KIRILLOV EVGUENI (FR)
THOMAS CHRISTOPHE (FR)
RAZAVI ABBAS (BE)
CARPENTIER JEAN-FRANCOIS (FR)
KIRILLOV EVGUENI (FR)
THOMAS CHRISTOPHE (FR)
RAZAVI ABBAS (BE)
TIMMONS ET AL: "TEMPLATE SYNTHESIS AND CRYSTAL AND MOLECULAR STRUCTURE OF BIS(1,1,1,12,12,12-HEXAFLUORO-2,11-BIS(TRIFLUOROMETHYL)-4,9-DIMETHYL- 2,11-DIOLATO-5,8-DIAZADODECA-4,8-DIENE(2-))CERIUM(IV), CEC28H28F24O4N4. A FLUORINATED SCHIFF BASE COMPLEX OF", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 19, no. 12, 1980, pages 3553 - 3557, XP009079419, ISSN: 0020-1669
KONEFAL ET AL: "COORDINATION MODES OF POLYDENTATE LIGANDS. 1. TEMPLATE SYNTHESIS OF COMPLEXES OF NICKEL(2+), COPPER(2+), AND COBALT(2+) WITH PENTADENTATE AND HEXADENTATE LIGANDS: STRUCTURE OF A HIGHLY DISTORTED SIX-COORDINATE COBALT(2+) COMPLEX", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 23, no. 5, 1984, pages 538 - 545, XP009079427, ISSN: 0020-1669
BARTEN J A ET AL: "Simple access to novel beta-hydroxy-beta-trifluoromethyl imines", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 113, no. 1, 28 January 2002 (2002-01-28), pages 105 - 109, XP004332458, ISSN: 0022-1139
BARTEN J A ET AL: "Novel beta-hydroxy-beta-bis(trifluoromethyl) imines", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 125, no. 6, June 2004 (2004-06-01), pages 1039 - 1049, XP004528011, ISSN: 0022-1139
MARQUET ET AL: "Convenient synthesis of mono- and di-beta-hydroxy-beta-bis(trifluorom ethyl)-(di)imines from beta-hydroxy-beta-bis(trifluoromethyl)-ketones and (di)amines", TETRAHEDRON, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 64, no. 1, 1 November 2007 (2007-11-01), pages 75 - 83, XP022361254, ISSN: 0040-4020
| CLAIMS.
1. A fluorinated dialcohol-diimine pro-ligand of general formula
wherein
R 1 is a bridge having from 1 to 6 carbon atoms, substituted or unsubstituted and wherein the substituents if present may form a ring either with each other or with R 2 ;
R 2 are each independently selected from hydrogen, aryl or alkyl having from 1 to 20 carbon atoms, optionally substituted with one or more fluorinated groups;
R 3 and R 4 are each independently selected from perfluorinated alkyl groups, from aryl or alkyl having from 1 to 20 carbon atoms, with the restriction that at least one of
R 3 and R 4 is a perfluorinated alkyl group;
R 5 and R 6 are each independently selected from hydrogen, alkyl or aryl having from 1 to 20 carbon atoms.
2. The fluorinated dialcohol-diimine pro-ligand of claim 1 wherein the perfluorinated alkyl group is selected from CF 3 or C n F 2n+ I, wherein n is an integer between 1 and 10.
3. The fluorinated dialcohol-diimine pro-ligand of claim 1 or claim 2 wherein both R 2 are the same and are phenyl groups unsubstituted or substituted or alkyl groups, preferably methyl.
4. The fluorinated dialcohol-diimine pro-ligand of claim 3 wherein the phenyl groups are substituted with H, F or CF 3 at positions 2 and/or 3 and/or 4 and/or 5 and/or 6 or with isopropyl at positions 2 and 6.
5. The fluorinated dialcohol-diimine pro-ligand of any one of claims 1 to 4 wherein R 3 and R 4 are the same and are CF 3 or C n F 2n+ I, preferably CF 3
6. The fluorinated dialcohol-diimine pro-ligand of any one of the preceding claims wherein R 5 and R 6 are the same and are hydrogen.
7. A metallic complex resulting from the metallation reaction of the fluorinated dialcohol-diimine pro-ligand of any one of claims 1 to 6 with a metal salt of formula MX 4 wherein M is a metal group 4 of the Periodic Table, and wherein each X is the same or different and is halogen, alkyl or benzyl.
8. The metallic complex of claim 7 wherein X is chlorine or methyl or benzyl.
9. A method for preparing the metallic complex of claim 7 or claim 8 by the steps of: a) providing the pro-ligand of any one of claims 1 to 6; b) complexing it with metal salt or precursor of formula MX 4 wherein M and X are as defined in any one of claims 7 or 8.
10. An active catalyst system comprising the metallic complex of claim 7 or claim 8, an activating agent having an ionising action and optionally a cocatalyst.
11. The active catalyst of claim 10 wherein the activating agent is an aluminoxane or an activating support.
12. A method for oligomerising or homo- or co-polymerising ethylene or alpha- olefins that comprises the steps of: a. injecting the active catalyst system of claim 10 or claim 11 into the reactor; b. injecting the monomer and optional comononner(s) simultaneously with or after step a); c. maintaining under polymerisation conditions; d. retrieving an oligomer or a polymer. |
FLUORINATED DIALKOXY-DIIMINO CATALYST COMPONENTS
The present invention discloses catalyst components based on fluohnated dialkoxy- diimino ligands, their method of preparation and their use in the polymerisation or oligomerisation of olefins.
Investigations to replace ubiquitous cyclopentadienyl-type ligands in modern coordination chemistry of early transition metals have become very popular in recent years. Hard, electronegative π-donor ligands such as aryloxides/alkoxides are attractive because they offer strong metal-oxygen bonds that are expected to stabilize complexes of these electropositive metals. Also, the great variety of these ligands conveniently obtained from alcohols allows considerable stereo-electronic variations. Accordingly, group 4 metal complexes of the type [MX 2 (OZ) 2 ] and [MX 2 (OZZO)], where OZ " and OZZO 2" are monoanionic and chelating dianionic ligands respectively, have retained considerable attention. Most successful developments in terms of synthetic organometallic chemistry and catalysis have appeared using aryloxide (phenolate) ligands, with significant contributions of the groups of Fujita such as for example Matsui et al. (S. Matsui, M. Mitani, J. Saito, Y. Tohi, H. Makio, N. Matsukawa, Y. Takagi, K. Tsuru, M. Nitabaru, T. Nakano, H. Tanaka, N. Kashiwa, T. Fujita, in J. Am. Chem. Soc. 2001 , 123, 6847-6856) or Kojoh et al. (S. Kojoh, T. Matsugi, J. Saito, M. Mitani, T. Fujita, N. Kashiwa, Chem. Lett. 2001 , 822-823) or Saito et al. (J. Saito, M. Mitani, S. Matsui, J. Y. Mohri, S. Kojoh, N. Kashiwa, T. Fujita, Angew. Chem., Int. Ed. 2001 , 40, 2918-2920; Angew. Chem. 2001 , 113, 3002-3004) or Mitani et al. (M. Mitani, J. Mohri, Y. Yoshida, J. Saito, S. Ishii, K. Tsuru, S. Matsui, R. Furuyama, T. Nakano, H. Tanaka, S. -I. Kojoh, T. Matsugi, N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 2002, 124, 3327-3336) or Saito et al. (J. Saito, M. Mitani, J. Mohri, S. Ishii, Y. Yoshida, T. Matsugi, S. Kojoh, N. Kashiwa, T. Fujita, T. Chem. Lett. 2001 , 576-577) or Mitani et al. (M. Mitani, R. Furuyama, J. -I. Mohri, J. Saito, S. Ishii, H. Terao, N. Kashiwa, T. Fujita, J. Am. Chem. Soc. 2002, 124, 7888-7889) or of the group of Coates such as for example Tian and Coates (J. Tian, G. W. Coates, Angew. Chem., Int. Ed. 2000, 39, 3626-3629; Angew. Chem. 2000, 112, 3772-3775 or Tian et al. (J. Tian, P. D. Hustad, G. W. Coates, J.
Am. Chem. Soc. 2001 , 123, 5134-5135) or Mason and Coates (A. F. Mason, G. W. Coates, J. Am. Chem. Soc. 2004, 126, 16326-16327).
Comparatively, group 4 metal [MX 2 (OZ) 2 ] and [MX 2 (OZZO)] type complexes that incorporate simple (amino-)alkoxide ligands have been much less studied. This is mainly due to aggregation problems traditionally encountered with these relatively more basic ligands (as compared to aryloxides). A valuable approach to overcome this issue consists in introducing electron-withdrawing CF 3 groups α to the alkoxides; this generates increased intra- and inter-molecular repulsions and a much less basic alkoxide O-atom, and in turn a much reduced bridging ability. On this principle, Jordan et al. have developed "fluorous" group 4 complexes with two pyhdine-alkoxide ligands such as for example in Tsukahara et al (T. Tsukahara, D. C. Swenson, R. F. Jordan, Organometallics 1997, 16, 3303-3313). Tetradentate diamino-dialkoxide {ON n NO} 2" ligands with a ethylene- (n = 2), propylene- (n = 3) or chiral 1 ,2- cyclohexyldiamine backbone flanked by two fluorinated tertiary alkoxides were recently prepared as well as neutral groups 3, 4 and 13 metal complexes derived thereof. They are described for example in Lavanant et al. (L. Lavanant, T. -Y. Chou, Y. Chi, C. W. Lehmann, L. Toupet, J.-F. Carpentier, Organometallics 2004, 23, 5450- 5458) or in Amgoune et al. (A. Amgoune, L. Lavanant, C. M. Thomas, Y. Chi, R. Welter, S. Dagorne, J.-F. Carpentier, Organometallics, 2005, 24, 6279-6282) or in Kirillov et al. (E. Kirillov, L. Lavanant, C. M. Thomas, T. Roisnel, Y. Chi, J.-F. Carpentier, Chem. Eur. J. 2006, in press).
There is a demand for new catalyst systems having good activity and able to produce polymers or oligomers tailored to specific needs.
It is an aim of the present invention to prepare new catalyst components that can be used in the polymerisation or oligomerisation 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 homo- or co- polymerising or oligomerising olefins.
The present invention reaches, at least partially, any one of those aims.
Accordingly, the present invention discloses a class of fluohnated dialkoxy-diimine pro-ligands of formula
wherein
R 1 is a bridge having from 1 to 6 carbon atoms, substituted or unsubstituted and wherein the substituents if present may form a ring either with each other or with R 2 ;
R 2 are each independently selected from hydrogen, aryl or alkyl having from 1 to 20 carbon atoms, optionally substituted with one or more fluohnated groups;
R 3 and R 4 are each independently selected from perfluorinated alkyl groups, from aryl or alkyl having from 1 to 20 carbon atoms, with the restriction that at least one of
R 3 and R 4 is a perfluorinated alkyl group;
R 5 and R 6 are each independently selected from hydrogen, alkyl or aryl having from 1 to 20 carbon atoms.
The perfluorinated alkyl groups are preferably selected from CF 3 or C n F 2n +i, wherein n is an integer between 1 and 10.
The perfluorinated alkyl group is acting as a strongly electron withdrawing group. This property plays two important roles:
1 ) it decreases the basicity of alcohol OH group and therefore inhibits the formation of aggregates around O " .
2) it increases the electrophility of the metal and thus its activity in the polymerisation of olefins.
Preferably both R 2 are the same and are alkyl or phenyl unsubstituted or substituted. The substituents, if present, can be selected from H, F, CF 3 or isopropyl. If the substituents are H, F or CF 3 they are located preferably at positions 2 and/or 3 and/or 4 and/or 5 and/or 6. If they are isopropyl, they preferably occupy positions 2 and 6.
Preferably R 3 and R 4 are the same and are CF 3 or C n F 2n+ I, more preferably CF 3 .
Preferably R 5 and R 6 are the same and are hydrogen.
The invention also discloses a metallic complex obtained by metallation of the fluohnated dialkoxy-diimine pro-ligand with a metal salt or precursor of formula MX 4 wherein M is a metal group 4 of the Periodic Table, wherein each X is the same or different and is halogen, preferably chlorine, or alkyl or benzyl.
Preferably M is selected from Ti and Zr.
The solvent may be selected from dichloromethane (DCM) or tetrahydrofuran (THF) or a hydrocarbon such as toluene and the complexation reaction is carried out at a temperature of from 20 0 C to reflux.
The amount of ligand is of 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.
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 thphenylcarbenium 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 fluohnated alumina silica.
The present invention further discloses a method for preparing an active catalyst system that comprises the steps of: a) providing a fluorinated dialcohol-diimine pro-ligand; b) complexing the pro-ligand of step a) with a metallic salt or precursor MX 4 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 cocatalyst; 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 a fluorinated activating support.
The cocatalyst may be selected from thethylaluminium, triisobutylaluminum, tris-n- octylaluminium, tetraisobutyldialuminoxane or diethyl zinc.
The active catalyst system is used in the oligomerisation and in the homo- or co- 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, 1 -hexene, 1 -octene or styrene.
The present invention also discloses the polymers and oligomer compositions obtained with the new catalyst systems.
List of figures.
Figure 1 represents the crystal structure of pro-ligand 3.
Figure 2 represents the crystal structure of complex 5.
Examples-
Synthesis of 1 ,1 ,1 -trifluoro-4-r(2-{r4,4,4-trifluoro-3-hvdroxy-1 -methyl-3- (thfluoromethyl)butylidene1amino)ethyl)imino1-2-(thfluoromet hyl)pentan-2-ol (1 ).
A Schlenk tube was charged with 0.80 g of montmorillonite, 10 ml_ of chloroform and 2.75 g (12.27 mmol) of 4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butan-2-one. Under an argon atmosphere, 0.36 g (6.13 mmol) of 1 ,2- ethylene-diamine (0.36 g, 6.13 mmol) were added and the reaction mixture was refluxed for a period of time of 72 h. The reaction mixture was filtered off and the filtrate was concentrated under reduced pressure. The resulting oily product was recrystallised from methanol at room temperature to give 3.88 g of 1 as an orange solid with a yield of 69%. NMR results for 1 were as follows:
1 H NMR (500 MHz, CDCI 3 , 298K): δ (ppm) 2.04 (s, 6H, Me), 2.73 (s, 4H, CH 2 ), 3.66 (s, 4H, CH 2 N), 9.88 (s, 2H, OH). 13 C NMR (75 MHz, CDCI 3 , 298K): δ (ppm) 20.63 (CH 2 ), 33.41 (Me), 50.42 (CH 2 -N), 121.1 (C-OH), 125.5 (C-F), 171.42 (C=N). 19 F NMR (182 MHz, CDCI 3, 298K): δ (ppm) -78.9 (s, 12F). Anal. Calcd. for Ci 4 Hi 6 Fi 2 N 2 O 2 : C, 35.60; H, 3.41. Found: C, 36.44; H, 3.89.
Synthesis of racemic 4,4'-(cvclohexane-1 ,2-diylbis(azan-1-yl-1-ylidene))bis(1 ,1 ,1- trifluoro-2-(trifluoromethyl)pentan-2-ol) (rac-trans-2).
pro-Ligand 2 was prepared using the same procedure as that described for pro- ligand 1 starting from 0.80 g of montmohllonite, 2.50 g (11.1 mmol) of fluorinated aldol 4,4,4-trifluoro-3-hydroxy-3-(thfluoromethyl)butan-2-one and 0.63 g (5.5 mmol) of trans^ ,2-diaminocyclohexane to give 3.97 g of 2 as a white solid with a yield of 68%.
The melting temperature was of 108.4 0 C.
NMR results for rac-2 were as follows:
1 H NMR (500 MHz, CDCI 3, 298K): δ (ppm) 1.38-1.84 (m, 8H, cyclohexyl), 2.01 (s, 6H,
Me), 2.65 (m, 2H, CH-N du cyclohexyl), 10.19 (s, 2H, OH).
13 C NMR (75 MHz, CDCI 3 , 298K): δ (ppm) 170,0 (2C, CN), 21.10 (2C, CH 2 -C-CF 3 ),
24.20 (2C, CH 3 ), 32.02 (2C, CH 2 from cyclohexyl), 39.10 (2C, CH 2 -CN from cyclohexyl), 64.30 (2C, CH-N de cyclohexyl), 122.0 (2C, CO), 126.0 (2C, q, J CF =
CF 3 ).
19 F NMR (182 MHz, CDCI 3, 298K): δ (ppm) -78.72 (q, J = 10.5 Hz, 6F), -79.20 (q, J =
10.34 Hz, 6F).
HR-MS (70 eV, El): m/z calc. for Ci 8 H 22 Fi 2 N 2 O 2 : 526.1490; found: 526.1521 (6 ppm).
[M-CF 3 T (Ci 7 H 22 N 2 O 2 F 9 ); theor. mol. weigh: 457.1538; found: 457.1568.
Synthesis of 4,4'-((1 R2f?)-cvclohexane-1 ,2-diylbis(azan-1-yl-1-ylidene))bis(1 ,1 ,1- trifluoro-2-(thfluoromethyl)pentan-2-ol) (R,R-2).
(RR)-diol 2 was prepared using a procedure similar to that used to prepare racemic diol 2, starting from 1.20 g of montmorillonite, 4.24 g (18.95 mmol) of fluorinated aldol 4,4,4-trifluoro-3-hydroxy-3-(thfluoromethyl)butan-2-one and 0.63 g (5.5 mmol) of (1 R,2R)-diaminocyclohexane to give 6.97 g of {R,R)-2 with a yield of 70%. NMR results for (R,R)-2 were as follows:
1 H NMR (200 MHz, CDCI 3 , 298K): δ (ppm) 1.42-1.85 (m, 8H, cyclohexyl), 2.02 (s, 6H, 2Me), 2.66 (s, 4H, cyclohexyl), 3.57 (m, 2H, CH-N), 10.19 (s, 2H, OH). 19 F NMR (182 MHz, CDCI 3 , 298K): δ (ppm) -78.74 (q, J = 10.35 Hz, 6F), -79.22 (q, J = 10.35 Hz, 6F).
Synthesis of 4,4'-(2,2'-(ethane-1 ,2-diyl)bis(2,1-phenylene))bis(azan-1 -yl-1 - ylidene)bis(1 ,1 ,1-trifluoro-2-(trifluoromethyl)pentan-2-ol) (3).
In a 50 ml_ flask, a mixture of 3.00 g (13.39 mmol) of fluorinated aldol 4,4,4-trifluoro- 3-hydroxy-3-(thfluoromethyl)butan-2-one and 0.95 g (4.48 mmol) of 2-[2-(2- aminophenyl)ethyl]phenylamine in 40 ml_ of toluene, in the presence of a catalytic amount of paratoluenesulfonic acid (PTSA), was refluxed for 100 h using a Dean- Stark apparatus. The reaction mixture was filtered off, the filtrate was evaporated in vacuum and the residue was recrystallised from a CH 2 Cl2/toluene mixture to give 1.10 g of 3 as colourless crystals with a yield of 39%. NMR results for 3 were as follows:
1 H NMR (200 MHz, CD 2 CI 2 , 298K): δ (ppm) 1.95 (s, 6H, CH 3 ), 2.70 (s, 4H, CH 2 ), 2.97 (s, 4H, CH 2 ), 6.62 (m, 2H, arom.), 7.19 (m, 6H, arom.), 9.35 (s, 2H, OH). 19 F NMR (188 MHz, CD 2 CI 2, 298K): δ (ppm) -78.9. Anal. Calcd. for C 26 H 24 Fi 2 N 2 O 2 : C, 50.01 ; H, 3.87. Found: C, 51.00; H, 4.28.
Synthesis of rOC(CF 3 ) ? CH ? C(CH 3 )=NCH ? CH ? N=C(CH 3 )CH ? C(CF 3 ) ? OlZr(CH ? Ph) ? (41
1 ) NMR-scale synthesis: A Teflon-valved NMR tube was charged with 25.7 mg (54.42 μmol) of diol 1 and 24.8 mg (54.42 μmol) of Zr(CH 2 Ph) 4 . About 0.5 ml_ of dry toluene-ds were added under vacuum. The tube was kept for a period of time of 3 to 4 hours at a temperature of -30 0 C and NMR spectra were recorded. The formation of 4 proceeded with a yield of about 95%, as determined by 1 H NMR.
2) Preparative synthesis: to a solution of 0.42 g (0.86 mmol) of fluorinated aldol 4,4,4-trifluoro-3-hydroxy-3-(thfluoromethyl)butan-2-one in 4 ml_ of toluene, was added a solution of 0.41 g (0.89 mmol) of Zr(CH 2 Ph) 4 in 3 ml_ of toluene at a temperature of -30 0 C under vigorous stirring. The reaction mixture was kept at a temperature of -30 0 C overnight, after which 4 precipitated as a yellow crystalline solid. The product was separated and dried under vacuum to give 0.25 g of 4 with a yield of 38 %.
NMR results for 4 were as follows:
1 H NMR (500 MHz, CD 2 CI 2 , 298K): δ (ppm) 2.13 (s, 4H, ZrCH 2 Ph), 2.16 (s, 6H, CH 3 ),
2.89 (s, 4H, OC(CFs) 2 CH 2 ), 3.66 (s, 4H, NCH 2 ), 6.68 (d, 3 J = 7.5 Hz, 4H, o-Ph), 6.75
(t, 3 J = 7.5 Hz, 2H, p-Ph), 7.04 (m, 3 J = 7.5 Hz, 4H, m-Ph).
13 C( 1 HJ NMR (125 MHz, CD 2 CI 2 , 298K): δ (ppm) 21.1 (CH 2 Ph), 24.0 (CH 3 ), 40.6
((CFs) 2 CH 2 ), 51.3 (NCH 2 ), 79.5 (C(CF 3 ) 2 ), 119.9 (p-Ph), 123.8 (C(CFs) 2 ), 125.5 (o-
Ph), 127.6 (m-Ph), 151.1 (i-Ph), 177.5 (N=C(CH 3 )).
19 F NMR (188 MHz, CD 2 CI 2, 298K): δ (ppm) -76.9. Anal. Calcd. for C 28 H 28 Fi 2 N 2 O 2 Zr:
C, 45.22; H, 3.79. Found: C, 45.77; H, 3.84.
Synthesis of [OC(CF 3 ) ? CH ? C(CH 3 )=NCH ? CH ? N=C(CH 3 )CH ? C(CF 3 ) ? OlTiCI ? (5).
To a solution of 100 mg (0.21 mmol) of diol 1 in 4 ml_ of toluene, was added a solution of 20.1 mg (0.105 mmol) Of TiCI 4 and 30.1 mg (0.105 mmol) of Ti(O'Pr) 4 in 4 ml_ of toluene at a temperature of -30 0 C. The reaction mixture was kept at a temperature of -30 0 C overnight, and colourless crystals precipitated. The crystals were separated, washed with a minimal amount of toluene and dried under vacuum to give 70 mg of 5 with a yield of 56 % .
NMR results for 5 were as follows:
1 H NMR (500 MHz, CD 2 CI 2 , 298K): δ (ppm) 2.41 (s, 6H, CH 3 ), 3.66 (s, 4H,
C(CFs) 2 CH 2 ), 4.20 (s, 4H, NCH 2 ). 13 C( 1 HJ NMR (125 MHz, CD 2 CI 2, 298K): δ (ppm)
23.6 (CH 3 ), 41.8 ((CFs) 2 CH 2 ), 46.7 (NCH 2 ), 85.3 (C(CF 3 J 2 ), 122.2 (C(CF 3 J 2 ), 173.9
(N=C(CH 3 )).
19 F NMR (188 MHz, CD 2 CI 2, 298K): δ (ppm) -76.2.
Anal. Calcd. for Ci 4 Hi 4 CI 2 Fi 2 N 2 O 2 Ti: C, 28.55; H, 2.40. Found: C, 28.96; H, 2.59.
Polymerisation of ethylene and styrene.
The polymerisations was carried out in 50 ml_ of toluene, at room temperature and for a period of time of 30 minutes.
12 mg of catalyst component
were used with 500 equivalents of methylaluminoxane (MAO) and under an ethylene pressure of 1 bar. No polymers were formed.
The same catalyst component was used for the polymerisation of styrene with 500 equivalents of MAO and 1000 equivalents of styrene and for a period of time of 2 hours.
At room temperature the activity was of 28 kg/mol/h and at a temperature of 50 0 C, it was of 7 kg/mol/h.