| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 09.99 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 21.09.99 |
| PATENT TITLE |
Polymerization of ethylene |
| PATENT ABSTRACT |
Ethylene may be polymerized by contacting it with certain iron or cobalt complexes of selected 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines). The polymers produced are useful as molding resins. Novel 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines), and novel complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines) with iron and cobalt are also disclosed. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 16.12.97 |
| PATENT REFERENCES CITED |
L. Sacconi, et al., High-spin Five-co-ordinate Nickel(II) and Cobalt(II) Complexes with 2,6-Diacetylpyridinebis(imines), J. Chem. Soc., A, 1510-1515, 1968. Paul E. Figgins, et al., Complexes of Iron (II), Cobalt(II) and Nickel(II) with Biacetyl-bis-methylimine, 2-Pyridinal-methylimine and 2,6-Pyridindial-bis-methylimine, J. Am. Chem. Soc., 82, 820-824, Feb. 20, 1960. Thomas W. Bell, et al., Molecular Architecture. 1. Sodium, Potassium, and Strontium Complexes of a Hexaazamacrocycle, an 18-Crown-6/Torand Analogue, J. Am. Chem. Soc., 113, 3115-3122, 1991. Francis Lions, et al., Tridentate Chelate Compounds. I, J. Am. Chem. Soc., 79, 2733-2738, Jun. 5, 1957. PCT/US97/23556 International Search Report dated May 13, 1998. Reinhard Nesper, et al., Palladium (II) complexes of chiral tridentate nitrogen pybox ligands, Journal of Organometallic Chemistry, vol. 1, No. 507, 85-101, 1996. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. A process for the polymerization of ethylene, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., a compound of the formula ##STR21## with ethylene and: (a) a first compound W, which is a neutral Lewis acid capable of abstracting X.sup.- and alkyl group or a hydride group from M to form WX.sup.-, WR.sup.20 or WH and which is also capable of transferring an alkyl group or a hydride to M, provided that WX.sup.- is a weakly coordinating anion; or (b) a combination of a second compound which is capable of transferring an alkyl or hydride group to M and a third compound which is a neutral Lewis acid which is capable of abstracting X.sup.-, a hydride or an alkyl group from M to form a weakly coordinating anion; wherein: M is Co or Fe; 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 said Fe or Co atom present in (II); 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.6 and R.sup.7 are aryl or substituted aryl; and R.sup.20 is alkyl. 2. A process for the polymerization of ethylene, comprising contacting, at a temperature of about -100.degree. C. to about +200.degree. C., a Co›II!, Co›III!, Fe›II! or Fe›III! complex of a tridentate ligand of the formula ##STR22## 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; and R.sup.6 and R.sup.7 are aryl or substituted aryl; and provided that said Co›II!, Co›III!, Fe›II! or Fe›III! atom also has an empty coordination site or bonded to it a ligand that may be displaced by said ethylene, and a ligand that may add to said ethylene. 3. The process as recited in claim 1 or 2 wherein: R.sup.6 is ##STR23## R.sup.7 is ##STR24## R.sup.8 and R.sup.13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.12 and R.sup.17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. 4. The process as recited in claim 3 wherein: R.sup.1, R.sup.2 and R.sup.3 are hydrogen; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R.sup.8 and R.sup.13 is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R.sup.12 and R.sup.17 is each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R.sup.4 and R.sup.5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms. 5. The process as recited in claim 4 wherein R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, and R.sup.16 are each hydrogen. 6. The process as recited in claim 4 wherein R.sup.8, R.sup.12, R.sup.13, and R.sup.17 are each alkyl containing 1-6 carbon atoms. 7. The process as recited in claim 4 wherein R.sup.4 and R.sup.5 are each hydrogen or methyl. 8. The process as recited in claim 4 wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.11, R.sup.14 and R.sup.16 are hydrogen, and R.sup.4, R.sup.5, R.sup.8, R.sup.10, R.sup.12, R.sup.13, R.sup.15 and R.sup.17 are methyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.8 and R.sup.13 are chloro, and R.sup.4, R.sup.5, R.sup.12 and R.sup.17 are methyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 are hydrogen, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methylthio, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are 1-imidazolyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8 and R.sup.13 are t-butyl. 9. The process as recited in claim 4 wherein X is chloride, bromide or tetrafluoroborate. 10. The process as recited in claim 4 wherein said neutral Lewis acid is an alkyl aluminum compound. 11. The process as recited in claim 10 wherein said alkyl aluminum compound is polymethylaluminoxane. 12. The process as recited in claim 4 wherein said temperature is about -50.degree. C. to about 100.degree. C. 13. The process as recited in claim 1 or 2 wherein a pressure of said ethylene is about atmospheric pressure to about 275 MPa. 14. The process as recited in claim 1 or 2 wherein polyethylene with an average DP of 40 or more is produced. 15. The process as recited in claim 1 wherein R.sup.20 contains 1 to 4 carbon atoms. 16. The process as recited in claim 1 wherein said compound is or becomes part of a heterogeneous catalyst on a solid support. 17. The process as recited in claim 16 carried out in the gas phase or liquid phase. 18. The process as recited in claim 2 wherein said complex is or becomes part of a heterogeneous catalyst on a solid support. 19. The process as recited in claim 18 carried out in the gas or liquid phase. 20. A compound of the formula ##STR25## wherein: M is Co or Fe; 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 said Fe or Co atom present in (II); 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.6 is ##STR26## R.sup.7 is ##STR27## R.sup.8 and R.sup.13 are each independently hydrocarbyl, substituted hydrocarbyl or a functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.12 and R.sup.17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. 21. The compound as recited in claim 20 wherein: R.sup.1, R.sup.2 and R.sup.3 are hydrogen; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, and R.sup.16 is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R.sup.8, R.sup.13, R.sup.12 and R.sup.17 is each independently halogen, phenyl, or alkyl containing 1 to 6 carbon atoms; and R.sup.4 and R.sup.5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms. 22. The compound as recited in claim 20 or 21 wherein R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, and R.sup.16 are each hydrogen. 23. The compound as recited in claim 20 or 21 wherein R.sup.8, R.sup.12, R.sup.13, and R.sup.17 are each alkyl containing 1-6 carbon atoms. 24. The compound as recited in claim 23 R.sup.4 and R.sup.5 are each hydrogen or methyl. 25. The compound as recited in claim 20 wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.11, R.sup.14 and R.sup.16 are hydrogen, and R.sup.4, R.sup.5, R.sup.8, R.sup.10, R.sup.12, R.sup.13, R.sup.15 and R.sup.17 are methyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.8 and R.sup.13 are chloro, and R.sup.4, R.sup.5, R.sup.12 and R.sup.17 are methyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8 and R.sup.13 are phenyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, and R.sup.16 are hydrogen, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methylthio, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are 1-imidazolyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; or R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8 and R.sup.13 are t-butyl. 26. A compound of the formula ##STR28## wherein: M is Co or Fe; 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.6 and R.sup.7 are aryl or substituted aryl; T.sup.1 is hydride or alkyl or any other anionic ligand into which ethylene can insert; Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordinating anion; 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 T.sup.2 is an end group. 27. The compound as recited in claim 26 wherein: R.sup.6 is ##STR29## R.sup.7 is ##STR30## R.sup.8 and R.sup.13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.12 and R.sup.17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. 28. The compound as recited in claim 27 wherein: R.sup.1, R.sup.2 and R.sup.3 are hydrogen; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R.sup.8 and R.sup.13 is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R.sup.12 and R.sup.17 is each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R.sup.4 and R.sup.5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms. 29. The compound as recited in claim 28 wherein R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each hydrogen. 30. The compound as recited in claim 26 which is (VII). 31. The compound as recited in claim 26 which is (XII). 32. The compound as recited in claim 26 which is (IX). 33. A process for the polymerization of ethylene, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., ethylene and a compound of the formula ##STR31## wherein: M is Co or Fe; 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.6 and R.sup.7 are aryl or substituted aryl; T.sup.1 is hydride or alkyl or any other anionic ligand into which ethylene can insert; Y is a neutral ligand capable of being displaced by ethylene or a vacant contamination site; Q is a relatively non-coordinating anion; 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 T.sup.2 is an end group. 34. The process as recited in claim 33 wherein said compound is (VII). 35. The process as recited in claim 33 wherein said compound is (IX). 36. The process as recited in claim 33 wherein said compound is (XII). 37. The process as recited in claim 33 wherein: R.sup.6 is ##STR32## R.sup.7 is ##STR33## R.sup.8 and R.sup.13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.12 and R.sup.17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. 38. The process as recited in claim 37 wherein: R.sup.1, R.sup.2 and R.sup.3 are hydrogen; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R.sup.8 and R.sup.13 is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R.sup.12 and R.sup.17 is each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R.sup.4 and R.sup.5 are each independently hydrogen or alkyl containing 1 to 6 carbon atoms. 39. The process as recited in claim 38 wherein R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, and R.sup.16 are each hydrogen. 40. The process as recited in claim 33, 34, 35 or 36 wherein said temperature is about -50.degree. C. to about 100.degree. C. 41. The process as recited in claim 33, 34, 35 or 36 wherein a pressure of said ethylene is about atmospheric pressure to about 275 MPa. 42. The process as recited in claim 33 wherein polyethylene with an average DP of 40 or more is produced. 43. The process as recited in claim 33 wherein (VI), (IX) or (XII) is part of a heterogeneous catalyst on a solid support. 44. The process as recited in claim 43 carried out in the gas or liquid phase. 45. The process as recited in claim 16, 18 or 43 wherein said solid support is silica or alumina. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION Selected iron and cobalt complexes of 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines) are catalysts for the polymerization of ethylene. Also disclosed herein are novel 2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines), and cobalt and iron complexes of such compounds. FIELD OF THE INVENTION Polymers of ethylene are important items of commerce, millions of tons being produced annually. These polymers are used in a myriad of ways, from low molecular weight polyethylene (PE) being used as a lubricant and mold release, to higher molecular weight grades being used for fiber, films, molding resins, etc. In most cases, ethylene is polymerized using a catalyst, often a transition metal compound or complex. These catalysts vary in cost per unit weight of PE produced, the structure of the polymer produced, the possible need to remove the catalyst from the PE, the toxicity of the catalyst, etc. Due to the commercial importance of polymerizing ethylene, new polymerization catalysts are constantly being sought. L. Sacconi, et al., J. Chem. Soc. (A), 1968 p. 1510-1515 report the synthesis of certain cobalt complexes of 2,6-diacetylpyridinebis(imines). None of these cobalt complexes or the 2,6-diacetylpyridinebis(imines) disclosed in this reference are claimed herein. P. E. Figgins, et al., J. Am. Chem. Soc., vol. 82, p. 820-824, and/or F. Lions, et al., J. Am. Chem. Soc., vol. 79, p. 2733-2738 report the synthesis of certain 2,6-diacetylpyridinebis(imines) and certain iron and cobalt complexes of these tridentate ligands. The structures of the tridentate ligands reported in these references is different from those claimed herein, and all of the iron and cobalt complexes contain 2 molecules of the 2,6-diacetylpyridinebis(imines). Japanese Patent Application 89-045,712 reports the compound ##STR1## T. W. Bell, et al., J. Am. Chem. Soc., vol. 113, p. 3115-3122 (1991) reports the compound ##STR2## and Japanese Patent Application 02-078,663 reports the compound ##STR3## and an iron›II! complex of this latter compound in which two molecules of the 2,6-diacetylpyridinebis(imine) are present in the complex. None of these compounds are claimed herein. SUMMARY OF THE INVENTION This invention concerns a first process for the polymerization of ethylene, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., a compound of the formula ##STR4## with ethylene and: (a) a first compound W, which is a neutral Lewis acid capable of abstracting X.sup.- and alkyl group or a hydride group from M 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 M, 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 M and a third compound which is a neutral Lewis acid which is capable of abstracting X.sup.-, a hydride or an alkyl group from M to form a weakly coordinating anion; wherein: M is Co or Fe; 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 sate of a Fe or Co atom present in (II); 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.6 and R.sup.7 are aryl or substituted aryl; and R.sup.20 is alkyl. Also disclosed herein is a compound of the formula ##STR5## wherein: M is Co or Fe; 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 a Fe or Co atom present in (II); 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.6 is ##STR6## R.sup.7 is ##STR7## R.sup.8 and R.sup.13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.12 and R.sup.17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. This invention includes a compound of the formula ##STR8## 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.8, R.sup.12, R.sup.13 and R.sup.17 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. This invention also concerns a second process for the polymerization of ethylene, comprising contacting, at a temperature of about -100.degree. C. to about +200.degree. C., a Co›II!, Co›III!, Fe›II! or Fe›III! complex of a tridentate ligand of the formula ##STR9## 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; and R.sup.6 and R.sup.7 are aryl or substituted aryl; and provided that a Co›II!, Co›III!, 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. This invention also includes a compound of the formula ##STR10## wherein: M is Co or Fe; 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.6 and R.sup.7 are aryl or substituted aryl; T.sup.1 is hydride or alkyl or any other anionic ligand into which ethylene can insert; Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordinating anion; 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 T.sup.2 is an end group. This invention also concerns a third process for the polymerization of ethylene, comprising, contacting, at a temperature of about -100.degree. C. to about +200.degree. C., ethylene and a compound of the formula ##STR11## wherein: M is Co or Fe; 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; and R.sup.6 and R.sup.7 are aryl or substituted aryl; T.sup.1 is hydride or alkyl or any other anionic ligand into which ethylene can insert; Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site; Q is a relatively non-coordinating anion; 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 T.sup.2 is an end group. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1, 2 and 3 are three different views of the X-ray crystallographic structure of the compound made in Example 7. DETAILS OF THE INVENTION Herein, certain terms are used. Some of them are: A "hydrocarbyl group" is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms. By "substituted hydrocarbyl" herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are heteroaromatic rings. By "(inert) functional group" herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected. The functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as --OR.sup.18 wherein R.sup.18 is hydrocarbyl or substituted hydrocarbyl. In cases in which the functional group may be near a cobalt or iron atom, such as R.sup.4, R.sup.5, R.sup.8, R.sup.12, R.sup.13, and R.sup.17 the functional group should not coordinate to the metal atom more strongly than the groups in compounds containing R.sup.4, R.sup.5, R.sup.8, R.sup.12, R.sup.13, and R.sup.17 which are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group. By an "alkyl aluminum compound" is meant a compound in which at least one alkyl group is bound to an 15 aluminum atom. Other groups such as alkoxide, hydride, and halogen may also be bound to aluminum atoms in the compound. By "neutral Lewis base" is meant a compound, which is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitrites. By "cationic Lewis acid" is meant a cation which can act as a Lewis acid. Examples of such cations are sodium and silver cations. By relatively noncoordinating (or weakly coordinating) anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al., Chem. Rev., vol. 88 p. 1405-1421 (1988), and S. H. Stares, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X.sup.-, including R.sup.19.sub.3 AlX.sup.-, R.sup.19.sub.2 AlClX.sup.-, R.sup.19 AlCl.sub.2 X.sup.-, and "R.sup.19 AlOX.sup.- ", wherein R.sup.19 is alkyl. Other useful noncoordinating anions include BAF.sup.- {BAF=tetrakis›3,5-bis(trifluoromethyl)phenyl!borate}, SbF.sub.6.sup.-, PF.sub.6.sup.-, and BF.sub.4.sup.-, trifluoromethanesulfonate, p-toluenesulfonate, (R.sub.f SO.sub.2).sub.2 N.sup.-, and (C.sub.6 F.sub.5).sub.4 B.sup.-. By an empty coordination site is meant a potential coordination site that does not have a ligand bound to it. Thus if an ethylene molecule is in the proximity of the empty coordination site, the ethylene molecule may coordinate to the metal atom. By a ligand that may add to ethylene is meant a ligand coordinated to a metal atom into which an ethylene molecule (or a coordinated ethylene molecule) may insert to start or continue a polymerization. For instance, this may take the form of the reaction (wherein L is a ligand): ##STR12## Note the similarity of the structure on the left-hand side of this equation to compound (IX) (see below). Compounds useful as ligands herein in iron and cobalt complexes are diimines of 2,6-pyridinedicarboxaldehyde or 2,6-diacylpyridines of the general formula ##STR13## 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, and R.sup.6 and R.sup.7 are aryl or substituted aryl. (IV) may be made by the reaction of a compound of the formula ##STR14## with a compound of the formula H.sub.2 NR.sup.6 or H.sub.2 NR.sup.7, 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 or substituted hydrocarbyl, R.sup.4 and R.sup.5 are each hydrocarbyl or substituted hydrocarbyl, and R.sup.6 and R.sup.7 are aryl or substituted aryl. These reactions are often catalyzed by carboxylic acids, such as formic acid. Reactions such as these are described in Examples 1-6. Preferred compounds of formula (IV) and compounds in which (IV) is a ligand are those of compound (III) ›note that (III) is a subset of (IV)!, whether present in compounds such as (I), (II), (IV), (VII), (IX) and (XII). In (III), and hence in (I), (II), (IV) (VII), (IX) and (XII) that match the formula of (III), it is preferred that: R.sup.1, R.sup.2 and R.sup.3 are hydrogen; and/or R.sup.1 and R.sup.3 are hydrogen and R.sup.2 is trifluoromethyl; and/or R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen, and it is more preferred that each of these is hydrogen; and/or R.sup.10 and R.sup.15 are methyl; and/or R.sup.8 and R.sup.13 is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms, and it is it especially preferred that each R.sup.8 and R.sup.13 is alkyl containing 1-6 carbon atoms, and it is more preferred that R.sup.8 and R.sup.13 are i-propyl or t-butyl (but both R.sup.8 and R.sup.12 or both R.sup.13 and R.sup.17 can't be t-butyl in the same compound); R.sup.12 and R.sup.17 is each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that each R.sup.12 and R.sup.17 is alkyl containing 1-6 carbon atoms, and it is more preferred that R.sup.12 and R.sup.17 are i-propyl; R.sup.4 and R.sup.5 are each independently halogen, thioalkyl, hydrogen or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that R.sup.4 and R.sup.5 are each independently hydrogen or methyl. Also in (III), and hence in (I), (II), (IV) (VII), (IX) and (XII) that match the formula of (III), it is preferred that: R.sup.6 is ##STR15## R.sup.7 is ##STR16## R.sup.8 and R.sup.13 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R.sup.12 and R.sup.17 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; and provided that 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 that are vicinal to one another, taken together may form a ring. Specific preferred compounds (III) ›and also in (I), (II), (IV), (VII), (IX) and (XII)! are: R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.11, R.sup.14 and R.sup.16 are hydrogen, and R.sup.4, R.sup.5, R.sup.8, R.sup.10, R.sup.12, R.sup.13, R.sup.15 and R.sup.17 are methyl; R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.8 and R.sup.13 are chloro, and R.sup.4, R.sup.5, R.sup.12 and R.sup.17 are methyl; R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8 and R.sup.13 are phenyl; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15, and R.sup.16 are hydrogen, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methylthio (CH.sub.3 S--), and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are 1-imidazolyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; R.sup.1, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.14, R.sup.15 and R.sup.16 are hydrogen, R.sup.4 and R.sup.5 are methyl, R.sup.2 is trifluoromethyl, and R.sup.8, R.sup.12, R.sup.13 and R.sup.17 are i-propyl; and R.sup.1, R.sup.2, R.sup.3, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.14, R.sup.15, R.sup.16 and R.sup.17 are hydrogen, R.sup.4 and R.sup.5 are methyl, and R.sup.8 and R.sup.13 are t-butyl. In the polymerization processes described herein, it can be seen from the results that it is preferred that there be at least some steric crowding caused by the tridentate ligand about the Co or Fe atom. Therefore, it is preferred that groups close to the metal atom be relatively large. It is relatively simple to control steric crowding if (III) is the tridentate ligand, since control of steric crowding can be achieved simply by controlling the size of R.sup.8, R.sup.12, R.sup.13 and R.sup.16. These groups may also be part of fused ring systems, such as 9-anthracenyl. In the first polymerization process it is preferred that X is chloride, bromide and tetrafluoroborate. It is also preferred that M is Fe›II!, Fe›III!, or Co›II!. In the first polymerization process described herein an iron or cobalt complex (II) is contacted with ethylene and a neutral Lewis acid W capable of abstracting X.sup.-, hydride or alkyl from (II) to form a weakly coordinating anion, and must alkylate or be capable of adding a hydride ion to the metal atom, or an additional alkylating agent or an agent capable of adding a hydride anion to the metal atom must be present. The neutral Lewis acid is originally uncharged (i.e., not ionic). Suitable neutral Lewis acids include SbF.sub.5, Ar.sub.3 B (wherein Ar is aryl), and BF.sub.3. Suitable cationic Lewis acids or Bronsted acids include NaBAF, silver trifluoromethanesulfonate, HBF.sub.4, or ›C.sub.6 H.sub.5 N(CH.sub.3).sub.2 !.sup.+ ›B(C.sub.6 F.sub.5).sub.4 !.sup.-. In those instances in which (II) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid), does not contain an alkyl or hydride group already bonded to the metal atom, the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal or a separate alkylating or hydriding agent is present, i.e., causes an alkyl group or hydride to become bonded to the metal atom. It is preferred that R.sup.20 contains 1 to 4 carbon atoms, and more preferred that R.sup.20 is methyl or ethyl. For instance, alkyl aluminum compounds (see next paragraph) may alkylate (II). However, not all alkyl aluminum compounds may be strong enough Lewis acids to abstract X.sup.- or an alkyl group from the metal atom. In that case a separate Lewis acid strong enough to do the abstraction must be present. For instance, in Example 37, polymethyaluminoxane is used as the "sole" Lewis acid, it both alkylates and does the abstraction from the metal atom. In Examples 60 and 61 triethylaluminum alkylates the metal atom, but is not a strong enough Lewis acid to abstract an anion from the metal atom, so another (stronger) Lewis acid, B(C.sub.6 F.sub.5).sub.3, was also added to the polymerization. Without the stronger Lewis acid B(C.sub.6 F.sub.5).sub.3 present, the polymerization does not proceed. A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R.sup.19.sub.3 Al, R.sup.19 AlCl.sub.2, R.sup.19.sub.2 AlCl, and "R.sup.19 AlO" (alkylaluminoxanes), wherein R.sup.19 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula ›MeAlO!.sub.n), (C.sub.2 H.sub.5).sub.2 AlCl, C.sub.2 H.sub.5 AlCl.sub.2, and ›(CH.sub.3).sub.2 CHCH.sub.2 !.sub.3 Al. Metal hydrides such as NaBH.sub.4 may be used to bond hydride groups to the metal M. In the second polymerization process described herein a cobalt or iron complex of (I) is either added to the polymerization process or formed in situ in the process. In fact, more than one such complex may be formed during the course of the process, for instance formation of an initial complex and then reaction of that complex to form a living ended polymer containing such a complex. Examples of such complexes which may be formed initially in situ include ##STR17## wherein R.sup.1 through R.sup.7, and M are as defined above, T.sup.1 is hydride or alkyl or any other anionic ligand into which ethylene can insert, Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site, the "parallel lines" are an ethylene molecule coordinated to the metal, and Q is a relatively non-coordinating anion. Complexes may be added directly to the process or formed in situ. For instance, (VII) may be formed by the reaction of (II) with a neutral Lewis acid such as an alkyl aluminum compound. Another method of forming such a complex in situ is adding a suitable iron or cobalt compound such cobalt ›II! acetylacetonate (see Example 18), (I) and an alkyl aluminum compound. Other metal salts in which anions similar to acetylacetonate are present, and which may be removed by reaction with the Lewis or Bronsted acid. For instance metal halides and carboxylates (such as acetates) may be used, particularly if they are slightly soluble in the process medium. It is preferred that these precursor metal salts be at least somewhat soluble in the process medium. After the ethylene polymerization has started, the complex may be in a form such as ##STR18## wherein R.sup.1 through R.sup.7, M, and Q are as defined above, 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 T.sup.2 is an end group, for example the groups listed for T.sup.1 above. Those skilled in the art will note that (IX) is in essence a polymer containing a so-called living end. It is preferred that M be in +2 oxidation state in (VII), (VIII) and (IX). Compounds such as (VII), (IX) and (XII) may or may not be stable away from an environment similar to that of the polymerization process, but they may be detected by NMR spectroscopy, particularly one or both of .sup.1 H and .sup.13 C NMR, and particularly at lower temperatures. Such techniques, especially for polymerization "intermediates" of these types are known, see for instance World Patent Application 96/23010, especially Examples 197-203, which is hereby included by reference. (VII), (IX) and (XII) may also be used, in the absence of any "co-catalysts" or "activators" to polymerize ethylene in a third polymerization process. Except for the ingredients in the process, the process conditions for the third process, such as temperature pressure, polymerization medium, etc., may be the same as for the first and second polymerization processes, and preferred conditions for those processes are also preferred for the third polymerization process. In all the polymerization processes herein, the temperature at which the ethylene polymerization is carried out is about -100.degree. C. to about +200.degree. C., preferably about -60.degree. C. to about 150.degree. C., more preferably about -50.degree. C. to about 100.degree. C. The ethylene pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. The polymerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, ethylene, and polyethylene may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene. The ethylene polymerizations herein may also initially be carried out in the solid state ›assuming (II), (III) (IV) or (VII) is a solid! by, for instance, supporting (II), (III) (IV) or (VII) on a substrate such as silica or alumina, activating it with the Lewis (such as W, for instance an alkylaluminum compound) or Bronsted acid and exposing it to ethylene. The support may also be able to take the place of the Lewis or Bronsted acid, for instance an acidic clay such as montmorillonite. Another method of making a supported catalyst is to start a polymerization or at least make an iron or cobalt complex of another olefin or oligomer of an olefin such as cyclopentene on a support such as silica or alumina. These "heterogeneous" catalysts may be used to catalyze polymerization in the gas phase or the liquid phase. By gas phase is meant that the ethylene is transported to contact with the catalyst particle while the ethylene is in the gas phase. Preparations of these types of heterogeneous catalysts are found in Examples 43-46. In all of the polymerization processes described herein oligomers and polymers of ethylene are made. They may range in molecular weight from oligomeric olefins (see Example 32, which is mostly decenes), to lower molecular weight polyethylene oils and waxes, to higher molecular weight polyethylenes. One preferred product is a polymer with a degree of polymerization (DP) of about 10 or more, preferably about 40 or more. By "DP" is meant the average number of repeat (monomer) units in a polymer molecule. In the Examples, the pressures given are gauge pressures. The following abbreviations and terms are used: Branching--reported as the number of methyl groups per 1000 methylene groups in the polymer. Not corrected for end groups. It is determined by .sup.1 H NMR. Dispersity--weight average molecular weight divided by number average molecular weight (Mn). DSC--differential scanning calorimetry FW--formula weight GC--gas chromatography GPC--gel permeation chromatography .DELTA.H--heat of fusion (of polyethylene) Mn--number average molecular weight MeOH--methanol PMAO--polymethylaluminoxane RT--room temperature THF--tetrahydrofuran Tm--melting point Turnover #--the number of moles of ethylene polymerized per mole of cobalt or iron compound present. Structures were determined by X-ray crystallography using a Rigaku RU300 instrument with an R-AXIS image plate detector using MoK.alpha. radiation. The structure was solved by direct methods (SHELXS or MULTAN), using a refinement by full-matrix least squares on F. Metals analyses of heterogeneous catalysts were performed by Inductively Coupled Plasma Atomic Absorption (ICP) analysis. In the Examples, the apparatus for polymerization run at about 34.5 kPa ethylene pressure were run in Schlenk tubes. In general the metal complex (or metal compound and ligand) was dissolved or slurried in dry "solvent" under nitrogen. The stoppered flask was then brought to the desired reaction temperature, flushed well with ethylene, placed under a pressure of about 34.5 kPa of ethylene and stirred vigorously. The other catalyst component(s) were then added and the polymerization was allowed to proceed. Polymerizations run at higher pressures were done in a Parr.RTM. 100 ml stirred autoclave. The procedure was similar to that used in the Schlenk tubes (above). |
| PATENT EXAMPLES | This data is not available for free |
| PATENT PHOTOCOPY | Available on request |
|
Want more information ? Interested in the hidden information ? Click here and do your request. |