Shell Oil Comapny

Eric Johannes Maria De Boer

Harry Van Der Heijden

Arie Van Zon

Quoc An On

Johan Paul Smit

Aart Bartus Van Oort

Nicolaas Meijboom

Hendrikus Hyacinthus Deuling

Henderikus Hyacinthus Deuling

Marijke De Boer-Wildschut

Inge Oosterveld

John Smit

Wilhelmina Cornelia Verhoef-Van Wijk

Arie Von Zon

Arie Vah Zon

Wihelmina Cornelia Verhoef-Van Wijk

The present invention relates to a ligand and its use in a catalyst for the oligomerization of olefinic monomers, the ligand having the general formula (IV);(R)(R)P&#x2014;N(R)&#x2014;P(R)&#x2003;&#x2003;(IV).

Catalyst systems for the catalytic oligomerization of olefinic monomers

The present invention relates to a ligand and its use in a catalyst for the oligomerization of olefinic monomers, the ligand having the general formula (VI);(R)(R)P&#x2014;N(R)&#x2014;P(R)&#x2003;&#x2003;(VI)wherein:the Rand Rgroups are independently selected from optionally substituted alkyl or heteroalkyl groups; the Rgroup 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.

The present invention relates to a ligand and its use in a catalyst for the oligomerization of olefinic monomers, the ligand having the general formula (VI):(R)(R)P&#x2014;N(R)&#x2014;P(R)&#x2003;&#x2003;(VI)

The present invention relates to catalyst systems and a process for the simultaneous trimerization and tetramerization of olefinic monomers using those ligands.

Catalyst systems for the oligomerization of olefin monomers

The present invention relates to ligands and catalyst systems and a process for the simultaneous trimerization and tetramerization of olefinic monomers using said ligands, the ligands having the general formula (I):(R)P&#x2014;P(R)(R)&#x2550;N(R)&#x2003;&#x2003;(I)wherein Ris selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof;the Rgroups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions; andthe Rgroups 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;with the proviso that m is 0 or 1, n is 1 or 2 and the total of m+n is 2.

Ligands and catalyst systems for the oligomerization of olefinic monomers

The present invention relates to a ligand and its use in a catalyst for the oligomerization of olefinic monomers, the ligand having the general formula (II);P(R)(R)&#x2014;P(R)&#x2550;N(R)&#x2003;&#x2003;(II)wherein:the Rgroup is selected from a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl group; the Rgroup is selected from a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl group; the Ris selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the Rgroup 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.

Ligands and catalyst systems thereof for the catalytic oligomerization of olefinic monomers

A catalyst precursor composition comprising: a source of chromium, molybdenum or tungsten; a first ligand having the general formula (R)(RP&#x2014;X&#x2014;P(R)(R); and a second ligand having the general formula (R)(R)P&#x2014;X'&#x2014;P(R)(R). The present invention also relates to a catalyst system comprising the catalyst precursor composition of the present invention and 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.

Catalytic oligomerization of olefinic monomers

The present invention relates to a ligand and its use in a catalyst for the oligomerization of olefinic monomers, the ligand having the general formula (I);P(R)&#x2014;P(R)(R)&#x2550;N(R)&#x2003;&#x2003;(I)

A process for the preparation of linear alpha olefins having 2n carbon atoms from linear alpha olefins having n carbon atoms comprising the steps of (a) dimerizing a linear alpha olefin having n carbon atoms in the presence of a dimerization catalyst to produce a linear internal olefin having 2n carbon atoms; (b)(i) reacting the linear internal olefin having 2n carbon atoms produced in step (a) with a trialkylaluminium compound in the presence of a catalytic amount of an isomerization/displacement catalyst in order to cause isomerization of the linear internal olefin and to displace alkyl group(s) from said trialkylaluminium compound to form an alkyl aluminium compound wherein at least one of the alkyl groups bound to aluminium is a linear alkyl which has been derived from the isomerization of said linear internal olefin; and (b)(ii) reacting said alkyl aluminium compound with an alpha olefin optionally in the presence of a displacement catalyst so as to displace said linear alkyl from said alkyl aluminium compound to form a linear alpha olefin having 2n carbon atoms.

Process for preparing linear alpha olefins

A transition metal complex which is a bis-arylimine pyridine MXcomplex or a [bis-arylimine pyridine MXp+][NC&#x2212;]q complex comprising a bis-arylimine pyridine ligand and M is a transition metal atom; n matches the formal oxidation state of the transition metal atom M; X is halide, optionally substituted hydrocarbyl, alkoxide, amide, or hydride; NC&#x2212; is a non-coordinating anion; and p+q matches the formal oxidation state of the transition metal atom M. The transition metal complexes of the present invention, their complexes with non-coordinating anions and catalyst systems containing such complexes have good solubility in non-polar media and chemically inert non-polar solvents especially aromatic hydrocarbon solvents. The catalyst systems can be used for a wide range of (co-)oligomerization, polymerization and dimerization reactions.

Transition metal complexes

A catalyst precursor composition comprising a) a source of chromium, molybdenum or tungsten; b) a first ligand having the general formula (I):(R)(R)P-X-P(R)(R)&#x2003;&#x2003;(I)where X is a bivalent organic bridging group, Rand Rare hydrocarbyl groups, and Rand Rare aromatic groups; and c) a second ligand having the general formula (II):(R)(R)P-X'-P(R)(R)&#x2003;&#x2003;(II)where X&#x2032; is a bridging group containing nitrogen and R, R, Rand Rare hydrocarbyl groups. The present invention also relates to a catalyst system comprising the catalyst precursor composition of the present invention and a cocatalyst.

Catalytic trimerization and tetramerization of olefinic monomers

Mixed bis-imine pyridine ligands of formula (I), wherein Z, which is different from Z, is an optionally substituted aryl group; and Zcomprises an optionally substituted heterohydrocarbyl moiety, or an optionally substituted aryl group in combination with a metal, said optionally substituted aryl group being &#x3c0;-co-ordinated to the metal; mixed bis-imine pyridine complexes comprising a ligand of formula (I); mixed ionic bis-imine pyridine complexes comprising a ligand of formula (I); and processes for the production of alpha olefins from ethylene, using said complexes.

Ligands and catalyst systems thereof for ethylene oligomerisation to linear alpha olefins

A catalyst precursor composition comprising a) a source of chromium, molybdenum or tungsten; b) a first ligand having the general formula (I);(R)(R)P&#x2014;X&#x2014;P(R)(R)&#x2003;&#x2003;(I)wherein X is a bivalent organic bridging group; Rand Rare independently selected from, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups, with the proviso that when Rand Rare aromatic groups they do not contain a polar substituent at any of the ortho-positions; Rand Rare independently selected from optionally substituted aromatic groups, each Rand Rbearing a polar substituent on at least one of the ortho-positions; and c) a second ligand having the general formula (II);(R)(R)P&#x2014;X'&#x2014;P(R)(R)&#x2003;&#x2003;(II)

A process for production of higher linear alpha olefins and/or alkyl-branched alpha olefins, which comprises the co-oligomerisation of one or more alpha olefins with ethylene in the presence of a metal catalyst system employing one or more bis-aryliminepyridine MXcomplexes and/or one or more [bis-aryliminepyridine MY.L][NC]complexes; and said process is carried out at an ethylene pressure of less than 2.5 MPa.

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Amsterdam, Netherlands

Eric Johannes Maria De Boer