Olefin trimerisation using a catalyst comprising a source of chromium,molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group
AssigneeBP Chemicals Limited
InventorDuncan Frank Wass
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Abstract
A process for the trimerisation of olefins is disclosed, comprising contacting a monomeric olefin or mixture of olefins under trimerisation conditions with a catalyst which comprises (a) a source of chromium, molybdenum or tungsten (b) a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibana groups; and optionally (c) an activator.
Claims45
Catalyst comprising
- (a) a source of chromium, molybdenum or tungsten;
- (b) a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or beterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups;
- and optionally
- (c) an activator.
Supported catalyst having a productivity per mole of catalyst of at least 50%, preferably at least 70% of its productivity when unsupported, which catalyst preferably comprises
- (a) a source of a Group 3 to 10 transition metal;
- (b) a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups;
- and optionally
- (c) an activator.
Catalyst according to any preceding claim, wherein component (a) is a source of chromium.
Catalyst according to any preceding claim, wherein the ligand of component (b) has the formula
- (R1)(R2)X-Y-X(R3)(R4) or X(R1)(R2)(R3), wherein
- X is phosphorus, arsenic or antimony;
- Y is a linking group;
- and R1, R2, R3 and R4 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl groups, at least one of which in each formula has a polar substituent which is not a phosphane, arsane or stibane group, and any of the groups R1-R4 may independently be linked to one or more of each other or to the bridging group Y, to form a cyclic structure together with X or X and Y.
Catalyst according to any preceding claim, wherein X is phosphorus.
Catalyst according to any preceding claim, wherein component (b) is selected from the following:
- (2-methoxyphenyl)(phenyl)PN(Me)P(phenyl)2
- (2-methoxyphenyl)2PN(Me)P(phenyl)2
- (2-methoxyphenyl)(phenyl)PN(Me)P(2-methoxyphenyl)(phenyl)
- (2-methoxyphenyl)2PN(Me)P(2-methoxyphenyl)2
- (2-ethoxyphenyl)2PN(Me)P(2-ethoxyphenyl)2
- (2-isopropoxyphenyl)2PN(Me)P(2-isopropoxyphenyl)2
- (2-hydroxyphenyl)2PN(Me)P(2-hydroxyphenyl)2
- (2-nitrophenyl)2PN(Me)P(2-nitrophenyl)2
- (2,3-dimethoxyphenyl)2PN(Me)P(2,3-dimethoxyphenyl)2
- (2,4-dimethoxyphenyl)2PN(Me)P(2,4-dimethoxyphenyl)2
- (2,6-dimethoxyphenyl)2PN(Me)P(2,6-dimethoxyphenyl)2
- (2,4,6-trimethoxyphenyl)2PN(Me)P(2,4,6-trimethoxyphenyl)2
- (2-dimethoxyphenyl)(2-methylphenyl)PN(Me)P(2-methylphenyl)2
- [2-(dimethylamino)phenyl]2PN(Me)P[2-(dimethylamino)phenyl]2
- (2-methoxymethoxyphenyl)2PN(Me)P(2-methoxymethoxyphenyl)2
- (2-methoxyphenyl)2PN(Ethyl)P(2-methoxyphenyl)2
- (2-methoxyphenyl)2PN(Phenyl)P(2-methoxyphenyl)2
- (2-methoxyphenyl)2PN(Me)N(Me)P(2-methoxyphenyl)2
- (2-methoxyphenyl)2PCH2P(2-methoxyphenyl)2
- (2-methoxyphenyl)2PCH2CH2P(2-methoxyphenyl)2
- tri(2-methoxymethoxyphenyl)phosphane i.e.
- 2
- tri(2-methoxyphenyl) phosphane.
Catalyst according to any preceding claim, wherein component (c) is selected from trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium (TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride, ethylaluminiumsesquichloride, methylaluminiumsesquichloride, alumoxanes, tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate, boroxines, NaBH4, trimethylboron, triethylboron, dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, H+(OEt2)2[(bis-3,5-trifluoromethyl)phenyl]borate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron, or mixtures thereof.
Catalyst for the trimerisation and polymerisation of 1-olefins, further comprising one or more catalysts (d) suitable for the polymerisation, oligomerisation or other chemical transformation of olefins.
Catalyst according to any preceding claim, which has a trimerisation productivity of at least 15000 g product per mmol catalyst per hour, preferably at least 30000 g product per mmol catalyst per hour, at a temperature of 110° C. or less and an ethylene partial pressure of 21 bar or less.
Catalyst for the trimerisation of olefins, wherein the catalyst productivity decays at a rate of less than 10% per hour.
Catalyst for the trimerisation of ethylene, which has a trimerisation productivity of at least 15000 g product per mmol catalyst per hour, preferably at least 30000 g product per mmol catalyst per hour, at a temperature of 110° C. or less and an ethylene partial pressure of 21 bar or less.
Process for the trimerisation of olefins, comprising contacting a monomeric olefin or mixture of olefins under trimerisation conditions with a catalyst which comprises
- (a) a source of a Group 3 to 10 transition metal;
- (b) a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups;
- and optionally
- (c) an activator.
Dependencies are inferred from the claim text.