WO2004056477A1 - Trimerisation of olefins - Google Patents

Trimerisation of olefins Download PDF

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Publication number
WO2004056477A1
WO2004056477A1 PCT/ZA2003/000185 ZA0300185W WO2004056477A1 WO 2004056477 A1 WO2004056477 A1 WO 2004056477A1 ZA 0300185 W ZA0300185 W ZA 0300185W WO 2004056477 A1 WO2004056477 A1 WO 2004056477A1
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WO
WIPO (PCT)
Prior art keywords
ethylphenyl
catalyst system
group
transition metal
methyl
Prior art date
Application number
PCT/ZA2003/000185
Other languages
French (fr)
Inventor
Kevin Blann
Annette Bollmann
John Thomas Dixon
Arno Neveling
David Hedley Morgan
Hulisani Maumela
Esna Killian
Fiona Millicent Hess
Stefanus Otto
Matthew James Overett
Original Assignee
Sasol Technology (Pty) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sasol Technology (Pty) Limited filed Critical Sasol Technology (Pty) Limited
Priority to BRPI0316870-0A priority Critical patent/BRPI0316870B1/en
Priority to AU2003297544A priority patent/AU2003297544A1/en
Priority to DE60331252T priority patent/DE60331252D1/en
Priority to CNB2003801091332A priority patent/CN100540514C/en
Priority to US10/539,137 priority patent/US7525009B2/en
Priority to CA2510190A priority patent/CA2510190C/en
Priority to EP03813852A priority patent/EP1581341B1/en
Priority to BR0316870-0A priority patent/BR0316870A/en
Priority to ES03813852T priority patent/ES2340483T3/en
Priority to AT03813852T priority patent/ATE457196T1/en
Priority to JP2005511967A priority patent/JP2006516265A/en
Publication of WO2004056477A1 publication Critical patent/WO2004056477A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
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    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • This invention relates to an olefin trimerisation process, a catalyst system for trimerisation of olefins and the identification and use of ligands for a catalyst system for trimerisation of olefins.
  • 1-Hexene is an important commercial product. In addition to its use as a specific chemical, it is also extensively used in polymerisation processes either as a monomer or co-monomer. This invention defines a catalyst system that facilitates the production of 1-hexene from ethylene in high selectivity, while avoiding the co-production of significant quantities of other higher oligomers and polyethylene.
  • a nickel catalyst comprising a chelating ligand, preferably 2-diphenyl phosphino benzoic acid (DPPBA), a nickel precursor, preferably NiCI 2 6H 2 O, and a catalyst activator, preferably sodium tetraphenylborate, catalyses the oligomerisation of ethylene to yield a mixture of linear olefins containing 1-hexene.
  • DPPBA 2-diphenyl phosphino benzoic acid
  • a nickel precursor preferably NiCI 2 6H 2 O
  • a catalyst activator preferably sodium tetraphenylborate
  • Ziegler-type technologies based on trialkylaluminium catalysts are also commercially used to oligomerise ethylene to mixtures of olefins that reportedly contain 14-25 mass % 1- hexene (Chem Systems PERP reports 90-1 , 93-6, and 94/95S12).
  • trimerisation catalysts F469
  • ligands include a spacer of at least one carbon atom between the heteroatoms to allow true tridentate coordination with the chromium. Tridentate coordination complexes are generally believed to be more selective towards 1-hexene than bidentate complexes.
  • An example of such a heteroatomic ligand for ethylene trimerisation is bis-(2- diethylphosphino-ethyl)-amine. Although the catalyst system containing this ligand is extremely selective towards 1-hexene (with overall 1-hexene selectivity exceeding 96 mass %), it exhibits only moderate catalyst activities.
  • the ethylene trimerisation catalyst system containing (o-methoxyphenyl) 2 PN(Me)P(o-methoxyphenyl) 2 is somewhat less selective (claimed selectivities towards 1-hexene range between 75 and 91.5 mass %) than the system described in WO 03/053891 , but it is more active.
  • an essential attribute of the ligands disclosed in this patent application is that at least one of the R 1 , R 2 , R 3 and R 4 groups must have a polar, or electron donating, substituent.
  • This invention relates to a process for selectively producing trimeric products such as 1- hexene from olefins by using a transition metal catalyst system containing a heteroatomic ligand.
  • a process for the trimerisation of olefins which process includes the step of contacting an olefinic feed stream with a catalyst system which includes a heteroatomic ligand and a transition metal compound.
  • trimerisation means the catalytic reaction of a single olefinic monomer or a mixture of olefinic monomers giving products enriched in trimers derived from those olefinic monomers.
  • the product stream may consist of linear and/or branched olefins
  • the feedstream includes an olefin or a mixture of olefins to be trimerised and can be introduced into the process according to the invention in a continuous or batch fashion.
  • the product stream includes a trimer, which trimer is produced according to the invention in a continuous or batch fashion.
  • the process may include a process for trimerisation of ⁇ -olefins wherein ⁇ -olefins include all hydrocarbon compounds with terminal double bonds.
  • This definition includes ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene and the like.
  • the process may include a process for trimerisation of ⁇ -olefins to yield trimeric ⁇ -olefin products selectively.
  • the ethylene may be contacted with the catalyst system at a pressure of 1 barg, preferably greater than 10 barg, more preferably greater than 30 barg.
  • heteroatomic a ligand that contains at least two heteroatoms, which may be the same or different, and may be independently selected from any one of a group which comprises phosphorus, arsenic, antimony, sulphur, nitrogen, oxygen, bismuth and selenium.
  • the heteroatomic ligand may be described by the following general formula (R) n A-B-C(R) m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C, and R is independently selected from any homo or hetero hydrocarbyl group and n and m are determined by the respective valence and oxidation state of A and C.
  • the ligand may be described by the following general formula: (R 1 )(R 2 )A-B-C(R 3 )(R 4 ), where A and C are independently phosphorus, arsenic, antimony, nitrogen and bismuth and B is a linking group between A and C.
  • a and/or C may be a potential donor site for coordination with the transition metal.
  • An electron donor is defined as that entity that donates electrons used in chemical, including dative covalent, bond formation.
  • a and/or C may be independently oxidised by S, Se, N or O.
  • a and C may be independently phosphorus or phosphorus oxidised by S or Se or N or O.
  • the heteroatomic ligand may be selected from a group of ligands having at least two heteroatoms, wherein each heteroatom contains hydrocarbyl or heterohydrocarbyl groups without any electron donating substituents.
  • the applicant believes that if the catalyst system contains a bidentate heteroatomic coordination complex with substituents on the ortho position of any aromatic group bound to A or C, it would lead to improvements in the selectivity of the catalyst system due to suppression of secondary trimerisation reactions.
  • the applicant has surprisingly found that in most instances the presence of non-electron donating substituents is beneficial in terms of the overall reaction selectivity towards 1-hexene.
  • B may be selected from any one of a group comprising: organic linking groups comprising a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl group; inorganic linking groups comprising single atom links; ionic linking groups and a group comprising methylene, dimethylmethylene, 1 ,2-ethane, 1 ,2- phenylene, 1 ,2-propane, 1 ,2-catechol, 1 ,2-dimethylhydrazine, -B(R 5 )-, -Si(R 5 ) 2 -, -P(R 5 )- and -N(R 5 )- where R 5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen.
  • B may be -N(R 5 )- and R 5 is a hydrocarbyl or a substituted hydrocarbyl group.
  • R 5 may be hydrogen or may be selected from the groups consisting of alkyl, aryl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, and aryl substituted with any of these substituents.
  • Preferred R 5 groups include alkyl groups such as methyl.
  • B may exclude (CH 2 ) x Y(CH 2 ) y , where Y is -P(R 6 )-, -N(R 6 )-, -As(R 6 )-, -Sb(R 6 )- or -S- and x and y are individually 1-15 and wherein R 6 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl group.
  • a single atom linking spacer is defined as a substituted or non-substituted atom that is bound directly to A and C.
  • R 1 , R 2 , R 3 and R 4 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl groups where any substituents are non-electron donating.
  • the substituents may be non-polar groups.
  • R 1 , R 2 , R 3 and R 4 may be substituted aromatic or substituted hetero-aromatic groups containing non-electron donating substituents on the atom adjacent to the atom bound to A or C.
  • R 1 , R 2 , R 3 and R 4 may be substituted aromatic or substituted hetero-aromatic groups containing non-polar substituents on the atom adjacent to the atom bound to A or C.
  • Non-polar is defined by IUPAC as an entity without a permanent electric dipole moment.
  • Suitable non-polar substituents may be a methyl, ethyl, propyl, propenyl, propynyl, butyl, isopropyl, isobutyl, f-butyl, pentyl, hexyl, cyclopentyl, 2-methylcyclohexyl, cyclohexyl, cylopentadienyl, phenyl, bi-phenyl, naphthyl, tolyl, xylyl, mesityl, ethenyl, and benzyl group, or the like.
  • R 1 , R 2 , R 3 and R 4 may be aromatic or hetero aromatic containing at least one non-electron donating substituent on the atom adjacent to the atom bound to A or C. More preferably R 1 , R 2 , R 3 and R 4 may be aromatic or hetero aromatic containing at least one non-polar substituent on the atom adjacent to the atom bound to A or C.
  • R 1 , R 2 , R 3 and R 4 include, but are not limited to, methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2- ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o- ethylphenyl, o-isopropylphenyl, o-t-butylphenyl, cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, thiophenyl, trimethylsilyl, dimethylhydrazyl and the like.
  • R 1 , R 2 , R 3 and R 4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is non-electron donating.
  • R 1 , R 2 , R 3 and R 4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is not a polar group.
  • R 1 , R 2 , R 3 and R 4 may be aromatic or hetero aromatic and each of R 1 , R 2 , R 3 and R 4 should be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non-electron donating group. It is also preferred that R 1 , R 2 , R 3 and R 4 be aromatic or hetero aromatic and each of R 1 , R 2 , R 3 and R 4 be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non- polar group.
  • any of the groups R 1 , R 2 , R 3 and R 4 may independently be linked to one or more of each other or to the linking group B to form a cyclic structure together with A and C, A and B or B and C.
  • the ligand may also contain multiple (R) n A-B-C(R) m units. Not limiting examples of such ligands include dendrimeric ligands as well as ligands where the individual units are coupled either via one or more of the R groups or via the linking group B.
  • examples of such ligands may include 1 ,2-di-(N(P(o-ethylphenyl) 2 ) 2 )- benzene, 1 ,4-di-(N(P(o-ethylphenyl) 2 ) 2 )-benzene, N(CH 2 CH 2 N(P(o-ethylphenyl) 2 ) 2 ) 3 and 1 ,4-di-(P(o-ethylphenyl)N(methyl)P(o-ethylphenyl) 2 )-benzene.
  • the ligands can be prepared using procedures known to one skilled in the art and procedures disclosed in published literature. Examples of these ligands are: (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 , (o-isopropylphenyl) 2 PN(methyl)P(o- isopropylphenyl) 2 , (o-methylphenyl) 2 PN(methyl)P(o-methylphenyl) 2 , (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl)(phenyl), (o-ethylphenyl) 2 PN(isopropyl)P(o- ethylphenyl) 2 , (o-isopropyl) 2 PN(isopropyl)P(o-isopropyl) 2 , (o-methyl) 2 PN(isopropyl)P(o- methyl) 2
  • the process conditions may be selected such that the catalyst activity is more than 1 gram product per gram transition metal.
  • the process may be an ⁇ -olefins trimerisation process.
  • the process may be an ethylene trimerisation process.
  • the process includes the step of combining, in any order, a heteroatomic ligand with a transition metal compound and an activator.
  • the process may include the step of generating a heteroatomic coordination complex in situ from a transition metal compound and a heteroatomic ligand.
  • the process may include the step of adding a pre-formed coordination complex, prepared using a heteroatomic ligand and a transition metal compound, to a reaction mixture, or the step of adding separately to the reactor, a heteroatomic ligand and a transition metal compound such that a heteroatomic coordination complex of a transition metal is generated in situ.
  • generating a heteroatomic coordination complex in situ is meant that the complex is generated in the medium in which catalysis takes place.
  • the heteroatomic coordination complex is generated in situ.
  • the transition metal compound, and heteroatomic ligand are combined (both in situ and ex situ) to provide metal/ligand ratios from about 0.01:100 to 10 000:1 , and preferably, from about 0.1 :1 to 10:1.
  • the transition metal may be selected from chromium, molybdenum, tungsten, tantalum, vanadium and titanium.
  • the transition metal is chromium.
  • the transition metal compound which, upon mixing with the heteroatomic ligand and an activator, catalyses ethylene trimerisation in accordance with the invention may be simple inorganic or organic salts, for example halides, acetylacetonoates, carboxylates, oxides, nitrates, sulfates and the like, as well as a co-ordination or organometallic complex, for example, chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium hexacarbonyl, molybdenum hexacarbonyl and the like.
  • the preferred transition metal compounds are chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.
  • the heteroatomic ligand can be modified to be attached, for example, to a polymer chain so that the resulting heteroatomic coordination complex of the transition metal is soluble at elevated temperatures, but becomes insoluble at 25°C. This approach would enable the recovery of the complex from the reaction mixture for reuse and has been used for another catalyst as described by D.E. Bergbreiter et al., J. Am. Chem. Soc, 1987, 109, 177-179.
  • transition metal complexes can also be immobilised by binding the heteroatomic ligands to silica, silica gel, polysiloxane or alumina backbone as, for example, demonstrated by C. Yuanyin et al., Chinese J. React Pol., 1992, 1(2), 152-159 for immobilising platinum complexes.
  • the activator for use in the process may in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and the transition metal compound. Some systems may be self activating. Mixtures of activators may also be used. Suitable compounds include organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like.
  • Suitable organoaluminium compounds include compounds of the formula AIR 3 , where each R is independently a C r C ⁇ 2 alkyl, an oxygen containing moiety or a halide, and compounds such as LiAIH 4 and the like.
  • Examples include trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TIBA), tri-/7-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, aluminium isopropoxide, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, and aluminoxanes.
  • TMA trimethylaluminium
  • TEA triethylaluminium
  • TIBA tri-isobutylaluminium
  • tri-/7-octylaluminium methylalum
  • Aluminoxanes are well known in the art as typically oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example trimethylaluminium. Such compounds can be linear, cyclic, cages or mixtures thereof. Mixtures of different aluminoxanes may also be used in the process.
  • organoboron compounds examples include boroxines, NaBH 4 , triethylborane, tris(pentafluoropheny)borane, tributyl borate and the like.
  • the activator may also be or contain a compound that acts as a reducing or oxidising agent, such as sodium or zinc metal and the like, or oxygen and the like.
  • the activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
  • alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO)
  • modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
  • Modified methylaluminoxane (a commercial product from Akzo Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups.
  • the transition metal compound and the aluminoxane may be combined in proportions to provide Al/metal ratios from about 1 :1 to 10 000:1 , preferably from about 1 :1 to 1000:1 , and more preferably from 1 :1 to 300:1.
  • the process may include the step of adding to the catalyst system a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol of alkylaluminoxane.
  • aluminoxanes generally also contain considerable quantities of the corresponding trialkylaluminium compounds used in their preparation. The presence of these trialkylaluminium compounds in aluminoxanes can be attributed to their incomplete hydrolysis with water. Any quantity of a trialkylaluminium compound quoted in this disclosure is additional to alkylaluminium compounds contained within the aluminoxanes.
  • the process may include the step of mixing the components of the catalyst system at any temperature between -20°C and 250°C in the presence of an olefin.
  • an olefin may stabilise the catalyst system.
  • the individual components of the catalyst system described herein may be combined simultaneously or sequentially in any order, and in the presence or absence of a solvent, in order to give an active catalyst.
  • the mixing of the catalyst components can be conducted at any temperature between -20°C and 250 C C.
  • the presence of an olefin during the mixing of the catalyst components generally provides a protective effect which may result in improved catalyst performance.
  • the preferred temperature range may be between 20°C and 100°C.
  • the catalyst system in accordance with the invention, or its individual components, may also be immobilised by supporting it on a support material, for example, silica, alumina, MgCI 2 , zirconia or mixtures thereof, or on a polymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene).
  • a support material for example, silica, alumina, MgCI 2 , zirconia or mixtures thereof, or on a polymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene).
  • the catalyst can be formed in situ in the presence of the support material, or the support can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components.
  • the support material can also act as or as a component of the activator. This approach would also facilitate the recovery of the catalyst from the reaction mixture for reuse.
  • the support can also act as a catalyst component, for example where such supports contain aluminoxane functionalities or where the support is capable of performing similar chemical functions as an aluminoxane, which is for instance the case with IOLATM(a product from Grace Davison).
  • reaction products may be prepared with the disclosed catalyst system by homogeneous liquid phase reaction in the presence or absence of an inert solvent, and/or by slurry reaction where the catalyst system is in a form that displays little or no solubility, and/or a two-phase liquid/liquid reaction, and/or a bulk phase reaction in which neat reagent and/or product olefins serve as the dominant medium, and/or gas phase reaction, using conventional equipment and contacting techniques.
  • the process may therefore also be carried out in an inert solvent.
  • Any inert solvent that does not react with the activator can be used.
  • These inert solvents may include any saturated aliphatic and unsaturated aliphatic as well as aromatic hydrocarbon and halogenated hydrocarbon.
  • Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, 1-hexene, ionic liquids and the like.
  • the process may be carried out at pressures from atmospheric to 500 barg. Ethylene pressures in the range of 10-100 barg are preferred. Particularly preferred pressures range from above 30-50 barg. Catalyst activities and/or selectivities improve with pressures above 1 barg. F469
  • the process may be carried out at temperatures from -20-250 °C. Temperatures in the range of 0-120 °C are preferred. Particularly preferred temperatures range from 25- 100°C.
  • the catalyst its individual components, reagents, solvents and reaction products are generally employed on a once-through basis, any of these materials can, and are indeed preferred to, be recycled to some extent in order to minimise production costs.
  • the process may be carried out in a plant which includes any type of reactor.
  • reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors.
  • the plant may include, in combination a) a reactor, b) at least one inlet line into this reactor for olefin reactant and the catalyst system, c) effluent lines from this reactor for oligomerisation reaction products, and d) at least one separator to separate the desired oligomerisation reaction products, wherein the catalyst system may include a heteroatomic coordination complex of a transition metal compound and an activator, as described herein.
  • the reactor and a separator may be combined to facilitate the simultaneous formation of reaction products and separation of these compounds from the reactor.
  • This process principle is commonly known as reactive distillation.
  • the catalyst system exhibits no solubility in the solvent or reaction products, and is fixed in the reactor so that it does not exit the reactor with the reactor product, solvent and unreacted olefin, the process principle is commonly known as catalytic distillation.
  • trimerisation process described herein may be used in a process in which the trimerisation of ethylene and co-polymerisation occur simultaneously leading to the incorporation of the trimerisation products into a copolymer.
  • trimerisation process described in US Patent No. 5,786,431.
  • the catalyst system may include a F469
  • the catalyst system may also include an activator as described above.
  • the heteroatomic ligand may be described by the following general formula (R) n A-B-C(R) m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C, and R is independently selected from any homo or hetero hydrocarbyl group and n and m is determined by the respective valence and oxidation state of A and C.
  • the ligand may be described by the following general formula: (R 1 )(R 2 )A-B-C(R 3 )(R 4 ), where A and C are independently phosphorus, arsenic, antimony, nitrogen and bismuth and B is a linking group between A and C.
  • a and/or C may be a potential donor site for coordination with the transition metal.
  • a and/or C may be independently oxidised by S, Se, N or O.
  • a and C may be independently phosphorus or phosphorus oxidised by S or Se or N or O.
  • the heteroatomic ligand may be selected from a group of ligands having at least two heteroatoms, wherein each heteroatom contains hydrocarbyl, or heterohydrocarbyl groups without any electron donating substituents.
  • the applicant believes that if the catalyst system contains a bidentate heteroatomic coordination complex with substituents on the ortho position of any aromatic group bound to A or C, it would lead to improvements in the selectivity of the catalyst system due to suppression of secondary trimerisation reactions. The applicant therefore believes that in most instances the absence of such electron donating substituents is beneficial in terms of the overall reaction selectivity towards 1-hexene.
  • B may be selected from any one of a group comprising: organic linking groups comprising a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl group; inorganic linking groups comprising single atom links; ionic links and a group comprising methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, F469
  • R 5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen.
  • B may be -N(R 5 )- and R 5 is a hydrocarbyl or a substituted hydrocarbyl group.
  • R 5 may be hydrogen or may be selected from the groups consisting of alkyl, aryl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, and aryl substituted with any of these substituents.
  • Preferred R 5 groups include alkyl groups such as methyl.
  • B may exclude (CH 2 ) x Y(CH 2 ) y , where Y is -P(R 6 )-, -N(R 6 )-, -As(R 6 )-, -Sb(R 6 )- or -S- and x and y are individually 1-15 and wherein R 6 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl group.
  • a single atom linking spacer is defined as a substituted or non-substituted atom that is bound directly to A and C.
  • R 1 , R 2 , R 3 and R 4 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl groups where any substituents are non-electron donating.
  • the substituents may be non-polar groups.
  • R 1 , R 2 , R 3 and R 4 may be substituted aromatic or substituted hetero-aromatic groups containing non-electron donating substituents on the atom adjacent to the atom bound to A or C.
  • R ⁇ R 2 , R 3 and R 4 may be substituted aromatic or substituted hetero-aromatic groups containing non-polar substituents on the atom adjacent to the atom bound to A or C.
  • Non-polar is defined by IUPAC as an entity without a permanent electric dipole moment.
  • Suitable non polar substituents may be a methyl, ethyl, propyl, propenyl, propynyl, butyl, isopropyl, isobutyl, t-butyl, pentyl, hexyl, cyclopentyl, 2-methylcyclohexyl, cyclohexyl, cylopentadienyl, phenyl, bi-phenyl, naphthyl, tolyl, xylyl, mesityl, ethenyl, and benzyl group, or the like.
  • R 1 , R 2 , R 3 and R 4 may be aromatic or heteroaromatic containing at least one non-electron donating substituent on the atom adjacent to the atom bound to A or C. More preferably R 1 , R 2 , R 3 and R 4 may be aromatic or hetero aromatic containing at least one non-polar substituent on the atom adjacent to the atom bound to A or C.
  • R 1 , R 2 , R 3 and R 4 include, but are not limited to, methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2- ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o- ethylphenyl, o-isopropylphenyl, o-f-butylphenyl, cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, thiophenyl, trimethylsilyl, dimethylhydrazyl and the like.
  • R 1 , R 2 , R 3 and R 4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is non-electron donating.
  • R 1 , R 2 , R 3 and R 4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is not a polar group.
  • R 1 , R 2 , R 3 and R 4 may be aromatic or hetero aromatic and each of R 1 , R 2 , R 3 and R 4 should be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non-electron donating group. It is also preferred that R 1 , R 2 , R 3 and R 4 be aromatic or heteroaromatic and each of R 1 , R 2 , R 3 and R 4 be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non- polar group.
  • any of the groups R 1 , R 2 , R 3 and R 4 may independently be linked to one or more of each other or to the linking group B to form a cyclic structure together with A and C, A and B or B and C.
  • the ligand may also comprise multiple (R) n A-B-C(R) m units.
  • R may also comprise multiple (R) n A-B-C(R) m units.
  • ligands include dendrimeric ligands as well as ligands where the individual units are coupled either via one or more of the R groups or via the linking group B. More specific, but not limiting, examples of such ligands may include 1 ,2-di-(N(P(o- F469
  • the ligands can be prepared using procedures known to one skilled in the art and procedures disclosed in published literature. Specific examples of these ligands are: (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 , (o-isopropylphenyl) 2 PN(methyl)P(o- isopropylphenyl) 2 , (o-methylphenyl) 2 PN(methyl)P(o-methylphenyl) 2 , (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl)(phenyl), (o-ethylphenyl) 2 PN(isopropyl)P(o- ethylphenyl) 2 , (o-isopropyl) 2 PN(isopropyl)P(o-isopropyl) 2 ⁇ (o-methyl) 2 PN(isopropyl)P(o- methyl) 2, (
  • the catalyst system may have a catalyst activity of more than 1 gram product per gram transition metal.
  • the transition metal may be selected from chromium, molybdenum, tungsten, tantalum and titanium.
  • the transition metal is chromium.
  • the transition metal compound which, upon mixing with the heteroatomic ligand and an activator, catalyses ethylene trimerisation in accordance with the invention may be a simple inorganic or organic salt, for example halides, acetylacetonoates, carboxylates, oxides, nitrates, sulfates and the like, as well as a co-ordination or organometallic complex, for example, chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium hexacarbonyl, molybdenum hexacarbonyl and the like.
  • the preferred transition metal compounds are chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.
  • the activator may in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and the transition metal compound. Mixtures of activators may also be used. Suitable compounds include organoaluminium compounds, organoboron compounds, organic salts, such as methyHithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like.
  • the activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
  • alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO)
  • modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
  • Modified methylaluminoxane (a commercial product from Akzo Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups.
  • the transition metal compound and the aluminoxane may be in such proportions relative to each other to provide Al/metal ratios from about 1 :1 to 10 000:1 , preferably from about 1 :1 to 1000 : 1 , and more preferably from 1 :1 to 300:1.
  • the catalyst system may also include a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol aluminoxane.
  • a ligand as described above, for a catalyst system, as described above, for the trimerisation of olefins.
  • the invention also extends to the identification and use of ligands suitable for use in a trimerisation of olefins process or catalyst system.
  • EAO ethylaluminoxane
  • the mixed heteroatomic PNP ligands were synthesised by reacting amines and phosphine chlorides R 2 PCI as described in (a) Ewart et al, J. Chem. Soc. 1964, 1543; (b) Dossett, S.J. et al, Chem. Commun., 2001, 8, 699; (c) Balakrishna, M.S. et al, J. Organomet. Chem. 1990, 390, 2, 203).
  • the respective phosphine chlorides R 2 PCI were prepared as described in literature (Casalnuovo, A.L. et al, J. Am. Chem. Soc. 1994, 116, 22, 9869; Rajanbabu, T.V. et al, J. Org. Chem. 1997, 62, 17, 6012).
  • Example 2 Ethylene trimerisation reaction using CrC fTetrahydrofuran (o- ethvIphenyl)?PN(methyl)P(o-ethylphenyl) 7 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was allowed to gradually increase to 45 barg over a period of 15 minutes. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 15 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.4358 g of F469
  • Example 3 Ethylene trimerisation reaction using CrC Tetrahydrofuran ⁇ , (o- ethylphenyl) ? PN(methyl)P(o-ethylphenyl)2 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 4 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and MAO
  • Example 5 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 6 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 7 Ethylene trimerisation reaction using Cr(lll) (2-ethylhexanoate), (o- ethylphenvD PNfmethvDPfo-ethylphenyl)? and MAO
  • Example 8 Ethylene trimerisation reaction using Cr(lll) (2-ethylhexanoate), (o- methylphenyl)?PN(methyl)P(o-methylphenyl) ? and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 60°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC- FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 9 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- methylphenyl) 2 PN(Me)P(o-methylphenyl) 2 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 13 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 10 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- isopropylphenyl) 2 PN(methyl)P(o-isopropylphenyl) 2 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 13 minutes by discontinuing the F469
  • Example 11 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and MMAO-3A
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 12 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and EAO/TMA
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 46 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC- FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID.
  • Example 13 Ethylene trimerisation reaction using Cr(octanoate) 3 , (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and MAO
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer.
  • the reaction F469
  • Example 14 Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl) 2 PN(methyl)P(o-ethylphenyl) 2 and MAO in cyclohexane as solvent
  • the pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC- FID.
  • Example 15 Tandem trimerisation and co-polymerisation using Cr(acacW(o- ethylphenyl) 2 -PN(methyl)P(o-ethylphenyl) 2 , cyclopentadienyl dimethylsilyl titanium dichloride and MAO
  • the 300 ml Parr autoclave was charged with 60 ml anhydrous toluene as well as the previously stirred Cr(acac) 3 /(o-ethylphenyl) 2 -PN(methyl)P(o-ethylphenyl) 2 ligand solution under inert conditions.
  • Approximately 600 eq methylaluminoxane (MAO) was added to the autoclave under inert conditions.
  • the autoclave was connected to the HPLC pump outlet and heated to 45 °C, sealed and pressurized to 630 PSI with ethylene whilst stirring was commenced at 1200 rpm.
  • the polymerization catalyst solution was added to the autoclave through the HPLC pump.
  • the polymerization catalyst was added at a rate of 0.33 ml/min over a period of 60 minutes after which the reaction vessel was cooled down and quenched with ethanol.
  • the autoclave was opened and the contents collected for analysis.
  • the polymer collected was washed in acetone and dried in a vacuum oven for 12h at 60 °C.
  • the dried polymer amounted to 12.5 g.
  • Analysis of the polymer revealed two melting points at 96 °C (broad, onset at 114.92 °C) and one at 120.48 °C.
  • the total amount of 1-hexene incorporated was 7 mol % ( 13 C NMR).

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Abstract

The invention describes a process for trimerisation of olefins, which process includes the step of contacting an olefinic feedstream with a catalyst system which includes a transition metal compound and a heteroatomic ligand and wherein the trimer is an olefin and wherein the heteroatomic ligand is described by the following general formula (R)nA-B-C(R)m.

Description

F469
TRIMERISATION OF OLEFINS
Field of the invention:
This invention relates to an olefin trimerisation process, a catalyst system for trimerisation of olefins and the identification and use of ligands for a catalyst system for trimerisation of olefins.
Background of the invention
1-Hexene is an important commercial product. In addition to its use as a specific chemical, it is also extensively used in polymerisation processes either as a monomer or co-monomer. This invention defines a catalyst system that facilitates the production of 1-hexene from ethylene in high selectivity, while avoiding the co-production of significant quantities of other higher oligomers and polyethylene.
In this regard, it is known from prior art (US patent 6,184,428) that a nickel catalyst comprising a chelating ligand, preferably 2-diphenyl phosphino benzoic acid (DPPBA), a nickel precursor, preferably NiCI26H2O, and a catalyst activator, preferably sodium tetraphenylborate, catalyses the oligomerisation of ethylene to yield a mixture of linear olefins containing 1-hexene. The selectivity towards the linear C6 α-olefin is claimed to be 33%. Similarly the Shell Higher Olefins Process (SHOP process, US patents 3,676,523 and 3,635,937) using a similar catalyst system is reported to yield 11 mass % 1-hexene in its product mixture (Chem Systems PERP reports 90-1 , 93-6 and 94/95S12).
Ziegler-type technologies based on trialkylaluminium catalysts, independently developed by Gulf Oil Chemicals Company (Chevron, e.g. DE patent 1,443,927) and Ethyl Corporation (BP/Amoco, e.g. US patent 3,906,053), are also commercially used to oligomerise ethylene to mixtures of olefins that reportedly contain 14-25 mass % 1- hexene (Chem Systems PERP reports 90-1 , 93-6, and 94/95S12).
The selective trimerisation of ethylene to 1-hexene via transition metal catalysis has been extensively studied and patented. Some of these trimerisation catalysts are F469
capable of trimerising longer chain olefins. This is an important feature, since the trimeric products derived from longer chain olefins could be utilised as synthetic lubricants (e.g. polyalphaolefins / PAOs), as well as in various other applications such as components of drilling muds and as feedstock to prepare detergents and plasticisers. Most of the known catalysts for selective ethylene trimerisation are chromium-based. Recently, chromium- based trimerisation catalyst systems, containing heteroatomic ligands with both phosphorus and nitrogen heteroatoms (WO 03/053891 ) as well as sulphur and nitrogen heteroatoms (WO 03/053890), have been developed by the applicant. These ligands include a spacer of at least one carbon atom between the heteroatoms to allow true tridentate coordination with the chromium. Tridentate coordination complexes are generally believed to be more selective towards 1-hexene than bidentate complexes. An example of such a heteroatomic ligand for ethylene trimerisation is bis-(2- diethylphosphino-ethyl)-amine. Although the catalyst system containing this ligand is extremely selective towards 1-hexene (with overall 1-hexene selectivity exceeding 96 mass %), it exhibits only moderate catalyst activities.
Another example of such a heteroatomic ligand with both phosphorus and nitrogen heteroatoms for ethylene trimerisation is (o-methoxyphenyl)2PN(Me)P(o- methoxyphenyl)2 as described in WO 02/04119. This patent application discloses the use of ligands described by the following general formula: (R1)(R2)X-Y-X(R3)(R4) wherein X is phosphorus, arsenic or antimony; Y is a linking group such as -N(R5)- and R1, R2, R3 and R4 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl groups, at least one of which has a polar substituent which is not a phosphane, arsane or stibane group. The ethylene trimerisation catalyst system containing (o-methoxyphenyl)2PN(Me)P(o-methoxyphenyl)2 is somewhat less selective (claimed selectivities towards 1-hexene range between 75 and 91.5 mass %) than the system described in WO 03/053891 , but it is more active. Thus, based on the above description, an essential attribute of the ligands disclosed in this patent application, is that at least one of the R1, R2, R3 and R4 groups must have a polar, or electron donating, substituent. Open literature shows that the use of (o- ethylphenyl)2PN(Me)P(o-ethylphenyl)2, a compound without any such polar substituents on at least one of R1, R2, R3 and R4, as a ligand under catalytic conditions resulted in no catalytic activity towards 1-hexene (Anthea Carter et al., Chem. Commun., 2002, 858- 859). The coordinating phosphorus heteroatoms in the above-mentioned ligand are F469
spaced apart by one nitrogen atom. It is believed that the nitrogen atom does not coordinate with the chromium (at least in the absence of an activator) and that without any further electron donating atoms on the ligand, it is a bidentate system. It is further believed that any polar, or electron donating substituents especially in the ortho-position of the phenyl groups (R1, R2, R3 and R4) facilitate the formation of a tridentate system. This feature is reiterated in Chem. Commun., 2002, 858-859 by stating; "This has led us to hypothesise that the potential for ortho-methoxy groups to act as pendent donors and increase the coordinative saturation of the chromium centre is an important factor."
The applicant has now shown that, contrary to the findings of Carter et. al., excellent ethylene trimerisation activities and selectivities are indeed possible using inexpensive PNP ligands containing non-polar substituents on the ortho positions of the phenyl rings attached to the phosphorus. Higher overall selectivities are in fact achievable when using these ligand systems compared to ligands in which the ortho position has a polar substituent as was reported by Carter et al.
Summary of the invention
This invention relates to a process for selectively producing trimeric products such as 1- hexene from olefins by using a transition metal catalyst system containing a heteroatomic ligand.
According to a first aspect of the invention there is provided a process for the trimerisation of olefins, which process includes the step of contacting an olefinic feed stream with a catalyst system which includes a heteroatomic ligand and a transition metal compound.
The term trimerisation means the catalytic reaction of a single olefinic monomer or a mixture of olefinic monomers giving products enriched in trimers derived from those olefinic monomers. The product stream may consist of linear and/or branched olefins
The feedstream includes an olefin or a mixture of olefins to be trimerised and can be introduced into the process according to the invention in a continuous or batch fashion. The product stream includes a trimer, which trimer is produced according to the invention in a continuous or batch fashion.
The process may include a process for trimerisation of α-olefins wherein α-olefins include all hydrocarbon compounds with terminal double bonds. This definition includes ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene and the like.
The process may include a process for trimerisation of α-olefins to yield trimeric α-olefin products selectively.
The ethylene may be contacted with the catalyst system at a pressure of 1 barg, preferably greater than 10 barg, more preferably greater than 30 barg.
By heteroatomic is meant a ligand that contains at least two heteroatoms, which may be the same or different, and may be independently selected from any one of a group which comprises phosphorus, arsenic, antimony, sulphur, nitrogen, oxygen, bismuth and selenium. The heteroatomic ligand may be described by the following general formula (R)nA-B-C(R)m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C, and R is independently selected from any homo or hetero hydrocarbyl group and n and m are determined by the respective valence and oxidation state of A and C.
More specifically the ligand may be described by the following general formula: (R1)(R2)A-B-C(R3)(R4), where A and C are independently phosphorus, arsenic, antimony, nitrogen and bismuth and B is a linking group between A and C. A and/or C may be a potential donor site for coordination with the transition metal.
An electron donor is defined as that entity that donates electrons used in chemical, including dative covalent, bond formation.
A and/or C may be independently oxidised by S, Se, N or O. F469
A and C may be independently phosphorus or phosphorus oxidised by S or Se or N or O.
The heteroatomic ligand may be selected from a group of ligands having at least two heteroatoms, wherein each heteroatom contains hydrocarbyl or heterohydrocarbyl groups without any electron donating substituents. The applicant believes that if the catalyst system contains a bidentate heteroatomic coordination complex with substituents on the ortho position of any aromatic group bound to A or C, it would lead to improvements in the selectivity of the catalyst system due to suppression of secondary trimerisation reactions. In addition, the applicant has surprisingly found that in most instances the presence of non-electron donating substituents is beneficial in terms of the overall reaction selectivity towards 1-hexene.
B may be selected from any one of a group comprising: organic linking groups comprising a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl group; inorganic linking groups comprising single atom links; ionic linking groups and a group comprising methylene, dimethylmethylene, 1 ,2-ethane, 1 ,2- phenylene, 1 ,2-propane, 1 ,2-catechol, 1 ,2-dimethylhydrazine, -B(R5)-, -Si(R5)2-, -P(R5)- and -N(R5)- where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen. Preferably, B may be -N(R5)- and R5 is a hydrocarbyl or a substituted hydrocarbyl group. R5 may be hydrogen or may be selected from the groups consisting of alkyl, aryl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, and aryl substituted with any of these substituents.
Preferred R5 groups include alkyl groups such as methyl.
B may exclude (CH2)xY(CH2)y, where Y is -P(R6)-, -N(R6)-, -As(R6)-, -Sb(R6)- or -S- and x and y are individually 1-15 and wherein R6 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl group.
B may be selected to be a single atom spacer. A single atom linking spacer is defined as a substituted or non-substituted atom that is bound directly to A and C. R1, R2, R3 and R4 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl groups where any substituents are non-electron donating. The substituents may be non-polar groups. Preferably R1, R2, R3 and R4 may be substituted aromatic or substituted hetero-aromatic groups containing non-electron donating substituents on the atom adjacent to the atom bound to A or C. R1, R2, R3 and R4 may be substituted aromatic or substituted hetero-aromatic groups containing non-polar substituents on the atom adjacent to the atom bound to A or C.
Non-polar is defined by IUPAC as an entity without a permanent electric dipole moment.
Suitable non-polar substituents may be a methyl, ethyl, propyl, propenyl, propynyl, butyl, isopropyl, isobutyl, f-butyl, pentyl, hexyl, cyclopentyl, 2-methylcyclohexyl, cyclohexyl, cylopentadienyl, phenyl, bi-phenyl, naphthyl, tolyl, xylyl, mesityl, ethenyl, and benzyl group, or the like.
Preferably two or more of R1, R2, R3 and R4 may be aromatic or hetero aromatic containing at least one non-electron donating substituent on the atom adjacent to the atom bound to A or C. More preferably R1, R2, R3 and R4 may be aromatic or hetero aromatic containing at least one non-polar substituent on the atom adjacent to the atom bound to A or C.
Suitable examples of R1, R2, R3 and R4 include, but are not limited to, methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2- ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o- ethylphenyl, o-isopropylphenyl, o-t-butylphenyl, cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, thiophenyl, trimethylsilyl, dimethylhydrazyl and the like.
R1, R2, R3 and R4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is non-electron donating. R1, R2, R3 and R4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is not a polar group. F469
It is most preferred that all of R1, R2, R3 and R4 may be aromatic or hetero aromatic and each of R1 , R2, R3 and R4 should be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non-electron donating group. It is also preferred that R1, R2, R3 and R4 be aromatic or hetero aromatic and each of R1, R2, R3 and R4 be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non- polar group.
Any of the groups R1, R2, R3 and R4 may independently be linked to one or more of each other or to the linking group B to form a cyclic structure together with A and C, A and B or B and C.
The ligand may also contain multiple (R)nA-B-C(R)m units. Not limiting examples of such ligands include dendrimeric ligands as well as ligands where the individual units are coupled either via one or more of the R groups or via the linking group B. More specific, but not limiting, examples of such ligands may include 1 ,2-di-(N(P(o-ethylphenyl)2)2)- benzene, 1 ,4-di-(N(P(o-ethylphenyl)2)2)-benzene, N(CH2CH2N(P(o-ethylphenyl)2)2)3 and 1 ,4-di-(P(o-ethylphenyl)N(methyl)P(o-ethylphenyl)2)-benzene.
The ligands can be prepared using procedures known to one skilled in the art and procedures disclosed in published literature. Examples of these ligands are: (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2, (o-isopropylphenyl)2PN(methyl)P(o- isopropylphenyl)2, (o-methylphenyl)2PN(methyl)P(o-methylphenyl)2, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)(phenyl), (o-ethylphenyl)2PN(isopropyl)P(o- ethylphenyl)2, (o-isopropyl)2PN(isopropyl)P(o-isopropyl)2, (o-methyl)2PN(isopropyl)P(o- methyl)2, (o-t-butylphenyl)2PN(methyl)P(o-f-butylphenyl)2, (o-t- butylphenyl)2PN(isopropyl)P(o-t-butylphenyl)2, (o-ethylphenyl)2PN(pentyl)P(o- ethylphenyl)2, (o-ethylphenyl)2PN(phenyl)P(o-ethylphenyl)2, (o-ethylphenyl) PN(p- methoxyphenyl)P(o-ethyIphenyl)2, (o-ethylphenyl)2PN(benzyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(1-cyclohexylethyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(2- methylcyclohexyl)P(o-ethylphenyl)2, (σ-ethylphenyl)2PN(cyclohexyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(allyl)P(o-ethylphenyl)2, (3-ethyl-2-thiophenyl)2PN(methyl)P(3-ethyl-2- thiophenyl)2, (2-ethyl-3-thiophenyl)2PN(methyl)P(2-ethyl-3-thiophenyl)2 and (2-ethyl-4- pyridyl)2PN(methyl)P(2-ethyl-4-pyridyl)2. F469
The process conditions may be selected such that the catalyst activity is more than 1 gram product per gram transition metal.
The process may be an α-olefins trimerisation process.
The process may be an ethylene trimerisation process.
The process includes the step of combining, in any order, a heteroatomic ligand with a transition metal compound and an activator.
The process may include the step of generating a heteroatomic coordination complex in situ from a transition metal compound and a heteroatomic ligand. The process may include the step of adding a pre-formed coordination complex, prepared using a heteroatomic ligand and a transition metal compound, to a reaction mixture, or the step of adding separately to the reactor, a heteroatomic ligand and a transition metal compound such that a heteroatomic coordination complex of a transition metal is generated in situ. By generating a heteroatomic coordination complex in situ is meant that the complex is generated in the medium in which catalysis takes place. Typically, the heteroatomic coordination complex is generated in situ. Typically, the transition metal compound, and heteroatomic ligand are combined (both in situ and ex situ) to provide metal/ligand ratios from about 0.01:100 to 10 000:1 , and preferably, from about 0.1 :1 to 10:1.
The transition metal may be selected from chromium, molybdenum, tungsten, tantalum, vanadium and titanium. Preferably, the transition metal is chromium.
The transition metal compound which, upon mixing with the heteroatomic ligand and an activator, catalyses ethylene trimerisation in accordance with the invention, may be simple inorganic or organic salts, for example halides, acetylacetonoates, carboxylates, oxides, nitrates, sulfates and the like, as well as a co-ordination or organometallic complex, for example, chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium hexacarbonyl, molybdenum hexacarbonyl and the like. The preferred transition metal compounds are chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate. The heteroatomic ligand can be modified to be attached, for example, to a polymer chain so that the resulting heteroatomic coordination complex of the transition metal is soluble at elevated temperatures, but becomes insoluble at 25°C. This approach would enable the recovery of the complex from the reaction mixture for reuse and has been used for another catalyst as described by D.E. Bergbreiter et al., J. Am. Chem. Soc, 1987, 109, 177-179. In a similar vein these transition metal complexes can also be immobilised by binding the heteroatomic ligands to silica, silica gel, polysiloxane or alumina backbone as, for example, demonstrated by C. Yuanyin et al., Chinese J. React Pol., 1992, 1(2), 152-159 for immobilising platinum complexes.
The activator for use in the process may in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and the transition metal compound. Some systems may be self activating. Mixtures of activators may also be used. Suitable compounds include organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like.
Suitable organoaluminium compounds include compounds of the formula AIR3, where each R is independently a CrCι2 alkyl, an oxygen containing moiety or a halide, and compounds such as LiAIH4 and the like. Examples include trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TIBA), tri-/7-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, aluminium isopropoxide, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, and aluminoxanes. Aluminoxanes are well known in the art as typically oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example trimethylaluminium. Such compounds can be linear, cyclic, cages or mixtures thereof. Mixtures of different aluminoxanes may also be used in the process.
Examples of suitable organoboron compounds are boroxines, NaBH4, triethylborane, tris(pentafluoropheny)borane, tributyl borate and the like. F469
The activator may also be or contain a compound that acts as a reducing or oxidising agent, such as sodium or zinc metal and the like, or oxygen and the like.
The activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO). Modified methylaluminoxane (a commercial product from Akzo Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups.
The transition metal compound and the aluminoxane may be combined in proportions to provide Al/metal ratios from about 1 :1 to 10 000:1 , preferably from about 1 :1 to 1000:1 , and more preferably from 1 :1 to 300:1.
The process may include the step of adding to the catalyst system a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol of alkylaluminoxane.
It should be noted that aluminoxanes generally also contain considerable quantities of the corresponding trialkylaluminium compounds used in their preparation. The presence of these trialkylaluminium compounds in aluminoxanes can be attributed to their incomplete hydrolysis with water. Any quantity of a trialkylaluminium compound quoted in this disclosure is additional to alkylaluminium compounds contained within the aluminoxanes.
The process may include the step of mixing the components of the catalyst system at any temperature between -20°C and 250°C in the presence of an olefin. The applicant has found that the presence of an olefin may stabilise the catalyst system.
The individual components of the catalyst system described herein may be combined simultaneously or sequentially in any order, and in the presence or absence of a solvent, in order to give an active catalyst. The mixing of the catalyst components can be conducted at any temperature between -20°C and 250CC. The presence of an olefin during the mixing of the catalyst components generally provides a protective effect which may result in improved catalyst performance. The preferred temperature range may be between 20°C and 100°C. F469
The catalyst system, in accordance with the invention, or its individual components, may also be immobilised by supporting it on a support material, for example, silica, alumina, MgCI2, zirconia or mixtures thereof, or on a polymer, for example polyethylene, polypropylene, polystyrene, or poly(aminostyrene). The catalyst can be formed in situ in the presence of the support material, or the support can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components. In some cases, the support material can also act as or as a component of the activator. This approach would also facilitate the recovery of the catalyst from the reaction mixture for reuse. The concept was successfully demonstrated with a chromium-based ethylene trimerisation catalyst by T. Monoi and Y. Sasaki, J. Mol. Cat.A:Chem., 1987, 109, 177- 179. In some cases, the support can also act as a catalyst component, for example where such supports contain aluminoxane functionalities or where the support is capable of performing similar chemical functions as an aluminoxane, which is for instance the case with IOLA™(a product from Grace Davison).
The reaction products, or in other words olefin oligomers, as described herein, may be prepared with the disclosed catalyst system by homogeneous liquid phase reaction in the presence or absence of an inert solvent, and/or by slurry reaction where the catalyst system is in a form that displays little or no solubility, and/or a two-phase liquid/liquid reaction, and/or a bulk phase reaction in which neat reagent and/or product olefins serve as the dominant medium, and/or gas phase reaction, using conventional equipment and contacting techniques.
The process may therefore also be carried out in an inert solvent. Any inert solvent that does not react with the activator can be used. These inert solvents may include any saturated aliphatic and unsaturated aliphatic as well as aromatic hydrocarbon and halogenated hydrocarbon. Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclohexane, 1-hexene, ionic liquids and the like.
The process may be carried out at pressures from atmospheric to 500 barg. Ethylene pressures in the range of 10-100 barg are preferred. Particularly preferred pressures range from above 30-50 barg. Catalyst activities and/or selectivities improve with pressures above 1 barg. F469
The process may be carried out at temperatures from -20-250 °C. Temperatures in the range of 0-120 °C are preferred. Particularly preferred temperatures range from 25- 100°C.
Although the catalyst, its individual components, reagents, solvents and reaction products are generally employed on a once-through basis, any of these materials can, and are indeed preferred to, be recycled to some extent in order to minimise production costs.
The process may be carried out in a plant which includes any type of reactor. Examples of such reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors. The plant may include, in combination a) a reactor, b) at least one inlet line into this reactor for olefin reactant and the catalyst system, c) effluent lines from this reactor for oligomerisation reaction products, and d) at least one separator to separate the desired oligomerisation reaction products, wherein the catalyst system may include a heteroatomic coordination complex of a transition metal compound and an activator, as described herein.
In another embodiment of the process the reactor and a separator may be combined to facilitate the simultaneous formation of reaction products and separation of these compounds from the reactor. This process principle is commonly known as reactive distillation. When the catalyst system exhibits no solubility in the solvent or reaction products, and is fixed in the reactor so that it does not exit the reactor with the reactor product, solvent and unreacted olefin, the process principle is commonly known as catalytic distillation.
The trimerisation process described herein may be used in a process in which the trimerisation of ethylene and co-polymerisation occur simultaneously leading to the incorporation of the trimerisation products into a copolymer. One example of this type of process is described in US Patent No. 5,786,431.
According to a further aspect of the invention, there is provided a catalyst system, as described above, for the trimerisation of olefins. The catalyst system may include a F469
heteroatomic ligand as described above and a transition metal compound. The catalyst system may also include an activator as described above.
The heteroatomic ligand may be described by the following general formula (R)nA-B-C(R)m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C, and R is independently selected from any homo or hetero hydrocarbyl group and n and m is determined by the respective valence and oxidation state of A and C.
More specifically the ligand may be described by the following general formula: (R1)(R2)A-B-C(R3)(R4), where A and C are independently phosphorus, arsenic, antimony, nitrogen and bismuth and B is a linking group between A and C. A and/or C may be a potential donor site for coordination with the transition metal.
A and/or C may be independently oxidised by S, Se, N or O.
A and C may be independently phosphorus or phosphorus oxidised by S or Se or N or O.
The heteroatomic ligand may be selected from a group of ligands having at least two heteroatoms, wherein each heteroatom contains hydrocarbyl, or heterohydrocarbyl groups without any electron donating substituents. The applicant believes that if the catalyst system contains a bidentate heteroatomic coordination complex with substituents on the ortho position of any aromatic group bound to A or C, it would lead to improvements in the selectivity of the catalyst system due to suppression of secondary trimerisation reactions. The applicant therefore believes that in most instances the absence of such electron donating substituents is beneficial in terms of the overall reaction selectivity towards 1-hexene.
B may be selected from any one of a group comprising: organic linking groups comprising a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl group; inorganic linking groups comprising single atom links; ionic links and a group comprising methylene, dimethylmethylene, 1,2-ethane, 1,2-phenylene, F469
1,2-propane, 1 ,2-catechol, 1,2-dimethylhydrazine, -B(phenyl)-, -Si(CH3)2-, -P(phenyl)- and -N(R5)- where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom or a halogen. Preferably, B may be -N(R5)- and R5 is a hydrocarbyl or a substituted hydrocarbyl group. R5 may be hydrogen or may be selected from the groups consisting of alkyl, aryl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, or derivatives thereof, and aryl substituted with any of these substituents.
Preferred R5 groups include alkyl groups such as methyl.
B may exclude (CH2)xY(CH2)y, where Y is -P(R6)-, -N(R6)-, -As(R6)-, -Sb(R6)- or -S- and x and y are individually 1-15 and wherein R6 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl group.
B may be selected to be a single atom spacer. A single atom linking spacer is defined as a substituted or non-substituted atom that is bound directly to A and C.
R1, R2, R3 and R4 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl groups where any substituents are non-electron donating. The substituents may be non-polar groups. Preferably R1, R2, R3 and R4 may be substituted aromatic or substituted hetero-aromatic groups containing non-electron donating substituents on the atom adjacent to the atom bound to A or C. R\ R2, R3 and R4 may be substituted aromatic or substituted hetero-aromatic groups containing non-polar substituents on the atom adjacent to the atom bound to A or C.
Non-polar is defined by IUPAC as an entity without a permanent electric dipole moment.
Suitable non polar substituents may be a methyl, ethyl, propyl, propenyl, propynyl, butyl, isopropyl, isobutyl, t-butyl, pentyl, hexyl, cyclopentyl, 2-methylcyclohexyl, cyclohexyl, cylopentadienyl, phenyl, bi-phenyl, naphthyl, tolyl, xylyl, mesityl, ethenyl, and benzyl group, or the like. F469
Preferably two or more of R1, R2, R3 and R4 may be aromatic or heteroaromatic containing at least one non-electron donating substituent on the atom adjacent to the atom bound to A or C. More preferably R1, R2, R3 and R4 may be aromatic or hetero aromatic containing at least one non-polar substituent on the atom adjacent to the atom bound to A or C.
Suitable examples of R1, R2, R3 and R4 include, but are not limited to, methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2- ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o- ethylphenyl, o-isopropylphenyl, o-f-butylphenyl, cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, thiophenyl, trimethylsilyl, dimethylhydrazyl and the like.
R1, R2, R3 and R4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is non-electron donating. R1, R2, R3 and R4 may be independently aromatic or substituted aromatic groups where the substituent on the atom adjacent to the atom bound to A or C is not a polar group.
It is most preferred that all of R1, R2, R3 and R4 may be aromatic or hetero aromatic and each of R1, R2, R3 and R4 should be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non-electron donating group. It is also preferred that R1, R2, R3 and R4 be aromatic or heteroaromatic and each of R1, R2, R3 and R4 be substituted on at least one of the atoms adjacent to the atom bound to A or C by a non- polar group.
Any of the groups R1, R2, R3 and R4 may independently be linked to one or more of each other or to the linking group B to form a cyclic structure together with A and C, A and B or B and C.
The ligand may also comprise multiple (R)nA-B-C(R)m units. Not limiting examples of such ligands include dendrimeric ligands as well as ligands where the individual units are coupled either via one or more of the R groups or via the linking group B. More specific, but not limiting, examples of such ligands may include 1 ,2-di-(N(P(o- F469
ethylphenyl)2)2)-benzene, 1 ,4-di-(N(P(o-ethylphenyl)2)2)-benzene, N(CH2CH2N(P(o- ethylphenyl)2)2)3 and 1 ,4-di-(P(o-ethylphenyl)N(methyl)P(o-ethylphenyl)2)-benzene.
The ligands can be prepared using procedures known to one skilled in the art and procedures disclosed in published literature. Specific examples of these ligands are: (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2, (o-isopropylphenyl)2PN(methyl)P(o- isopropylphenyl)2, (o-methylphenyl)2PN(methyl)P(o-methylphenyl)2, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)(phenyl), (o-ethylphenyl)2PN(isopropyl)P(o- ethylphenyl)2, (o-isopropyl)2PN(isopropyl)P(o-isopropyl)2ι (o-methyl)2PN(isopropyl)P(o- methyl)2, (o-f-butylphenyl)2PN(methyl)P(o-t-butylphenyl)2, (o-t: butylphenyl)2PN(isopropyl)P(o-f-butylphenyl)2, (o-ethylphenyl)2PN(pentyl)P(o- ethylphenyl)2, (o-ethylphenyl)2PN(phenyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(p- methoxyphenyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(benzyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(1-cyclohexylethyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(2- methylcyclohexyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(cyclohexyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(allyl)P(o-ethylphenyl)2, (3-ethyl-2-thiophenyl)2PN(methyl)P(3-ethyl-2- thiophenyl)2, (2-ethyl-3-thiophenyl)2PN(methyl)P(2-ethyl-3-thiophenyl)2 and (2-ethyl-4- pyridyl)2PN(methyl)P(2-ethyl-4-pyridyl)2.
The catalyst system may have a catalyst activity of more than 1 gram product per gram transition metal.
The transition metal may be selected from chromium, molybdenum, tungsten, tantalum and titanium. Preferably, the transition metal is chromium.
The transition metal compound which, upon mixing with the heteroatomic ligand and an activator, catalyses ethylene trimerisation in accordance with the invention, may be a simple inorganic or organic salt, for example halides, acetylacetonoates, carboxylates, oxides, nitrates, sulfates and the like, as well as a co-ordination or organometallic complex, for example, chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium hexacarbonyl, molybdenum hexacarbonyl and the like. The preferred transition metal compounds are chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate. F469
The activator may in principle be any compound that generates an active catalyst when combined with the heteroatomic ligand and the transition metal compound. Mixtures of activators may also be used. Suitable compounds include organoaluminium compounds, organoboron compounds, organic salts, such as methyHithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and the like.
The activator may be selected from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO). Modified methylaluminoxane (a commercial product from Akzo Nobel) contains modifier groups such as isobutyl or n-octyl groups, in addition to methyl groups.
The transition metal compound and the aluminoxane may be in such proportions relative to each other to provide Al/metal ratios from about 1 :1 to 10 000:1 , preferably from about 1 :1 to 1000 : 1 , and more preferably from 1 :1 to 300:1.
The catalyst system may also include a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol aluminoxane.
According to a further aspect of the invention, there is provided a ligand, as described above, for a catalyst system, as described above, for the trimerisation of olefins.
The invention also extends to the identification and use of ligands suitable for use in a trimerisation of olefins process or catalyst system.
EXAMPLES OF PERFORMING THE INVENTION
The invention will now be described with reference to the following examples which are not in any way intended to limit the scope of the invention. The individual components of the examples may conceivably be omitted or substituted and, although not necessarily ideal, the invention may conceivably still be performed and these components are not to be taken as essential to the working of the invention. F469
In the examples that follow all procedures were carried out under inert conditions, using pre-dried reagents. Chemicals were obtained from Sigma-Aldrich or Strem Chemicals unless stated otherwise. All trialkylaluminium and aluminoxane compounds and solutions thereof were obtained from Crompton Gmbh, Akzo Nobel and Albemarle Corporation. In all the examples, the molar mass of methylaluminoxane (MAO) was taken to be 58.016 g/mol, corresponding to the (CH3-AI-O) unit, in order to calculate the molar quantities of MAO used in the preparation of the catalysts described in the examples below. Similarly the molar mass of ethylaluminoxane (EAO) was taken as 72.042 g/mol, corresponding to the (CH3CH2-AI-O) building block, and that of modified ( methylaluminoxane prepared from a 70:30 mixture of trimethylaluminium and tri- isobutylaluminium as 70.7 g/mol corresponding to the (Me0. oisonBu0.3o-AI-O) unit. Ethylene oligomerisation products were analysed by GC-MS and GC-FID.
The mixed heteroatomic PNP ligands were synthesised by reacting amines and phosphine chlorides R2PCI as described in (a) Ewart et al, J. Chem. Soc. 1964, 1543; (b) Dossett, S.J. et al, Chem. Commun., 2001, 8, 699; (c) Balakrishna, M.S. et al, J. Organomet. Chem. 1990, 390, 2, 203). The respective phosphine chlorides R2PCI were prepared as described in literature (Casalnuovo, A.L. et al, J. Am. Chem. Soc. 1994, 116, 22, 9869; Rajanbabu, T.V. et al, J. Org. Chem. 1997, 62, 17, 6012).
Example 1 : Preparation of the (o-Ethylphenyl)?PN(methyl)P(o-Ethylphenyl)? ligand
Example 1a) : Preparation of o-ethylphenyl-magnesium bromide
Magnesium turnings (9.11 g, 0.375 mol) were treated with the 1-bromo-2-ethyl-benzene (10.37 ml, 0.075 mol) in THF (200 ml). A vigorous reaction ensued which was cooled in an ice bath. Once the reaction had dissipated, the reaction mixture was heated under reflux for 2 hours yielding the Grignard reagent.
Example 1b) : Preparation of Bis(o-ethylphenyl) Phosphorus Chloride
The Grignard reagent was added dropwise over 2 hours with stirring to a solution of PCI3 (2.62 ml, 0.03 mol) in THF (200 ml) at - 78 °C. After complete addition the dry ice/acetone bath was removed and the reaction was allowed to warm to room F469
temperature. The reaction was left stirring overnight and the solvent removed in vacuo. The crude product was found to be a mixture of (BπCI)-phosphines. This crude product was not isolated and all was used in the next step
Example 1c) : Preparation of (o-EthylphenvQgPNfmethvQPfo-Ethylphenyl)?
The Bis(o-ethylphenyl) phosphorus chloride (30 mmol from the crude reaction mixture) was added to a solution of methylamine (2.0 M sol. in THF, 6.5 ml, 13.0 mmol) in DCM (80 ml) and triethylamine (15 ml) at 0 °C. The reaction was stirred for 30 min after which the ice bath was removed. After stirring for a total of 14 hrs the solution was filtered to remove the triethylammonium salt formed. The product was isolated after crystallisation in 85 % yield. 31P {H} NMR: 57.45 ppm (s)
Example 2: Ethylene trimerisation reaction using CrC fTetrahydrofuran (o- ethvIphenyl)?PN(methyl)P(o-ethylphenyl)7 and MAO
A solution of 33.7 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 12.4 mg CrCI3.(Tetrahydrofuran)3 (0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 9.9 mmol) at 35°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was allowed to gradually increase to 45 barg over a period of 15 minutes. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 15 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid wax polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.4358 g of F469
polyethylene. The GC analyses indicated that the reaction mixture contained 68.91 g oligomers. The product distribution of this example is summarised in Table 1.
Example 3: Ethylene trimerisation reaction using CrC Tetrahydrofuran^, (o- ethylphenyl)?PN(methyl)P(o-ethylphenyl)2 and MAO
A solution of 22.5 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.044 mmol) in 5 ml of toluene was added to a solution of 8.3 mg CrCI3.(Tetrahydrofuran)3 (0.022 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 6.6 mmol) at 35°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.5033 g of polyethylene. The GC analyses indicated that the reaction mixture contained 102.60 g oligomers. The product distribution of this example is summarised in Table 1.
Example 4: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and MAO
A solution of 33.7 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 11.5 mg Cr(lll) acetylacetonoate (0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 9.9 mmol) at 45°C. The pressure reactor was charged with ethylene after which the reactor F469
temperature was maintained at 55°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.3665g of polyethylene. The GC analyses indicated that the reaction mixture contained 41.72 g oligomers. The product distribution of this example is summarised in Table 1.
Example 5: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and MAO
A solution of 33.7 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 11.5 mg Cr(III) acetylacetonoate (0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 4.95 mmol) at 45°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 2.03 g of polyethylene. The GC analyses indicated that the reaction mixture contained 15.63 g oligomers. The product distribution of this example is summarised in Table 1. F469
Example 6: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and MAO
A solution of 11.1 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.022 mmol) in 5 ml of toluene was added to a solution of 4 mg Cr(lll) acetylacetonoate (0.012 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 3.3 mmol) at 45°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 1.1 g of polyethylene. The GC analyses indicated that the reaction mixture contained 32.16 g oligomers. The product distribution of this example is summarised in Table 1.
Example 7: Ethylene trimerisation reaction using Cr(lll) (2-ethylhexanoate), (o- ethylphenvD PNfmethvDPfo-ethylphenyl)? and MAO
A solution of 33.7 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 22.7 mg Cr(lll) (2-ethylhexanoate) (70 mass % in mineral oil, 0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 9.9 mmol) at 35°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 55°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas F469
entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.8270 g of polyethylene. The GC analyses indicated that the reaction mixture contained 86.57 g oligomers. The product distribution of this example is summarised in Table 1.
Example 8: Ethylene trimerisation reaction using Cr(lll) (2-ethylhexanoate), (o- methylphenyl)?PN(methyl)P(o-methylphenyl)? and MAO
A solution of 30.1 mg of (o-methylphenyl)2PN(methyl)P(o-methylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 22.7 mg Cr(lll) (2-ethylhexanoate) (70 mass % in mineral oil, 0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 9.9 mmol) at 55°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 60°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC- FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.5009 g of polyethylene. The GC analyses indicated that the reaction mixture contained 70.18 g oligomers. The product distribution of this example is summarised in Table 1. F469
Example 9: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- methylphenyl)2PN(Me)P(o-methylphenyl)2 and MAO
A solution of 30.1 mg of (o-methylphenyl)2PN(Me)P(o-methylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 11.5 mg Cr(lll) acetylacetonoate (0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 9.9 mmol) at 45°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 13 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.9579g of polyethylene. The GC analyses indicated that the reaction mixture contained 70.89 g oligomers. The product distribution of this example is summarised in Table 1.
Example 10: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- isopropylphenyl)2PN(methyl)P(o-isopropylphenyl)2 and MAO
A solution of 37.5 mg of (o-isopropylphenyl)2PN(Me)P(o-isopropylphenyl)2 (0.066 mmol) in 5 ml of toluene was added to a solution of 11.5 mg Cr( III) acetylacetonoate (0.033 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 9.9 mmol) at 45°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 13 minutes by discontinuing the F469
ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 1.3748g of polyethylene. The GC analyses indicated that the reaction mixture contained 56.30 g oligomers. The product distribution of this example is summarised in Table 1.
Example 11: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and MMAO-3A
A solution of 6.9 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.0135 mmol) in 10 ml of toluene was added to a solution of 3.5 mg Cr(acac)3 (0.01 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (77ml) and MMAO-3A (modified methylaluminoxane, Akzo Nobel, 3.0 mmol) at 35°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 2.931 g of polyethylene. The GC analyses indicated that the reaction mixture contained 48.29 g oligomers. The product distribution of this example is summarised in Table 1. F469
Example 12: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and EAO/TMA
A solution of 33.7 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.066 mmol) in 10 ml of toluene was added to a solution of 11.5 mg Cr(acac)3 (0.033 mmol) in 10 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml), EAO (ethylaluminoxane, 33 mmol) and TMA (trimethylaluminium, 0.80ml, 8.3 mmol) at 40°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 46 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC- FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 1.0g of polyethylene. The GC analyses indicated that the reaction mixture contained 45.27 g oligomers. The product distribution of this example is summarised in Table 1.
Example 13: Ethylene trimerisation reaction using Cr(octanoate)3, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and MAO
A solution of 16.0 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.031 mmol) in 5 ml of toluene was added to a solution of 14.5 mg Cr(octanoate) . (0.021 mmol) in 15 ml toluene in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of toluene (80ml) and MAO (methylaluminoxane, 4.0 mmol) at 35°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction F469
was terminated after 30 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC-FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 0.331 g of polyethylene. The GC analyses indicated that the reaction mixture contained 18.56 g oligomers. The product distribution of this example is summarised in Table 1.
Example 14: Ethylene trimerisation reaction using Cr(lll) acetylacetonoate, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 and MAO in cyclohexane as solvent
A solution of 33.9 mg of (o-ethylphenyl)2PN(methyl)P(o-ethylphenyl)2 (0.066 mmol) in 5 ml of cyclohexane was added to a solution of 11.7 mg Cr(lll) acetylacetonoate (0.033 mmol) in 15 ml cyclohexane in a Schlenk vessel. The mixture was stirred for 5 min at ambient temperature and was then transferred to a 300 ml pressure reactor (autoclave) containing a mixture of cyclohexane (71ml) and MAO (methylaluminoxane, 9.9 mmol) in toluene (9 ml) at 45°C. The pressure reactor was charged with ethylene after which the reactor temperature was maintained at 45°C, while the ethylene pressure was kept at 45 barg. Thorough mixing was ensured throughout by mixing speeds of 1100 RPM's using a gas entraining stirrer. The reaction was terminated after 10 minutes by discontinuing the ethylene feed to the reactor and cooling the reactor to below 20°C. After releasing the excess ethylene from the autoclave, the reaction mixture in the autoclave was quenched with ethanol followed by 10% hydrochloric acid in water. Nonane was added as an internal standard for the analysis of the liquid phase by GC-FID. A small sample of the organic layer was dried over anhydrous sodium sulfate and then analysed by GC- FID. The remainder of the organic layer was filtered to isolate the solid polymeric products. These solid products were dried overnight in an oven at 100°C and then weighed to yield 3.2g of polyethylene. The GC analyses indicated that the reaction mixture contained 37.53 g oligomers. The product distribution of this example is summarised in Table 1. F469
Example 15: Tandem trimerisation and co-polymerisation using Cr(acacW(o- ethylphenyl)2-PN(methyl)P(o-ethylphenyl)2, cyclopentadienyl dimethylsilyl titanium dichloride and MAO
In this example, 0,025 g of (o-ethylphenyl)2-PN(methyl)P(o-ethylphenyl)2 [0.06 mmol] was added to 10 ml of a toluene solution of Cr(acac)3 [0.03 mmol] in a Schlenk tube under an argon atmosphere and allowed to stir for 5 minutes until fully dissolved. At the same time, 10 ml of a cyclopentadienyl dimethylsilyl titanium dichloride solution in toluene (0.03 mmol) was added to an external reservoir along with 10 ml anhydrous toluene. The external reservoir was connected to the inlet of an HPLC pump. After this, the 300 ml Parr autoclave was charged with 60 ml anhydrous toluene as well as the previously stirred Cr(acac)3/(o-ethylphenyl)2-PN(methyl)P(o-ethylphenyl)2 ligand solution under inert conditions. Approximately 600 eq methylaluminoxane (MAO) was added to the autoclave under inert conditions. The autoclave was connected to the HPLC pump outlet and heated to 45 °C, sealed and pressurized to 630 PSI with ethylene whilst stirring was commenced at 1200 rpm. At the same time the polymerization catalyst solution was added to the autoclave through the HPLC pump. The polymerization catalyst was added at a rate of 0.33 ml/min over a period of 60 minutes after which the reaction vessel was cooled down and quenched with ethanol. The autoclave was opened and the contents collected for analysis. The polymer collected was washed in acetone and dried in a vacuum oven for 12h at 60 °C. The dried polymer amounted to 12.5 g. Analysis of the polymer revealed two melting points at 96 °C (broad, onset at 114.92 °C) and one at 120.48 °C. The total amount of 1-hexene incorporated was 7 mol % (13C NMR).
F469
Figure imgf000030_0001

Claims

F469Claims
1. A process for trimerisation of olefins, which process includes the step of contacting an olefinic feedstream with a catalyst system which includes a transition metal compound and a heteroatomic ligand and wherein the trimer is an olefin and wherein the heteroatomic ligand is described by the following general formula (R)nA-B-C(R)m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C and is selected to exclude (CH2)xY(CH2)y, where Y is -P(R6)-, -N(R6)-, -As(R6)-, -Sb(R6)- or -S- and x and y are individually 1-15 and wherein R6 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl, and each R is independently selected from any non aromatic, aromatic or heteroaromatic group and any substituents on any R do not contain electron donating substituents, and n and m is determined by the respective valence and oxidation state of A and C.
2. A process as claimed in Claim 1 , wherein the ligand is described by the following general formula (R1)(R2)A-B-C(R3)(R4) where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, bismuth, and nitrogen.
3. A process as claimed in Claim 2, wherein R1, R2, R3 and R4 are independently selected from aromatic, including hetero aromatic, groups of which two or more of R1, R2, R3 and R4 are substituted on the atom adjacent to the atom bound to A or C and any substituent is non-electron donating.
4. A process as claimed in Claim 2, wherein all of R1, R2, R3 and R4 have non- electron donating substituents on the atom adjacent to the atom bound to A and C.
5. A process as claimed in any one of claims 1 to 4, wherein any non-electron donating substituent is non-polar.
6. A process as claimed in any one of claims 1 to 5, wherein ethylene is contacted with the catalyst system at a pressure of more than 10 barg. F469
7. A process as claimed in any one of claims 1 to 6, wherein B is selected from any one of a group comprising: organic linking groups containing a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl group; inorganic linking groups comprising single atom links; ionic links and a group comprising methylene, dimethylmethylene, 1 ,2-ethane, 1 ,2-phenylene, 1,2-propane, 1 ,2-catechol, 1 ,2-dimethylhydrazine, -B(R5)-, -Si(R5)2-, -P(R5)- and -N(R5)- where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom and a halogen.
8. A process as claimed in any one of claims 1 to 7, wherein B is selected to be a single atom spacer.
9. A process as claimed in any one of claims 1 to 8, wherein B is selected to be - N(R5)-, wherein R5 is hydrogen or selected from the groups consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted with any of these substituents.
10. A process as claimed in any one of claims 1 to 9, wherein A and/or C is independently oxidised by S, Se, N or O, where the valence of A and/or C allows for such oxidation.
11. A process as claimed in any one of claims 1 to 10, wherein A and C is independently phosphorus or phosphorus oxidised by S or Se or N or O.
12. A process as claimed in any one of claims 1 to 9 and 11 , wherein R1, R2, R3 and R4 are independently selected from a group comprising a methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2- isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o-ethylphenyl, o- isopropylphenyl, o-f-butylphenyl, cu yl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, thiophenyl, trimethylsilyl and dimethylhydrazyl group. F469
13. A process as claimed in Claim 12, wherein R1, R2, R3 and R4 are independently selected from a group comprising an o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, o-t-butylphenyl, phenyl, tolyl, biphenyl, and naphthyl group.
14. A process as claimed in any one of claims 1 to 9 and 11 to 13 wherein the ligand is selected from any one of a group comprising: (o-ethylphenyl)2PN(methyl)P(o- ethylphenyl)2, (o-isopropylphenyl)2PN(methyl)P(o-isopropylphenyl)2, (o- methylphenyl)2PN(methyl)P(o-methylphenyl)2, (o-ethylphenyl)2PN(methyl)P(o- ethylphenyl)(phenyl), (o-ethylphenyl)2PN(isopropyl)P(o-ethylphenyl)2, (o- isopropyl)2PN(isopropyl)P(o-isopropyl)2, (o-methyl)2PN(isopropyl)P(o-methyl)2, (o-t- butylphenyl)2PN(methyl)P(o-£-butylphenyl)2, (o-f-butylphenyl)2PN(isopropyl)P(o-t- butylphenyl)2, (o-ethylphenyl)2PN(pentyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(phenyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(p-methoxyphenyl)P(o- ethylphenyl)2, (o-ethylphenyl)2PN(benzyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(1 - cyclohexylethyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(2-methylcyclohexyl)P(o- ethylphenyl)2, (o-ethylphenyl)2PN(cyclohexyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(allyl)P(o-ethylphenyl)2, (3-ethyl-2-thiophenyl)2PN(methyl)P(3-ethyl-2- thiophenyl)2, (2-ethyl-3-thiophenyl)2PN(methyl)P(2-ethyl-3-thiophenyl)2 and (2-ethyl-4- pyridyl)2PN(methyl)P(2-ethyl-4-pyridyl)2.
15. A process as claimed in any one of the claims 1 to 14, which process includes the step of combining in any order a heteroatomic ligand with a transition metal compound and an activator.
16. A process as claimed in Claim 15, which includes the step of generating a heteroatomic coordination complex in situ from a transition metal compound and a heteroatomic ligand.
17. A process as claimed in any one of claims 1 to 16, which process includes the step of adding a pre-formed coordination complex, prepared using the heteroatomic ligand and the transition metal compound, to a reaction mixture containing an activator. F469
18. A process as claimed in any one of the claims 1 to 17, wherein the transition metal is selected from any one of a group comprising chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.
19. A process as claimed in any one of the claims 16 to 18, wherein the transition metal is chromium.
20. A process as claimed in Claim 15 or Claim 16, wherein the transition metal compound is selected from an inorganic or organic salt, a co-ordination or organometallic complex.
21. A process as claimed in Claim 20, wherein the transition metal compound is selected from any one of a group comprising chromium trichloride tris-tetrahydrofuran complex, (benzene)tricarbonyl chromium, chromium (III) octanoate, • chromium (III) acetylacetonoate, chromium hexacarbonyl, and chromium (111) 2-ethylhexanoate.
22. A process as claimed in any one of claims 16 to 21, wherein the transition metal is selected from a complex selected from chromium (111) acetylacetonoate and chromium (III) 2-ethylhexanoate.
23. A process as claimed in any one of claims 16 to 22, wherein the transition metal compound and heteroatomic ligand are combined to provide metal/ligand ratios from about 0.01 :100 to 10 000:1.
24. A process as claimed in Claim 23, wherein the transition metal compound and heteroatomic ligand are combined to provide metal/ligand ratios from about 0.1 :1 to 10:1.
25. A process as claimed in any one of claims 15 to 24, wherein the activator is selected from any one of a group consisting of organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate and sodium hexafluoroantimonate. F469
26. A process as claimed in any one of claims 15 to 25, wherein the activator is selected from alkylaluminoxanes.
27. A process as claimed in Claim 26, wherein the alkylaluminoxane, or mixtures thereof, is selected from group which consists of methylaluminoxane (MAO), ethylaluminoxane (EAO) and modified alkylaluminoxanes (MMAO).
28. A process as claimed in Claim 26 or Claim 27, wherein the transition metal from the transition metal compound and the aluminoxane are combined in proportions to provide Al/metal ratios from about 1:1 to 10 000:1.
29. A process as claimed in Claim 28, wherein the transition metal compound and the aluminoxane are combined in proportions to provide Al/metal ratios from about 1 :1 to 1000:1.
30. A process as claimed in Claim 29, wherein the transition metal compound and the aluminoxane are combined in proportions to provide Al/metal ratios from about 1 :1 to 300:1.
31. A process as claimed in any one of claims 26 to 30, which includes the step of adding to the catalyst system a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol of alkylaluminoxane.
32. A process as claimed in any one of claims 1 to 31 , which includes the step of mixing the components of the catalyst system at any temperature between -20°C and 250°C in the presence of an olefin.
33. A process as claimed in Claim 32, wherein the temperature range is between 20°C and 100°C
34. A process as claimed in any one of the claims 1 to 33, wherein the process is carried out at temperatures in the range of 0-120 °C. F469
35. A process as claimed in any one of the claims 1 to 33, wherein the process is carried out at a temperature range from 25-100°C.
36. A process as claimed in any one of the claims 1 to 35, which includes the step of contacting the olefin and the trimerisation product simultaneously with the trimerisation catalyst and a polymerisation catalyst so that co-polymerisation occur simultaneously leading to the incorporation of the trimerisation products into a copolymer.
37. A trimerisation catalyst system, which includes a transition metal compound and a heteroatomic ligand described by the following general formula (R)nA-B-C(R)m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C and is selected to exclude (CH2)xY(CH2)y, where Y is -P(R6)-, -N(R6)-, -As(R6)-, -Sb(R6)- or -S- and x and y are individually 1-15 and wherein R6 is hydrogen or a halogen or a nitro group or a hydrocarbyl or a substituted hydrocarbyl, and each R is independently selected from any non aromatic, aromatic or heteroaromatic group and any substituents on any R do not contain electron donating substituents, and n and m is determined by the respective valence and oxidation state of A and C.
38. A catalyst system as claimed in Claim 37, wherein the ligand is described by the following general formula (R1)(R2)A-B-C(R3)(R4) where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, bismuth, and nitrogen.
39. A catalyst system as claimed in Claim 38, wherein R1, R2, R3 and R4 are independently selected from aromatic, including hetero aromatic, groups of which two or more of R1, R2, R3 and R4 are substituted on the atom adjacent to the atom bound to A or C and any substituent is non-electron donating.
40. A catalyst system as claimed in Claim 37 wherein all of R , R2, R3 and R4 have non-electron donating substituents on the atom adjacent to the atom bound to A and C. F469
41. A catalyst system as claimed in any one of claims 37 to 40, wherein any non- electron donating substituent is non-polar.
42. A catalyst system as claimed in any one of claims 37 to 41 , wherein B is selected from any one of a group comprising: organic linking groups containing a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and a substituted heterohydrocarbyl group; inorganic linking groups comprising single atom links; ionic links and a group comprising methylene, dimethylmethylene, 1 ,2-ethane, 1 ,2-phenylene, 1 ,2-propane, 1 ,2-catechol, 1 ,2-dimethylhydrazine, -B(R5)-, -Si(R5)2-, -P(R5)- and -N(R5)- where R5 is hydrogen, a hydrocarbyl or substituted hydrocarbyl, a substituted heteroatom and a halogen.
43. A catalyst system as claimed in any one of claims 37 to 42, wherein B is selected to be a single atom spacer.
44. A catalyst system as claimed in any one of claims 37 to 43, wherein B is selected to be -N(R5)-, wherein R5 is hydrogen or selected from the groups consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, carbonylamino, dialkylamino, silyl groups or derivatives thereof, and aryl substituted with any of these substituents.
45. A catalyst system as claimed in any one of claims 37 to 44, wherein A and/or C is independently oxidised by S, Se, N or O, where the valence of A and/or C allows for such oxidation.
46. A catalyst system as claimed in any one of claims 37 to 45, wherein A and C is independently phosphorus or phosphorus oxidised by S or Se or N or O.
47. A catalyst system as claimed in any one of claims 37 to 44 and 46, wherein R1, R2, R3 and R4 are independently selected from a group comprising a methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 2-methylcyclohexyl, 2- ethylcyclohexyl, 2-isopropylcyclohexyl, benzyl, phenyl, tolyl, xylyl, o-methylphenyl, o- ethylphenyl, o-isopropylphenyl, cumyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, thiophenyl, trimethylsilyl and dimethylhydrazyl group. F469
48. A catalyst system as claimed in Claim 47, wherein R1, R2, R3 and R4 are independently selected from a group comprising an o-methylphenyl, o-ethylphenyl, o- isopropylphenyl phenyl, tolyl, biphenyl and naphthyl group.
49. A catalyst system as claimed in any one of claims 37 to 44 and 46 to 48 wherein the ligand is selected from any one of a group comprising: (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)2, (o-isopropylphenyl)2PN(methyl)P(o- isopropylphenyl)2, (o-methylphenyl)2PN(methyl)P(o-methylphenyl)2, (o- ethylphenyl)2PN(methyl)P(o-ethylphenyl)(phenyl), (o-ethylphenyl)2PN(isopropyl)P(o- ethylphenyl)2, (o-isopropyl)2PN(isopropyl)P(o-isopropyl)2, (o-methyl)2PN(isopropyl)P(o- methyl)2, (o-f-butylphenyl)2PN(methyl)P(o-t-butylphenyl)2, (o-t- butylphenyl)2PN(isopropyl)P(o-t-butylphenyl)2, (o-ethylphenyl)2PN(pentyl)P(o- ethylphenyl)2, (o-ethylphenyl)2PN(phenyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(p- methoxyphenyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(benzyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(1-cyclohexylethyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(2- methylcyclohexyl)P(o-ethylphenyl)2, (o-ethylphenyl)2PN(cyclohexyl)P(o-ethylphenyl)2, (o- ethylphenyl)2PN(allyl)P(o-ethylphenyl)2, (3-ethyl-2-thiophenyl)2PN(methyl)P(3-ethyl-2- thiophenyl)2, (2-ethyl-3-thiophenyl)2PN(methyl)P(2-ethyl-3-thiophenyl)2 and (2-ethyl-4- pyridyl)2PN(methyl)P(2-ethyl-4-pyridyl)2.
50. A catalyst system as claimed in any one of the claims 37 to 49, wherein the transition metal is selected from any one of a group comprising chromium, molybdenum, tungsten, titanium, tantalum, vanadium and zirconium.
51. A catalyst system as claimed in any one of the claims 37 to 50, wherein the transition metal is chromium.
52. A catalyst system as claimed in Claim 50 or Claim 51 , wherein the transition metal is derived from a transition metal compound selected from a group comprising of an inorganic salt, organic salt, a co-ordination complex and organometallic complex.
53. A catalyst system as claimed in Claim 52, wherein the transition metal compound is selected from a group comprising chromium trichloride tris-tetrahydrofuran complex, F469
(benzene)tricarbonyl chromium, chromium (III) octanoate, chromium (III) acetylacetonoate, chromium hexacarbonyl, and chromium (III) 2-ethylhexanoate.
54. A catalyst system as claimed in Claim 52 or Claim 53, wherein the transition metal compound is selected from a complex selected from chromium (III) acetylacetonoate and chromium (III) 2-ethylhexanoate.
55. A catalyst system as claimed in claims 52 to 54 wherein the transition metal compound and heteroatomic ligand have metal/ligand ratios from about 0.01 :100 to 10 000:1.
56. A catalyst system as claimed in Claim 55, wherein the transition metal compound and heteroatomic ligand are combined to provide metal/ligand ratios from about 0.1:1 to 10:1.
57. A catalyst system as claimed in any one of the claims 37 to 56, which includes an activator.
58. A catalyst system as claimed in Claim 57, wherein the activator is selected from any one of a group consisting of organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide, inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate and sodium hexafluoroantimonate.
59. A catalyst system as claimed in Claim 58, wherein the activator is selected from alkylaluminoxanes.
60. A catalyst system as claimed in Claim 59, wherein the alkylaluminoxane, or mixtures thereof, is selected from group which consists of methylaluminoxane (MAO), ethylaluminoxane (EAO) and modified alkylaluminoxanes (MMAO).
61. A catalyst system as claimed in Claim 59 or Claim 60, wherein the transition metal compound and the aluminoxane are in such proportions relative to each other to provide Al/metal ratios from about 1 :1 to 10 000:1. F469
62. A catalyst system as claimed in Claim 61, wherein the transition metal compound and the aluminoxane are combined in proportions to provide Al/metal ratios from about 1 :1 to 1000:1.
63. A catalyst system as claimed in Claim 62, wherein the transition metal compound and the aluminoxane are combined in proportions to provide Al/metal ratios from about 1 :1 to 300:1.
64. A catalyst system as claimed in any one of claims 59 to 63, which includes a trialkylaluminium compound in amounts of between 0.01 to 100 mol per mol of aluminoxane.
65. Use of a trimerisation catalyst system as claimed in any one of claims 37 to 64 for the tetramerisation of olefins.
66. Use of a trimerisation catalyst system as claimed in any one of claims 37 to 64 for the tetramerisation of ethylene.
67. Use of a ligand for a trimerisation process as claimed in any one of claims 1 to 36.
68. Use of a ligand for a trimerisation catalyst system as claimed in any one of claims 37 to 64.
69. An olefin trimerisation process substantially as described herein.
70. An olefin trimerisation catalyst system substantially as described herein.
PCT/ZA2003/000185 2002-12-20 2003-12-19 Trimerisation of olefins WO2004056477A1 (en)

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BRPI0316870-0A BRPI0316870B1 (en) 2002-12-20 2003-12-19 OLEFIN TRIMERIZATION
AU2003297544A AU2003297544A1 (en) 2002-12-20 2003-12-19 Trimerisation of olefins
DE60331252T DE60331252D1 (en) 2002-12-20 2003-12-19 TRIMERIZATION OF OLEFINES
CNB2003801091332A CN100540514C (en) 2002-12-20 2003-12-19 The trimerization of alkene
US10/539,137 US7525009B2 (en) 2002-12-20 2003-12-19 Trimerisation of olefins
CA2510190A CA2510190C (en) 2002-12-20 2003-12-19 Trimerisation of olefins
EP03813852A EP1581341B1 (en) 2002-12-20 2003-12-19 Trimerisation of olefins
BR0316870-0A BR0316870A (en) 2002-12-20 2003-12-19 Olefin Trimerization
ES03813852T ES2340483T3 (en) 2002-12-20 2003-12-19 TRIMERIZATION OF OLEFINS.
AT03813852T ATE457196T1 (en) 2002-12-20 2003-12-19 TRIMERIZATION OF OLEFINS
JP2005511967A JP2006516265A (en) 2002-12-20 2003-12-19 Olefin trimerization

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US43540502P 2002-12-20 2002-12-20
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US60/435,405 2002-12-20
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US47837903P 2003-06-13 2003-06-13
ZA2003/4632 2003-06-13
ZA200304632 2003-06-13
US60/478,379 2003-06-13
US50930903P 2003-10-06 2003-10-06
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