LAVASTRE OLIVIER (FR)
SIROL SABINE (BE)
CENTRE NAT RECH SCIENT (FR)
REVAULT CYRIL (FR)
LAVASTRE OLIVIER (FR)
SIROL SABINE (BE)
GIBSON V C ET AL: "Synthetic, spectroscopic and olefin oligomerisation studies on nickel and palladium complexes containing ferrocene substituted nitrogen donor ligands", DALTON TRANSACTIONS, no. 5, 7 March 2003 (2003-03-07), pages 918 - 926, XP009072752, ISSN: 1477-9226
LOPEZ ET AL: "Relationships between 57Fe NMR, Mossbauer parameters, electrochemical properties and the structures of ferrocenylketimines", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 691, no. 3, 15 January 2006 (2006-01-15), pages 475 - 484, XP005226193, ISSN: 0022-328X
CUI X ET AL: "Bis[1,1'-N,N'-(2-picolyl)aminomethyl]ferrocene as a redox sensor for transition metal ions", DALTON TRANSACTIONS, no. 11, 7 June 2004 (2004-06-07), pages 1743 - 1751, XP009072787, ISSN: 1477-9226
BERNARDI L ET AL: "Diastereoselective additions of organometallic reagents to (SFc)-2-p-tolylsulfanylferrocene carboxaldehyde and to (SFc)-2-p-tolylsulfanyl ferrocenyl imines. Synthesis of new central and planar chiral ferrocenyl alcohols and amines", ARKIVOC, no. 2, 2004, pages 72 - 90, XP007901151, Retrieved from the Internet
LEWKOWSKI J ET AL: "Alpha-(Ferrocenyl)-aminomethanephosphonous acids. First synthesis and preparation of their esters with cholesterol and adenosine", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 689, no. 9, 1 May 2004 (2004-05-01), pages 1684 - 1690, XP004502214, ISSN: 0022-328X
LEWKOWSKI J ET AL: "First synthesis of 1,1'-ferrocene bis-aminophosphonic esters", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 689, no. 7, 1 April 2004 (2004-04-01), pages 1265 - 1270, XP004496429, ISSN: 0022-328X
WALTHER D ET AL: "Furfurylidene-imines as components of the oxidative coupling with carbon dioxide at nickel(0) centers: influence of the substituents on the structure of the resulting nickelacycles", ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 628, no. 4, 2002, pages 851 - 862, XP009072801, ISSN: 0044-2313
LEWKOWSKI J ET AL: "The first synthesis of ferrocenyl aminophosphonic esters", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 631, no. 1-2, 10 August 2001 (2001-08-10), pages 105 - 109, XP004305486, ISSN: 0022-328X
BONINI B F ET AL: "One pot synthesis of new beta-lactams containing the ferrocene moiety", SYNLETT, no. 7, 2001, pages 1092 - 1096, XP009072796, ISSN: 0936-5214
PEREZ S ET AL: "Trans-influences in mononuclear cyclopalladated compounds containing a sigma(Pd-Csp2, ferrocene) bond. X-ray crystal structures of [Pd{[(eta5-C5H3)-CH=N-CH2-C6H5]Fe(eta5-C5H5)}(X)(PPh3)] with X = Br- and I-", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 625, no. 1, 15 April 2001 (2001-04-15), pages 67 - 76, XP004234567, ISSN: 0022-328X
ZHAO G ET AL: "Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(mu-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives", ORGANOMETALLICS, vol. 18, no. 8, 1999, pages 3623 - 3636, XP009072780, ISSN: 0276-7333
BULLITA E ET AL: "Synthesis, X-ray structural determination and Mossbauer characterization of Schiff bases bearing ferrocene groups, their reduced analogs and related complexes", INORGANICA CHIMICA ACTA, vol. 287, no. 2, 1999, pages 117 - 133, XP009072782, ISSN: 0020-1693
BOSQUE R ET AL: "Heterodi- and Heterotrimetallic Compounds Containing Five-Membered Rings and .sigma.(Pd-Csp2, ferrocene) Bonds. X-ray Crystal Structure of the meso-Form of [Pd2{Fe[(eta5-C5H3) C(CH3)=NC6H5]}2Cl2(PPh3)2]", ORGANOMETALLICS, vol. 18, no. 7, 1999, pages 1267 - 1274, XP009072781, ISSN: 0276-7333
BOSQUE R ET AL: "Substituent effects on the electrochemical behavior of iron(II) in Schiff bases derived from ferrocene and their cyclopalladated compounds", INORGANICA CHIMICA ACTA, vol. 244, no. 1, 1996, pages 141 - 145, XP009072783, ISSN: 0020-1693
LOPEZ C ET AL: "Effects of the nature of the nitrogen donor atom (sp2 versus sp3) upon the properties and chemistry of palladated complexes with sigma(Pd-Csp2, ferrocene) bonds", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS: INORGANIC CHEMISTRY, no. 20, 1994, pages 3039 - 3046, XP009072837, ISSN: 0300-9246
BOSQUE R ET AL: "Influences of the substituents at the iminic carbon atoms (hydrogen versus methyl) upon the properties of ferrocenylimines and their cyclopalladated derivatives", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS: INORGANIC CHEMISTRY, no. 5, 1994, pages 735 - 745, XP009072834, ISSN: 0300-9246
LOPEZ C ET AL: "Cyclopalladated compounds derived from ferrocenylimines. Crystal structure of [Pd[(eta5-C5H5)Fe [eta5-C5H3CH=N(CH2)2Ph]]Cl(PEt3)]", JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS: INORGANIC CHEMISTRY, no. 15, 1992, pages 2321 - 2328, XP009072836, ISSN: 0300-9246
PEET J H J ET AL: "Novel photoreaction products of N-substituted ferrocenylimines", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 88, no. 1, 1975, pages C1 - C3, XP009072795, ISSN: 0022-328X
CLAIMS.
1. A method for preparing a catalyst system that comprises the steps of:
a) providing a metallic precursor M(HaI) n RV n in a solvent, wherein M is a metal Group 6 to 10 of the Periodic Table, each Hal is the same or different and is halogen, each R' is the same or different and is substituted or unsubstituted hydrocarbyl having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy or alkoxy, v is the valence of M and n is zero or an integer at most equal to v; b) complexing the metallic precursor of step a) with a ligand of formula
N-CH 2 -Y p (/
Fe
Cp
wherein Cp is a cyclopentadienyl group, unsubstituted or substituted, and wherein Y may have the form Y-Z and Y and Z, if present, may be the same or different and are selected from alkyl, aryl, heterocycle or a non- heterocycle group containing ether, thioether, phosphine, imine, amine or amide and Y and Z. c) adding an activating agent having an ionizing action.
2. The method of claim 1 wherein group CH 2 — Y or group CH 2 — Y — Z include atoms O, N, P, S or groups -CR=CR-, -CR=N-, -N=CR- or - C≡C- wherein R is H, alkyl or aryl groups having at most 20 carbon atoms and wherein the link between Y and Z can include a conjugation or not.
3. The method of claim 1 or claim 2 wherein group CH 2 — Y is either of
4. The method of any one of claims 1 to 3 M is Ni, Co, Cr, Pd or Fe.
5. The method of claim 4 wherein M is Cr.
6. The method of any one of the preceding claims wherein Hal is chlorine and wherein (v-n) is 0.
7. An active catalyst system obtainable by the method of any one of claims 1 to 6.
8. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins that comprises the steps of: a) injecting the active catalyst system of claim 7 into the reactor; b) injecting the monomer and optional comonomer; c) maintaining under polymerisation conditions; d) retrieving the oligomers and/or polymer.
9. The method of claim 8 wherein the monomer and comonomer are selected from ethylene, propylene or hexene. |
CATALYST COMPONENTS BASED ON FERROCENYL COMPLEXES USED FOR OLEFIN POLYMERISATION
The present invention discloses catalyst components based on ferrocenyl ligands their method of preparation and their use in the polymerisation of olefins.
In the search for new catalyst components capable of producing highly tunable polymers, some ferrocene complexes have been known to polymerise or co- polymerise ethylene such as for example the ferrocene-substituted bis(imino) pirydine iron and cobalt complexes disclosed by Gibson et al. in Gibson V.C., Long NJ., Oxford, PJ. , White AJ. P., and Williams DJ., in Organometallics ASAP article DOI : 10.1021/om0509589 or the ferrocene-substituted bis(imino) nickel and palladium complexes disclosed by Gibson et al. in J. Chem. Soc. Dalton Trans 2003, 918-926.
There is a need to develop new catalyst system having good activity and able to produce polymers tailored to specific needs.
It is an aim of the present invention to prepare new catalyst components that can be used in the polymerisation of olefins.
It is also an aim of the present invention to provide very active catalyst components.
It is another aim of the present invention to provide a method for polymerising or copolymerising olefins.
The present invention reaches, at least partially, any one of those aims.
Accordingly, the present invention discloses a catalyst system that comprises:
a) a metallic component obtained by complexation reaction of a metallic precursor M(HaI) n RVn in a solvent, wherein M is a metal Group 6 to 10 of the Periodic Table, each Hal is the same or different and is halogen, each
R' is the same or different and is substituted or unsubstituted hydrocarbyl having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy or alkoxy, v is the valence of M and n is zero or an integer at most equal to v with a ligand of formula
N-CH 2 -Y
Fe
Cp
wherein Cp is a cyclopentadienyl group, unsubstituted or substituted, and wherein Y may have the form Y-Z and Y and Z, if present, may be the same or different and are selected from alkyl, aryl, heterocycle or a non- heterocycle group containing ether, thioether, phosphine, imine, amine or amide and Y and Z. b) an activating agent having an ionizing action.
Alternatively, CH 2 — Y can be replaced by CH 2 Z — Y wherein Y is as defined here-above and Z is alkyl, aryl, heterocycle or a non-heterocycle group containing ether, thioether, phosphine, imine, amine or amide. Y and Z may be the same or different.
In a preferred embodiment according to the present invention, Z includes atoms O, N, P, S or groups -CR=CR-, -CR=N-, -N=CR- or -C≡C- wherein R is H, alkyl or aryl groups having at most 20 carbon atoms. The link between Y and Z can include a conjugation or not.
More preferably, Y is phenyl, furyl or pyridine group and CH 2 — Y is represented by formulas
\ /
The ligands of the present invention can be prepared following the method disclosed for example in Gibson et al. ((Chem. Soc. Rev., 2004, 33,313-328) or in Samuelson et al. (Journal of Organometallic Chemistry, 1999, 575, 108-118) or in Lewkowski et al. (Journal of Organometallic Chemistry, 2001 , 631 , 105-109) or in Vigota et al. (Inorganica Chimica Acta, 1999, 287, 117-133) or in Wright (Organometallics, 1990, 9, 853-856).
The ferrocenyl ligand is prepared by reacting a precursor of formula
(CHO-Cp) Fe (Cp) with an amine of formula
N H 2 - CH 2 - Y wherein Cp and Y are as defined previously.
List of figures.
Figure 1 represents the voltamograms of ferrocene ligand carrying different substituents Y. It is expressed as intensity in Amperes as a function of potential in Volts. Curve a represents the voltamogram of ligand 1 wherein Y is phenyl, curve b represents the voltamogram of ligand 2 wherein Y is pyridine and curve c represents the voltamogram of ligand 3 wherein Y is furyl.
The ligands of the present invention are characterised by a fully reversible status for the ferrocenylimine unit and by a total absence of conjugation between substituent group Y and metal Fe in the ligand. As the ferrocene and functional group Y are not conjugated it is allowed to modify or alter one entity, for example the ferrocene without influencing the other entity, for example the substituent Y. The electrochemical properties of the ferrocenylimines are thus fully reversible, even after modification of substituent Y. This behaviour is confirmed by electrochemical analysis of ferrocene ligands carrying different substituents Y, presented in Figure 1. Iron has the same electronic potential for all tested substituents Y. There is thus no conjugation between the two entities.
The invention also discloses a metallic complex obtained by metallation of the ferrrocene ligand with a metal salt of formula M(Hal) n R'v- n wherein M is a metal group 6 to 10 of the Periodic Table, wherein each Hal is the same or different and is halogen, wherein each R' is the same or different and is substituted or unsubstituted hydrocarbyl having from 1 to 20 carbon atoms, substituted or unsubstituted aryloxy or alkoxy, wherein v is the valence of M and n is zero or an integer at most equal to v.
Preferably M is Ni, Co, Fe, Pd or Cr. Preferably Hal is chlorine. Preferably n is equal to v.
The solvent may be selected from dichloromethane or tetrahydrofuran and the complexation reaction is carried out at room temperature or at reflux.
Typically, two types of metallic complexes could be formed, one where the metal is coordinated to one ligand and one where the metal is coordinated to two ligands. The relative amounts of each ligand and metal unit depend upon the nature of ligand and of the metal. The amount of ligand must therefore be of at least one equivalent of ligand per metallic equivalent.
The present invention further discloses an active catalyst system comprising the metallic complex and an activating agent having an ionising action.
Suitable activating agents are well known in the art. The activating agent can be an aluminium alkyl represented by formula AIR + n X3 -n wherein R + is an alkyl having from 1 to 20 carbon atoms and X is a halogen. The preferred alkylating agents are triisobutyl aluminium (TIBAL) or triethyl aluminium (TEAL).
Alternatively, it can be aluminoxane and comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by formula
R - (Al-O) n -Al R * 2
R*
for oligomeric, linear aluminoxanes and by formula
R*
for oligomeric, cyclic aluminoxane,
wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R * is a Ci-C 8 alkyl group and preferably methyl.
The amount of activating is selected to give an Al/M ratio of from 100 to 3000, preferably of about 1000.
Suitable boron-containing activating agents may comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L'-H] + [B An Ar 2 X3 X 4 ]- as described in EP-A-0277004 (page 6, line 30 to page 7, line 7). The amount of boron -containing activating agent is selected to give B/M ratio of from 0.5 to 5, preferably of about 1.
In another embodiment, according to the present invention, the metallic complex may be deposited on a conventional support impregnated with an activating agent. Preferably, the conventional support is silica impregnated with methylaluminoxane (MAO). Alternatively, it can be an activating support such as fluorinated alumina silica.
The present invention further discloses a method for preparing an active catalyst system that comprises the steps of: a) providing a ferrocenylimine ligand;
b) complexing the ligand of step a) with a metallic salt M(HaI) n RVn in a solvent; c) retrieving a catalyst component; d) activating the catalyst component with an activating agent having an ionising action; e) optionally adding a scavenger; f) retrieving an active oligomerisation or polymerisation catalyst system.
Alternatively, in step d), the catalyst component is deposited on a support impregnated with an activating agent or on an activating support.
The cocatalyst may be selected from thethylaluminium, thisobutylaluminum, tris-n- octylaluminium, tetraisobutyldialuminoxane or diethyl zinc.
The active catalyst system is used in the oligomerisation and in the polymerisation of ethylene and alpha-olefins.
The present invention discloses a method for the oligomerisation or the homo- or co- polymerisation of ethylene and alpha-olefins that comprises the steps of: a) injecting the active catalyst system into the reactor; b) injecting the monomer and optional comonomer; c) maintaining under polymerisation conditions; d) retrieving the oligomers and/or polymer.
The pressure in the reactor can vary from 0.5 to 50 bars, preferably from 5 to 25 bars.
The polymerisation temperature can range from 10 to 100 0 C, preferably from 50 to 85°C.
Preferably the monomer and optional comonomer are selected from ethylene, propylene or 1-hexene.
The present invention also discloses the polymers obtained with the new catalyst systems.
Examples.
All reactions were performed using standard Schlenk techniques or in an argon-filled glove-box. The starting materials and reagents, purchased from commercial suppliers, were degassed and purified by distillation under nitrogen using standard drying agents.
Preparation of ligands.
Synthesis of N-ferrocenylidenebenzylamine (1 ).
All complexes were prepared according to the method described for example in Gibson et al. (Chem Soc Rev., 2004, 33, 313-328) or in Samuelson et al. (Journal of Organometallic Chemistry, 1999, 575, 108-118).
300 mg (1.4 mmol) of solid ferrocenecarboxaldehyde were introduced in a schlenk. 90 μl_ (2.1 mmol) of benzylamine and 2 mg of p-toluene sulfonic acid were added. The mixture was dissolved in 20 ml_ of toluene and the homogeneous mixture was stirred and heated at reflux overnight (16h). The solution was cooled down to room temperature (25 0 C) and the solvent was vaporised under vacuum. After drying overnight under vacuum and at a temperature of 50 0 C, 374.7 mg (1.28 mmol) of orange solid were obtained with a yield of 91 %.
RMN 1 H (200MHz, CDCI 3 ): δ 8,26(s, CH=N, 1 H); 7,4-7,3 (m, ArH, 5H); 4,73 (m, C 5 H 4 , 2H); 4,69 (s, CH 2 Ph, 2H); 4,31 (m, C 5 H 4 , 2H); 4,20 (s, C 5 H 5 , 5H)
Synthesis of N-ferrocenylidenepyridinylmethanamine (2).
300 mg (1.4 mmol) of solid ferrocenecarboxaldehyde were introduced in a schlenk. 138 μl_ (2.1 mmol) of aminomethylpyridine were added. The mixture was dissolved in 20 ml_ of toluene and the homogeneous mixture was stirred and heated at reflux overnight (16h). The solution was cooled down to room temperature and the solvent was vaporised under vacuum. After drying overnight under vacuum and at a temperature of 50 0 C, 379 mg (1.25 mmol) of orange solid were obtained with a yield of 89 %.
RMN 1 H (200MHz, CDCI3): δ 8,58 (m, H pyr , 1 H); 8,34 (s, CH=N, 1 H); 7,68 (m, H pyr , 1 H); 7,38 (m, H pyr , 1 H); 7,17 (m, H pyr , 1 H), 4,80 (s, CH 2 , 2H); 4,70 (m, C 5 H 4 , 2H); 4,40 (m, C 5 H 4 , 2H); 4,18 (s, C 5 H 5 , 5H).
Synthesis of N-ferrocenylidenefurfurylamine (3).
300 mg (1.4 mmol) of solid ferrocenecarboxaldehyde were introduced in a schlenk. 138 μl_ (2.1 mmol) of furylamine and 2 mg of p-toluene sulfonic acid were added. The mixture was dissolved in 20 ml_ of toluene and the homogeneous mixture was stirred and heated at reflux overnight (16h). The solution was cooled down to room temperature and the solvent was vaporised under vacuum. After drying overnight under vacuum and at a temperature of 50 0 C, 381 mg (1.30 mmol) of orange solid were obtained with a yield of 93 %.
RMN 1 H (200MHz, CDCI 3 ): δ 8,20 (s, CH=N, 1H); 7,39 (m, H fur , 1H); 6,35 (m, H fur , 1H); 6,26 (m, H fur , 1H); 4,68 (m, C 5 H 4 , 2H); 4,61 (s, CH 2 , 2H), 4,39 (m, C 5 H 4 , 2H); 4,18(s, C 5 H 5 , 5H).
Complexation of ferrocenyl ligands with metallic precursors.
Complexation of ligand N-ferrocenylidenebenzylamine (1 ).
With CrCb.
2.46 mg (20 μmol) of metallic precursor CrCb were introduced in a schlenk. 11.7 mg (40 μmol) of ligand 1 were added. The solids were dissolved in 200 μl_ of tetrahydrofuran (THF) to reach a concentration of 0.1 mol/L. The solution was stirred at room temperature for a period of time of 3 h and the solvent was vaporised. A dark solid was obtained.
With CrCIa.
7.49 mg (20 μmol) of metallic precursor CrCl3.3THFwere introduced in a schlenk. 11.7 mg (40 μmol) of ligand 1 were added. The solids were dissolved in 200 μl_ of tetrahydrofuran (THF) to reach a concentration of 0.1 mol/L. The solution was stirred at room temperature for a period of time of 3 h and the solvent was vaporised. A dark solid was obtained.
Complexation of ligand N-ferrocenylidenepyridinylmethanamine (2).
With CrCb.
2.46 mg (20 μmol) of metallic precursor CrCb were introduced in a schlenk. 11.7 mg (40 μmol) of ligand 2 were added. The solids were dissolved in 200 μl_ of tetrahydrofuran (THF) to reach a concentration of 0.1 mol/L. The solution was stirred at room temperature for a period of time of 3 h and the solvent was vaporised. A dark solid was obtained.
With CrCIa.
7.49 mg (20 μmol) of metallic precursor CrCl3.3THFwere introduced in a schlenk. 11.7 mg (40 μmol) of ligand 2 were added. The solids were dissolved in 200 μL of tetrahydrofuran (THF) to reach a concentration of 0.1 mol/L. The solution was stirred at room temperature for a period of time of 3 h and the solvent was vaporised. A dark solid was obtained.
Complexation of ligand N-ferrocenylidenefurfurylamine (3).
With CrCb.
2.46 mg (20 μmol) of metallic precursor CrC^ were introduced in a schlenk. 12.2 mg (40 μmol) of ligand 3 were added. The solids were dissolved in 200 μl_ of tetrahydrofuran (THF) to reach a concentration of 0.1 mol/L. The solution was stirred at room temperature for a period of time of 3 h and the solvent was vaporised. A dark solid was obtained.
With CrCIa.
7.49 mg (20 μmol) of metallic precursor CrCl3.3THFwere introduced in a schlenk. 12.2 mg (40 μmol) of ligand 3 were added. The solids were dissolved in 200 μl_ of tetrahydrofuran (THF) to reach a concentration of 0.1 mol/L. The solution was stirred at room temperature for a period of time of 3 h and the solvent was vaporised. A dark solid was obtained.
Polymerisation of ethylene.
The metallic complexes obtained in the previous step were activated with 100 equivalents with respect to metal Cr of methylaluminoxane (MAO) 30 % in toluene.
The addition of total MAO was carried out in two steps:
1. as activator; and
2. as scavenger, mixed with toluene.
The catalyst component was deposited in a schlenk and 325 μl_ of MAO (30%) were added to the schlenk as activating agent. The solution was stirred for 5 minutes and then diluted with 4.7 ml_ of toluene.
The reactor was dried under nitrogen at a temperature of 110 0 C for a period of time of 30 minutes. The temperature was raised to 35 0 C and 50 ml_ of toluene were added to the reactor under nitrogen reflux. A solution of scavenger consisting of 100
μl of MAO at 30 % and 4.9 ml_ of toluene were added to the reactor and the solution was stirred during a few minutes. 20 μmol of the selected catalyst component were added to the reactor under nitrogen reflux. The nitrogen flux was stopped, the reactor was purged and placed under an ethylene pressure of 15 bars. Stirring was continued for a period of time of one hour. The reactor was then purged and the polymerisation was stopped by addition of a 10 % solution of MeOH/HCI. The polymer was washed three times with 30 ml_ of methanol and 30 ml_ of acetone and dried under vacuum overnight at room temperature. The results are presented in Table I.
TABLE I.