(19)
(11)EP 3 131 935 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
03.06.2020 Bulletin 2020/23

(21)Application number: 15716058.1

(22)Date of filing:  15.04.2015
(51)Int. Cl.: 
C08F 210/16  (2006.01)
C07F 15/00  (2006.01)
C08F 4/6592  (2006.01)
(86)International application number:
PCT/EP2015/058205
(87)International publication number:
WO 2015/158791 (22.10.2015 Gazette  2015/42)

(54)

NEW CATALYST SYSTEM FOR PRODUCING POLYETHYLENE COPOLYMERS IN A HIGH TEMPERATURE SOLUTION POLYMERIZATION PROCESS

NEUES KATALYSATORSYSTEM ZUR HERSTELLUNG VON POLYETHYLEN-COPOLYMEREN IN EINEM HOCHTEMPERATURLÖSUNGSPOLYMERISATIONSVERFAHREN

NOUVEAU SYSTÈME DE CATALYSEUR POUR LA PRODUCTION DE COPOLYMÈRES DE POLYÉTHYLÈNE DANS UN PROCÉDÉ DE POLYMÉRISATION EN SOLUTION À HAUTE TEMPÉRATURE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 17.04.2014 EP 14165143

(43)Date of publication of application:
22.02.2017 Bulletin 2017/08

(73)Proprietor: Borealis AG
1220 Vienna (AT)

(72)Inventors:
  • AJELLAL, Noureddine
    FI-00970 Helsinki (FI)
  • RESCONI, Luigi
    I-44100 Ferrara (IT)
  • HUBNER, Gerhard
    A-4075 Breitenaich (AT)

(74)Representative: Dehns 
St. Bride's House 10 Salisbury Square
London EC4Y 8JD
London EC4Y 8JD (GB)


(56)References cited: : 
EP-A2- 2 532 687
EP-A2- 2 532 687
WO-A1-2013/007650
EP-A2- 2 532 687
WO-A1-03/049856
WO-A1-2013/007650
  
  • USHAKOVA T M ET AL: "Ethylene polymerization and ethylene-1-hexene copolymerization over immobilized metallocene catalysts", KINETICS AND CATALYSIS, KLUWER ACADEMIC PUBLISHERS, BO, vol. 53, no. 1, 14 February 2012 (2012-02-14), pages 75-83, XP035014728, ISSN: 1608-3210, DOI: 10.1134/S0023158412010156
  • USHAKOVA T M ET AL: "Ethylene polymerization and ethylene-1-hexene copolymerization over immobilized metallocene catalysts", KINETICS AND CATALYSIS, KLUWER ACADEMIC PUBLISHERS, BO, vol. 53, no. 1, 14 February 2012 (2012-02-14), pages 75-83, XP035014728, ISSN: 1608-3210, DOI: 10.1134/S0023158412010156
  • EWEN J A ET AL: "EVALUATION OF THE DIMETHYLSILYL-BIS(2-METHYL-4-PHENYL-1-INDE NYL) LIGAND WITH GROUP 4 TRIAD METALS IN PROPENE POLYMERIZATIONS WITH METHYLALUMINOXANE", MACROMOLECULAR RAPID COMMUNICATIONS, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 19, 1 January 1998 (1998-01-01), pages 71-73, XP000738940, ISSN: 1022-1336
  • USHAKOVA T M ET AL: "Ethylene polymerization and ethylene-1-hexene copolymerization over immobilized metallocene catalysts", KINETICS AND CATALYSIS, KLUWER ACADEMIC PUBLISHERS, BO, vol. 53, no. 1, 14 February 2012 (2012-02-14), pages 75-83, XP035014728, ISSN: 1608-3210, DOI: 10.1134/S0023158412010156
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] The present invention is related to a new process for producing polyethylene copolymers in a high temperature solution polymerization process. The catalyst systems used in said process comprise a combination of selected Hf-bisindenyl complexes, substituted at least in position 2 and 4 of both indenyls along with a cocatalyst comprising an aluminoxane cocatalyst and a boron based cocatalyst, optionally in the presence of an aluminium alkyl compound. This combination remarkably gives rise to catalyst systems with excellent stability and allows production of polyethylene copolymers with increased comonomer incorporation.

[0002] Metallocene catalysts have been used to manufacture polyolefins for many years. Countless academic and patent publications describe the use of these catalysts in olefin polymerization. Ushakova et al. (Kinetics and Catalysis, 2012, Vol 53, No 1, pp 75-83), for example, discloses ethylene polymerisation and ethylene-1-hexene copolymerisation over immobilized metallocene catalysts.
Metallocenes are now used industrially and polyethylenes and in particular polypropylenes are often produced using cyclopentadienyl based catalyst systems with different substitution patterns.

[0003] Several of these metallocene catalysts have been described for the use in solution polymerization in particular for producing polypropylene.
For example WO 2007/116034 describes i.a. a catalyst system comprising racemic dimethylsilylbis(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)dichlorozirconium and methylalumoxane cocatalyst for producing polypropylene in a solution polymerization process at temperatures between 100°C and 120°C.
It is mentioned that the metallocene compounds can also be used for preparing ethylene copolymers, preferably ethylene-butene copolymers, but it is said that such copolymers are obtained by using gas phase processes.
Also WO 2007/122098 describes the use of the complex racemic dimethylsilylbis(2-methyl-4-(4-tert-butylphenyl)-1,5,6,7-tetrahydro-s-indacen-1-yl)dichlorozirconium in combination with an alumoxane cocatalyst for producing ethylene copolymers at 100°C.

[0004] WO 2011/135004 complexes as described in WO 2007/116034, like racemic dimethylsilylbis(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)dichlorozirconium and prepared according to the emulsion/solidification method as described in WO 2003/051934 are disclosed. These complexes are activated with an alumoxane cocatalyst and used for propylene polymerization.

[0005] WO 2012/075560 further describes a multi stage (at least two stage) solution polymerization process for preparing ethylene copolymers, wherein a phosphinimine catalyst is used with a cocatalyst comprising an alkylaluminoxane and an ionic activator, like a boron compound.

[0006] In none of the above cited literatures the problem of effective comonomer incorporation is mentioned.
However, for a process for producing ethylene copolymers to be efficient, it is important that the catalyst system used has a high reactivity for the C4-10 alpha-olefins used as comonomer.
Drawbacks arising from a low reactivity for the C4-10 alpha-olefin comonomer are e.g. increasing amounts of the alpha-olefin comonomer that are needed for introducing a certain amount of higher alpha-olefin comonomer units into the polymer and/or removal of non-reacted higher alpha-olefin from the polymer powder.
One further point to be noted is that high-temperature solution processes for olefin polymerization require a thermally robust catalyst.
As is discussed in WO 2003/102042 solution processes are characterized by short residence times. Consequently, in addition to having temperature stability, the catalyst systems used in these processes must activate quickly and thoroughly. This contrasts sharply with the requirements for catalysts used in slurry and gas-phase processes, where residence times are longer and catalyst lifetime is more important. Thus, a catalyst that is valuable for slurry and gas-phase processes might be a poor choice for use in a high-temperature solution process, and vice-versa. As solution to this problem WO 2003/102042 suggests to use organometallic complexes having Group 3-10 transition metal and a bridged indeno-indolyl ligand in combination with an activator, which is preferably methylalumoxane.

[0007] Although a lot of work has been done in the field of metallocene catalysts, there still remains a need to find new catalyst systems for ethylene copolymerization, which are able to produce polymers with desired properties and which have high reactivity for the used comonomers in order to achieve high comonomer incorporation and high thermal stability.

[0008] As a consequence, the inventors set out to develop a new catalyst system having superior polymerization behaviour than the above mentioned polymerization catalyst systems regarding to comonomer incorporation and thermal stability.

[0009] The present inventors have now found a new class of homogeneous olefin polymerization catalyst systems, which are able to solve the problems disclosed above. In particular, the invention combines the use of special Hf-bisindenyl complexes with aluminoxane cocatalysts and a boron cocatalyst, optionally in the presence of an aluminium alkyl compound.

Summary of Invention



[0010] Thus, viewed from one aspect the invention relates to a process for the preparation of an ethylene copolymer comprising polymerizing ethylene and a C4-10-alpha-olefin comonomer in a high temperature solution process at a temperature greater than 100°C in the presence of a homogeneous catalyst system comprising:
  1. (i) a metallocene complex of formula (I)

    wherein
    X
    M is Hf is a sigma ligand
    L
    is a bridge of the formula -SiR82-, wherein each R8 is independently a C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl,
    n
    is 0, 1 or 2,
    R1 and R1'
    are the same or can be different and can be a linear or branched C1-C6-alkyl group,
    R2 and R2'
    are the same or can be different and are a CH2-R9 group, with R9 being H or linear or branched C1-C6-alkyl group
    R5 and R5'
    are the same and are H, or R5 and R5' are different and can be H or a OR group, wherein R is a C1-C6-alkyl group
    R6 and R6'
    are the same or are different and can be H or a C(R10)3 group, with R10 being the same or different and R10 can be H or a linear or branched C1-C6-alkyl group, and
    R7 and R7'
    can be the same or are different and can be H or a linear or branched C1-C6-alkyl group
  2. (ii) an aluminoxane cocatalyst
  3. (iii) a boron containing cocatalyst and
  4. (iv) optionally an aluminium alkyl compound.

Detailed Description of the Invention


Metallocene Complex



[0011] The Hf-bisindenyl metallocene complex, especially the complexes defined by the formula (I) specified in the present invention, used for manufacture of the ethylene copolymer are symmetrical or asymmetrical. For asymmetrical complexes that means that the two indenyl ligands forming the metallocene complex are different, that is, each indenyl ligand bears a set of substituents that are either chemically different, or located in different positions with respect to the other indenyl ligand. More precisely, they are chiral, racemic bridged bisindenyl metallocene complexes.
Whilst the complexes of the invention may be in their syn configuration, ideally they are in their anti configuration. 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 Figure below.



[0012] Formula (I) is intended to cover both syn and anti configurations.

[0013] By nature of their chemistry, both anti and syn enantiomer pairs are formed during the synthesis of the complexes. However, by using the ligands of this invention, separation of the preferred anti isomers from the syn isomers is straightforward.

[0014] It is preferred if the metallocene complexes of the invention are employed as the rac anti isomer. Ideally therefore at least 95% mol, such as at least 98% mol, especially at least 99% mol of the metallocene catalyst is in the racemic anti isomeric form.

[0015] The invention can be effected with a Hf-metallocene complex of formula (I)

wherein
X
M is Hf is a sigma ligand
L
is a bridge of the formula -SiR82-, wherein each R8 is independently a C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl,
n
is 0, 1 or 2,
R1 and R1'
are the same or can be different and can be a linear or branched C1-C6-alkyl group,
R2 and R2'
are the same or can be different and are a CH2-R9 group, with R9 being H or linear or branched C1-C6-alkyl group
R5 and R5'
are the same and are H, or R5 and R5' are different and can be H or a OR group, wherein R is a C1-C6-alkyl group
R6 and R6
are the same or are different and can be H or a C(R10)3 group, with R10 being the same or different and R10 can be H or a linear or branched C1-C6-alkyl group, and
R7 and R7'
can be the same or are different and can be H or a linear or branched C1-C6-alkyl group.


[0016] In the formula (I) each X, which may be the same or different, is a sigma ligand, preferably a hydrogen atom, a halogen atom, a R11, OR11, OSO2CF3, OCOR11, SR11, NR112 or PR112 group wherein R11 is a linear or branched, cyclic or acyclic, C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C6-C20-aryl, C7-C20-alkylaryl or C7-C20-arylalkyl radical; optionally containing heteroatoms belonging to groups 14-16 or is SiR113, SiHR112 or SiH2R11. R11 is preferably a C1-6-alkyl, phenyl or benzyl group, whereby the term halogen includes fluoro, chloro, bromo and iodo groups, preferably chloro groups.
More preferably each X is independently a hydrogen atom, a halogen atom, C1-6-alkoxy group or an R11 group, e.g. preferably a C1-6-alkyl, phenyl or benzyl group.
Most preferably X is chlorine or a methyl radical. Preferably both X groups are the same.

[0017] R1 and R1' are the same and are a linear or branched C1-C6-alkyl group, preferably a linear or branched C1-C4-alkyl group, more preferably a linear or branched butyl-group and most preferably R1 and R1' are tert.-butyl.
n is 0, 1 or 2, preferably 1 or 2,
If n is 1, then R1 and R1' are preferably on position 4 (para) of the phenyl ring and if n is 2 then R1 and R1' are preferably on positions 3 and 5 of the phenyl ring.
In a preferred embodiment at least one of the phenyl groups is substituted with at least one of R1 or R1',

[0018] R2 and R2' are the same or can be different and are a CH2-R9 group, with R9 being H or linear or branched C1-C6-alkyl group, like methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl and tert.-butyl. Preferably R2 and R2' are the same and are a CH2-R9 group, with R9 being H or linear or branched C1-C4-alkyl group, more preferably R2 and R2' are the same and are a CH2-R9 group, with R9 being H or linear or branched C1-C3-alkyl group and most preferably R2 and R2' are either both methyl or both i-butyl.

[0019] R5 and R5' are the same and are H, or R5 and R5' are different and can be H or a OR group, wherein R is a linear or branched C1-C6-alkyl group, and R6 and R6' are the same or are different and can be H or a C(R10)3 group, with R10 being the same or different and R10 can be H or a linear or branched C1-C6-alkyl group.

[0020] It is also possible that at both ligands R5 and R6 as well as R5 and R6' are hydrogen. A further possibility is that only one of the ligands is unsubstituted in position 5 and 6.

[0021] R7 and R7' can be the same or are different and can be H or a linear or branched C1-C6-alkyl group, preferably R7 and R7' are the same or are different and can be H or a linear or branched C1-C4-alkyl group and more preferably R7 and R7' are the same or are different and can be H or a C1-C2-alkyl group.
For preferred complexes R7 and R7' are the same and are both H,
or for a further class of preferred complexes one of R7 or R7' is a linear or branched C1-C6-alkyl group, preferably a linear or branched C1-C4-alkyl group and more preferably a C1-C2-alkyl group and the other is H.

[0022] L is a bridge of the formula -SiR82-, wherein each R8 is independently a C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl.
The term C1-20 hydrocarbyl group therefore includes C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-20 cycloalkyl, C3-20 cycloalkenyl, C6-20 aryl groups, C7-20 alkylaryl groups or C7-20 arylalkyl groups or of course mixtures of these groups such as cycloalkyl substituted by alkyl.
Unless otherwise stated, preferred C1-20 hydrocarbyl groups are C1-20 alkyl, C4-20 cycloalkyl, C5-20 cycloalkyl-alkyl groups, C7-20 alkylaryl groups, C7-20 arylalkyl groups or C6-20 aryl groups. Preferably R8 are the same and are a C1-C10-hydrocarbyl or C6-C10-aryl group, like methyl, ethyl, propyl, isopropyl, tertbutyl, isobutyl, C5-6-cycloalkyl, cyclohexylmethyl, phenyl or benzyl, more preferably both R8 are a C1-C4-hydrocarbyl or C6-aryl group and most preferably both R8 are a C1-alkyl group.

[0023] Especially preferred complexes of formula (I) are
racemic dimethylsilyl[(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)-(2-methyl-4-(4'-tertbutylphenyl)-inden-1-yl)] hafnium dichloride or dimethyl and
racemic dimethylsilyl[(2-methyl-4-(3',5'-di-tert-butylphenyl)-7-methylinden-1-yl)-(2-methyl-4-(4-tert-butylphenyl)-inden-1-yl)]hafnium dichloride or dimethyl
either in their syn or anti configuration.

[0024] For the purpose of this invention, the terms dimethylsilyl, dimethylsilanediyl and dimethylsililene are equivalent.

Synthesis



[0025] 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 and WO2011/076780.

Cocatalyst



[0026] To form an active catalytic species it is normally necessary to employ a cocatalyst as is well known in the art. The present invention requires the use of an aluminoxane cocatalyst and a boron containing cocatalyst, optionally in the presence of an aluminium alkyl compound.

[0027] The aluminoxane cocatalyst can be one of formula (II):

where n is usually from 6 to 20 and R has the meaning below.
Aluminoxanes are formed on partial hydrolysis of organoaluminum compounds, for example those of the formula AlR3, AlR2Y and Al2R3Y3 where R can be, for example, C1-C10 alkyl, preferably C1-C5 alkyl, or C3-10-cycloalkyl, C7-C12 -arylalkyl or alkylaryl and/or phenyl or naphthyl, and where Y can be hydrogen, halogen, preferably chlorine or bromine, or C1-C10 alkoxy, preferably methoxy or ethoxy. The resulting oxygen-containing aluminoxanes are not in general pure compounds but mixtures of oligomers of the formula (I).

[0028] The preferred aluminoxane in the process according to the invention 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.

[0029] Boron based cocatalysts of interest include boron compounds containing a borate 3+ ion, i.e. borate compounds. These compounds generally contain an anion of formula:

        (Z)4B-     (III)

where Z is an optionally substituted phenyl derivative, said substituent being a haloC1-6-alkyl or halo group. Preferred options are fluoro or trifluoromethyl. Most preferably, the phenyl group is perfluorinated.
Such ionic cocatalysts preferably contain a non-coordinating anion such as tetrakis(pentafluorophenyl)borate.

[0030] Suitable counterions are protonated amine or aniline derivatives or phosphonium ions. These may have the general formula (IV) or (V):

        NQ4+ (IV) or PQ4+     (V)

where Q is independently H, C1-6-alkyl, C3-8 cycloalkyl, phenylC1-6-alkylene- or optionally substituted Ph. Optional substituents may be C1-6-alkyl, halo or nitro. There may be one or more than one such substituent. Preferred substituted Ph groups include therefore para-substituted phenyl, preferably tolyl or dimethylphenyl.
It is preferred if at least one Q group is H, thus preferred compounds are those of formula:

        NHQ3+ (VI) or PHQ3+     (VII)



[0031] Preferred phenylC1-6-alkyl- groups include benzyl.

[0032] Suitable counterions therefore include: methylammonium, anilinium, dimethylammonium, diethylammonium, N-methylanilinium, diphenylammonium, N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri-n-butylammonium, methyldiphenylammonium, p-bromo-N,N- dimethylanilinium or p-nitro-N,N-dimethylanilinium, especially dimethylammonium or N,N-dimethylanilinium. The use of pyridinium as an ion is a further option.

[0033] Phosphonium ions of interest include triphenylphosphonium, triethylphosphonium, diphenylphosphonium, tri(methylphenyl)phosphonium and tri(dimethylphenyl)phosphonium. A more preferred counterion is trityl (CPh3+) or analogues thereof in which the Ph group is functionalised to carry one or more alkyl groups. Highly preferred borates of use in the invention therefore comprise the tetrakis(pentafluorophenyl)borate ion.

[0034] Preferred ionic compounds which can be used according to the present invention include:

tributylammoniumtetra(pentafluorophenyl)borate,

tributylammoniumtetra(trifluoromethylphenyl)borate,

tributylammoniumtetra-(4-fluorophenyl)borate,

N,N-dimethylcyclohexylammoniumtetrakis-(pentafluorophenyl)borate,

N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate,

N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,

N,N- di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,

di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,

triphenylcarbeniumtetrakis(pentafluorophenyl)borate,

ferroceniumtetrakis(pentafluorophenyl)borate.



[0035] Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl) borate,
N,N- dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,
N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate or
N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

[0036] 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 Ph3CB(PhF5)4 and analogues therefore are especially favoured.

[0037] Suitable aluminium alkyl compounds are compounds of the formula (VIII) AIR3 with R being a linear or branched C2-C8-alkyl group.
Preferred aluminium alkyl compounds are triethylaluminium, tri-isobutylaluminium, tri-isohexylaluminium, tri-n-octylaluminium and tri-isooctylaluminium.

[0038] In a further embodiment it is possible to use the boron containing cocatalyst together with an aluminium alkyl compound in order to preactivate the boron containing cocatalyst by reaction thereof with the aluminium alkyl compound. This procedure is well known in the art.

[0039] An aluminoxane together with a boron based cocatalyst, optionally in the presence of an aluminium alkyl compound, are used in the homogeneous catalyst system of the present invention.

[0040] Suitable amounts of cocatalyst will be well known to the skilled man.
The molar ratio of boron to the Hf 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.

[0041] The molar ratio of AI in the aluminoxane to the Hf ion of the metallocene may be in the range 1:1 to 2000:1 mol/mol, preferably 10:1 to 1000:1, more preferably 50:1 to 500:1 mol/mol.

Catalyst Manufacture



[0042] The metallocene complex of the present invention is used in combination with the cocatalysts as a homogeneous catalyst system for the polymerization of ethylene and C4-10 alpha-olefin comonomer in a high temperature solution polymerization process.

[0043] The catalyst system of the invention is used in non-supported form. The catalyst system of the invention is used as a homogeneous catalyst.

Non-supported



[0044] Non-supported catalyst systems, suitable for the present invention 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(s), for example methylaluminoxane and/or a borane or a borate salt previously dissolved in an aromatic solvent, or can be prepared by sequentially adding the catalyst components to the polymerization medium.

[0045] In the present case, it is particularly preferred if the aluminoxane is contacted with the metallocene before the borate is added. Both cocatalyst components and the metallocene are preferably present in one solution.

[0046] Full disclosure of the necessary process steps can be found in WO03/051934 which is herein incorporated by reference.
All or part of the preparation steps can be done in a continuous manner.

[0047] The formed catalyst preferably has good stability/kinetics in terms of longevity of reaction, high activity and the catalysts enable low ash contents.

[0048] Prepolymerization 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. Preferable embodiments of this aspect of the invention are described herein.

Polymer



[0049] The polymer to be produced using the homogeneous catalyst system of the invention is copolymer of ethylene and a C4-10-alpha-olefin comonomer, like 1-butene, 1-hexene, 4-methyl-1-pentene, or 1-octene. Preferably butene, hexene or octene and more preferably octene is used as comonomer.
The comonomer content in such a polymer may be up to 40 wt%, preferably between 5 to 40 wt%, more preferably 10 to 38 wt% and more preferable 15 to 36 wt%.

[0050] The density (measured according to ISO 1183-187) of the polymers is in the range of 0.850 g/cm3 to 0.950 g/cm3, preferably in the range of 0.850 g/cm3 to 0.945 g/cm3 and more preferably in the range of 0.850 g/cm3 to 0.940 g/cm3.

[0051] Mw/Mn value of the polymers of the invention is less than 5, e.g. in the range of 2.0 to 4.5.

[0052] The melting points (measured with DSC according to ISO 11357-3:1999) of the polymers to be produced are below 130°C, preferably below 120°C, more preferably below 110°C and most preferably below 100°C

Polymerization



[0053] The homogeneous catalyst system of the present invention is used to produce the above defined ethylene copolymers in a high temperature solution polymerization process at temperatures higher than 100°C.

[0054] In view of this invention such process is essentially based on polymerizing the monomer and a suitable comonomer in a liquid hydrocarbon solvent in which the resulting polymer is soluble. The polymerization is carried out at a temperature above the melting point of the polymer, as a result of which a polymer solution is obtained. This solution is flashed in order to separate the polymer from the unreacted monomer and the solvent. The solvent is then recovered and recycled in the process.
A solution polymerization process is known for its short reactor residence times (compared to Gas-phase or slurry processes) allowing, thus, very fast grade transitions and significant flexibility in producing a wide product range in a short production cycle.

[0055] According to the present invention the used solution polymerization process is a high temperature solution polymerization process, using a polymerization temperature of higher than 100°C. Preferably the polymerization temperature is at least 110°, more preferably at least 150°C. The polymerization temperature can be up to 250°C.

[0056] The pressure in the used solution polymerization process according to the invention is preferably in a range of 10 × 105 to 100 × 105 Pa (10 to 100 bar), preferably 15 × 105 to 100 × 105 Pa (15 to 100 bar) and more preferably 20 × 105 to 100 × 105 Pa (20 to 100 bar).

[0057] The liquid hydrocarbon solvent used is preferably a C5-12-hydrocarbon which may be unsubstituted or substituted by C1-4 alkyl group such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. More preferably unsubstituted C6-10-hydrocarbon solvents are used.

[0058] A known solution technology suitable for the process according to the invention is the COMPACT technology.

Advantage



[0059] The new catalyst systems, comprising component (i), (ii) and (iii) are used for ethylene copolymerization in high temperature solution polymerization process.
The catalyst systems according to the present invention show excellent comonomer incorporation and thermal stability compared to their Zr-analogues if used for ethylene copolymerization in high temperature solution polymerization process.

Applications



[0060] The polymers made by the catalyst system of the invention are useful in all kinds of end articles such as pipes, films (cast or blown films), fibers, moulded articles (e.g. injection moulded, blow moulded, rotomoulded articles), extrusion coatings and so on.

[0061] The invention will now be illustrated by reference to the following non-limiting examples

Examples:


Methods


Al and Zr determination (ICP-method)



[0062] The elemental analysis of a catalyst was performed by taking a solid sample of mass, m. The catalyst was deactivated by substituting the inert storing conditions with ambient air, first passively through a needle and the actively by applying vacuum three times to the sampling container. Samples were dissolved to a volume V by first cooling on dry ice while adding freshly deionised water (5% of V) and nitric acid (HNO3, 65 %, 5 % of V). The samples were transferred in full to volumetric flasks using deionised water and rinsing the sampling containers. Hydrofluoric acid (HF, 40 %, 3 % of V) was added to the volumetric flasks and volume V obtained by addition of freshly deionised water. The prepared sample solutions were left to stabilise for two hours.

[0063] 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, 5 % HF in deionised 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 B and P in solutions of 5 % HNO3, 3 % HF in deionised water. Immediately before analysis the calibration is 'resloped' using the blank and 100 ppm Al, 50 ppm B, P standard, a quality control sample (20 ppm Al, 5 ppm B, P 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.

[0064] 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, m, and the dilution volume, V, into the software.

DSC analysis



[0065] The melting point (Tm) and crystallization temperature (Tc) were determined on a DSC200 TA instrument, by placing a 5-7 mg polymer sample, into a closed DSC aluminum pan, heating the sample from -30 °C to 180 °C at 10 °C/min, holding for 5 min at 180 °C, cooling from 180 °C to -30 °C, holding for 5 min at -30 °C, heating from -30 °C to 180 °C at 10 °C/min. The reported Tm is the maximum of the curve from the second heating scan and Tc is the maximum of the curve of the cooling scan.

Quantification of comonomer content by NMR spectroscopy



[0066] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0067] Quantitative 13C{1H} NMR spectra recorded in the molten-state using a Bruker Advance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for 1H and 13C respectively. All spectra were recorded using a 13C optimised 7 mm magic-angle spinning (MAS) probehead at 150°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.{klimke06, parkinson07, castignolles09, parkinson11} Standard single-pulse excitation was employed utilising the transient NOE at short recycle delays of 3s {pollard04, klimke06} and the RS-HEPT decoupling scheme{fillip05,griffin07}. A total of 1024 (1k) transients were acquired per spectrum. This setup was chosen due its high sensitivity towards low comonomer contents.

[0068] Quantitative 13C{1H} NMR spectra were processed, integrated and quantitative properties determined using custom spectral analysis automation programs. All chemical shifts are internally referenced to the bulk methylene signal (δ+) at 30.00 ppm {randall89}.

[0069] Characteristic signals corresponding to the incorporation of 1-octene were observed (randall89, liu01, qiu07) and all comonomer contents calculated with respect to all other monomers present in the polymer.

[0070] Characteristic signals resulting from isolated 1-octene incorporation i.e. EEOEE comonomer sequences, were observed. Isolated 1-octene incorporation was quantified using the integral of the signal at 38.32 ppm. This integral is assigned to the unresolved signals corresponding to both *B6 and *βB6B6 sites of isolated (EEOEE) and isolated double non-consecutive (EEOEOEE) 1-octene sequences respectively. To compensate for the influence of the two *βB6B6 sites the integral of the ββB6B6 site at 24.7 ppm is used:



[0071] Characteristic signals resulting from consecutive 1-octene incorporation, i.e. EEOOEE comonomer sequences, were also observed. Such consecutive 1-octene incorporation was quantified using the integral of the signal at 40.48 ppm assigned to the ααB6B6 sites accounting for the number of reporting sites per comonomer:



[0072] Characteristic signals resulting from isolated non-consecutive 1-octene incorporation, i.e. EEOEOEE comonomer sequences, were also observed. Such isolated non-consecutive 1-octene incorporation was quantified using the integral of the signal at 24.7 ppm assigned to the ββB6B6 sites accounting for the number of reporting sites per comonomer:



[0073] Characteristic signals resulting from isolated triple-consecutive 1-octene incorporation, i.e. EEOOOEE comonomer sequences, were also observed. Such isolated triple-consecutive 1-octene incorporation was quantified using the integral of the signal at 41.2 ppm assigned to the ααγB6B6B6 sites accounting for the number of reporting sites per comonomer:



[0074] With no other signals indicative of other comonomer sequences observed the total 1-octene comonomer content was calculated based solely on the amount of isolated (EEOEE), isolated double-consecutive (EEOOEE), isolated non-consecutive (EEOEOEE) and isolated triple-consecutive (EEOOOEE) 1-octene comonomer sequences:



[0075] Characteristic signals resulting from saturated end-groups were observed. Such saturated end-groups were quantified using the average integral of the two resolved signals at 22.84 and 32.23 ppm. The 22.84 ppm integral is assigned to the unresolved signals corresponding to both 2B6 and 2S sites of 1-octene and the saturated chain end respectively. The 32.23 ppm integral is assigned to the unresolved signals corresponding to both 3B6 and 3S sites of 1-octene and the saturated chain end respectively. To compensate for the influence of the 2B6 and 3B6 1-octene sites the total 1-octene content is used:



[0076] The ethylene comonomer content was quantified using the integral of the bulk methylene (bulk) signals at 30.00 ppm. This integral included the γ and 4B6 sites from 1-octene as well as the δ+ sites. The total ethylene comonomer content was calculated based on the bulk integral and compensating for the observed 1-octene sequences and end-groups:



[0077] It should be noted that compensation of the bulk integral for the presence of isolated triple-incorporation (EEOOOEE) 1-octene sequences is not required as the number of under and over accounted ethylene units is equal.

[0078] The total mole fraction of 1-octene in the polymer was then calculated as:



[0079] The total comonomer incorporation of 1-octene in weight percent was calculated from the mole fraction in the standard manner:

klimke06
Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2006;207:382.

parkinson07
Parkinson, M., Klimke, K., Spiess, H.W., Wilhelm, M., Macromol. Chem. Phys. 2007;208:2128.

parkinson 11
NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules, Chapter 24, 401 (2011)

pollard04
Pollard, M., Klimke, K., Graf, R., Spiess, H.W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004;37:813.

filip05
Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239

griffin07
Griffin, J.M., Tripon, C., Samoson, A., Filip, C., and Brown, S.P., Mag. Res. in Chem. 2007 45, S1, S198

castignolles09
Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373

zhou07
Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225

busico07
Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128

randall89
J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

qui07
Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007, 40, 6879

liu01
Liu, W., Rinaldi, P., Mclntosh, L., Quirk, P., Macromolecules 2001, 34, 4757

GPC: Molecular weight averages, molecular weight distribution, and polydispersity index (Mn, Mw, Mw/Mn)
Molecular weight averages (Mw, Mn), Molecular weight distribution (MWD) and its 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 16014-4:2003 and ASTM D 6474-99. A Waters GPCV2000 instrument, equipped with differential refractive index detector and online viscosimeter was used with 2 x GMHXL-HT and 1x G7000HXL-HT TSK-gel columns from Tosoh Bioscience and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 140 °C and at a constant flow rate of 1 mL/min. 209.5 µL of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 1 kg/mol to 12 000 kg/mol. Mark Houwink constants for PS, PE and PP used are as per ASTM D 6474-99. All samples were prepared by dissolving 0.5 - 4.0 mg of polymer in 4 mL (at 140 °C) of stabilized TCB (same as mobile phase) and keeping for max. 3 hours at max. 160°C with continuous gentle shaking prior sampling into the GPC instrument.


Chemicals



[0080] MAO was purchased from Chemtura and used as a 30 wt-% solution in toluene.
Triphenylcarbeniumtetrakis(pentafluorophenyl)borate (alternative name trityl tetrakis-(pentafluorophenyl)borate) (CAS 136040-19-2) was purchased from Acros (tritylBF20)
1-octene as co-monomer (99%, Sigma Aldrich) was dried over molecular sieves and degassed with nitrogen before use.

[0081] Heptane and decane (99.9 %, Sigma Aldrich) were dried under molecular sieves and degassed with nitrogen before use.

Catalyst Preparation Examples



[0082] For the purpose of this invention, the terms dimethylsilyl, dimethylsilanediyl and dimethylsililene are equivalent.

a) Complex preparation:



[0083] 
  1. 1. Complex 1-Hf: anti-dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butyl-phenyl)indenyl)hafnium dichloride (C1-Hf) was prepared in the same way as described in the patent application WO2013/007650A1 by using HfCl4 instead of ZrCl4. Thus, the yield of the anti-hafnocene isolated in this synthesis was 15%.
  2. 2. As Comparative Example Complex 1-Zr was used:
    anti-dimethylsilylene(2-methyl-4-phenyl-5-methoxy-6-tert-butyl-indenyl)(2-methyl-4-(4-tert-butyl-phenyl)indenyl)zirconium dichloride (C1-Zr) was prepared as described in the patent application WO2013/007650A1
  3. 3. Complex 2-Hf: anti-dimethylsilylene(2-methyl-4-(3,5-di-tert.-butylphenyl)-7-methyl-indenyl)(2-methyl-4-(4-tert-butyl-phenyl)indenyl)hafnium dichloride (C2-Hf) was prepared according to the following procedure:

3.a) 5-Bromo-2-methylbenzaldehyde



[0084] 



[0085] To a suspension of 344 g (2.58 mol, 1.5 eq.) of AlCl3 in 1100 cm3 of dichloromethane 206.8 g (1.72 mol) of 2-methylbenzaldehyde was added dropwise by vigorous stirring for 15 min at 5°C. The resulting mixture was stirred for 15 min at 5°C, and then 88.9 ml (276 g, 1.73mol) of bromine was added for 1 h at this temperature. The final mixture was additionally stirred for 6 h at room temperature and then poured on 2 kg of ice. The organic layer was separated, the aqueous layer was extracted with 2 x 200 ml of dichloromethane. The combined organic extract was washed by aqueous NaHCO3, dried over Na2SO4, and then evaporated to dryness to yield reddish liquid. This crude product was distilled in vacuum, b.p. 100-120°C/5 MM Hg. The obtained colorless liquid (which crystallizes at 5°C) was dissolved in 900 ml of n-hexane. Crystals precipitated from this solution for 3 days at 5°C were collected and dried in vacuum. On the evidence of NMR spectroscopy this mixture consists of 5-bromo-2-methylbenzaldehyde and 3-bromo-2-methylbenzaldehyde in ratio equal ca. 3 to 1. This mixture was recrystallized from 500 ml of hot n-hexane. White crystals precipitated at 5°C were collected, washed by150 ml of cold (+5°C) n-hexane, and dried in vacuum (∼60 °C/20 MM Hg) to give colorless liquid which crystallizes at room temperature. Yield 80.9 g (24%) of 5-bromo-2-methylbenzaldehyde including ca. 2% of 3-bromo-2-methylbenzaldehyde.
Anal. calc. for C8H7BrO: C, 48.27; H, 3.54. Found: C, 48.05; H, 3.41.
1H NMR (CDCl3): δ 10.21 (s, 1H, CHO), 7.90 (d, J = 2.2 Hz, 1H, 6-H), 7.57 (dd, J = 8.2 Hz, J = 2.3 Hz, 1H, 4-H), 7.14 (d, J = 8.2 Hz, 1H, 3-H), 2.61 (s, 3H, Me). 13C{1H} NMR (CDCl3): δ 191.0, 139.3, 136.4, 135.5, 134.1, 133.4, 120.0, 18.85.

3.b) 5-Bromo-2-methylbenzyl chloride



[0086] 



[0087] To a mixture of 80.9 g (0.406 mol) of 5-bromo-2-methylbenzaldehyde and 7.80 g (0.206 mol) of NaBH4 in 300 ml of THF 200 ml of methanol was added dropwise by vigorous stirring for 5 h at 0-5°C. This mixture was stirred overnight at room temperature and then added to 1 liter of cold water. The resulting mixture was acidified by 2 M HCI to pH∼1, and the formed (5-bromo-2-methylphenyl)methanol was extracted with 3 x 250 ml of dichloromethane. The combined organic extract was dried over Na2SO4 and evaporated to dryness. To the residue dissolved in 450 ml of dichloromethane 37 ml of SOCl2 was added dropwise at +5°C. The resulting solution was stirred overnight at room temperature, evaporated to dryness, the residue was dissolved in 500 ml CH2Cl2, and the obtained solution was washed with 500 ml of water. The organic layer was separated, the aqueous layer was additionally extracted with 2 x 100 ml of dichloromethane. The combined organic extract was passed through a short pad of silica gel 60 (40-63 um), the filtrate was evaporated to dryness, and the residue was dried in vacuum to yield 5-bromo-2-methylbenzyl chloride as a slightly yellowish liquid which was further used without an additional purification.
Anal. calc. for C8H8BrCl: C, 43.77; H, 3.67. Found: C, 43.89; H, 3.80.
1H NMR (CDCl3): δ 7.45 (d, J = 2.0 Hz, 1H, 3-H), 7.35 (dd, J = 8.2 Hz, J = 2.0 Hz, 1H, 5-H), 7.06 (d, J = 8.2 Hz, 1H, 6-H), 4.53 (s, 2H, CH2Cl), 2.36 (s, 3H, Me). 13C{1H} NMR (CDCl3): δ 137.5, 136.0, 132.4, 132.3, 131.7, 119.5, 43.8, 18.3.

3.c) 3-(5-Bromo-2-methylphenyl)-2-methylpropanoyl chloride



[0088] 



[0089] In a three-necked round-bottom flask 9.50 g (0.413 mol) of sodium metal was dissolved in 260 ml of dry ethanol. To the resulting solution 72.0 g (0.413mol) of diethyl methylmalonate was added. This mixture was stirred for 15 min, then 5-bromo-2-methylbenzyl chloride prepared above was added by vigorous stirring at such a rate as to maintain gentle reflux. This mixture was refluxed for an additional 2 h and then cooled to room temperature. A solution of 85 g of KOH in 250 ml of water was added. The resulting mixture was refluxed for 4 h to saponificate the ester formed. Ethanol and water were distilled off until temperature reached 95°C, and 1000 ml of water and then 12 M HCI (to pH 1) were added to the residue. The precipitated substituted methylmalonic acid was filtered off, washed with 3 x 100 ml of water, and then decarboxylated at 180°C to give 3-(5-bromo-2-methylphenyl)-2-methylpropanoic. A mixture of this acid and 105 ml of SOCl2 was stirred at room temperature for 24 hours. After evaporation of an excess of thionyl chloride, the residue was distilled in vacuum to give 85.3 g (75% from 5-bromo-2-methylbenzaldehyde) 3-(5-bromo-2-methylphenyl)-2-methylpropanoyl chloride, b.p. 115°C/1 mm Hg.
Anal. calc. for C11H12BrCIO: C, 47.94; H, 4.39. Found: C, 48.12; H, 4.45.
1H NMR (CDCl3): δ 7.28-7.26 (m, 2H, 6,4-H in Ph), 7.03 (d, J = 7.7 Hz, 1H, 3-H in Ph), 3.18 (dd, J = 13.8 Hz, J = 5.9 Hz, 1H, ArCHH'), 3.10 (m, 1H, CHCOCI), 2.65 (dd, J = 13.8 Hz, J = 8.1 Hz, 1H, ArCHH'), 2.28 (s, 3H, ArMe), 1.29 (d, J = 6.7 Hz, 3H, CHMe). 13C{1H} NMR (CDCl3): δ 176.9, 138.1, 135.2, 132.4, 132.2, 130.0, 119.5, 51.8, 36.1, 19.0, 16.6.

3.d) 2,4-dimethyl-7-Bromo-indan-1-one



[0090] 



[0091] To a stirred suspension of 49.5 g (0.371 mol, 1.2 eq.) of AlCl3 in 300 ml of dichloromethane a solution of 85.3 g (0.310 mol) of 3-(5-bromo-2-methylphenyl)-2-methylpropanoyl chloride in 50 ml of dichloromethane was added dropwise. This mixture was stirred overnight at room temperature and then poured on 500 g of ice. The organic layer was separated, and the aqueous layer was additionally extracted with 3 x 75 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3, dried over K2CO3, passed through a short pad of silica gel, and then evaporated to dryness. This procedure gave 74.0 g (>99%) of 2,4-dimethyl-7-bromo-indan-1-one as a light-orange liquid, solidified at room temperature, which was further used without an additional purification.
Anal. calc. for C11H11BrO: C, 55.25; H, 4.64. Found: C, 55.40; H, 4.81.
1H NMR (CDCl3): δ 7.41 (d, J = 8.0 Hz, 1H, 6-H in indan-1-one), 7.21 (d, J = 8.0 Hz, 1H, 5-H in indan-1-one), 3.24 (dd, J = 17.3 Hz, J = 7.9 Hz, 3-H in indan-1-one), 2.73 (m, 1H, 2-H in indan-1-one), 2.54 (dd, J = 17.3 Hz, J = 4.1 Hz, 1H, 3'-H in indan-1-one), 2.29 (s, 3H, 4-Me in indan-1-one), 1.33 (d, J = 7.3 Hz, 3H, 2-Me in indan-1-one). 13C{1H} NMR (CDCl3): δ 207.0, 155.0, 135.6, 134.8, 133.1, 132.3, 116.5, 42.4, 33.0, 17.4, 16.4.

3.e) 1-methoxy-2,4-dimethyl-7-Bromoindane



[0092] 



[0093] To a mixture of 74.0 g (0.310 mol) of 2,4-dimethyl-7-bromoindan-1-one and 5.86 g (0.155 mol) of NaBH4 in 310 ml of THF 155 ml of methanol was added dropwise by vigorous stirring for 5 h at 0-5°C. This mixture was stirred overnight at room temperature and then added to 1 liter of cold water. The resulting mixture was acidified by 2 M HCI to pH∼5, and then it was extracted with 3 x 250 ml of dichloromethane. The combined organic extract was dried over Na2SO4 and evaporated. The resulting orange oil was dissolved in 600 ml of DMSO, then 70 g (1.25 mol) of KOH and 88 g (0.62 mol) of Mel were added to the resulting solution. This mixture was stirred for 3 h at ambient temperature. Further on, the solution was decanted from an excess of KOH, the latter was washed with 2 x 200 ml of dichloromethane, and 2000 cm3 of water was added to the combined solution. The organic layer was separated, and the aqueous layer was additionally extracted with 2 x 100 ml of dichloromethane. The combined organic extract was additionally washed with 5 x 1500 ml of water, dried over Na2SO4, and evaporated to dryness. Fractional distillation of the residue in vacuum gave 72.3 g (92%) of 1-methoxy-2,4-dimethyl-7-bromoindane, b.p. 107-112°C/5 mm Hg.
Anal. calc. for C12H15BrO: C, 56.49; H, 5.93. Found: C, 56.43; H, 6.02.
1H NMR (CDCl3): δ 7.26 (d, J = 8.6 Hz, 1H, 6-H of anti-isomer), 7.24 (d, J = 8.6 Hz, 1H, 6-H of syn-isomer), 6.94 (d, J = 8.6 Hz, 1H, 5H of anti-isomer), 6.92 (d, J = 8.6 Hz, 1H, 5H of syn-isomer), 4.57 (d, J = 5.5 Hz, 1H, 1-H of syn-isomer), 4.42 (m, 1H, 1-H of anti-isomer), 3.53 (s, 3H, OMe of syn-isomer), 3.45 (s, 3H, OMe of anti-isomer), 3.27 (dd, J = 16.6 Hz, J = 7.3 Hz, 1H, 3-H of anti-isomer), 2.87 (dd, J = 15.7 Hz, J = 7.5 Hz, 1H, 3-H of syn-isomer), 2.68 (dd, J = 15.7 Hz, J = 9.8 Hz, 1H, 3'-H of syn-isomer), 2.57 (m, 1H, 2-H of anti-isomer), 2.44 (m, 1H, 2-H of syn-isomer), 2.39 (dd, J = 16.6 Hz, J = 1.4 Hz, 3'-H of anti-isomer), 2.18 (s, 6H, 4-Me of syn- and anti-isomers), 1.26 (d, J = 6.9 Hz, 3H, 2-Me of syn-isomer), 1.05 (d, J = 7.3 Hz, 2-Me of anti-isomer).

3.f) 2,7-dimethyl-4-(3,5-Di-tert-butylphenyl)-1H-indene



[0094] 



[0095] To a solution of 3,5-di-tert-butylphenylmagnesium bromide obtained from 59.0 g (0.219 mol) of 1-bromo-3,5-di-tert-butylbenzene and 9.31 g (0.383 mol, 1.75 eq.) of magnesium turnings in 550 ml of THF 1.0 g (1.28 mmol, 0.71 mol.%) NiCl2(PPh3)IPr and a solution of 46.1 g (0.181 mol) of 1-methoxy-2,4-dimethyl-7-bromoindane in 50 ml of THF were added. A moderate reflux occurs approximately after one minute which ceased after the following 30 sec. This mixture was refluxed additionally for 1 h. Finally, 50 ml of water was added, and the main part of THF was distilled off on rotary evaporator. Further on, 500 ml of dichloromethane and 500 ml of 2 M HCI were added to the residue. 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 yellowish oil. To a solution of this oil in 700 ml of toluene 0.8 g of TsOH was added. The resulting mixture was refluxed using Dean-Stark head for 20 min, one more portion (0.8 g) of TsOH was added, and the mixture was refluxed for another 20 min. The resulting mixture cooled to room temperature was washed with 200 ml of 10% aqueous NaHCO3. The organic layer was separated, the aqueous layer was additionally extracted with 2 x 100 ml of dichloromethane. The combined organic extract was evaporated to dryness, a solution of the residue in 500 ml of dichloromethane was passed through a short pad of silica gel 60 (40-63 um) and then evaporated to dryness to give yellowish crystalline material. This crude product was recrystallization from 200 ml of hot n-hexane. Crystals precipitated from this solution at 5°C were collected and dried in vacuum. This procedure gave 49.8 g of white microcrystalline product. The mother liquor was evaporated to dryness, and the main part of 1,3-di-tert-butylbenzene was distilled off at elevated temperature on rotary evaporator. The residue was then re-crystallized from 80 ml of hot n-hexane. This gave additional 6.21 g of the product. Thus, the total yield of 2,7-dimethyl-4-(3,5-di-tert-butylphenyl)-1H-indene was 56.0 g (93%). Anal. calc. for C25H32: C, 90.30; H, 9.70. Found: C, 90.44; H, 9.89.
1H NMR (CDCl3): δ (t, J = 1.8 Hz, 1H, 4-H in C6H3tBu2), 7.33 (d, J = 1.8 Hz, 2H, 2,6-H in C6H3tBu2), 7.24 (d, J = 7.7 Hz, 1H, 5-H in indenyl), 7.01 (d, J = 7.7 Hz, 1H, 6-H in indenyl), 6.67 (m, 1H, 3-H in indenyl), 3.27 (s, 2H, 1-H in indenyl), 2.37 (s, 3H, 7-Me in indenyl), 2.16 (s, 3H, 2-Me in indenyl), 1.37 (s, 18H, tBu). 13C{1H} NMR (CDCl3): δ 150.5, 146.0, 143.1, 142.4, 140.2, 133.0, 131.3, 127.2, 126.7, 125.2, 123.3, 120.4, 42.0, 34.9, 31.5, 18.5, 17.0.

3.g) [2-methyl-4-(4-tert-Butylphenyl)-1H-inden-1-yl](chloro)dimethylsilane



[0096] 



[0097] To a solution of 9.84 g (37.5 mmol) of 2-methyl-7-(4-tert-butylphenyl)-1H-indene in a mixture of 200 ml of toluene and 10 ml of THF 15.0 ml (37.5 mmol) of 2.5 M nBuLi in hexanes was added at room temperature. The resulting solution was stirred for 2 h at 60°C, then cooled to 0°C, and 24.0 g (186 mmol, 5 eq.) of dichlorodimethylsilane was added in one portion. The formed solution was refluxed for 1 h, then evaporated to ca. 150 ml, and filtered through glass frit (G3). The precipitate was additionally washed by 2 x 30 ml of toluene. The combined filtrate was evaporated to dryness to give [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl](chloro)dimethylsilane as viscous yellowish oil which was further used without an additional purification.
Anal. calc. for C22H27CISi: C, 74.44; H, 7.67. Found: C, 74.75; H, 7.89.
1H NMR (CDCl3): δ 7.54 (m, 4H, 2,3,5,6-H in C6H4tBu), 7.49 (d, J = 7.5 Hz, 1H, 7-H in indenyl), 7.35 (d, J = 7.3 Hz, 5-H in indenyl), 7.24 (t, J = 7.5, 6-H in indenyl), 6.91 (m, 1H, 3-H in indenyl), 3.72 (s, 1H, 1-H in indenyl), 2.33 (s, 3H, 2-Me in indenyl), 1.45 (s, 9H, tBu), 0.49 (s, 3H, SiMeMe'), 0.24 (s, 3H, SiMeMe'). 13C{1H} NMR (CDCl3): δ 149.7, 146.1, 143.1, 142.9, 138.1, 134.1, 128.5, 126.7, 126.1, 125.3, 123.3, 122.3, 50.4, 34.5, 31.4, 17.6, 1.0, 0.7.

3.h) A mixture of [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl][2,7-dimethyl-4-(3,5-di-tert-butylphenyl)-1H-inden-1-yl]dimethylsilane and [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl][2,4-dimethyl-7-(3,5-di-tert-butylphenyl)-1H-inden-1-yl]dimethylsilane



[0098] 



[0099] To a solution of 12.5 g (37.5 mmol) of 2,7-dimethyl-4-(3,5-di-tert-butylphenyl)-1H-indene in 200 ml of ether 15.0 ml (37.5 mmol) of 2.5 M nBuLi in hexanes was added in one portion at - 40°C. The resulting mixture was stirred overnight at room temperature, then cooled to -40°C, and 1.68 g (18.8 mmol, 0.5 eq.) of CuCN was added. The formed mixture was stirred for 1 h at -20°C, then cooled to -40°C, and then a solution 13.3 g (37.5 mmol) of [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl](chloro)dimethylsilane in 200 ml of ether was added in one portion. Further on, this mixture was stirred overnight at ambient temperature, and then 0.5 ml of water was added. The formed mixture was filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by dichloromethane. The combined organic elute was evaporated to dryness and dried in vacuum. This procedure gave 24.0 g (36.9 mmol, 98%) of a mixture of [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl][2,7-dimethyl-4-(3,5-di-tert-butylphenyl)-1H-inden-1-yl]dimethylsilane and [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl][2,4-dimethyl-7-(3,5-di-tert-butylphenyl)-1H-inden-1-yl]dimethylsilane (>90% purity by NMR spectroscopy; ca. 1:1 mixture of the regioisomers) as yellowish glass which was further used without an additional purification.
Anal. calc. for C47H58Si: C, 86.71; H, 8.98. Found: C, 86.92; H, 9.12.
1H NMR (CDCl3): δ 7.52-7.36 (m), 7.31-6.93 (m), 6.83 (s), 6.80 (s), 6.77 (s), 6.74 (s), 6.73 (s), 6.61 (s), 6.59 (s), 4.41 (s), 4.32 (s), 4.00 (s), 3.90 (s), 3.74 (s), 3.73 (s), 3.11 (s), 2.94 (s), 2.46 (s), 2.45 (s), 2.39 (s), 2.30 (s), 2.29 (s), 2.28 (s), 2.24 (s), 2.22 (s), 2.10 (s), 1.91 (s), 1.81 (s), 1.39 (s), 1.38 (s), 1.37 (s), 1.35 (s), 1.33 (s), 1.29 (s), -0.17 (s), -0.26 (s), -0.26 (s), - 0.59 (s), -0.62 (s), -0.68 (s), -0.69 (s).

3.i) Dimethylsilanediyl[2-methyl-4-(4-tert-butylphenyl)inden-1-yl][2,7-dimethyl-4-(3,5-di-tert-butylphenyl)inden-1-yl]hafnium dichloride



[0100] 



[0101] To a solution of 24.0 g (36.9 mmol, >90% purity) of a mixture of [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl][2,7-dimethyl-4-(3,5-di-tert-butylphenyl)-1H-inden-1-yl]dimethylsilane and [2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl][2,4-dimethyl-7-(3,5-di-tert-butylphenyl)-1H-inden-1-yl]dimethylsilane (as described above) in 250 ml of ether 29.5 ml (73.8 mmol) of 2.5 M "BuLi in hexanes was added in one portion at -20°C. This mixture was stirred overnight at room temperature, then cooled to -60°C, and 11.8 g (36.9 mmol) of HfCl4 was added. The resulting mixture was stirred for 24 h, then filtered through glass frit (G4), and the precipitate was washed with 30 ml of ether. On the evidence of NMR spectroscopy, this precipitate was pure syn-zirconocene while the filtrate included a mixture of three isomeric complexes, i.e. the desired anti-hafnocene (55%), anti-hafnocene (25%), and one more isomeric ansa-hafnocene of unknown structure (20%). The precipitate was dissolved in 100 ml of hot toluene, and the formed suspension was filtered through glass frit (G4). The filtrate was evaporated to ca. 30 ml and then heated to obtain clear solution. Crystals precipitated from this solution at room temperature were collected, washed by 15 ml of cold n-hexane, and then dried in vacuum. This procedure gave 4.30 g (13%) of pure syn-complex. The mother liquor was evaporated to ca. 5 ml, and 80 ml of n-hexane was added. Crystals precipitated from the formed solution at room temperature were collected and dried in vacuum. This procedure gave 1.38 g (4%) of syn-complex contaminated with ca. 8% of anti-isomer. The mother liquor was evaporated to dryness, the residue was re-crystallized from 40 ml of hot n-hexane. Crystals precipitated from this solution after 4 h at room temperature were collected and dried in vacuum to give 0.28 g (1%) of the desired anti-complex contaminated with ca. 5% of syn-isomer. Additional crystalline material was obtained from the mother liquor after 3 days at room temperature. These crystals were collected and dried in vacuum to give 1.31 g (4%) of anti-complex of ca. 93% purity (i.e. 7% of unknown impurity). Assignment in NMR spectra was made using the following abbreviations: L1 for 2-methyl-4-(4-tert-butylphenyl)-1H-inden-1-yl and L2 for 2,7-dimethyl-4-(3,5-di-tert-butylphenyl)-1H-inden-1-yl.
anti-Hafnocene.
Anal. calc. for C47H56Cl2HfSi: C, 62.83; H, 6.28. Found: C, 62.87; H, 6.39.
1H NMR (CDCl3): δ 7.69 (d, J = 8.5 Hz, 1H, 7-H in L1), 7.58-7.56 (m, 2H, 2,6-H in C6H4tBu), 7.48 (d, J = 1.1 Hz, 2H, 2,6-H in C6H3tBu2), 7.46-7.44 (m, 2H, 3,5-H in C6H4tBu), 7.40-7.36 (m, 2H, 5-H in L1 and 4-H in C6H3tBu2), 7.31 (d, J = 7.1 Hz, 1H, 5-H in L2), 7.09 (dd, J = 8.5 Hz, J = 7.3 Hz, 1H, 6-H in L1), 7.01-6.94 (m, 3H, 3-H in L2, 3-H in L1, 6-H in L2), 2.68 (s, 3H, 7-Me in L2), 2.45 (s, 3H, 2-Me in L2), 2.24 (s, 3H, 2-Me in L1), 1.38 (s, 3H, SiMeMe'), 1.35 (s, 9H, tBu in C6H4tBu), 1.32 (s, 18H, tBu in C6H3tBu2), 1.29 (s, 3H, SiMeMe').
syn-Hafnocenes.
Anal. calc. for C47H56Cl2HfSi: C, 62.83; H, 6.28. Found: C, 62.98; H, 6.44.
1H NMR (CDCl3): δ 7.79 (d, J = 8.7 Hz, 1H, 7-H in L1), 7.51-7.49 (m, 2H, 2,6-H in C6H4tBu), 7.45-7.43 (m, 4H, 3,5-H in C6H4tBu and 2,6-H in C6H3tBu2), 7.38 (s, 4-H in C6H3tBu2), 7.16 (d, J = 6.9 Hz, 1H, 5-H in L1), 7.11 (d, J = 6.9 Hz, 1H, 5-H in L2), 6.88-6.86 (m, 2H, 3-H in L2 and 6-H in L1), 6.84 (s, 1H, 3-H in L1), 6.77 (d, J = 6.9 Hz, 1H, 6-H in L2), 2.77 (s, 3H, 7-Me in L2), 2.61 (s, 3H, 2-Me in L1), 2.61 (s, 3H, 2-Me in L2), 1.39 (s, 3H, SiMeMe'), 1.35 (s, 9H, tBu in C6H4tBu), 1.34 (s, 18H, tBu in C6H3tBu2), 1.28 (s, 3H, SiMeMe').

b) Catalyst system


Inventive Example 1:


Anti-Complex 1-Hf was used for preparing Inventive Catalyst system ICS-1



[0102] Inside the glovebox, 97,85 mg of complex 1-Hf was mixed with 5 ml MAO in a septum bottle and the solution was stirred for 60 minutes and then 105.15 mg of tritylBF20 was added. The mixture was left to react overnight at room temperature inside the glovebox.

Inventive Example 2:


Anti-Complex 2-Hf was used for preparing Inventive Catalyst system ICS-2



[0103] Inside the glovebox, 102,65 mg of complex 2-Hf was mixed with 5 ml MAO in a septum bottle and the solution was stirred for 60 minutes and then 105.15 mg of tritylBF20 was added. The mixture was left to react overnight at room temperature inside the glovebox.

Comparative Example 1


Anti-Complex 1-Zr was used for preparing Inventive Catalyst system CCS-1



[0104] Inside the glovebox, 88.03 mg of complex 1-Zr was mixed with 5 ml MAO in a septum bottle and the solution was stirred for 60 minutes and then 105.15 mg of tritylBF20 was added. The mixture was left to react overnight at room temperature inside the glovebox.
Table 1: Catalyst System Composition
cat.MetalloceneAI/M1B/M2
  [mol/mol][mol/mol]
CE-1 C1-Zr 200 1.0
IE-1 C1-Hf 200 1.0
IE-2 C2-Hf 200 1.0
1 AI/M molar ratio in catalyst, with M being Zr or Hf
2 B/M molar ratio in catalyst, with M being Zr or Hf

Polymerization



[0105] In Examples IE-1, IE-1 and CE-1 the polymerization reaction were carried out in Parallel Polymerization Reactors (PPR) (provided by Symyx) (10 mL Reactor Volume) at 190°C

Pre-catalyst preparation procedure (ternary system MC/MAO/trityIBF20):



[0106] Inside a glovebox, desired amount of metallocene was mixed with 5 ml MAO solution in a septum bottle and the solution was stirred for 60 minutes and then 105.15 mg of tritylBF20 was added. The mixture was left to react overnight at room temperature inside the glovebox. All catalysts were prepared according to the below recipe (Table 2).
Table 2: pre-catalyst preparation of the selected metallocenes.
ExampleCE-1IE-1IE-2
C1-Zr [mg] 88.03    
C1-Hf [mg]   97.85  
C2-Hf [mg]     102.65
MAO [mg] 1320 1320 1320
TritylBF20 [mg] 105.15 105.15 105.15
AI/M1 200 200 200
B/M2 1.0 1.0 1.0
MAO was used as 30% solution in toluene
1 Al/M molar ratio in catalyst, with M being Zr or Hf
2 B/M molar ratio in catalyst, with M being Zr or Hf

Polymerization procedure for PPR:



[0107] The selected catalysts were screened at 190°C, with polymerization solvent decane, at one MAO/M ratio (200), one B/M ratio (1.0) and 1-octene/ethylene ratios of 1 wt/wt (C8/C2 = 1.0 wt/wt). (M being Hf or Zr)
Stock solutions of the metallocenes and co-catalysts (MAO and Borate) were prepared to be used for each set of reactions.

[0108] The vessels were loaded inside a glovebox utilizing a 3-axis liquid handling robot. A preweighed glass vial with stirring paddles was sealed and purged with nitrogen. A volume of about 4 mL of corresponding solvent (decane) was filled in each PPR reactor. Then, adequate amount of triethyl aluminium (TEA) as scavenger was added, along with precise volume of octene as co-monomer at room temperature. The ethylene pressure was set to 10 × 105 Pa (10 bar) to check any leaks. Then, the temperature and pressure had been increased to the set value (T = 190°C and 24 × 105 Pa (24 bar)) and once the steady state was reached, the corresponding volume of pre-activated catalyst as a slurry in toluene had been injected in the reactor to start the polymerization under mechanical stirring. The run was quenched with CO2 after the set amount of ethylene uptake had been reached (20 min as a maximum run time).The glass vials had been dried by vacuum centrifuge and weighed.
Table 3: PPR experiments conditions for ethylene/1-octene solution co-polymerization
 CCS-1ICS-1ICS-2
Catalyst system [µl] 51.8 116.5 111.1
Used 1-octene [g] 0.45 0.45 0.45
Decane [g] 3.14 3.10 3.10
TEAL Scavenger [µmol] 15.0 15.0 15.0
Table 4: PPR experiments results for ethylene/1-octene solution co-polymerization
ExampleMCComplex amount [mg]Quench time [min]1-octene incorporation [wt% NMR]
CE-1 Complex 1-Zr 0.08 9.1 24.2
IE-1 Complex 1-Hf 0.20 9.7 31.5
IE-2 Complex 2-Hf 0.20 13.2 32.2


[0109] As can be seen from Table 4 the Hf-containing catalyst systems lead to clearly higher comonomer incorporation than the Zr-analogue.


Claims

1. Process for the preparation of an ethylene copolymer comprising polymerizing ethylene and a C4-10-alpha-olefin comonomer in a high temperature solution process at a temperature greater than 100°C in the presence of a homogeneous catalyst system comprising:

(i) a metallocene complex of formula (I)

wherein

X M is Hf is a sigma ligand,

L is a bridge of the formula -SiR82-, wherein each R8 is independently a C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl

n is 0, 1 or 2

R1 and R1' are the same or can be different and can be a linear or branched C1-C6-alkyl group,

R2 and R2' are the same or are different and are a CH2-R9 group, with R9 being H or linear or branched C1-C6-alkyl group

R5 and R5' are the same and are H, or R5 and R5' are different and can be H or a OR group, wherein R is a C1-C6-alkyl group

R6 and R6 are the same or are different and can be H or a C(R10)3 group, with R10 being the same or different and R10 can be H or a linear or branched C1-C6-alkyl group , and

R7 and R7' can be the same or are different and can be H or a linear or branched C1-C6-alkyl group

(ii) an aluminoxane cocatalyst

(iii) a boron containing cocatalyst and

(iv) optionally an aluminium alkyl compound.


 
2. Process according to any preceding claim, wherein the polymerization is performed

a) at a polymerization temperature of at least 110°C,

b) a pressure in the range of 10 × 105 to 100 × 105 Pa (10 to 100 bar) and

c) in a liquid hydrocarbon solvent selected from the group of C5-12-hydrocarbons, which may be unsubstituted or substituted by C1-4 alkyl group


 
3. Process according to any preceding claim, wherein in the formula (I)
M is Hf,
X which may be the same or different, and is a hydrogen atom, a halogen atom, a R11, OR11, OSO2CF3, OCOR11, SR11, NR112 or PR112 group, wherein R11 is a linear or branched, cyclic or acyclic, C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C6-C20-aryl, C7-C20-alkylaryl or C7-C20-arylalkyl radical; optionally containing heteroatoms belonging to groups 14-16 or is SiR113, SiHR112 or SiH2R11,
L is a bridge of the formula -SiR82-, wherein both R8 are the same C1-C10-hydrocarbyl or C6-C10-aryl group,
R1 and R1' are the same and are a linear or branched C1-C6-alkyl group,
n is 0, 1 or 2, with the proviso that n is not 0 for at least one of the phenyls groups,
R2 and R2' are the same and are a CH2-R9 group, with R9 being H or linear or branched C1-C4-alkyl group
R5 and R5' are the same and are H, or R5 and R5' are different and can be H a OR group, wherein R is a C1-C4-alkyl group
R6 and R6' are the same or are different and can be H or a C(R10)3 group, with R10 being the same or different and R10 can be a linear or branched C1-C4-alkyl group,
R7 and R7' can be the same or are different and can be H or a linear or branched C1-C4-alkyl group.
 
4. Process according to any preceding claim, wherein in the formula (I)
M is Hf,
X is independently a hydrogen atom, a halogen atom, C1-6-alkoxy group or an R11 group, wherein R11 a C1-6-alkyl, phenyl or benzyl group,
L is a bridge of the formula -SiR82-, wherein both R8 are the same C1-C10-hydrocarbyl or C6-C10-aryl group,
R1 and R1' are the same and are a linear or branched C1-C6-alkyl group,
n is 0, 1 or 2, with the proviso that n is 1 for at least one of the phenyls groups,
R2 and R2' are the same and are a CH2-R9 group, with R9 being H or linear or branched C1-C4-alkyl group
R5 and R5' are the same and are H, or R5 and R5' are different and can be a H or a OR group, wherein R is a C1-C4-alkyl group
R6 and R6' are the same or are different and can be H or a C(R10)3 group, with R10 being the same or different and R10 can be a linear or branched C1-C4-alkyl group, whereby at least one of the ligands is unsubstituted in position 5 and 6.
R7 and R7' can be the same or are different and can be H or a linear or branched C1-C4-alkyl group
 
5. Process according to any preceding claim, wherein the metallocene of formula (I) is selected from
racemic dimethylsilyl[(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)-(2-methyl-4-(4'-tertbutylphenyl)-inden-1-yl)] hafnium dichloride or dimethyl and
racemic dimethylsilyl[(2-methyl-4-(3',5'-di-tert-butylphenyl)-7-methylinden-1-yl)-(2-methyl-4-(4-tert-butylphenyl)-inden-1-yl)] hafnium dichloride or dimethyl
either in their syn or anti configuration.
 
6. Process according to any preceding claim, wherein the catalyst system is a non-supported catalyst system obtainable by contacting the metallocene of formula (I) as a solid or as a solution with the cocatalyst(s) previously dissolved in an aromatic solvent, or being obtainable by sequentially adding the catalyst components to the polymerization medium.
 
7. Process according to any preceding claim, wherein the catalyst system comprises an aluminium alkyl compound.
 
8. Process as claimed in any preceding claim wherein said aluminoxane cocatalyst is MAO.
 
9. Process as claimed in any preceding claim wherein said boron containing cocatalyst comprises an anion of formula:

        (Z)4B-     (III)

where Z is an optionally substituted phenyl derivative, said substituent being a halo-C1-6-alkyl or halo group, preferably triphenylcarbeniumtetrakis(pentafluorophenyl) borate,
N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N- dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, or N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.
 
10. Process as claimed in any preceding claim wherein said aluminium alkyl compound is a compound of the formula (VIII) AIR3, with R being a linear or branched C2-C8-alkyl group.
 


Ansprüche

1. Verfahren zur Herstellung eines Ethylen-Copolymers, das das Polymerisieren von Ethylen und einem C4-10-alpha-Olefin-Comonomer in einem Hochtemperatur-Lösungsverfahren bei einer Temperatur von mehr als 100 °C in der Gegenwart eines homogenen Katalysatorsystems umfasst, welches umfasst:

(i) einen Metallocen-Komplex der Formel (I)

wobei

M Hf ist,

X ein Sigmaligand ist,

L eine Brücke der Formel -SiR82- ist, wobei jedes R8 unabhängig ein C1-C20-Hydrocarbyl, Tri(C1-C20-alkyl)silyl, C6-C20-Aryl, C7-C20-Arylalkyl oder C7-C20-Alkylaryl ist,

n 0, 1 oder 2 ist,

R1 und R1' gleich sind oder unterschiedlich sein können und eine lineare oder verzweigte C1-C6-Alkylgruppe sein können,

R2 und R2' gleich sind oder unterschiedlich sind und eine CH2-R9-Gruppe sind, wobei R9 H oder eine lineare oder verzweigte C1-C6-Alkylgruppe ist,

R5 und R5' gleich sind und H sind, oder R5 und R5' unterschiedlich sind und H oder eine OR-Gruppe sein können, wobei R eine C1-C6-Alkylgruppe ist,

R6 und R6' gleich sind oder unterschiedlich sind und H oder eine C(R10)3-Gruppe sein können, wobei R10 gleich oder unterschiedlich ist und R10 H oder eine lineare oder verzweigte C1-C6-Alkylgruppe sein kann, und

R7 und R7' gleich sein können oder unterschiedlich sind und H oder eine lineare oder verzweigte C1-C6-Alkylgruppe sein können,

(ii) einen Aluminoxan-Cokatalysator,

(iii) einen borhaltigen Cokatalysator, und

(iv) gegebenenfalls eine Aluminium-Alkyl-Verbindung.


 
2. Verfahren nach einem vorstehenden Anspruch, wobei das Polymerisieren durchgeführt wird

a) bei einer Polymerisationstemperatur von mindestens 110 °C,

b) einem Druck im Bereich von 10 x 105 bis 100 x 105 Pa (10 bis 100 Bar), und

c) in einem flüssigen Kohlenwasserstoff-Lösungsmittel, ausgewählt aus der Gruppe von C5-12-Kohlenwasserstoffen, die unsubstituiert oder durch eine C1-4-Alkylgruppe substituiert sein können


 
3. Verfahren nach einem vorstehenden Anspruch, wobei in der Formel (I)
M Hf ist,
X, das gleich oder unterschiedlich sein kann und ein Wasserstoffatom, ein Halogenatom, eine R11-, OR11-, OSO2CF3-, OCOR11-, SR11-, NR112- oder PR112-Gruppe ist, wobei R11 ein linearer oder verzweigter, cyclischer oder acyclischer C1-C20-Alkyl-, C2-C20-Alkenyl-, C2-C20-Alkinyl-, C6-C20-Aryl-, C7-C20-Alkylaryl- oder C7-C20-Arylalkylrest ist; gegebenenfalls Heteroatome enthält, die zu den Gruppen 14-16 gehören, oder SiR113, SiHR112 oder SiH2R11 ist,
L eine Brücke der Formel -SiR82- ist, wobei beide R8 die gleiche C1-C10-Hydrocarbyl- oder C6-C10-Arylgruppe sind,
R1 und R1' gleich sind und eine lineare oder verzweigte C1-C6-Alkylgruppe sind,
n 0, 1 oder 2 ist, mit der Maßgabe, dass n bei mindestens einer der Phenylgruppen nicht 0 ist,
R2 und R2' gleich sind und eine CH2-R9-Gruppe sind, wobei R9 H oder eine lineare oder verzweigte C1-C4-Alkylgruppe ist,
R5 und R5' gleich sind und H sind, oder R5 und R5' unterschiedlich sind und H eine OR-Gruppe sein können, wobei R eine C1-C4-Alkylgruppe ist,
R6 und R6' gleich sind oder unterschiedlich sind und H oder eine C(R10)3-Gruppe sein können, wobei R10 gleich oder unterschiedlich ist und R10 eine lineare oder verzweigte C1-C4-Alkylgruppe sein kann,
R7 und R7' gleich sein können oder unterschiedlich sind und H oder eine lineare oder verzweigte C1-C4-Alkylgruppe sein können.
 
4. Verfahren nach einem vorstehenden Anspruch, wobei in der Formel (I)
M Hf ist,
X unabhängig ein Wasserstoffatom, ein Halogenatom, C1-6-Alkoxygruppe oder eine R11-Gruppe ist, wobei R11 eine C1-6-Alkyl-, Phenyl- oder Benzylgruppe ist,
L eine Brücke der Formel -SiR82- ist, wobei beide R8 die gleiche C1-C10-Hydrocarbyl- oder C6-C10-Arylgruppe sind,
R1 und R1' gleich sind und eine lineare oder verzweigte C1-C6-Alkylgruppe sind,
n 0, 1 oder 2 ist, mit der Maßgabe, dass n bei mindestens einer der Phenylgruppen 1 ist,
R2 und R2' gleich sind und eine CH2-R9-Gruppe sind, wobei R9 H oder eine lineare oder verzweigte C1-C4-Alkylgruppe ist,
R5 und R5' gleich sind und H sind, oder R5 und R5' unterschiedlich sind und eine H oder eine OR-Gruppe sein können, wobei R eine C1-C4-Alkylgruppe ist,
R6 und R6' gleich sind oder unterschiedlich sind und H oder eine C(R10)3-Gruppe sein können, wobei R10 gleich oder unterschiedlich ist und R10 eine lineare oder verzweigte C1-C4-Alkylgruppe sein kann,
wobei mindestens einer der Liganden an Position 5 und 6 unsubstituiert ist.
R7 und R7' gleich sein können oder unterschiedlich sind und H oder eine lineare oder verzweigte C1-C4-Alkylgruppe sein können
 
5. Verfahren nach einem vorstehenden Anspruch, wobei das Metallocen der Formel (I) ausgewählt ist aus
racemischem Dimethylsilyl[(2-methyl-4-phenyl-5-methoxy-6-tert-butylinden-1-yl)-(2-methyl-4-(4'-tertbutylphenyl)-inden-1-yl)]hafniumdichlorid oder -dimethyl, und
racemischem Dimethylsilyl[(2-methyl-4-(3',5'-di-tert-butylphenyl)-7-methylinden-1-yl)-(2-methyl-4-(4-tert-butylphenyl)-inden-1-yl)]hafniumdichlorid oder -dimethyl
entweder in ihrer syn- oder anti-Konfiguration.
 
6. Verfahren nach einem vorstehenden Anspruch, wobei das Katalysatorsystem ein nicht unterstütztes Katalysatorsystem ist, das durch Inkontaktbringen des Metallocens der Formel (I) als einen Feststoff oder als eine Lösung mit dem/den zuvor in einem aromatischen Lösungsmittel gelösten Cokatalysator(en) erhalten werden kann, oder durch sequentielles Zugeben der Katalysatorkomponenten zum Polymerisationsmedium erhalten werden kann.
 
7. Verfahren nach einem vorstehenden Anspruch, wobei das Katalysatorsystem eine Aluminium-Alkyl-Verbindung umfasst.
 
8. Verfahren nach einem vorstehenden Anspruch, wobei der Aluminoxan-Cokatalysator MAO ist.
 
9. Verfahren nach einem vorstehenden Anspruch, wobei der borhaltige Cokatalysator ein Anion der Formel:

        (Z)4B-     (III)

umfasst,

wobei Z ein gegebenenfalls substituiertes Phenylderivat ist, wobei der Substituent eine Halo-C1-6-Alkyl- oder Halogruppe ist, vorzugsweise

Triphenylcarbeniumtetrakis(pentafluorphenyl)borat,

N,N-Dimethylcyclohexylammoniumtetrakis(pentafluorphenyl)borat,

N,N-Dimethylbenzylammoniumtetrakis(pentafluorphenyl)borat, oder

N,N-Dimethylaniliniumtetrakis(pentafluorphenyl)borat.


 
10. Verfahren nach einem vorstehenden Anspruch, wobei die Aluminium-Alkyl-Verbindung eine Verbindung der Formel (VIII) AIR3 ist, wobei R eine lineare oder verzweigte C2-C8-Alkylgruppe ist.
 


Revendications

1. Procédé de préparation d'un copolymère d'éthylène comprenant la polymérisation d'éthylène et d'un comonomère de C4-10-alpha-oléfine dans un procédé en solution à haute température à une température supérieure à 100 °C en présence d'un système de catalyseur homogène comprenant :

(i) un complexe métallocène de formule (I)

Dans lequel

M est Hf

X est un ligand sigma,

L est un pont de formule -SiR82-, où chaque R8 est indépendamment un C1-C20-hydrocarbyle, un tri(alkyl-C1-C20)silyle, un C6-C20-aryle, un C7-C20-arylalkyle ou un C7-C20-alkylaryle

n est 0, 1 ou 2

R1 et R1' sont identiques ou peuvent être différents et peuvent être un groupe C1-C6-alkyle linéaire ou ramifié,

R2 et R2' sont identiques ou différents et sont un groupe CH2-R9, R9 étant H ou un groupe C1-C6-alkyle linéaire ou ramifié

R5 et R5' sont identiques et sont H, ou R5 et R5' sont différents et peuvent être H ou un groupe OR, où R est un groupe C1-C6-alkyle

R6 et R6' sont identiques ou différents et peuvent être H ou un groupe C(R10)3, R10 étant identique ou différent et R10 peut être H ou un groupe C1-C6-alkyle linéaire ou ramifié, et

R7 et R7' peuvent être identiques ou différents et peuvent être H ou un groupe C1-C6-alkyle linéaire ou ramifié

(ii) un cocatalyseur de type aluminoxane

(iii) un cocatalyseur contenant du bore et

(iv) éventuellement un composé d'aluminium-alkyle.


 
2. Procédé selon l'une quelconque des revendications précédentes, dans lequel la polymérisation est effectuée

a) à une température de polymérisation d'au moins 110 °C,

b) à une pression comprise entre 10 x 105 et 100 x 105 Pa (10 et 100 bars) et

c) dans un solvant hydrocarboné liquide sélectionné dans le groupe consistant en les C5-12-hydrocarbures, qui peuvent être non substitués ou substitués par un groupe C1-4-alkyle


 
3. Procédé selon l'une quelconque des revendications précédentes, dans lequel, dans la formule (I)
M est Hf,
X qui peut être identique ou différent, et est un atome d'hydrogène, un atome d'halogène, un groupe R11, OR11, OSO2CF3, OCOR11, SR11, NR112 ou PR112, où R11 est un radical C1-C20-alkyle, C2-C20-alcényle, C2-C20-alcynyle, C6-C20-aryle, C7-C20-alkylaryle ou C7-C20-arylalkyle linéaire ou ramifié, cyclique ou acyclique ; contenant éventuellement des hétéroatomes appartenant aux groupes 14-16 ou est SiR113, SiHR112 ou SiH2R11,
L est un pont de formule -SiR82-, où les deux R8 sont le même groupe C1-C10-hydrocarbyle ou C6-C10-aryle,
R1 et R1' sont identiques et sont un groupe C1-C6-alkyle linéaire ou ramifié,
n est 0, 1 ou 2, à condition que n ne soit pas 0 pour au moins l'un des groupes phényle,
R2 et R2' sont identiques et sont un groupe CH2-R9, R9 étant H ou un groupe C1-C4-alkyle linéaire ou ramifié
R5 et R5' sont identiques et sont H, ou R5 et R5' sont différents et peuvent être H ou un groupe OR, où R est un groupe C1-C4-alkyle
R6 et R6' sont identiques ou différents et peuvent être H ou un groupe C(R10)3, R10 étant identique ou différent et R10 peut être H ou un groupe C1-C4-alkyle linéaire ou ramifié,
R7 et R7' peuvent être identiques ou différents et peuvent être H ou un groupe C1-C4-alkyle linéaire ou ramifié.
 
4. Procédé selon l'une quelconque des revendications précédentes, dans lequel, dans la formule (I)
M est Hf,
X est indépendamment un atome d'hydrogène, un atome d'halogène, un groupe C1-6-alcoxy ou un groupe R11, où R11 est un groupe C1-6-alkyle, phényle ou benzyle,
L est un pont de formule -SiR82-, où les deux R8 sont le même groupe C1-C10-hydrocarbyle ou C6-C10-aryle,
R1 et R1' sont identiques et sont un groupe C1-C6-alkyle linéaire ou ramifié,
n est 0, 1 ou 2, à condition que n soit 1 pour au moins l'un des groupes phényle, R2 et R2' sont identiques et sont un groupe CH2-R9, R9 étant H ou un groupe C1-C4-alkyle linéaire ou ramifié
R5 et R5' sont identiques et sont H, ou R5 et R5' sont différents et peuvent être H ou un groupe OR, où R est un groupe C1-C4-alkyle
R6 et R6' sont identiques ou différents et peuvent être H ou un groupe C(R10)3, R10 étant identique ou différent et R10 peut être un groupe C1-C4-alkyle linéaire ou ramifié,
au moins un des ligands étant ainsi non substitué en position 5 et 6.
R7 et R7' peuvent être identiques ou différents et peuvent être H ou un groupe C1-C4-alkyle linéaire ou ramifié
 
5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le métallocène de formule (I) est sélectionné parmi
le diméthyle ou dichlorure de diméthylsilyl[(2-méthyl-4-phényl-5-méthoxy-6-tert-butylinden-1-yl)-(2-méthyl-4-(4'-tertbutylphényl)-inden-1-yl)]hafnium racémique et
le diméthyle ou dichlorure de diméthylsilyl[(2-méthyl-4-(3',5'-di-tert-butylphényl)-7-méthylindène-1-yl)-(2-méthyl-4-(4-tert-butylphényl)-inden-1-yl)] hafnium racémique
dans leur configuration soit syn, soit anti.
 
6. Procédé selon l'une quelconque des revendications précédentes, dans lequel le système de catalyseur est un système de catalyseur non supporté pouvant être obtenu en mettant en contact le métallocène de formule (I) sous forme solide ou en solution avec le ou les cocatalyseurs préalablement dissous dans un solvant aromatique, ou pouvant être obtenu en ajoutant séquentiellement les composants du catalyseur au milieu de polymérisation.
 
7. Procédé selon l'une quelconque des revendications précédentes, dans lequel le système de catalyseur comprend un composé d'aluminium-alkyle.
 
8. Procédé selon l'une quelconque des revendications précédentes dans lequel ledit cocatalyseur d'aluminoxane est le MAO.
 
9. Procédé selon l'une quelconque des revendications précédentes dans lequel ledit cocatalyseur contenant du bore comprend un anion de formule :

        (Z)4B-     (III)

où Z est un dérivé phényle éventuellement substitué, ledit substituant étant un groupe halo-C1-6-alkyle ou halo, de préférence

borate de triphénylcarbéniumtétrakis(pentafluorophényl),

borate de N,N-diméthylcyclohexylammoniumtétrakis(pentafluorophényl),

borate de N,N-diméthylbenzylammoniumtétrakis(pentafluorophényl), ou

borate de N,N-diméthylaniliniumtétrakis(pentafluorophényl).


 
10. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit composé d'aluminium-alkyle est un composé de formule (VIII) AlR3, R étant un groupe C2-C8-alkyle linéaire ou ramifié.
 




REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description