Title of Invention

ACTIVATING FLUORINATED SUPPORTS WITH IRON-BASED NON-METALLOCENE COMPLEXES

Abstract The invention discloses a method for preparing an active supported catalyst system that comprises the steps of: a) preparing an activating support; b) eacting an iron-based non-metallocene coordinating complex with the activating support; c) adding an organo-metallic compound having at least one metal-carbon bond; wherein the activating support is prepared by the steps of: providing a support prepared from one or more porous mineral oxides chosen from silica, alumina and mixtures thereof; optionally heating the support under inert gas; functionalising the support with a solution containing an alkylating agent; fluorinating the support with a solution containing a fluorinating agent; retrieving an active fluorinated support; and wherein the iron-based non-metallocene coordinating complex is of formula I wherein A1, A2, A3, Y, Y\ R2, R4, R7, R8, N T, X, L, b and n are as defined in the specification.
Full Text

ACTIVATING FLUORINATED SUPPORTS WITH IRON-BASED NON-METALLOCENE COMPLEXES
This invention relates to the field of olefin polymerisation with non-metallocene
complexes supported on activating support. These catalysts have a longer catalyst
life - such as 30 minutes and more, than the one containing expensive
organoaluminum oxy-compound or organoboron compound.
It is known in the art that mono-1-olefins, such as ethylene and propylene, can be
polymerised with catalyst system employing transition metals such as titanium,
vanadium, chromium, nickel and/or other metals, either unsupported or on a
support such as alumina, silica, titania, and other refractory metals. Supported
polymerization catalyst systems frequently are used with a cocatalyst, such as
alkyl boron compounds and/or alkyl aluminum compounds and/or alkyl aluminoxy
compounds. Organometallic catalyst systems or Ziegler-Natta-type catalyst
systems, usually are unsupported and frequently are used with a cocatalyst, such
as methylaluminoxane. Other components may be used in addition to the catalyst
and cocatalyst.
It is also well known that, while no polymer production process is easy, slurry, or
loop, polymerization processes are more commercially desirable than other
polymerization processes, due to ease of operation. Furthermore, the type of
polymerization process used can have an effect on the resultant polymer. For
example, high reactor temperatures can result in low catalyst activity and
productivity, as well as a low molecular weight polymer product. High reactor
pressures also can decrease 13 amount of desirable branching in the resultant
polymer.
Most polymer products made using slurry processes, especially polymer products
made using supported chromium catalyst systems, have a broad molecular
weight distribution and, therefore, the polymer product is very easy to process

into a final product. Polymers made by other processes, such as, for example,
high temperature and/or high pressure solution processes, can produce polymers
having a narrow molecular weight distribution; these polymers can be very difficult
to process into an article of manufacture.
Many homogeneous organometallic catalyst systems have low activity, high
consumption of very costly cocatalysts like methylaluminoxane (MAO), and can
produce low molecular weight polymers with a narrow molecular weight
distribution. Furthermore, even though MAO can be helpful or even necessary to
produce a polymer with desired characteristics, an excess of MAO can result in
decreased catalyst system activity. Additionally, these types of homogeneous
catalyst systems preferably are used only in solution or gas phase polymerisation
processes.
US-A-5,852,145 discloses polymerisation processes for olefins using catalyst sys-
tems containing a nickel or palladium alpha-diimine complex, a metal containing
hydrocarbylation compound, and a selected Lewis acid. The metal containing hydro-
carbylation compound was defined as a compound that could transfer a hydrocarbyl
group to a nickel or palladium compound. The patent disclosed that useful alkylating
agents (defined as a form of metal containing hydrocarbylation compound) could be
represented by formulas MX2Rn6 or [AI(0)R11]q, that included alkylaluminium and
alkylzinc compounds with or without halogen groups, as well as alkyl aluminoxanes.
In that patent, the selected Lewis acids were referred to as compound (II) and it was
additionally specified that when the hydrocarbylation compound was not an alky-
laluminium compound containing one or more halogen atoms bound to an alumiium
atom or an alkyl aluminoxane, compound (II) was compulsory.
US-A-6583235 discloses the use of aluminophosphate in catalyst systems
comprising nickel and palladium catalysts and metal alkyl cocatalysts.
DE-A-19959251 discloses active catalyst systems based on group 8, 9,10 metal
complexes.

Diimine nickel dihalide complexes suitable for the homo- or copolymerisation of
ethylene are disclosed in EP-A-884331.
US-A-4,716,208 also discloses a broad variety of late transition metal complexes
that are suitable for the polymerisation of olefins and more particularly, Ittel et al.
(Ittel S.D., Johnson L.K. and Brookhart M.; in Chem. Rev., 100,1169, 2000.)
disclose late-metal catalysts that can be used in the homo- and copolymerisation of
ethylene.
All these catalyst components suffer from the disadvantage that they must be used
with activating agents, more preferably with aluminoxane in order to become suitable
for polymerising olefins.
EP 1238989 discloses polymerisation catalysts and a process for producing an
olefin catalyst, which contains neither an organoaluminium oxy-compound nor an
organoboron compounds. These catalysts have higher polymerisation activity
without the expensive organo-aluminium oxy-compound or organoboron
compound and which has a higher activity for a long catalyst life. The olefin
polymerisation catalyst comprise:
(A) a transition metal compound or lanthanoid compound containing two or
more atoms selected from the group consisting of boron, nitrogen, oxygen,
phosphorus, sulphur and selenium - named in this patent non-metallocene
complexes
(B) a Lewis Acid with could be ionic-bounding compounds having a layered
crystal structure of a CdCI2 type such as MgCI2 - aluminium is excluded
from the list of metal, a clay - clays minerals, or ion-exchange layered
compounds, or an heteropoly compounds, or halogenated lanthanoid
compounds.
(C) an oxygen-containing compound or nitrogen-containing compound
(D)an inactivating compound which is capable of reacting with the oxygen-
containing compound or nitrogen containing compound to make an

inactive the oxygen-containing compound or nitrogen-containing
compound (C) to the coumpound (A).
It is known to use activating supports with metallocene catalyst components such as
disclosed for example in FR-2769245, with or without expensive organoaluminum
oxy-compound.
There is thus a need to prepare active catalyst systems based on transition metal
complexes that require no aluminoxane and are simple to prepare.
It is an aim of the present invention to prepare active catalyst system produced with
either non-metallocene complexes as described above, or non-metallocene (I) to (III)
described in patent EP 1 238 989, wherein the activation step is provided by an
activating support, which contains a fluorinated aluminium Lewis Acid in combination
with an alkylating agent for the non-metallocene compound.
It is another aim of the present invention to prepare polyolefin having a good
morphology.
It is a further aim of the present invention to provide catalyst systems having a high
life time activity compatible with a conventional industrial process, typically of 30
minutes or more.
Accordingly, the present invention discloses a catalyst system comprising:
a) a non-metallocene coordinating complex containing two or more atoms
selected from the group consisting of boron, nitrogen, oxygen, phosphorus,
sulphur and selenium, preferably nitrogen or oxygen ;
b) an activating support that contains a fluorinated aluminium Lewis Acid;
c) an organo-metallic compound having at least one metal-carbon bond able to
generate a metal carbon bound on the non metallocene complex.

In a preferred embodiment according to the present invention the metal-based
component can be represented by formula I:

wherein L is a heteroatom-containing ligand; n is an integer of 1, 2, or 3;
wherein X represents an atom or group covalently or ionically bound to the transition
metal M;
wherein R2 and R4 are each independently selected from hydrogen, halogen,
substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl or SiR'3 wherein R' is independently selected from hydrogen,
halogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl and any adjacent R's may be joined together to form a ring;
wherein M is Fe;
wherein T is the oxidation state of the transition metal and b is the valence of the
atom or group X;
wherein Y and Y' are each independently selected from C or P(R3);
wherein A1, A2 and A3 are each independently N, P or CR9 with the proviso that at
least one is CR9;
wherein R3, R7, R8 and R9 are each independently selected from hydrogen, halogen,
substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl or SiR'3 wherein R' is independently selected from hydrogen,

halogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl.
Preferably, Y or Y" is C. Preferably A1 to A3 are each independently CR9, or A1 and
A3 are both N and A2 is CR9, or one of A1 or A3 is N and the other two are
independently CR9 and more preferably, CR9 is CH.
Preferably, R2 and R4 are independently selected from substituted or unsubstituted
aiicyclic, heterocyclic or aromatic groups such as for example phenyl, 1-naphtyl, 2-
naphtyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl,
2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,6-dimethylphenyl,
2,6-dimethylphenyl, 2-di-t-butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl,
2,6-trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl, 3,5-dichloro-2,6-
diethylphenyl, 2,6-bis(2,6-dimethylphenyl)phenyl, cyclohexyl, pyrolyl, 2,5-
dimethylpyrolyl and pyridinyl.
In another embodiment according to the present invention, the non-metallocene
complex can be represent by formula lla, llb or llc



wherein all symbols are described in EP-A-1238989 from page 4, line 32 to page 9,
line 17, with the restriction that M is Fe.
The non-metallocene coordinating complex or a combination of metallocene and/or
non-metallocene coordinating complexes is/are deposited on and reacted with an
activating support, wherein said activating support is prepared by the steps of:
a) providing a support prepared from one or more porous mineral oxides;

b) optionally heating the support under inert gas;
c) functionalising the support with a solution containing an alkylating agent;
d) fluorinating the support with a solution containing a fluorinating agent;
e) retrieving an active fluorinated support.
Optionally the functionalisation and the fluorination can be carried out in one step, by
providing an appropriate solution containing a functionalising and fluorinating agent.
The present invention is characterised by the fact that the functionalised and
fluorinated support does not need to be heated and oxydised in order to activate the
iron complex. This is not the case when metals other than iron must be activated.
The porous mineral oxide is advantageously chosen from silica, alumina and
mixtures thereof. Preferably it is silica.
The porous mineral oxide particles preferably have at least one of the following
characteristics:
they include pores having a diameter ranging from 7.5 to 30 nm;
they have a porosity ranging from 1 to 4 cm3 /g;
they have a specific surface area ranging from 100 to 1000 m2 /g; and
they have an average diameter ranging from 1 to 100 urn.
Before it is functionalised, the support has -OH radicals on its surface, in particular
from 0.25 to 10, and even more preferably from 0.5 to 4 -OH radicals, per nm2
resulting either from a thermal treatment under inert gas at a temperature of from
100 to 1000 °C, preferably at a temperature of from 120 to 800 °C and more
preferably at a temperature of from 140 to 700 °C, during at least 60 minutes or from
a chemical treatment. After it has been functionalised, said support has as many at
least partially fluorinated aluminium and/or magnesium Lewis-acid sites per nm2.
The support may be of various kinds. Depending on its nature, its state of hydration
and its ability to retain water, it may undergo dehydration treatments of greater or

lesser intensity depending on the desired surface content of -OH radicals.
Those skilled in the art may determine, by routine tests, the dehydration treatment
that should be applied to the support that they have chosen, depending on the
desired surface content of -OH radicals.
More preferably, the starting support is made of silica. Typically, the silica may be
heated between 100 and 1000 ° C, preferably between 120 and 800 ° C, more
preferably between 140 and 700 °C under an inert gas atmosphere, such as for
example under nitrogen or argon, at atmospheric pressure or under a vacuum of
about 10-5 bars, for at least 60 minutes. For such heat treatment, the silica may be
mixed, for example, with NH4CI so as to accelerate the dehydration.
Alternatively, the heat treatment can be carried out at a temperature of from 100 to
450 ° C, in combination with a silanisation treatment. This results in a species
derived from silicon being grafted on the surface of the support thereby making said
surface more hydrophobic.
The silane may, for example, be an alkoxytrialkylsilane, such as for example
methoxytrimethylsilane, or a trialkylchlorosilane, such as for example
trimethylchlorosilalne or triethylchlorosilane. It is typically applied to the support by
forming a suspension of this support in an organic silane solution, said silane
solution having a concentration of between 0.1 and 10 mol per mole of OH radicals
on the support. The solvent for this solution may be chosen from linear or branched
aliphatic hydrocarbons, such as hexane or heptane, alicyclic hydrocarbons,
optionally substituted, such as cyclohexane, and aromatic hydrocarbons, such as
toluene, benzene or xylene. The treatment of the support by the silane solution is
generally carried out under stirring at a temperature of from 50 to 150 ° C, during 1 to
48 hours.
After silanisation, the solvent is removed, for example, by siphoning or filtration, and
the support is then being washed thoroughly, using for example 0.31 of solvent per

gram of support.
The surface -OH radical content of the support may be assayed using known
techniques such as, for example, by reacting an organomagnesium compound such
as CH3 Mgl with the support and by measuring the amount of methane given off as
described in McDaniel (McDaniel MP., in J. Catal., 67, 71,1981) or by reacting
triethylaluminium with the support and by measuring the amount of ethane given off •
as described by Gachard-Pasquet (Thesis of Veronique Gachard-Pasquet,
Universite Claude Bernard, Lyon 1, France, pages 221-224,1985).
In a first embodiment according to the present invention, functionalisation and
fluorination are carried out as two separate steps. The activating supports are then
formed by the reaction of -OH radicals carried by the support base particles with at
least one functionalisation agent. Any functionalisation agent or mixture thereof
described in FR -2,769,245 from page 5, line 9 to page 6, line 11 can be used in the
present invention.
In a preferred embodiment of the present invention, the functionalisation step is
carried out by treating a suspension of the support particles in a solvent medium
containing the functionalisation agent at a temperature ranging from -150 to +150 °
C for a period of time ranging from 1 minute to 12 hours, and then by recovering the
grafted particles after washing. The solvent is preferably selected from aliphatic,
alicyclic and aromatic hydrocarbons. Preferably, the treatment is carried out at a
temperature of from 30 to 100 °C and for a period of time of from 1 to 3 hours.
Preferably the concentration of functionalisation agent is of from 0.5 to 20 mmol per
g of support particles.
The functionalised support is then treated with a fluorinating agent that partially
replaces the radicals of the functionalising agent with fluor. The functionalised
support particles may then be brought into contact with gaseous hydrofluoric acid in
order to carry out the fluorination treatment. This contacting step is carried out for a
period of time ranging from 1 minute to 24 hours, at a temperature of from 20 to 800

°C. Alternatively, hydrofluoric acid may advantageously be replaced by powdered
(NH4)2SiF6; the fluorination treatment with (NH4)2 SiF6 is carried out by gently
fluidising the mixture of support particles and (NH4)2 SiF6 under an inert gas, such as
argon or nitrogen, and by submitting to a heat treatment at a temperature of from
300 to 500 ° C for a period of time of from 1 to 10 hours. An amount of fluorine of
from 1 to 10% by weight, based on the total weight of the support is used for the
fluorination treatment. The preferred minimum amount of fluorine is 3 wt%. The
preferred maximum amount is 7 wt%, more preferably 6 wt%, most preferably 5 wt%.
In a second embodiment according to the present invention, the fluorinating step is
suppressed and the support is treated with a compound comprising at least one
aluminium, one fluor and one organic group, optionally in combination with any one
or more compounds selected from M"F, M"RP, M'F2, M'RPF, or M'RP2 wherein M" is a
group 1 metal, M' is a group 2 metal and Rp is an alkyl having from 1 to 20 carbon
atoms. The organic group is preferably an hydrocarbyl and more preferably an alkyl
having from 1 to 12 carbon atoms. Preferably, the functionalisation and fluorinating
agent is of formula III

wherein the R groups, can be the same or different and are alkyl groups having from
1 to 20 carbon atoms. Preferably, R is methyl, ethyl, butyl and hexyl, and more
preferably the R1 groups are the same. The most preferred compound of formula (III)
is diethylaluminiumfluoride. Fluorinated alkylaluminium can be obtained as described
in H. Roesky review, Journal of Fluorinated Chemistry, 2003,122,125.
11 functionalisation agent can be used alone or in combination with any one or
more groups selected from M"F, M"RP, M'F2l M'RP F or M' Rp2 wherein M" is a group
1 metal, preferably Na, M' is a group 2 metal, preferably Mg and Rp is an alkyl having
from 1 to 20 carbon atoms.

The non-metallocene coordinating complex as described in any one of formula I or
formulae Ha, lib or lic, or a combination thereof, is impregnated on and reacted with
the activating support.
The nature, the size and the position of the substituents determine the structure of
the polymer they are thus selected according to the desired properties and structure
of the resulting polymer. The polymer obtained may be isotactic or syndiotactic
depending upon the nature and position of the substituents.
In the present invention, an alkylation step must be carried out with an organo-
metallic compound that is able to alkylate the complex without activating it. The
alkylating agent is an organometallic compound or a mixture thereof that is able to
transform a metal-L group bond into a metal-carbon bond or a metal-hydrogen bond.
It can be selected from an alkylated derivative of Al, Li or Mg or Zn. Preferably, it is
selected from an alkylated derivative of aluminium of formula (IV)

wherein the Rm groups, may be the same or different, and are a substituted or
unsubstituted alkyl, containing from 1 to 12 carbon atoms such as for example ethyl,
isobutyl, n-hexyl and n-octyl, X' is a halogen or hydrogen and n is an integer from 1
to 3, with the restriction that at least one Rm group is an alkyl. It can also be any
organometallic compound able to create a metal-carbon bond provided it does not
interfere with the activity of the final catalytic system.
Preferably, the alkylating agent is an aluminium alkyl, and more preferably it is
triisobutylaluminium (TIBAL) or triethylalum, mm (TEAL).
An alternatively, the alkylating agent is diethyl zinc.
The activating functionalised support, the alkylating agent and the non-metallocene
complex are added, in any order, to prepare an active catalyst system.

In one embodiment according to the present invention, the alkylating agent is first
added to the activating functionalised support. The non-metallocene complex is then
dissolved in an aromatic solvent and added to the treated support.
In another embodiment according to the present invention, the alkylating agent is
mixed with the non-metallocene complex and the mixture is added to the activating
support.
The amount of alkylating agent is variable and the ratio Al/M is of from 1 to 10000.
The amount of activating support is of from 0.01 to 2000 mg of support per
micromole of iron-based non-metallocene complex.
The monomers that can be used in the present invention are alpha-olefins or
ethylene, preferably ethylene and propylene.
The polymerisation conditions are not particularly limited and depend upon the
monomer and the late transition metal complex. The polymerisation temperature is
typically of from 0 to 120 °C and the pressure defined as the monomer pressure can
be from atmospheric up to 100 bars, preferably between 3 and 50 bars.
Hydrogen may be added to the system in order to control the chain length.
When compared to homogeneous polymerisation, the catalyst system of the present
invention has the great advantage of leaving the reactor clean.
Another advantage of the present invention is a higher catalyst life time than the one
containing expensive organoaluminum oxy-compound or organoboron compound.
Examples.

All the experiments were carried out under argon and with the classical Schlenk
techniques. Heptane and toluene solvents were dried on a 0.3 nm molecular sieve.
The number average molecular weight Mn, the weight average molecular weight
Mw, the polydispersity index Mw/Mn were all determined by Steric Exclusion
Chromatography (SEC) with trichlorobenzene (TCB) solvent at 135 °C, with
polystyrene scaling and with Mark-Houwinck coefficients for polyethylene of
K=5.25.10-4anda=0.76.
The melting temperatures were measured by Differential Scanning Calorimetry
(DSC) method and the density was measured following the method of standard test
ASTM 1505 at a temperature of 23°C.
The polymer morphologies were determined either by granulometric analysis if
sufficient amount of polymer was produced or with an electronic microscope
otherwise.
List of figure:
Figure 1 represents the structure of complex C1,2,6-bis[1-2,6-
bis(isopropyl)phenyl)imido)ethyl]pyridine Fe(ll) dichloride.
Figure 2 represents activity profiles obtained respectively for example 3 and example
4.
Figure 3 represents molecular weight distribution of polymers obtained respectively
in example 3 and example 4.
Figures 4a and 4b represent the morphology of polyethylene prepared according to
example 4.
Example 1

Synthesis of Support S1
The starting silica was a type 332 Grace Davidson® silica having the following
characteristics:
- mean particle size = 70 um
- mean specific area = 300 m2/g
- porous volume = 1.65 mL/g
- apparent density = 0.35 g/cm3
Step A.
5 g of the silica were heated under dynamic vacuum (102 mbars) according to the
following temperature scheme:
- from 30 °C to 100 "C in one hour;
- from 100 °C to 130 °C in 30 minutes;
- from 130 °C to 450 °C in one hour;
- maintained at 450 °C for four hours.
The resulting silica had an amount of surface silanol of 1.3 mmol/g.
Step B.
In a 250 cm3 tricol equipped with a mechanical stirrer, 2.32 g of the heated silica
were suspended in 100 mL of anhydrous heptane. That suspension was treated with
15 mL of a 0.6 M solution in toluene of diiethylaluminium fluoride (DEAF), or 3
equivalents with respect to silanol, during a period of time of one hour, at room
temperature (about 25 °C). 100 ML of toluene were then added and the solution was
maintained under stirring for a period of time of 10 minutes. The suspension was
then decanted to retrieve the supernatant. The product was washed three times with
30 mL of heptane. The impregnated support was then dried under vacuum (10"2
mbars) during a period of time of one hour.
Elemental analysis of the treated support by atomic emission spectroscopy
(Inductively Coupled Plasma) gave 4.56 % Al and 2.21 % F.

Example 2
Synthesis of complex 2.6-bisH-2.64)isflsopropvl)pheny0imido)ethvripvridine Fed!)
dichloride C1 (figure 1)
Ligand 2,6-bis[1-2,6-bis(isopropyl)phenyl)imido)ethyl]pyridine was prepared following
the method disclosed in Gibson (Gibson V. C, in J. Am. Chem. Soc, 121, 8728,
1999).
Elemental analysis of (C33H43N3) gave the following results:
- predicted: %C= 82:32; % H= 8.94; % N=8.73.
- measured: %C= 82.11; %H=8.91; %N=8.69.
1H NMR (CDCI3): 6 8.52 (d, 2H, 3J(HH)=7.8 Hz,Py-Hm), 7.94 (t, 1H, Py-Hp), 7.1 (m,
6H, Ar-H), 2.78 (sept, 4H, 3J(HH)=5.6 Hz, CHMe2), 2.28 (s, 6H, N=CMe), 1.18 (d,
24H,CHMe2).
Blue complex of 2,6-bis[1-2,6-bis(isopropyl)phenyl)imido)ethyl]pyridine Fe(ll)
dichloride, prepared from the ligand here-above was obtained following the method
described in Gibson also.
Elemental analysis of (C33H43N3FeCl2) gave the following results:
- predicted: %C= 64.19; %H= 7.18; %N=6.8%.
- measured: %C= 64.19 ; %H=6.9; %N=6.7.
Example 3.
Activation of complex C1 with MAO.
In a 1 L balloon, conditioned under argon, to 300 mL of heptane, 1.17 mL of MAO
solution (Albemarle, 10 wt% in toluene) were added. 5 mL of a suspension of
complex C1, (1.046 M in toluene), corresponding to 15 umol/L and a Al/Fe ratio of
333, were syringed in the balloon.
The yellow medium was kept under manual stirring during a period of time of 5
minutes at room temperature (about 25 °C) and then syringed into a 500 mL Buchi
type reactor.

The polymerisation was carried out at a temperature of 50 °C under a pressure of
ethylene of 3 bars and during a period of time of 25 minutes.
The polymer was filtered, washed with methanol and dried under vacuum. 24.29 g of
polymer were obtained corresponding to an activity of 1.1 107 g/moWh and it had
the following characteristics:
- Mw = 250000
- D = 27.1
- Tm = 137,3 °C
- crystallinity = 46%
- no morphology.
Example 4
Activation of complex C1 with Support S1 and TiBAI
In a 50 mL ballon conditioned under argon, 0.52 mL of TIBAI (1 M solution in
heptane) was added to a 2 mL suspension of blue complex C1 ([Fe] = 2,669 mM
solution in toluene); the solution immediately turned yellow.
In a 50 mL balloon, conditioned under argon, 194 mg of support S1 were weighted
and 1,57 mL of the yellow solution of complex C1/ TIBAI was added. The support
turned yellow and the remaining solution was colourless.
In a 1 L balloon conditioned under argon, to 333 mL of heptane, the overall
suspension of S1 support impregnated with the complex C1/TIBAI solution was
added. The supernatant was colourless and remained colourless during
polymerisation.
The medium was kept under manual stirring during a period of time of 5 minutes at
room temperature (about 25 °C) and then syringed into a 500 mL Buchi type reactor.
The polyn jrh tion was carried out at a temperature of 50 °C under a pressure of
ethylene of 3 bars and during a period of time of 60 minutes.
The polymer was filtered, washed with methanol and dried under vacuum. 1.02 g of
polymer were obtained corresponding to a productivity of 5 g/gSuppon and it had the
following characteristics:
- Mw = 837000 (figure 2)

- D = 18,7
- Tm= 137,2 °C
- crystallinity = 46%
- morphology represented in figure 3.
In conclusion, in all the examples according to the present invention, the catalyst
system had a higher catalyst life time than the one containing expensive
organoaluminum oxy-compound or organoboron compound described in example 2
and the polymers produced had an excellent morphology. The life time of the present
systems is larger than 30 minutes.

We claim:
1. A method for preparing an active supported catalyst system that comprises the
steps of:
a) preparing an activating support;
b) reacting an iron-based non-metallocene coordinating complex with the
activating support;
c) adding an organo-metallic compound having at least one metal-carbon
bond;
wherein the activating support is prepared by the steps of:
providing a support prepared from one or more porous mineral oxides chosen
from silica, alumina and mixtures thereof;
optionally heating the support under inert gas;
functionalising the support with a solution containing an alkylating agent;
fluorinating the support with a solution containing a fluorinating agent;
retrieving an active fluorinated support;
and wherein the iron-based non-metallocene coordinating complex is of formula I

wherein X represents an atom or group covalently or ionically bound to iron;
wherein L is a heteroatom-containing ligand; wherein n is an integer from 1 to 3;
wherein T is the oxidation state of the transition metal and b is the valence of the atom
or group X;
wherein R2 and R4 are each independently selected from hydrogen, halogen,
substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl or SiR'3, wherein R' is independently selected from hydrogen,
halogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl and any adjacent R's may be joined together to form a ring;
wherein Y and Y' are each independently selected from C or P(R3);

wherein A1, A2 and A3 are each independently N, P or CR9 with the proviso that at least
one is CR9;
wherein R3, R7, R8 and R9 are each independently selected from hydrogen, halogen,
substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl or SiR'3 wherein R' is independently selected from hydrogen,
halogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted
heterohydrocarbyl
said active supported catalyst being characterised in that it does not require any
aluminoxane as activating agent.
2. The method as claimed in claim 1 wherein Y and/or Y' is C.
3. The method as claimed in claim 1 or claim 2 wherein R2 and R4 are each
independently selected from substituted or unsubstituted alicyclic, heterocyclic or
aromatic groups.
4. The method as claimed in any one of claims 1 to 3 wherein organo-metallic
compound is aluminium alkyl.
5. An active iron-based catalyst system obtainable by the method of any one of
claims 1 to 4.
6. A method for homo- or co-polymerising olefins that comprises the steps of:

a) providing the active supported catalyst system as claimed in claim 5;
b) injecting a monomer and optional comonomer(s) in the reacting zone;
c) maintaining under polymerisation conditions;
d) retrieving a polymer.
7. The method as claimed in claim 6 wherein the monomer is ethylene or
propylene.




ABSTRACT


ACTIVATING FLUORINATED SUPPORTS WITH IRON-BASED
NON-METALLOCENE COMPLEXES
The invention discloses a method for preparing an active supported catalyst system
that comprises the steps of:
a) preparing an activating support;
b) eacting an iron-based non-metallocene coordinating complex with the activating
support;
c) adding an organo-metallic compound having at least one metal-carbon
bond;
wherein the activating support is prepared by the steps of:
providing a support prepared from one or more porous mineral oxides chosen
from silica, alumina and mixtures thereof;
optionally heating the support under inert gas;
functionalising the support with a solution containing an alkylating agent;
fluorinating the support with a solution containing a fluorinating agent;
retrieving an active fluorinated support;
and wherein the iron-based non-metallocene coordinating complex is of formula I

wherein A1, A2, A3, Y, Y\ R2, R4, R7, R8, N T, X, L, b and n are as defined in the
specification.

Documents:

00297-kolnp-2008-abstract.pdf

00297-kolnp-2008-claims.pdf

00297-kolnp-2008-correspondence others.pdf

00297-kolnp-2008-description complete.pdf

00297-kolnp-2008-form 1.pdf

00297-kolnp-2008-form 3.pdf

00297-kolnp-2008-form 5.pdf

00297-kolnp-2008-international publication.pdf

00297-kolnp-2008-international search report.pdf

00297-kolnp-2008-pct priority document notification.pdf

00297-kolnp-2008-pct request form.pdf

297-KOLNP-2008-(11-02-2013)-CORRESPONDENCE.pdf

297-KOLNP-2008-(11-02-2013)-OTHERS.pdf

297-KOLNP-2008-(22-05-2013)-ABSTRACT.pdf

297-KOLNP-2008-(22-05-2013)-CLAIMS.pdf

297-KOLNP-2008-(22-05-2013)-CORRESPONDENCE.pdf

297-KOLNP-2008-(22-05-2013)-FORM 2.pdf

297-KOLNP-2008-(22-05-2013)-FORM 3.pdf

297-KOLNP-2008-(22-05-2013)-OTHERS.pdf

297-KOLNP-2008-(22-05-2013)-PETITION UNDER RULE 137-1.1.pdf

297-KOLNP-2008-(22-05-2013)-PETITION UNDER RULE 137.pdf

297-KOLNP-2008-ASSIGNMENT-1.1.pdf

297-KOLNP-2008-ASSIGNMENT.pdf

297-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

297-KOLNP-2008-CORRESPONDENCE.pdf

297-KOLNP-2008-EXAMINATION REPORT.pdf

297-kolnp-2008-form 18.pdf

297-KOLNP-2008-GPA.pdf

297-KOLNP-2008-GRANTED-ABSTRACT.pdf

297-KOLNP-2008-GRANTED-CLAIMS.pdf

297-KOLNP-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

297-KOLNP-2008-GRANTED-FORM 1.pdf

297-KOLNP-2008-GRANTED-FORM 2.pdf

297-KOLNP-2008-GRANTED-FORM 3.pdf

297-KOLNP-2008-GRANTED-FORM 5.pdf

297-KOLNP-2008-GRANTED-SPECIFICATION-COMPLETE.pdf

297-KOLNP-2008-INTERNATIONAL PUBLICATION.pdf

297-KOLNP-2008-INTERNATIONAL SEARCH REPORT & OTHERS.pdf

297-KOLNP-2008-OTHERS.pdf

297-KOLNP-2008-PETITION UNDER RULE 137.pdf

297-KOLNP-2008-PRIORITY DOCUMENT.pdf

297-KOLNP-2008-REPLY TO EXAMINATION REPORT.pdf


Patent Number 258095
Indian Patent Application Number 297/KOLNP/2008
PG Journal Number 49/2013
Publication Date 06-Dec-2013
Grant Date 03-Dec-2013
Date of Filing 21-Jan-2008
Name of Patentee CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS)
Applicant Address 3, RUE MICHEL ANGE F-75016 PARIS
Inventors:
# Inventor's Name Inventor's Address
1 PRADES FLORAN FAUBOURG DE MONS, 37, B-1400 NIVELLES
2 SIROL SABINE RUE I. VANSCHEPDAEL 37, B-1440 WAUTHIER-BRAINE
3 RAZAVI ABBAS 35, DOMAINE DE LA BRISEE, B-7000 MONS
4 BOISSON CHRISTOPHE 155, RUE LEON BLUM, F-69100 VILLEURBA
5 SPITZ ROGER 30, RUE JEAN BROQUIN, F-69006 LYON
PCT International Classification Number C08F 10/00,C08F 4/02
PCT International Application Number PCT/EP2006/064676
PCT International Filing date 2006-07-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 05291668.1 2005-08-03 EUROPEAN UNION