WO2009015922A1 - New tridentate ligand compounds with imino furan units, method for manufacturing said compounds, and their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins. - Google Patents

New tridentate ligand compounds with imino furan units, method for manufacturing said compounds, and their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins. Download PDF

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Publication number
WO2009015922A1
WO2009015922A1 PCT/EP2008/056692 EP2008056692W WO2009015922A1 WO 2009015922 A1 WO2009015922 A1 WO 2009015922A1 EP 2008056692 W EP2008056692 W EP 2008056692W WO 2009015922 A1 WO2009015922 A1 WO 2009015922A1
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furan
methyleneamino
phenyl
trifluoromethyl
formula
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French (fr)
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Sabine Sirol
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Total Petrochemicals Research Feluy SA
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Total Petrochemicals Research Feluy SA
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Priority to CN200880019908XA priority Critical patent/CN101678319B/en
Priority to US12/664,461 priority patent/US8426540B2/en
Priority to JP2010511575A priority patent/JP5186559B2/en
Priority to EP08826827A priority patent/EP2155379A1/en
Priority to KR1020097025943A priority patent/KR101166402B1/en
Publication of WO2009015922A1 publication Critical patent/WO2009015922A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
    • C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to new tridentate ligand compounds with imino furan units, to a method for manufacturing said compounds and to their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins .
  • the present invention relates to the use of such new ligand compounds for preparing metallic complexes useful as catalysts for the homopolymerisation and copolymerisation of ethylene and ⁇ -olefins, to the catalytic systems including such metallic complexes and to a method for homopolymerising or copolymerising ethylene and ⁇ -olefins using such catalytic systems.
  • R a , R >2d, R c and R 2x x have different meanings.
  • the Applicant searched for other ligands in order to produce new catalysts for the polymerisation of ethylene and of ⁇ -olefins, and discovered the new tridentate anionic ligands with imino furane units, which are the subject-matter of the present invention.
  • the homopolymers of ethylene obtained with such new catalysts are linear and have a monomodal distribution of polydispersity of 3 to 9 with very small tail ends.
  • a first subject-matter of the present invention relates to a compound of formula (I) :
  • R 1 to R 8 each represent independently hydrogen, halogen, a substituted or unsubstituted C1-C20 hydrocarbyl group, an inert functional group, wherein each of the radicals R 1 to R 8 can be linked to a neighbouring radical in order to form a cycle with carbon atoms to which said radicals are attached ;
  • the hydrocarbyl groups encompass methyl, tert- butyl and phenyl groups.
  • the hydrocarbyl groups can include a heteroatom such as oxygen or nitrogen atoms in their chains.
  • the possible substituents of hydrocarbyl groups can be selected among CF 3 , NO2, OMe and halogen such as Cl.
  • the inert functional groups can be selected among CF 3 , NO 2 , OMe and halogen.
  • R 1 to R 3 are each preferably selected independently from the group consisting of hydrogen and aryl groups.
  • Aryl groups can be selected among phenyl, naphthyl, and substituted phenyl groups.
  • R 4 is preferably selected in the group consisting of hydrogen and methyl group.
  • R 5 to R 8 are preferably independently selected in the group consisting of hydrogen, alkyl, aryl, methoxy, halogen, nitro and cyano .
  • Y is preferably 0.
  • m is preferably 0 or 1.
  • Another subject-matter of the present invention relates to a method for manufacturing a compound of formula (I) as defined above, characterised in that a compound of formula (II) :
  • a further subject-matter of the present invention relates to the use of a compound as defined above or prepared by the method as defined above as a ligand of a metallic complex.
  • a further subject-matter of the present invention relates to a metallic complex of the formula (IV) :
  • R 1 to R 8 , Y and m are as defined above ;
  • - M is a metal belonging to groups 3 to 8 of the Periodic Classification ;
  • - X represents an halogen, a substituted or unsubstituted C1-C20 hydrocarbyl group, an amino group, an aryloxy group or an alkoxy group ;
  • - n is a numeral value determined by the oxidation state of the metal minus one.
  • R 1 to R 8 , Y and m are as mentioned above for the compound of formula (I) .
  • M is preferably selected from the metals belonging to groups 3 to 8 of the Periodic Classification, being in particular Ti, Cr, Fe, Zr, Hf, V, Mn, a rare-earth metal, being preferably Ti, Cr, Fe and Zr.
  • X preferably represents halogen, alkyl such as benzyl, amino such as dimethylamino, alkoxy such as isopropoxy, aryloxy such as phenoxy, preferably halogen such as chlorine.
  • a further subject-matter of the present invention relates to a method for manufacturing a metallic complex as defined above, wherein a metallic compound of formula (V) :
  • a further subject-matter of the present invention relates to the use of the metallic complex as defined above or prepared by the process as defined above as a catalyst in the homopolymerisation and the copolymerisation of ethylene and ⁇ -olefins.
  • Exemplary ⁇ -olefins are the ones having from 3 to 8 carbon atoms, preferably propylene.
  • a further subject-matter of the present invention relates to a catalytic system comprising : the metallic complex as defined above ; - an activating agent selected in particular from the aluminum alkyls, the aluminoxanes and the boron-based activators ; and optionally, a carrier of the said metallic complex.
  • the aluminum alkyls are represented by the formula AlR x , wherein R are all identical or different, and are selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3.
  • Especially suitable aluminum alkyls are dialkylaluminum chloride, the most preferred being diethylaluminum chloride (Et 2 AlCl) .
  • the preferred aluminoxanes comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by the formula :
  • R" for oligomeric, cyclic aluminoxanes, wherein :
  • - p is 1-40, preferably 10-20 ;
  • - o is 3-40, preferably 3-20 ; and - R' or R" is a Ci-Cs alkyl group, being preferably methyl. Methylaluminoxane is preferably used.
  • Suitable boron-based activating agents that can be used comprise a triphenyl carbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium
  • the support if present, can be a porous mineral oxide. It is advantageously selected from silica, alumina and mixtures thereof. Preferably, it is silica.
  • the activating agent is preferably an alkyl aluminum or an aluminoxane, the molar ratio Al/M being approximately 500 to 2000, preferably about 1000.
  • Still a further subject-matter of the present invention relates to a method for homopolymerising or copolymerising ethylene and ⁇ -olefins, comprising the steps of : (a) injecting into the reactor the catalytic system as defined above, a solvent and optionally a scavenger ; (b) injecting the monomer and optional comonomer(s) into the reactor either before or after or simultaneously with step (a) ; (c) maintaining under polymerisation conditions ;
  • the scavenger may be selected from aluminium alkyls or diethyl zinc.
  • the monomers that can be used in the present invention are selected among ethylene and ⁇ -olefins having from 3 to 8 carbon atoms, being preferably ethylene and propylene .
  • the conditions of temperature and pressure for the polymerisation process are not particularly limited.
  • the pressure in the reactor can vary from 0.5 to 50 bars, preferably from 15 to 29 bars.
  • the polymerisation temperature can range from 10 to 100 0 C, preferably from 40 to 90 0 C.
  • the solvent is typically selected from alcanes or toluene, being preferably toluene, heptane or isobutane.
  • the reaction is usually carried out for a period of time of from 15 minutes to 24 hours.
  • the polymer obtained according to the present invention is typically obtained as a powder.
  • the homopolyethylene that can be obtained have a Mn of 25 to 75 kDa , preferably of 30 - 60 kDa , a Mw of 150 - 400 kDa , preferably of 175-350 kDa, and a Mw/Mn of about 3 to 9.
  • the following Examples are intended to illustrate the present invention without limiting its scope.
  • the aminophenol (12 mmol) was added to a solution of furan-2-carbaldehyde (12 mmol) and acid acetic (0.4 ml) in ethanol (30 ml) . The mixture was stirred at room temperature for 18 hours. Then the solvent was removed by evaporation under reduced pressure at 50 0 C.
  • Example 1_ Preparation of 2- ⁇ [5- (2-
  • the yield is defined as follows: mass of complex obtained/mass of complex expected for 2.5 mmol
  • the yield is defined as follows: mass of complex obtained/mass of complex expected for 2.5 mmol
  • the support used was silica Sylopol® 952x1836 from Grace, modified with MAO to obtain a support with 60 wt% of MAO.
  • the complex and the support were stirred in 50 ml of toluene at room temperature during 2 hours. Then the toluene was removed, the resulting catalyst was washed 3 times with pentane and dried under vacuum. The data are given in table 3.
  • Ethylene polymerisation reactions were carried out in a 130 ml stainless steel autoclave equipped with mechanical stirring and a stainless steel injection cylinder.
  • the reactor was first dried under nitrogen flow at 100 0 C during 10 min. Then it was cooled down to the reaction temperature (85°C) and 35 ml of isobutane were introduced into the reactor with a syringe pump, followed by the comonomer if required. The pressure was adjusted to the desired value (23.8 bar) with ethylene.
  • Activity is expressed as g polyethylene per g catalyst per hour .
  • the melting temperature Tm of example 42 was of 132.3°C as measured by DSC.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Furan Compounds (AREA)

Abstract

The present invention relates to new tridentate ligand compounds with imino furan units, to a method for manufacturing said compounds and to their use in the preparation of catalysts for the homopolymerisation or copolymerisation of ethylene and alpha-olefins.

Description

NEW TRIDENTATE LIGAND COMPOUNDS WITH IMINO FURAN UNITS, METHOD FOR MANUFACTURING SAID COMPOUNDS, AND THEIR USE IN THE PREPARATION OF CATALYSTS FOR THE HOMOPOLYMERISATION AND COPOLYMERISATION OF ETHYLENE AND ALPHA-OLEFINS
The present invention relates to new tridentate ligand compounds with imino furan units, to a method for manufacturing said compounds and to their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins .
More precisely, the present invention relates to the use of such new ligand compounds for preparing metallic complexes useful as catalysts for the homopolymerisation and copolymerisation of ethylene and α-olefins, to the catalytic systems including such metallic complexes and to a method for homopolymerising or copolymerising ethylene and α-olefins using such catalytic systems.
Different neutral bidentate ligands with imino furan units are mentioned : In US patent 5,714,556 (ligand 78, column 36) :
Figure imgf000002_0001
in WO 00/50470 (ligand al8, p 28) or corresponding US patent 6,545,108 Bl
Figure imgf000002_0002
wherein R a, R >2d, R c and R 2xx have different meanings. The Applicant searched for other ligands in order to produce new catalysts for the polymerisation of ethylene and of α-olefins, and discovered the new tridentate anionic ligands with imino furane units, which are the subject-matter of the present invention. The homopolymers of ethylene obtained with such new catalysts are linear and have a monomodal distribution of polydispersity of 3 to 9 with very small tail ends.
A first subject-matter of the present invention relates to a compound of formula (I) :
Figure imgf000003_0001
wherein :
R1 to R8 each represent independently hydrogen, halogen, a substituted or unsubstituted C1-C20 hydrocarbyl group, an inert functional group, wherein each of the radicals R1 to R8 can be linked to a neighbouring radical in order to form a cycle with carbon atoms to which said radicals are attached ;
Y represents 0 or NR*, R* being a C1-C12 alkyl group or a C6-C12 aryl group ; m is 0 , 1 or 2.
The hydrocarbyl groups encompass methyl, tert- butyl and phenyl groups. The hydrocarbyl groups can include a heteroatom such as oxygen or nitrogen atoms in their chains.
The possible substituents of hydrocarbyl groups can be selected among CF3, NO2, OMe and halogen such as Cl. The inert functional groups can be selected among CF3, NO2, OMe and halogen.
R1 to R3 are each preferably selected independently from the group consisting of hydrogen and aryl groups. Aryl groups can be selected among phenyl, naphthyl, and substituted phenyl groups.
R4 is preferably selected in the group consisting of hydrogen and methyl group.
R5 to R8 are preferably independently selected in the group consisting of hydrogen, alkyl, aryl, methoxy, halogen, nitro and cyano .
Y is preferably 0. m is preferably 0 or 1.
Specific compounds of formula (I) are the following ones : • 2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino }phenol
• 4-methyl-2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino }phenol
• 4-tert-butyl-2- { [5- (2- (trifluoromethyl) phenyl) furan-2- 1 ] methyleneamino lphenol
• 3-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl ] methyleneamino }biphenyl-4-ol
• 4-chloro-2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino }phenol • 2-{ [5- (3- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino }phenol
• 4-nitro-2-{ [5- (4-nitrophenyl) furan-2- yl ] methyleneamino }phenol
• 2-{ [5- (4-nitrophenyl) furan-2-yl] methyleneamino lphenol • 2- { [5- (3-nitrophenyl) furan-2-yl] methyleneamino lphenol
• 2- { [ 5- (3-chlorophenyl) furan-2- yl) ] methyleneamino lphenol
• 2-{ [5- (2-chlorophenyl) furan-2-yl] methyleneamino lphenol
• 2-{ [5- (4-chlorophenyl) furan-2-yl] methyleneamino lphenol Another subject-matter of the present invention relates to a method for manufacturing a compound of formula (I) as defined above, characterised in that a compound of formula (II) :
Figure imgf000005_0001
wherein R1 to R4 are as defined above is reacted with a compound of formula (III!
Figure imgf000005_0002
wherein m is 0, 1 or 2 and R° to R8 are as defined above. The general conditions of such a reaction are as follows :
- Reacting compound (III) with compound (II) in an alcohol such as methanol or ethanol, in the presence of a catalytic amount of a protic acid such as acetic acid, at room temperature.
Removing the solvent by evaporation under reduced pressure to recover compound (I) .
- Recrystallising or washing the product in an alcane such as pentane or hexane .
A further subject-matter of the present invention relates to the use of a compound as defined above or prepared by the method as defined above as a ligand of a metallic complex.
A further subject-matter of the present invention relates to a metallic complex of the formula (IV) :
Figure imgf000006_0001
wherein :
- R1 to R8, Y and m are as defined above ;
- M is a metal belonging to groups 3 to 8 of the Periodic Classification ;
- X represents an halogen, a substituted or unsubstituted C1-C20 hydrocarbyl group, an amino group, an aryloxy group or an alkoxy group ; and
- n is a numeral value determined by the oxidation state of the metal minus one.
The preferred definitions for R1 to R8, Y and m are as mentioned above for the compound of formula (I) .
M is preferably selected from the metals belonging to groups 3 to 8 of the Periodic Classification, being in particular Ti, Cr, Fe, Zr, Hf, V, Mn, a rare-earth metal, being preferably Ti, Cr, Fe and Zr. X preferably represents halogen, alkyl such as benzyl, amino such as dimethylamino, alkoxy such as isopropoxy, aryloxy such as phenoxy, preferably halogen such as chlorine.
A further subject-matter of the present invention relates to a method for manufacturing a metallic complex as defined above, wherein a metallic compound of formula (V) :
MXn+I (V)
wherein M, X and n are as defined above is reacted with a ligand of the formula (I) as defined above .
The general conditions of such a reaction are as follows : - Optionally reacting compound (I) with an equimolar amount of a deprotonating agent such as sodium hydride or butyl lithium, in tetrahydrofuran or diethyl ether at low temperature, under inert atmosphere.
- Adding the resulting mixture or a solution of compound (I) in tetrahydrofuran or diethyl ether to compound (V) and stirring at room temperature.
Removing the solvent by evaporation under reduced pressure .
- Optionally dissolving the residue in an other solvent such as toluene or dichloromethane, filtering this solution to eliminate the sodium or the lithium salt and evaporating the filtrate to recover compound (IV) .
A further subject-matter of the present invention relates to the use of the metallic complex as defined above or prepared by the process as defined above as a catalyst in the homopolymerisation and the copolymerisation of ethylene and α-olefins.
Exemplary α-olefins are the ones having from 3 to 8 carbon atoms, preferably propylene.
A further subject-matter of the present invention relates to a catalytic system comprising : the metallic complex as defined above ; - an activating agent selected in particular from the aluminum alkyls, the aluminoxanes and the boron-based activators ; and optionally, a carrier of the said metallic complex.
• The aluminum alkyls are represented by the formula AlRx, wherein R are all identical or different, and are selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3. Especially suitable aluminum alkyls are dialkylaluminum chloride, the most preferred being diethylaluminum chloride (Et2AlCl) .
• The preferred aluminoxanes comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by the formula :
R1 (Al-O)p—AlR1 2
for oligomeric, linear aluminoxanes, and
(—Al-O—)o
I
R" for oligomeric, cyclic aluminoxanes, wherein :
- p is 1-40, preferably 10-20 ;
- o is 3-40, preferably 3-20 ; and - R' or R" is a Ci-Cs alkyl group, being preferably methyl. Methylaluminoxane is preferably used.
• Suitable boron-based activating agents that can be used comprise a triphenyl carbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium
[C(Ph3)+ B (C6H5T4] as described in EP-A-O, 427, 696, or those of the general formula [L-H'] + [BArIAr2XsX4]- as described in EP-A-O 277 004 (page 6, line 30 to page 7, line 7) .
The support, if present, can be a porous mineral oxide. It is advantageously selected from silica, alumina and mixtures thereof. Preferably, it is silica.
The activating agent is preferably an alkyl aluminum or an aluminoxane, the molar ratio Al/M being approximately 500 to 2000, preferably about 1000. Still a further subject-matter of the present invention relates to a method for homopolymerising or copolymerising ethylene and α-olefins, comprising the steps of : (a) injecting into the reactor the catalytic system as defined above, a solvent and optionally a scavenger ; (b) injecting the monomer and optional comonomer(s) into the reactor either before or after or simultaneously with step (a) ; (c) maintaining under polymerisation conditions ;
(d) optionally adding an acidic solution of an alcohol to precipitate and filtrate the polymer ;
(e) retrieving the polymer under the form of a powder.
The scavenger may be selected from aluminium alkyls or diethyl zinc.
The monomers that can be used in the present invention are selected among ethylene and α-olefins having from 3 to 8 carbon atoms, being preferably ethylene and propylene .
The conditions of temperature and pressure for the polymerisation process are not particularly limited.
The pressure in the reactor can vary from 0.5 to 50 bars, preferably from 15 to 29 bars.
The polymerisation temperature can range from 10 to 1000C, preferably from 40 to 900C.
The solvent is typically selected from alcanes or toluene, being preferably toluene, heptane or isobutane. The reaction is usually carried out for a period of time of from 15 minutes to 24 hours.
The polymer obtained according to the present invention is typically obtained as a powder. The homopolyethylene that can be obtained have a Mn of 25 to 75 kDa , preferably of 30 - 60 kDa , a Mw of 150 - 400 kDa , preferably of 175-350 kDa, and a Mw/Mn of about 3 to 9. The following Examples are intended to illustrate the present invention without limiting its scope.
In these Examples, the following abbreviation have been used : MAO : Methylaluminoxane Me : Methyl Ph : Phenyl tBu : tert-Butyl TiBAl : Triisobutylaluminium
Examples 1 to 12 : Synthesis of furan-iminophenol ligands
Figure imgf000010_0001
Furan-2-carbaldehyde Aminophenol Furan-iminophenol
General procedure
The aminophenol (12 mmol) was added to a solution of furan-2-carbaldehyde (12 mmol) and acid acetic (0.4 ml) in ethanol (30 ml) . The mixture was stirred at room temperature for 18 hours. Then the solvent was removed by evaporation under reduced pressure at 500C.
The residue was recrystallised in pentane at a temperature of -200C (Examples 1 to 6). Alternatively, the residue was stirred with 250 ml of pentane, filtered and dried under vacuum (Examples 7 to 12) . Example 1_ : Preparation of 2- { [5- (2-
( trifluoromethyl) phenyl) furan-2-yl ] methyleneamino } phenol (R1 = 2-CF3-C6H4 ; R6 = H)
Using 2-aminophenol and 5- (2-
(trifluoromethyl) phenyl) furan-2-carbaldehyde, 3.53 g of 2- { [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino jphenol were obtained as a yellow powder (yield 89%) .
RMN1 H (CD2Cl2, 500 MHz) : ppm 8.57 (s, IH, HC=N), 7.92 (d, IH, CF3-C6H4), 7.86 (d, IH, CF3-C6H4), 7.69 (t, IH, CF3-C6H4), 7.57 (t, IH, CF3-C6H4), 7.50 (s, IH, OH), 7.35 (dd, IH, C6H4OH), 7.23 (td, IH, C6H4OH), 7.18 (d, IH, C4H2O), 7.02 (dd, IH, C6H4OH), 6.95 (td, IH, C6H4OH), 6.94 (d, IH, C4H2O).
Example 2_ : Preparation of 4-methyl-2-{ [5- (2-
( trifluoromethyl) phenyl) furan-2-yl] methyleneamino } phenol (R1 = 2-CF3-C6H4 ; R6 = Me)
Using 2-amino-4-methylphenol and 5- (2- (trifluoromethyl) phenyl) furan-2-carbaldehyde, 3.82 g of 4- methyl-2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl ] methyleneamino jphenol were obtained as a yellow powder (yield 92 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.53 (s, IH, HC=N), 7.90 (d, IH, CF3-C6H4), 7.85 (d, IH, CF3-C6H4), 7.68 (t, IH, CF3-C6H4), 7.56 (t, IH, CF3-C6H4), 7.36 (s, IH, OH), 7.15 (m, 2H, C6H3OH and C4H2O), 7.05 (dq, IH, C6H3OH), 6.92 (m, 2H, C6H3OH and C4H2O), 2.35 (s, 3H, CH3). Example 3 : Preparation of 4-tert-butyl-2- { [5- (2- ( trifluoromethyl) phenyl) furan-2-yl ] methyleneamino } phenol (R1 = 2-CF3-C6H4 ; R6 = tBu)
Using 2-amino-4-tert-butylphenol and 5- (2-
( trifluoromethyl) phenyl) furan-2-carbaldehyde, 4.25 g of 4- tert-butyl-2- { [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino jphenol were obtained as a yellow powder (yield 91 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.57 (s, IH, HC=N), 7.91 (d, IH, CF3-C6H4), 7.85 (d, IH, CF3-C6H4), 7.67 (t, IH, CF3-C6H4), 7.56 (t, IH, CF3-C6H4), 7.39 (s, IH, OH), 7.35 (d, IH, C6H3OH), 7.28 (dd, IH, C6H3OH), 7.16 (d, IH, C4H2O), 6.94 (m, 2H, C6H3OH and C4H2O), 1.37 (s, 9H, tBu).
Example 4_ : Preparation of 3- { [5- (2-
( trifluoromethyl) phenyl) furan-2-yl] methyleneamino jbiphenyl- 4-ol (R1=2-CF3-C6H4; R6=Ph)
Using 3-aminobiphenyl-4-ol and 5- (2- (trifluoromethyl) phenyl) furan-2-carbaldehyde, 1.64 g of 3- { [5- (2- (trifluoromethyl) phenyl) furan-2- yl ] methyleneamino }biphenyl-4-ol was obtained as an orange powder (yield 34 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.62 (s, IH, HC=N), 7.91 (d, IH, CF3-C6H4), 7.85 (d, IH, CF3-C6H4), 7.67 (t, IH, CF3-C6H4), 7.63 (m, 3H, Ph), 7.56 (m, 2H, OH and CF3-C6H4), 7, 49 (m, 3H, C6H3OH and Ph), 7.37 (tt, IH, C6H3OH), 7.19 (d, IH, C4H2O), 7.11 (d, IH, C6H3OH), 6.95 (d, IH, C4H2O). Example 5 : Preparation of 4-chloro-2-{ [5- (2-
(trifluoromethyl) phenyl) furan-2-yl ] methyleneamino }phenol (R1 = 2-CF3-C6H4 ; R6 = Cl)
Using 2-amino-4-chlorophenol and 5- (2-
(trifluoromethyl) phenyl) furan-2-carbaldehyde, 3.76 g of 4- chloro-2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino lphenol were obtained as a yellow powder (yield 86 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.52 (s, IH, HC=N), 7.91 (d, IH, CF3-C6H4), 7.86 (d, IH, CF3-C6H4), 7.71 (t, IH, CF3-C6H4), 7.59 (t, IH, CF3-C6H4), 7.38 (s, IH, OH), 7.34 (d, IH, C6H3OH), 7.22 (d, IH, C4H2O), 7.19 (dd, IH, C6H3OH), 6.97 (d, IH, C6H3OH), 6.95 (d, IH, C4H2O).
Example 6 : Preparation of 2- { [5- (3-
( trifluoromethyl) phenyl) furan-2-yl] methyleneamino } phenol (R1 = 3-CF3-C6H4 ; R6 = H)
Using 2-aminophenol and 5- (3- (trifluoromethyl) phenyl) furan-2-carbaldehyde, 3.44 g of 2- { [5- (3- (trifluoromethyl) phenyl) furan-2- yl ] methyleneamino jphenol were obtained as a yellow powder (yield 86 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.59 (s, IH, HC=N), 8.10 (m,
IH, CF3-C6H4), 8.05 (dm, IH, CF3-C6H4), 7.64 (m, 2H, CF3-
C6H4), 7.44 (s, IH, OH), 7.36 (dd, IH, C6H4OH), 7.24 (ddd, IH, C6H4OH), 7.20 (d, IH, C4H2O), 7.03 (dd, IH, C6H4OH), 7.01
(d, IH, C4H2O), 6.96 (ddd, IH, C6H4OH).
Example 7 : Preparation of 4-nitro-2- { [5- (4- nitrophenyl) furan-2-yl] methyleneamino lphenol (R1 = 4-NO2- C6H4 ; R6 = NO2) Using 2-amino-4-nitrophenol and 5- (4- nitrophenyl) furan-2-carbaldehyde, 4.10 g of 4-nitro-2- { [5- (4-nitrophenyl) furan-2-yl] methyleneamino jphenol were obtained as a yellow powder (yield 97 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.72 (s, IH, HC=N), 8.36 (m, 2H, NO2-C6H4), 8.31 (d, IH, C6H3OH), 8.2 (dd, IH, C6H3OH), 8.04 (m, 2H, NO2-C6H4), 7.34 (d, IH, C6H3OH), 7.16 (m, 2H, C4H2O) .
Example 8 : Preparation of 2- {[ 5- (4-nitrophenyl) furan-2- yl]methyleneamino}phenol (R1 = 4-NO2-C6H4 ; R6 = H)
Using 2-aminophenol and 5- (4-nitrophenyl) furan-2- carbaldehyde, 3.62 g of 2- {[ 5- (4-nitrophenyl) furan-2- yl ] methyleneamino jphenol were obtained as a yellow powder (yield 98%) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.59 (s, IH, HC=N), 8.33 (m, 2H, NO2-C6H4), 7.99 (m, 2H, NO2-C6H4), 7.49 (s, IH, OH), 7.37
(dd, IH, C6H4OH), 7.25 (td, IH, C6H4OH), 7.21 (d, IH, C4H2O),
7.12 (d, IH, C4H2O), 7.04 (dd, IH, C6H4OH), 6.97 (td, IH,
C6H4OH) .
Example 9 : Preparation of 2- {[ 5- (3-nitrophenyl) furan-2- yl]methyleneamino}phenol (R1 = 3-NO2-C6H4 ; R6 = H)
Using 2-aminophenol and 5- (3-nitrophenyl) furan-2- carbaldehyde, 3.51 g of 2- {[ 5- (3-nitrophenyl) furan-2- yl] methyleneamino jphenol were obtained as a yellow powder (yield 95 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.62 (t, IH, NO2-C6H4), 8.55
(s, IH, HC=N), 8.24 (dm, IH, NO2-C6H4), 8.13 (dm, IH, NO2- C6H4), 7.65 (t, IH, NO2-C6H4), 7.34 (dd, IH, C6H4OH), 7.24
(td, IH, C6H4OH), 7.18 (d, IH, C4H2O), 7.05 (d, IH, C4H2),
7.04 (dd, IH, C6H4OH), 6.96 (td, IH, C6H4OH). Example 10 : Preparation of 2- { [5- (3-chlorophenyl) furan-2- yl) ]methyleneamino}phenol (R1 = 3-Cl-C6H4 ; R6 = H)
Using 2-aminophenol and 5- (3-chlorophenyl) furan-
2-carbaldehyde, 2.94 g of 2- { [5- (3-chlorophenyl) furan-2- yl ] methyleneamino jphenol were obtained as a yellow powder (yield 82 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.43 (s, IH, HC=N), 7.9 (s, IH, OH), 7.78 (m, IH, Cl-C6H4), 7.64 (dt, IH, Cl-C6H4), 7.35 (m, 2H, Cl-C6H4 and C6H4OH), 7.27 (m, 2H, Cl-C6H4 and C6H4OH), 7.06 (m, 2H, C6H4OH and C4H2O), 6.95 (td, IH, C6H4OH), 6.88 (d, IH, C4H2O).
Example 11 : Preparation of 2- { [5- (2-chlorophenyl) furan-2- yl]methyleneamino}phenol (R1 = 2-Cl-C6H4 ; R6 = H)
Using 2-aminophenol and 5- (2-chlorophenyl) furan- 2-carbaldehyde, 2.69 g of 2- { [5- (2-chlorophenyl) furan-2- yl] methyleneamino jphenol were obtained as a yellow powder (yield 75 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.59 (s, IH, HC=N), 8.08 (dd, IH, Cl-C6H4), 7.54 (dd, IH, Cl-C6H4), 7.44 (td, 2H, Cl-C6H4 and OH), 7.36 (m, 3H, Cl-C6H4 and C6H4OH and C4H2O), 7.23
(td, IH, C6H4OH), 7.21 (d, IH, C4H2O), 7.02 (dd, IH, C6H4OH),
6.96 (td, IH, C6H4OH) .
Example 12 : Preparation of 2- { [5- (4-chlorophenyl) furan-2- yl]methyleneamino}phenol (R1 = 4-Cl-C6H4, R6=H)
Using 2-aminophenol and 5- (4-chlorophenyl) furan- 2-carbaldehyde, 3.18 g of 2- { [5- (4-chlorophenyl) furan-2- yl] methyleneamino jphenol were obtained as a yellow powder (yield 89 %) . RMN 1H (CD2Cl2, 500 MHz) : ppm 8.55 (s, IH, HC=N), 7.81 (dm, 2H, Cl-C6H4), 7.47 (dm, 2H, Cl-C6H4), 7.35 (dd, IH, C6H4OH), 7.23 (td, IH, C6H4OH), 7.22 (d, IH, C4H2O), 7.03 (dd, IH, C6H4OH), 6.96 (dt, IH, C6H4OH), 6.92 (d, IH, C4H2O).
Example 13 Preparation of 4-chloro-2- { [5- (4- chlorophenyl) furan-2-yl ] methyleneamino lphenol (R1 = 4-C1- C6H4, R6=H)
Using 2-amino-4-chlorophenol and 5- (4- chlorophenyl) furan-2-carbaldehyde, 3.18 g of 4-chloro-2- { [5- (4-chlorophenyl) furan-2-yl] methyleneamino lphenol were obtained as a yellow powder (yield 95 %) .
RMN 1H (CD2Cl2, 500 MHz) : ppm 8.45 (s, IH, HC=N), 7.76 (dm, 2H, Cl-C6H4), 7.44 (dm, 2H, Cl-C6H4), 7.38 (bs, IH, OH), 7.29 (d, IH, C6H3OH), 7.16 (m, 2H, C6H3OH), 6.95 (d, IH, C4H2O), 6.89 (d, IH, C4H2O).
Examples 14 to 25 Synthesis of furan- iminophenoxyzirconium trichloride complexes
Figure imgf000016_0001
General procedure
The synthesis was done under inert atmosphere with dried solvents. Sodium hydride (2.5 mmol, 0.06 g) was added to a solution of a ligand (2.5 mmol as prepared in Examples 1 to 12, respectively) in THF (15 ml) at -200C. After 2 hours, this red solution was added dropwise to ZrCl4 (2.5 mmol, 0.583 g) and the mixture was stirred overnight at room temperature. Then the solvent was removed by evaporation under reduced pressure and the residue was dissolved in 30 ml of dichloromethane . The solution was filtered through a pad of celite and the filtrate was dried under vacuum. The residue was washed with pentane and dried under vacuum to result in a final product under the form of a red or orange powder.
In Table 1 thereafter are listed the complexes obtained thereby as well as for each of them the amount obtained and the yield.
The yield is defined as follows: mass of complex obtained/mass of complex expected for 2.5 mmol
Table 1
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0002
Figure imgf000019_0001
Figure imgf000019_0003
Figure imgf000020_0001
Examples 26 to 31 : Synthesis of furan-iminophenoxytitanium trichloride complexes
Figure imgf000020_0002
General procedure
The synthesis was done under inert atmosphere with dried solvents. Sodium hydride (2.5 mmol, 0.06 g) was added to a solution of a ligand (2.5 mmol as prepared in
Examples 1 to 13) in THF (15 ml) at -200C. Then, TiCl4
(2.5 mmol, 0.110 ml) was added dropwise to this red solution and the mixture was stirred overnight at room temperature. Then the solvent was removed by evaporation under reduced pressure and the residue was dissolved in 70 ml of dichloromethane . The solution was filtered through a pad of celite and the filtrate was dried under vacuum. The residue was washed with pentane and dried under vacuum to result in a final product under the form of a red or orange powder . In Table 2 thereafter are listed the complexes obtained thereby as well as for each of them the amount obtained and the yield.
The yield is defined as follows: mass of complex obtained/mass of complex expected for 2.5 mmol
Table 2
Figure imgf000021_0001
Figure imgf000022_0001
Examples 32 to 56 : Polymerisation of ethylene
General procedure
Polymerisation reactions were realised on a 24 parallel reactor unit containing 50 ml glass inserts with magnetic stirrers. In a glove box, 1 mg of complex (as prepared in Examples 14 to 31) was introduced into a vial. Then, 0,8 ml of MAO (30 wt % in toluene) and 24 ml of toluene were added. The vials were crimped with a septum and installed into the reactor unit heated at 600C. The septa of the vials were pierced by the needles of the reactor unit. The stirring was started and regulated at 1000 rpm. Ethylene was then injected and the pressure was regulated at 22 bar, while the temperature was increased to 80°C. These conditions were maintained during 30 min., then the reactors were depressurised and cooled down. The vials were opened and an acidic alcoholic solution was added. The polymers were filtered, washed and dried. GPC curves are illustrated in figure 1. Results are summarised as follows:
Table 3
Figure imgf000023_0001
*Activity = Mass of PE (g) /Mass of complex (g)/0.5 h or Mass of PE (g) /μmol of complex/0.5 h **Tm = measured by DSC method (Differential Scanning Calorimetry) at the second heating (Ramp of 50°C/min from -400C to 1800C
n.d. = not determined
Examples 57 to 60 : Preparation of supported catalysts
General procedure
The support used was silica Sylopol® 952x1836 from Grace, modified with MAO to obtain a support with 60 wt% of MAO. The complex and the support were stirred in 50 ml of toluene at room temperature during 2 hours. Then the toluene was removed, the resulting catalyst was washed 3 times with pentane and dried under vacuum. The data are given in table 3.
Table 4
Figure imgf000024_0001
Elemental analysis measured by ICP-AES [Inductively Complet Plasma Atomic Emission Spectrometry)
Examples 61 to 6ϊ Polymerisation of ethylene with supported catalysts
General procedure
Ethylene polymerisation reactions were carried out in a 130 ml stainless steel autoclave equipped with mechanical stirring and a stainless steel injection cylinder. In a typical reaction run, the reactor was first dried under nitrogen flow at 1000C during 10 min. Then it was cooled down to the reaction temperature (85°C) and 35 ml of isobutane were introduced into the reactor with a syringe pump, followed by the comonomer if required. The pressure was adjusted to the desired value (23.8 bar) with ethylene. In an argon-filled glove box, 100 mg of the supported catalyst of examples 57 to 60, the scavenger (0.3 ml of TiBAl 10 wt% in hexanes) and 0.4 ml of n-heptane were placed into the injection cylinder. The valve was closed and the cylinder was connected to the reactor under nitrogen flow. The active catalyst mixture was then introduced into the reactor with 40 ml of isobutane. After 1 hour, the reactor was cooled down to room temperature and slowly depressurised, and the polymer was recovered. The polymerisation results are displayed in table 4.
TABLE 5
Figure imgf000025_0001
Activity is expressed as g polyethylene per g catalyst per hour . The melting temperature Tm of example 42 was of 132.3°C as measured by DSC.

Claims

1. A metallic complex of formula (IV) :
Figure imgf000027_0001
:iv)
wherein :
- R1 to R8 each represent independently H, halogen, substituted or unsubstituted C1-C20 hydrocarbyl, an inert functional group, wherein each of the radicals R1 to R8 can be linked to a neighbouring substituent in order to form a cycle with carbon atoms to which said radicals are attached; - Y represents 0 or NR*, R* being C1-C12 alkyl or C6-C12 aryl; m is O, 1 0r 2 ;
- M is a metal belonging to the groups 4 to 7 of the Periodic Classification; - X represents an halogen, a substituted or unsubstituted C1-C20 hydrocarbyl group, an amino, an aryloxy group or an alkoxy group ; and
- n is a numeral value determined by the oxidation state of M minus one.
2. The metallic complex according to claim 1, wherein R1 to R3 are each selected independently from the group consisting of H, halogen, alkyl and aryl having up to 12 carbon atoms .
3. The metallic complex according to claim 1 or claim 2, wherein R4 is selected in the group consisting of hydrogen and methyl .
4. The metallic complex according to any one of claims 1 to 3, wherein R5 to R8 are each independently selected from the group consisting of H, alkyl or aryl having up to 12 carbon atoms, halogen, methoxy, nitro and cyano .
5. The metallic complex according to any one of the preceding claims, wherein Y is 0.
6. The metallic complex according to any one of the preceding claims, wherein M is selected from Ti, Cr, Zr, Hf and V.
7. The metallic complex according to any one of the preceding claims, wherein X is halogen, amino, alkyl, alkoxy, aryloxy having up to 12 carbon atoms, preferably halogen .
8. A method for manufacturing a metallic complex of formula IV as defined in any one of claims 1 to 7, that comprises the steps of: a) preparing a compound of formula I
Figure imgf000028_0001
(D by reacting a compound of formula II
Figure imgf000029_0001
(H)
wherein R to R are as defined in claim 1 with a compound of formula III
Figure imgf000029_0002
(in:
wherein m, Y, and R to R are as defined in claim 1 ; b) reacting compound of formula I with a metallic compound of formula V
MXn+I (V) wherein M, X and n are as defined in claim 1.
9. The method of claim 8 wherein the compound of formula I is selected from the group consisting of:
• 2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino jphenol
• 4-methyl-2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino }phenol
• 4-tert-butyl-2- { [5- (2- (trifluoromethyl) phenyl) furan-2- 1 ] methyleneamino }phenol • 3-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl] methyleneamino }biphenyl-4-ol
• 4-chloro-2-{ [5- (2- (trifluoromethyl) phenyl) furan-2- yl ] methyleneamino }phenol • 2- {[ 5- (3- (trifluoromethyl) phenyl) furan-2- yl ] methyleneamino }phenol
• 4-nitro-2-{ [5- (4-nitrophenyl) furan-2- yl] methyleneamino }phenol
• 2-{ [5- (4-nitrophenyl) furan-2-yl] methyleneamino lphenol • 2- {[ 5- (3-nitrophenyl) furan-2-yl ] methyleneamino lphenol
• 2-{ [5- (3-chlorophenyl) furan-2- yl) ] methyleneamino lphenol
• 2-{ [5- (2-chlorophenyl) furan-2-yl] methyleneamino lphenol
• 2-{ [5- (4-chlorophenyl) furan-2-yl] methyleneamino lphenol
10. A catalytic system comprising : the metallic complex as defined in anyone of claims 1 to 7; an activating agent selected in particular among aluminium alkyls, aluminoxanes and boron-based activators, in particular aluminoxanes, preferably methylaluminoxane ; and optionally, a support of said metallic complex.
11. The catalytic system according to claim 10, wherein the activating agent is aluminium alkyl or aluminoxane, the molar ratio Al/M being approximately 500 to 2000, preferably 1000.
12. A method for homopolymerising or copolymerising ethylene and α-olefins, that comprises the steps of :
(a) injecting into the reactor the catalytic system as defined in claim 10 or 11 and a solvent and optionally a scavenger ; (b) injecting the monomer and optional comonomer(s) into the reactor, either before or after or simultaneously with step (a) ;
(c) maintaining under polymerisation conditions ; (d) optionally adding an acidic solution of an alcohol to precipitate and filtrate the polymer ; (e) retrieving the polymer under the form of a powder.
13. The method of claim 12 wherein the monomer is ethylene or propylene and the comonomer is propylene or 1-hexene.
PCT/EP2008/056692 2007-06-14 2008-05-30 New tridentate ligand compounds with imino furan units, method for manufacturing said compounds, and their use in the preparation of catalysts for the homopolymerisation and copolymerisation of ethylene and alpha-olefins. Ceased WO2009015922A1 (en)

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