathrm{Catalyst}\mathrm{Activity}\left(\mathrm{kg}-\mathrm{PP}/g-\mathrm{Cat}/h\right)=\frac{\mathrm{amount}\mathrm{of}\mathrm{polymer}\mathrm{produced}\left(\mathrm{kg}\right)}{\mathrm{catalyst}\mathrm{loading}\left(g\right)\times \mathrm{polymerization}\mathrm{time}\left(h\right)}$

(298) Polymerization conditions and results are disclosed in Table 3.

(299) TABLE-US-00004 TABLE 3 Propylene bulk homopolymer results and polymer properties. Activity Polymer. Catalyst Catalyst H2 Polymer (kg-PP/g- Mw Mw/ Tm example Example (mg) (mmol) (g) cat/h) (kg/mol) Mn (° C.) PCE1 CE1  7.7 6 250 32.5 510 2.7 151 PIE1 IE1 11.8 6 678 57.5 520 2.6 152

(300) The overall performance obtained with the new metallocene of the invention is better than with the comparative example: high activity in homopolymerization, good homopolymer melting temperature and good molecular weight capability.

(301) Homopolymerisation of Propylene and Copolymerisation of Propylene with Hexene Using Silica Supported Metallocene Catalysts (Comparative Polymerisation Examples PCE2 and PCE3; Inventive Polymerisation Examples PIE2 and PIE3)

(302) Hexene Feed

(303) Hexene was purified in the M-Braun solvent station, transferred via fixed line to the syringe pump, and then fed via the syringe pump into the reactor before adding the triethylaluminium.

(304) hPP or C3C6 at 75° C. in Bulk

(305) A stainless-steel reactor equipped with a ribbon stirrer, with a total volume of 20.9 dm.sup.3 containing 0.2 bar-g propylene, is filled with additional 4.45 kg propylene and the chosen amount of 1-hexene. Triethylaluminium (0.8 ml of 0.62 molar solution in n-heptane) is added using a stream of 250 g propylene, then 1.44 NL of H2 is added via mass flow controller in one minute. The reactor temperature is stabilized at 20° C. (HB-Therm) and the solution is stirred and 250 rpm for at least 20 min.

(306) The desired amount of solid, catalyst is loaded into a 5 ml stainless steel vial inside a glovebox, then a second 5 ml vial containing 4 ml n-heptane and pressurized with 10 bars of nitrogen is added on top of it. This dual feeder system is mounted on a port on the lid of the autoclave. The valve between the two vials is opened and the solid catalyst is contacted with n-heptane under N2 pressure for 2 s, and then flushed into the reactor with 250 g propylene. Stirring speed is kept at 250 rpm and pre-polymerisation is run for 10 minutes at 20° C. Then the polymerisation temperature is increased to 75° C. The reactor temperature is kept constant throughout the polymerization. The polymerization time is measured starting when the temperature is 2° C. below the set polymerization temperature. When the polymerization time of 60 min has lapsed, the reaction is stopped by injecting 5 ml ethanol, cooling the reactor and simultaneously flashing the volatile components. After purging the reactor 3 times with N2 and one vacuum/N2 cycle, the reactor is opened, the polymer powder is taken out and dried overnight in a fume hood. 100 g of the polymer is additivated with 0.5 wt % Irganox B225 (dissolved in acetone) and then dried overnight in a fume hood and additionally one hour in a vacuum drying oven at 60° C. Results are disclosed in Tables 4A and 4B.

(307) TABLE-US-00005 TABLE 4A Propylene homopolymerisation and propylene/hexene copolymerisation settings and results MC content of H2 feed Catalyst catalyst before Hexene activity MC Polymerisation Catalyst (from ICP) prepolym. feed kg/ activity example Ex MC mg wt % NL g g.sub.cat/h kg/g.sub.MC/h PCE2 CE3 MC-C4 52 0.93 2.02 0 20.0 2148 PCE3 CE3 MC-C4 63 0.93 2.02 102 16..9 1814 PIE2 IE2 MC-2 61 0.86 2.02 0 27.1 3147 PIE3 IE2 MC-2 56 0.86 2.02 102 23.0 2672

(308) TABLE-US-00006 TABLE 4B Propylene homopolymerisation and propylene/hexene copolymerisation results MFR.sub.2 Powder Polymerisation powder bulk density C6 (IR-MMR) Tm Experiment g/10 min g/ml wt % ° C. PCE2 5.1 0.40 0 156 PCE3 18.1 0.46 2.4 139 PIE2 1.8 0.43 0 151 PIE3 15.6 0.44 2.1 137

(309) As can be seen from the results, the catalyst activity and MC-activity with inventive catalysts is higher in both propylene homopolymerisation and with hexane copolymerisation. In addition MFR.sub.2 of the polymers of the inventive examples is lower indicating higher molecular weight of the polymer.

(310) Homopolymerisation of Propylene and Copolymerisation of Propylene with Ethylene (Heterophasic Copolymers) Using Silica Supported Metallocene Catalysts

(311) (Comparative polymerisation examples PCE3, PCE4 and PCE5; inventive polymerisation example PIE4)

(312) Step 1: Prepolymerisation and Bulk Homopolymerisation

(313) A stainless-steel reactor equipped with a ribbon stirrer, with a total volume of 20.9 dm.sup.3 containing 0.2 bar-g propylene is filled with additional 3950 g propylene. Triethylaluminum (0.80 ml of a 0.62 molar solution in heptane) is injected into the reactor by additional 240 g propylene, then 2.0 NL of hydrogen is added via mass flow controller in one minute. The solution is stirred at 20° C. and 250 rpm for at least 20 min. The desired amount of solid, catalyst is loaded into a 5 ml stainless steel vial inside a glovebox and a second 5 ml vial containing 4 ml n-heptane pressurized with 10 bars of nitrogen is added on top of the first vial. This catalyst feeder system is mounted on a port on the lid of the reactor, The valve between the two vials is opened and the solid catalyst is contacted with heptane under nitrogen pressure for 2 s, then flushed into the reactor with 240 g propylene. The prepolymerisation is run for 10 min. At the end of the prepolymerisation step the temperature was raised to 80° C. In some experiments, additional hydrogen is fed, when the internal reactor temperature has reached 75° C., see tables for values) is added via mass flow controller in one minute. The reactor temperature is kept constant at 80° C. throughout the polymerisation. The polymerisation time is measured starting when the internal reactor temperature reached 2° C. below the set polymerisation temperature.

(314) Step 2:

(315) Gas Phase Ethylene-Propylene Copolymerisation

(316) After the homopolymerisation step is completed, the stirrer speed is reduced to 50 rpm and the pressure is reduced down to 0.3 bar-g by venting the monomers. Then triethylaluminum (0.80 ml of a 0.62 mol/1 solution in heptane) is injected into the reactor by additional 250 g propylene through a steel vial. The pressure is then again reduced down to 0.3 bar-g by venting the monomers. The stirrer speed is set to 180 rpm and the reactor temperature is set to 70° C. Then the reactor pressure is increased to 20 bar-g by feeding a C3/C2 gas mixture of composition defined by:

(317) ${\left(\frac{C_2}{C_3}\right)}_{\mathrm{gas}\mathrm{feed}\mathrm{in}\mathrm{transition}}=\frac{{\left(\frac{C_2}{C_3}\right)}_{\mathrm{target}\mathrm{polymer}\mathrm{composition}}}{R}$
where C2/C3 is the weight ratio of the two monomers and R is their reactivity ratio, determined experimentally. In the present experiments, R=0.50.

(318) The temperature is held constant by thermostat and the pressure is kept constant by feeding via mass flow controller a C3/C2 gas mixture of composition corresponding to the target polymer composition and, until the set duration for this step has lapsed.

(319) Then the reactor is cooled down to about 30° C. and the volatile components flashed out. After purging the reactor 3 times with N2 and one vacuum/N2 cycle, the product is taken out and dried overnight in a fume hood. 100 g of the polymer is additivated with 0.5 wt % Irganox B225 (solution in acetone) and dried overnight in a hood followed by 2 hours in a vacuum drying oven at 60° C. Results are disclosed in Tables 5 and 6.

(320) TABLE-US-00007 TABLE 5 Heterophasic copolymers: experimental settings MC Transition Gas phase content C2 C3 C2 C3 Overall MC Polym- Catalysts of cat. feed feed feed feed productivity productivity example Ex MC mg wt % g g g g Kg/gcat Kg/g.sub.MC PCE4 CE4 MC-C2 90 n.m. 234 339 80 250 14.1 n.m PCE5 CE3 MC-C4 54 0.93 234 345 21  63 16.7 1798 PCE6 CE2 MC-C3 59 0.84 230 339 77 239 19.7 2343 PIE4 IE2 MC-2 52 0.86 239 346 40 121 24.4 2838

(321) TABLE-US-00008 TABLE 6 Heterophasic copolymers: experimental results IV* C2(XS)* Polym. MFR2 powder XS Tm (Crystex) from IR Example g/10 min wt % ° C. dl/g % PCE4 0.6 24.7 153 3.6 22.5 PCE5 4.0 9.3 157 4.4 26.1 PCE6 2.1 29.9 155 2.3 23.1 PIE4 2.6 14.4 150 4.7 23.3 *xylene soluble fraction

(322) Inventive example PIE4 shows clearly better overall and MC productivity than the comparative examples PCE4-PCE6. Further, IV in the inventive example is higher with the similar amount of ethylene than in the comparative examples.