- Evaluation of Bis(phosphine) Ligands for Ethylene Oligomerization: Discovery of Alkyl Phosphines as Effective Ligands for Ethylene Tri- And Tetramerization
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Fifty-three bis(phosphines) were evaluated as ligands for chromium-catalyzed ethylene tetramerization in a high-throughput reactor. Selected ligands previously reported in the literature gave high activities with expected selectivities when evaluated under our reactor conditions. While the majority of ligands evaluated gave low activity catalysts that produced mostly high-density polyethylene (HDPE), alkyl phosphines were unexpectedly identified as a promising ligand class. In particular, the MeDuPhos ligand led to an active catalyst that produced 81.8 wt % α-olefins (50.0 wt % 1-octene, 31.8 wt % 1-hexene) and 3.5 wt % HDPE, approaching the selectivity of the state-of-the-art i-Pr-PNP ligand.
- Boelter, Scott D.,Davies, Dan R.,Milbrandt, Kara A.,Wilson, David R.,Wiltzius, Molly,Rosen, Mari S.,Klosin, Jerzy
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p. 967 - 975
(2020/02/28)
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- LIGANDS AND CATALYST SYSTEMS THEREOF FOR THE CATALYTIC OLIGOMERIZATION OF OLEFINIC MONOMERS
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The present invention relates to a ligand having the general Formula (I); P(R4J-P(R1) (R2)=N(R3) (I) wherein: the R1 group is selected from a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl group; the R2 group is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups; the R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R4 group is an optionally substituted alkylenedioxy, alkylenedimercapto or alkylenediamino structure which is bound to the phosphorus atom through the two oxygen, sulphur or nitrogen atoms of the alkylenedioxy, alkylenedimercapto or alkylenediamino structure or an optionally substituted arylenedioxy, arylenedimercapto or arylenediamino structure which is bound to the phosphorus atom through the two oxygen, sulphur or nitrogen atoms of the arylenedioxy, arylenedimercapto or arylenediamino structure.
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Page/Page column 51-52
(2008/12/06)
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- POLYMERISATION PROCESS CATALYSED BY A BIDENTATE BISPHOSPHINE-GROUP VIII METAL COMPLEX
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A process for the polymerization and copolymerization of olefins is disclosed, comprising contacting the monomeric olefin under polymerization conditions with a polymerization catalyst or catalyst system which comprises (a) a source of a Group VIII metal; (b) a bidentate phosphine ligand having the formula (R1)(R1)P-X-P(R1)(R1), where each R1 is independently selected from a phenyl group or a substitued phenyl group with the proviso that at least one of the R1 groups is a phenyl group having at least one ortho substituent, and X is a bridging group of the structure -[N]x-[P]y-[N]- where x and y are independently 0 or 1, or -C(R4)2- where R4 may be the same or different and is hydrogen or a monovavlent hydrocarbyl, substituted hydrocarbyl or hetero-hydrocarbyl group; and optionally (c) a promoter.
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Page/Page column 10
(2010/11/27)
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- CATALYTIC OLIGOMERIZATION OF OLEFINIC MONOMERS
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A catalyst precursor composition comprising: a) a source of chromium, molybdenum or tungsten; b) a first ligand having the general formula (I); [in-line-formulae](R1)(R2)P—X—P(R3)(R4)??(I) [/in-line-formulae] wherein: X is a bridging group of the formula —N(R5)—, wherein R5 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; at least three of R1 to R4 are independently selected from optionally substituted aromatic groups, each bearing a polar substituent on at least one of the ortho-positions; and optionally one of R1 to R4 is independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; c) a second ligand having the general formula (II); [in-line-formulae](R1′)(R2′)P—X′—P(R3′)(R4′)??(II) [/in-line-formulae] wherein: X′ is a bridging group as defined for X of the first ligand, component (b), of general formula (I); at least R1′ and R2′ of R1′ to R4′ are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; and optionally none, one or both of R3′ and R4′ are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions. The present invention also relates to a catalyst system comprising the catalyst precursor composition of the present invention and additional component; d) a cocatalyst. The present invention further relates to a process for the trimerization and tetramerization of olefinic monomers, particularly the trimerization and tetramerization of ethylene to 1-hexene and 1-octene, wherein the process comprises contacting at least one olefinic monomer with the catalyst system of the present invention.
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Page/Page column 12
(2008/06/13)
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- CATALYTIC PROCESS FOR THE OLIGOMERIZATION OF OLEFINIC MONOMERS
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A process for the simultaneous trimerization and tetramerization of olefinic monomers , wherein the process comprises contacting at least one olefinic monomer with catalyst system comprising : a) a source of chromium, molybdenum or tungsten; b) a ligand having the general formula (I) ; (R1)2P-X-P (R1)m(R2)n wherein : X is a bridging group of the formula -N(R3)-, wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups and c) a cocatalyst, at a pressure in the range of from below atmospheric to about 40 barg and at a temperature in the range of from about 0 °C to about 120 °C. The present invention further relates to a process for the simultaneous trimerization and tetramerization of ethylene to 1-hexene and 1-octene.
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Page/Page column 38-39
(2010/11/27)
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- Ethylene trimerisation and tetramerisation catalysts with polar-substituted diphosphinoamine ligands
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Chromium-based catalyst systems with polar-substituted diphosphinoamine ligands are selective for either trimerisation or tetramerisation of ethylene, depending on the position of the polar groups on the aryl rings. The Royal Society of Chemistry 2005.
- Overett, Matthew J.,Blann, Kevin,Bollmann, Annette,Dixon, John T.,Hess, Fiona,Killian, Esna,Maumela, Hulisani,Morgan, David H.,Neveling, Arno,Otto, Stephanus
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p. 622 - 624
(2007/10/03)
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- Steric activation of chelate catalysts: Efficient polyketone catalysts based on four-membered palladium(II) diphosphine chelates
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Palladium(II) complexes of ligands of the type Ar2PCH2-PAr2 and Ar2PN(Me)PAr2 (Ar = ortho-substituted phenyl group) are very efficient catalysts for copolymerisation of CO and C2H4/su
- Dossett,Gillon,Orpen,Fleming,Pringle,Wass,Jones
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p. 699 - 700
(2007/10/03)
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