WO2000006299A1 - Composition de catalyseur - Google Patents

Composition de catalyseur Download PDF

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Publication number
WO2000006299A1
WO2000006299A1 PCT/GB1999/002252 GB9902252W WO0006299A1 WO 2000006299 A1 WO2000006299 A1 WO 2000006299A1 GB 9902252 W GB9902252 W GB 9902252W WO 0006299 A1 WO0006299 A1 WO 0006299A1
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Prior art keywords
catalyst composition
formula
groups
group
methylphenyl
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PCT/GB1999/002252
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English (en)
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Stephen John Dossett
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Bp Chemicals Limited
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Priority to AU49207/99A priority Critical patent/AU4920799A/en
Publication of WO2000006299A1 publication Critical patent/WO2000006299A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B01J31/187—Amide derivatives thereof
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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 a novel catalyst composition and to a process for the preparation of interpolymers of olefins and carbon monoxide by polymerising a mixture of one or more olefins and carbon monoxide in the presence of such catalyst compositions.
  • EP 121965 discloses a process for the preparation of polyketones by polymerising a mixture of CO and an alkenically unsaturated hydrocarbon in the presence of a Group VIII metal catalyst containing a bidentate ligand of the general formula R 1 R 2 -M-R-M-R 3 R 4 , in which M represents phosphorus, arsenic or antimony, R represents a divalent organic bridging group having at least two carbon atoms in the bridge and R 1 , R 2 , R 3 , and R 4 are identical or different hydrocarbon groups.
  • WO 97/37765 relates to a catalyst composition for the preparation of polyketones which catalyst composition is prepared by reacting together:
  • R 1 ⁇ ⁇ R 1 where each R 1 may be the same or different and is an organic group, R 2 , R 3 , x and y are defined above.
  • R 1 may be hydrocarbyl (for example aryl, alkyl), alkoxy, amido and substituted derivatives thereof.
  • R 1 is aryl, it is for example phenyl or an aromatic group substituted at one or both ortho positions with respect to the phosphorus atoms with a polar substituent, for example, an alkoxy or an amido group, for example, a methoxy group, for example, o-anisyl preferably o-anisyl.
  • WO 97/37765 does not teach that where R 1 is aryl that the aromatic group may be substituted with an alkyl group. It is known from, for example, EP 121965 that the rate of the polymerisation process can be increased considerably by using a palladium catalyst with inter alia a bidentate phosphine and the anion of a carboxylic acid having a pKa of less than 2 (as measured in aqueous solution).
  • anions which can be used include trichloroacetate, dichloroacetate, tetrafluoro-borate, hexafluorophosphate p-toluene sulphonate and borosalicylate such anions being respectively the conjugate anions of trichloroacetic acid, dichloroacetic acid, tetrafluoroboric acid, hexafluorophosphoric acid, p-toluenesulphonic acid and borosalicylic acid.
  • catalyst compositions prepared by reacting together (a) a source of a Group Vffl metal (b) certain selected phosphines of the type described in WO 97/37765 and (c) a promoter are effective in producing polyketones having specific properties (for example, improved molecular weights).
  • a catalyst composition comprising:
  • R 1 groups are independently selected from a phenyl group or an alkyl substituted phenyl group with the proviso that at least one of the R 1 groups is an alkyl substituted phenyl group;
  • the present invention further provides a process for preparing polyketones by polymerising a mixture of carbon monoxide and one or more olefins in the presence of a catalyst composition as defined hereinabove.
  • polyketone is used herein to mean an interpolymer of one or more olefins with carbon monoxide.
  • the idealised structure of such a material would comprise a one, two or three dimensional network of strictly alternating units derived from the olefin and carbon monoxide units.
  • polyketones prepared according to the present invention correspond to this idealised structure, it is envisaged that materials corresponding to this structure in the main but containing small regimes (i.e. up to 10 wt
  • An advantage of using the selected catalyst compositions of the present invention is that higher reaction temperatures and hence higher reaction rates can be used to obtain polyketones having a desired target molecular weight (i.e. a particular high molecular weight) than when using the catalyst compositions specifically disclosed in WO 97/37765
  • the selected catalyst compositions of the present invention produce polyketones having higher molecular weights than polyketones produced using the catalyst compositions specifically disclosed in WO 97/37765.
  • the molecular weight of the polyketone produced using the selected catalyst compositions of the present invention is generally at least 200,000 higher, for example 300,000 higher than the molecular weight of a polyketone produced using the catalysts specifically disclosed in WO 97/37765, under substantially the same process conditions.
  • the selected catalyst compositions of the present invention provide increased flexibility with respect to balancing the target molecular weight and the reaction rate.
  • a catalyst composition obtainable by reacting together (a) a source of Group VIII metal, (b) a bidentate phosphine ligand having the formula (I) as shown above, and (c) a promoter.
  • the Group VIII metals are iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the second row Group VIII metals i.e. ruthenium, rhodium and palladium are preferred; particularly preferred is palladium.
  • each of the R 1 groups of the diphosphine of formula (I) are alkyl substituted phenyl groups. Where more than one of the R 1 groups is an alkyl substituted phenyl group, it is preferred that the alkyl substituted phenyl groups are the same.
  • the alkyl substituted phenyl groups may be substituted with one or more alkyl groups, preferably 1 to 3 alkyl groups.
  • the alkyl substituted phenyl groups are substituted at one or both ortho positions (the 2 and/or 6 positions) and optionally the para position (the 4 position) with respect to the phosphorus atoms.
  • the alkyl substituents may be independently selected from Ci to C 6 alkyl groups, preferably Ci to C 3 alkyl groups, for example methyl, ethyl or iso-propyl.
  • the alkyl substituted phenyl group is substituted with more than one alkyl substituent, it is preferred that the alkyl substituents are the same.
  • the R 1 groups may be phenyl groups having fluorinated alkyl substituents, for example, CF 3 .
  • alkyl substituted phenyl groups include 2-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6- trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 3,5-diethylphenyl, 2,6- diethylphenyl, 2,4,6-triethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4- isopropylphenyl, 2,6-diisopropylphenyl, 3,5-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-tertbutylphenyl, 3-tertbutylphenyl, 4-tertbutylphenyl, 2,6-ditertbutylphenyl, 3,5- ditertbutylphenyl, and 2,4,6-tritri
  • the atoms in the bridging group whether N or P are trivalent, two of the three bonds of each of the atoms that constitute the bridging group are directed to adjacent atoms.
  • the third bond can be directed to an adjacent atom in the bridging group (to give a double bond in the bridge), but is more likely to be directed to a monovalent, preferably organic, group which is directly bonded to the respective bridging atom but which does not form part of the bridging group itself.
  • the phosphorus atom forming part of the bridging group -(N) x -(P) y - N- may alternatively be pentavalent in which case two of the bonds are directed to the adjacent atoms to form part of the bridging group.
  • the other three bonds can, for example, be directed to three monovalent groups or preferably to one monovalent group and a double bond, for example, to oxygen or sulphur.
  • component (b) can be a compound of formula (II):
  • R 1 ' R 1 where the R 1 groups are as defined in formula (I).
  • R 2 and R 3 are monovalent groups, preferably monovalent organic groups.
  • R 2 can be hydrogen or a hydrocarbyl group, preferably a Ci to C ⁇ alkyl group, for example methyl or ethyl or an aryl group, preferably phenyl.
  • R 3 is a hydrocarbyl group or substituted hydrocarbyl, more preferably a Ci to C ⁇ alkyl group.
  • R 3 is an aryl group for example phenyl or substituted phenyl.
  • R 2 and/or R 3 can be a hetero group e.g. OR 5 , SR 5 or N(R 6 ) 2 where
  • R 5 and R 6 are independently a hydrocarbyl group e.g. OMe, OEt, OPh, NMe 2 , NEt 2 etc.
  • x and y are independently 0 or 1.
  • component (b) comprises a PNP unit (two phosphorus atoms with a single
  • Suitable diphosphines of formula (II) include:
  • the ligands can be prepared using procedures known to the man skilled in the art and disclosed in published literature.
  • R X halide
  • NH 2 R 2 in the presence of a base (for example, NR 3 ).
  • R' ⁇ X is preferably (R ⁇ PCl or (R ⁇ PBr.
  • R 2 NPC1 2 can be obtained commercially or by reacting NHR 2 and PC1 3 .
  • An alternative method of preparing (R 1 ) 2 PC1 is to react PC1 3 with the corresponding R 1 Grignard reagent in THF which may be followed by precipitation of magnesium halide by-product by adding dioxan.
  • the R 1 Grignard reagent is the R 1 bromo Grignard reagent or alternatively, the R 1 chloro Grignard may be employed in the presence of magnesium bromide.
  • the corresponding (R 1 ) 2 PNRP(R 1 )2 can be made by further reacting the product of the first step with H 2 NR in the presence of a base (e.g. NR 3 ) in THF.
  • component (c) which is a promoter
  • this can be a source of an anion which is either non-coordinating or weakly coordinating.
  • Such anions are suitably the conjugate bases of strong acids having e.g. a pKa of less than 6, preferably less than 2 (e.g. HBF 4 , HPF 6 , HSbF 6 , paratoluene sulphonic acid).
  • the promoter can be a boron hydrocarbyl compound, for example, a boron alkyl, or boron aryl compound.
  • the boron hydrocarbyl compound can be a Lewis acid of the formula BXYZ where at least one of X, Y and Z is a monovalent hydrocarbyl group.
  • any one of X, Y or Z is a monovalent hydrocarbyl group
  • it is suitably an alkyl, for example, a Ci to C ⁇ alkyl group, or an aryl group, for example, a substituted or unsubstituted phenyl group, for example, CH ⁇ Hs or CF 6 F 5 .
  • At least one of X, Y and Z is a monovalent hydrocarbyl group, however it is preferred that at least two, preferably three of X, Y and Z are each monovalent hydrocarbyl groups.
  • X, Y and Z is not a hydrocarbyl group, it is suitably a OH, OR or halide group, preferably a halide group, for example, fluoride, chloride or bromide, especially fluoride.
  • halide group for example, fluoride, chloride or bromide, especially fluoride.
  • examples of compounds where one of X, Y, Z is a group other than a hydrocarbyl group are boronic acids of the formula RB(OH) 2 where R is a hydrocarbyl group e.g. PhB (OH) 2 and hydrocarbyl 1,3,2 - benzodioxaboroles. Mixtures of the above promoters can be employed.
  • component (c) is a boron hydrocarbyl compound of the formula B(C6H 5 ) 3 .
  • component (c) is B(C 6 H 5 ) 3
  • the polyketone product of the process of the present invention has a higher molecular weight than when component (c) is B(C F 5 ) 3 (under substantially the same process conditions).
  • suitable boron hydrocarbyl compounds for use in this invention are borate salts of the formula MBP M where M is an alkali metal e.g. Li, Na and at least one of the groups R is a hydrocarbyl group (e.g. C ⁇ H 5 , C ⁇ Fs and substituted analogues).
  • a suitable compound could be LiB(C ⁇ F 5 ) or NaB(C6H 5 ) .
  • one or more of the R groups is not a hydrocarbyl group it is suitably an OH, OR or halide group for example OH.
  • a typical example of such a compound is NaBPh 3 (OH).
  • boron hydrocarbyl compound for example a Lewis Acid BXYZ
  • it is added to the reaction medium in an amount such that the Group VIII metal : boron ratio is in the range 10:1 to 1:200, preferably 1:1 to 1:100, most preferably 1 :5 to 1:70 e.g. 1:50.
  • the boron hydrocarbyl compound can be added in a single addition, preferably at the beginning of the polymerisation reaction, in several discrete additions throughout the reaction or continuously.
  • the promoter could be an anion containing a plurality of boron atoms such as those disclosed in EP 702045 A2 or an aluminoxane.
  • the source of palladium can include simple inorganic and organic salts, e.g. halides, nitrates, carboxylates and the like as well as organometallic and coordination complexes. In some cases, by suitable choice of coordination complex, it may be possible to add the palladium and the compound of formula (I) as a single entity.
  • the Group VIII metal compound may preferably comprise other groups or ligands bonded to the Group VIII metal; these groups or ligands may or may not derive from any Group VIII metal precursors that have been used in generating the Group VIII metal compound.
  • groups or ligands are suitably halides, especially chloride; acetate, trifluoroacetate, tosylate, nitrate, sulphate, acetyl acetonate, cyanide, preferably acetate or labile ligands e.g. trifluoroacetate, tosylate, nitriles, solvent molecules e.g. water, acetone.
  • the Group VIII metal compound can suitably be a neutral or cationic compound
  • L is typically a halide or carboxylate, for example CH 3 COO or CF 3 COO.
  • L 1 is typically a neutral ligand such as, benzonitrile, acetonitrile, diethyl ether, or water.
  • A is a weakly coordinating or non-coordinating anion as defined under component (c) above or (A) 2 together can be a weakly or non- coordinating dianion.
  • compounds of formulae (III) or (IV) as defined above. Particular examples of compounds of formulae (III) and (IV) are [Pd ⁇ (2-methylphenyl) 2 PN(Me)N(Me)P(2- methylphenyl) 2 ⁇ (Cl) 2 ] and [Pd ⁇ (2-methylphenyl) 2 PN(Me)N(Me)P(2- methylphenyl) 2 ⁇ (PhCN) 2 ][BF 4 ] 2 .
  • the promoter is a non-coordinating or weakly coordinating anion
  • this can also be incorporated into a discrete compound as a counter anion as in compounds of formula (IV).
  • the anion can be used in the form of a salt or its conjugate acid together with the Group VIII metal and the compound of formula (I) whether the latter two are added as a single discrete compound or are added as two compounds.
  • any source of the Group VIII metal can be used, it may be necessary when a metal complex having strongly coordinating ligands is employed, to ensure that such ligands are removed.
  • a metal complex having strongly coordinating ligands is employed, to ensure that such ligands are removed.
  • An example of such a complex is palladium acetate where the acetate anions bind to the palladium.
  • the acetate anions can be removed by adding component (c) above as the conjugate acid of a non-coordinating or weakly coordinating anion since such a conjugate acid will protonate the acetate anions and cause their removal.
  • metal halides e.g. palladium halides
  • a thallium or silver salt of a non-coordinating or weakly coordinating anion it is preferred to use a thallium or silver salt of a non-coordinating or weakly coordinating anion. In such cases a metathesis reaction occurs and the insoluble silver or thallium halide precipitates and can be removed by filtration.
  • the catalyst composition additionally comprises an organic oxidant, for example a quinone.
  • the quinone is a 1,4-quinone such as 1,4-benzoquinone or 1,4-naphthoquinone.
  • the ratio of organic oxidant to Group VIII metal is less than 20:1, more preferably, less than 10:1, for example less than 3:1.
  • a feedstock comprising any source of carbon monoxide may be used.
  • the carbon monoxide may contain nitrogen, inert gases and up to 10% hydrogen.
  • Any olefin can in theory, be used although the best reaction rates are obtained when either ethene or a mixture of olefins, for example, ethene, propene and the like is used.
  • polyketones prepared using the catalyst composition of the present invention have higher -olefin contents than polyketones prepared using prior art catalyst compositions. This allows the ⁇ -olefin charge to be reduced for a given ⁇ -olefin content in the final polymer.
  • the catalyst composition can be used in either the gas phase or in the presence of a liquid diluent.
  • the polymerisation is carried out in the gas phase, it is preferred to support the catalyst on a carrier which can be, for example, polyketone polymer or an inorganic carrier, for example, alumina or silica.
  • a carrier which can be, for example, polyketone polymer or an inorganic carrier, for example, alumina or silica.
  • the liquid diluent is suitably a solvent in which the catalyst is soluble.
  • solvents include alcohols e.g. methanol, ethanol, propanol, ethers, glycol ethers and chlorinated solvents e.g. chloroform and dichloromethane.
  • Preferred solvents are methanol, ethoxyethanol, chloroform or dichloromethane, especially dichloromethane.
  • an aliphatic tertiary alcohol can be used, preferably tertiary butanol.
  • This can be used as a solvent on its own or in combination with an aprotic solvent e.g. ketones.
  • a preferred solvent system is tertiary butanol/acetone mixture.
  • hydrocarbon solvents as the liquid diluent e.g. alkane (pentane, hexane, cyclohexane) or olefins especially where the olefin is a coreactant.
  • the liquid diluent may contain small quantities of water, for example, up to about 5% wt/wt.
  • the polymerisation process is suitably carried out at a temperature in the range of from 20 to 150°C, preferably, 50 to 120°C and at elevated pressure, e.g. 1 to 100 bar.
  • the overpressure of gas is suitably carbon monoxide or carbon monoxide and olefin, if the olefin is gaseous under the reaction conditions.
  • the process may be operated batchwise continuously or in cascade. The invention will be illustrated with reference to the following examples.
  • a carbon monoxide/ethene/propene terpolymer was prepared as follows: Dichloromethane (80 cm 3 ) was charged to a 300 cm 3 autoclave under nitrogen. The autoclave was cooled to a temperature of -78°C and then propene (12 g) was condensed into the autoclave. The autoclave contents were pressurised to 45 barg using a 1:1 mixture of carbon monoxide and ethene and then heated to a temperature of 70°C. A solution of B(C 6 F 5 ) 3 (0.160 g, 0.310 mmol) in dichloromethane (10 cm 3 ) was introduced, followed by more dichloromethane (10 cm 3 ).
  • a procatalyst solution comprising [Pd(OAc 2 ) ⁇ (C 6 H 4 Me-2) 2 PN(Me)P(C 6 H 4 Me-2) 2 ⁇ ] (0.011 g, 0.016 mmol), prepared as in Example 5, in dichloromethane (10 cm 3 ) was added followed by a further addition of dichloromethane (10 cm 3 ) bringing the total volume of dichloromethane in the autoclave to 120 cm 3 .
  • the pressure was adjusted to 50 barg by the addition of 1 : 1 carbon monoxide/ethene and this pressure was maintained by the addition of the aforementioned gas mixture on demand. After 2 hours the pressure was released and the reaction mixture was cooled to room temperature. The polymer was collected by filtration and dried under reduced pressure. 18 g of polymer was obtained. The properties of the polymer are summarised in Table 1 below.
  • Example 8 A carbon monoxide/ethene/propene terpolymer was prepared using substantially the same procedure to that detailed in Example 6, with the following differences:

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Abstract

L'invention concerne une composition de catalyseur que l'on peut obtenir en faisant réagir: a) une source d'un métal du groupe VIII; b) un ligand de phosphine bidenté de formule (I), dans laquelle x représente 0 ou 1, y désigne 0 ou 1, et les groupes R1 sont choisis indépendamment dans un groupe phényle ou un groupe phényle à substitution alkyle, à condition qu'au moins un de ces groupes R1 soit un groupe phényle à substitution alkyle; et c) un agent promoteur. Le métal du groupe VIII est de préférence du palladium, l'agent promoteur pouvant être un anion faiblement coordonnant ou non coordonnant. Dans une variante, cet agent promoteur peut être un composé hydrocarbyle de bore ou un aluminoxane. Les catalyseurs de cette invention sont utilisés pour préparer des polycétones.
PCT/GB1999/002252 1998-07-29 1999-07-13 Composition de catalyseur WO2000006299A1 (fr)

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AU49207/99A AU4920799A (en) 1998-07-29 1999-07-13 Catalyst composition

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GB9816550.9 1998-07-29
GBGB9816550.9A GB9816550D0 (en) 1998-07-29 1998-07-29 Catalyst composition

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Publication number Priority date Publication date Assignee Title
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US7605105B2 (en) 2005-02-01 2009-10-20 Exxonmobil Chemical Patents Inc. Transition metal polymerization catalysts, their synthesis and use in olefin polymerization

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