Manufacture of .alpha.-olefins
AssigneesE. I. Du Pont de Nemours and Company, University of North Carolina
InventorsMaurice S. Brookhart, III, Brooke L. Small
Life of this patent
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Abstract
Alpha-olefins are manufactured in high yield and with very high selectivity by contacting ethylene with an iron complex of a selected 2,6-pyridinedicarboxaldehyde bisimine or a selected 2,6-diacylpyridine bisimine, and in some cases a selected activator compound such as an alkyl aluminum compound. Novel bisimines and their iron complexes are also disclosed. The .alpha.-olefins are useful as monomers and chemical intermediates.
Claims41
A process for the production of .alpha.-olefins, comprising, contacting, at a temperature of about -100.degree. C. to about +300.degree. C., a compound of the formula ##STR15## with ethylene and:
- (a) a first compound W, which is a neutral Lewis acid capable of abstracting X.sup.- an alkyl group or a hydride group from Fe to form WX.sup.-, (WR.sup.20).sup.- or WH.sup.- and which is also capable of transferring an alkyl group or a hydride to Fe, provided that WX.sup.- is a weakly coordinating anion;
- or
- (b) a combination of second compound which is capable of transferring an alkyl or hydride group to Fe and a third compound which is a neutral Lewis acid which is capable of abstracting X.sup.-, a hydride or an alkyl group from Fe to form a weakly coordinating anion;
- wherein:
- each X is an anion;
- n is 1, 2 or 3 so that the total number of negative charges on said anion or anions is equal to the oxidation state of an Fe atom present in (I);
- R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
- R.sup.4 and R.sup.5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
- R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
- R.sup.8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
- and
- R.sup.20 is alkyl;
- and provided that:
- when R.sup.8 is a primary carbon group none, one or two of R.sup.12, R.sup.13 and R.sup.17 are primary carbon groups, and the remainder of R.sup.12, R.sup.13 and R.sup.17 are hydrogen;
- when R.sup.8 is a secondary carbon group, none or one of R.sup.12, R.sup.13 and R.sup.17 is a primary carbon group or a secondary carbon group and the remainder of R.sup.12, R.sup.13, and R.sup.17 are hydrogen;
- when R.sup.8 is a tertiary carbon group all of R.sup.12, R.sup.13 and R.sup.14 are hydrogen;
- and
- any two of R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 vicinal to one another, taken together may form a ring.
A process for the production of .alpha.-olefins, comprising contacting, at a temperature of about -100.degree. C. to about +300.degree. C., a Fe[II] or Fe[III] complex of a tridentate ligand of the formula ##STR16## with ethylene, wherein:
- R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
- R.sup.4 and R.sup.5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
- R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
- R.sup.8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
- and provided that:
- when R.sup.8 is a primary carbon group none, one or two of R.sup.12, R.sup.13 and R.sup.17 are primary carbon groups, and the remainder of R.sup.12, R.sup.13 and R.sup.17 are hydrogen;
- when R.sup.8 is a secondary carbon group, none or one of R.sup.12, R.sup.13 and R.sup.17 is a primary carbon group or a secondary carbon group and the remainder of R.sup.12, R.sup.13, and R.sup.17 are hydrogen;
- when R.sup.8 is a tertiary carbon group all of R.sup.12, R.sup.13 and R.sup.14 are hydrogen;
- any two of R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 vicinal to one another, taken together may form a ring;
- an Fe[II] or Fe[III] atom also has bonded to it an empty coordination site or a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene.
A process for the production of .alpha.-olefins, comprising, contacting, at a temperature of about -100.degree. C. to about +300.degree. C., ethylene and a compound of the formula ##STR17## wherein:
- R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;
- R.sup.4 and R.sup.5 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl,
- R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, an inert functional group or substituted hydrocarbyl;
- R.sup.8 is a primary carbon group, a secondary carbon group or a tertiary carbon group;
- T.sup.1 is hydride or alkyl or any other anionic ligand into which ethylene can insert;
- Y is a vacant coordination site, or a neutral ligand capable of being displaced by ethylene;
- Q is a relatively non-coordinating anion;
- and
- P is a divalent (poly)ethylene group of the formula --(CH.sub.2 CH.sub.2).sub.x -- wherein x is an integer of 1 or more;
- and provided that:
- when R.sup.8 is a primary carbon group none, one or two of R.sup.12, R.sup.13 and R.sup.17 are primary carbon groups, and the remainder of R.sup.12, R.sup.13 and R.sup.17 are hydrogen;
- when R.sup.8 is a secondary carbon group, none or one of R.sup.12, R.sup.13 and R.sup.17 is a primary carbon group or a secondary carbon group and the remainder of R.sup.12, R.sup.13, and R.sup.17 are hydrogen;
- when R.sup.8 is a tertiary carbon group all of R.sup.12, R.sup.13 and R.sup.14 are hydrogen;
- and
- any two of R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 vicinal to one another, taken together may form a ring.
Dependencies are inferred from the claim text.