Patent EA-002981-B1 (EA)
Title: Process for polymerization of ethylene, pyridinebisimines and pyridinebisimines complexes with iron and cobalt
Inventor: BENNETT ALISON MARGARET ANNE
IPC: C08F110/02
Filed: 1997-12-16
Abstract: 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:   with ethylene and: (a) a first compound W, which is a neutral Lewis acid capable of abstracting X<-> from M to from WX<->, and which is also capable of transferring an alkyl group or a hydride to M, provided that WX<-> 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<->, 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<1>, R<2> and R<3> are each independently hydrogen, CF3; R<4> and R<5> are each independently hydrogen, halogen, C1-6alkyl, C1-6alkylthio, 1-imidazolyl; R<6>and R<7> are optionally substituted phenyl. 2. The process according to claim 1 in which said compound is or becomes a part of heterogenic catalyst on a solid carrier. 3. The process according to claim 1 which is carried out in gas or liquid phases. 4. The process according to claim 1 wherein said neutral Lewis acid is an alkyl aluminum compound. 5. The process according to claim 1 wherein a pressure of said ethylene is about atmospheric pressure to about 275 MPa. 6. The process according to claim 1 wherein polyethylene with an average DP of 40 or more is produced. 7. The process for or 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   with ethylene, wherein: R<1>, R<2> and R<3> are each independently hydrogen, CF3; R<4> and R<5> are each independently hydrogen, halogen, C1-6alkyl, C1-6alkylthio, 1-imidazolyl; R<6>and R<7> are optionally substituted phenyl; 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. 8. The process according to claim 1 in which said compound is or becomes a part of heterogenic catalyst on a solid carrier. 9. The process according to claim 7 which is carried out in gas or liquid phases. 10. The process according to claim 7 wherein a pressure of said ethylene is about atmospheric pressure to about 275 MPa. 11. The process according to claim 7 wherein polyethylene with an average DP of 40 or more is produced. 12. The process according to any of claims 1 to 11 in which: R<6> is a group:   R<7> is a group:   where each of R<8>, R<9>, R<10>, R<11>, R<12>, R<13> R<14>, R<15>, R<16> and R<17> are independently hydrogen, C1-6alkyl, halogen, provided that any of two alkyl radicals R<8>, R<9>, R<10>, R<11>, R<12>, R<13> R<14>, R<15>, R<16> and R<17> that are vicinal to one another, taken together may form a ring. 13. The process according to claim 12, in which: R<1>, R<2> and R<3> are hydrogen; R<9>, R<10>, R<11>, R<14>, R<15> and R<16> is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R<8> and R<13> is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R<12> and R<17> is each independently halogen, phenyl, hydrogen, or alkyl containing 1 to 6 carbon atoms; and R<4> and R<5> are each independently hydrogen or alkyl containing 1 to 6 carbon atoms. 14. The process according to claim 12, wherein R<9>, R<10>, R<11>, R<14>, R<15>, and R<16> are each hydrogen. 15. The process according to claim 12 wherein R<8>, R<12>, R<13>, and R<17> are each alkyl containing 1-6 carbon atoms. 16. The process according to claim 12 wherein R<4> and R<5> are each hydrogen or methyl.: 3. The process as recited in claim 1 or 2 wherein: 17. The process according to claim 12 wherein: R<1>, R<2>, R<3>, R<9>, R<11>, R<14> and R<16> are hydrogen, and R<4>, R<5>, R<8>, R<10>, R<12>, R<13>, R<15> and R<17> are methyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<14>, R<15> and R<16> are hydrogen, R<8> and R<13> are chloro, and R<4>, R<5>, R<12> and R<17> are methyl; R<1>, R<2>, R<3>, R<4>, R<5>, R<9>, R<10>, R<11>, R<12>, R<14>, R<15>, R<16> and R<17> are hydrogen, and R<8>, R<12>, R<13> and R<17> are i-propyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<14>, R<15> and R<16> are hydrogen, R<4> and R<5> are methylthio, and R<8>, R<12>, R<13> and R<17> are i-propyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<14>, R<15> and R<16> are hydrogen, R<4> and R<5> are 1-imidazolyl, and R<8>, R<12>, R<13> and R<17> are i-propyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<14>, R<15> and R<16> are hydrogen, R<4> and R<5> are methyl, and R<8>, R<12>, R<13> and R<17> are i-propyl; or R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<12>, R<14>, R<15>, R<16> and R<17> are hydrogen, R<4> and R<5> are methyl, and R<8> and R<13> are t-butyl. 18. The process according to claim 12 wherein X is chloride, bromide or tetrafluoroborate. 19. A compound of the formula:   wherein: R<1>, R<2> and R<3> are each independently hydrogen, CF3; R<4> and R<5> are each independently hydrogen, halogen, C1-6alkyl, C1-6alkylthio, 1-imidazolyl; R<8>, R<12>, R<13>, and R<17> are each C1-6alkyl, halogen; R<9>, R<10>, R<11>, R<14>, R<15>, and R<16> are each independently hydrogen, C1-6alkyl, halogen; provided that any two of R<8>, R<9>, R<10>, R<11>, R<12>, R<13>, R<14>, R<15>, R<16> and R<17> that are vicinal to one another, taken together may form a ring. 20. A compound of the formula:   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<1>, R<2> and R<3> are each independently hydrogen, CF3; R<4> and R<5> are each independently hydrogen, halogen, C1-6alkyl, C1-6alkylthio, 1-imidazolyl; R<6> is    R<7> is    where each of R<8>, R<9>, R<10>, R<11>, R<12>, R<13> R<14>, R<15>, R<16> and R<17> are independently hydrogen, C1-6alkyl, halogen, provided that any of two alkyl radicals R<8>, R<9>, R<10>, R<11>, R<12>, R<13> R<14>, R<15>, R<16> and R<17> that are vicinal to one another, taken together may form a ring. 21. A compound according to claim 19 or 2-, wherein: R<1>, R<2> and R<3> are hydrogen; R<9>, R<10>, R<11>, R<14>, R<15> and R<16> is each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen; R<8>, R<12>, R<13> and R<17> is each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms; R<4> and R<5> are each independently hydrogen or alkyl containing 1 to 6 carbon atoms. 22. A compound according to claim 19 or 20, wherein R<10>, R<11>, R<12>, R<14>, R<15> and R<16> are each hydrogen. 23. A compound according to claim 19 or 20, wherein R<8>, R<12>, R<13>, and R<17> are each alkyl containing 1-6 carbon atoms. 24. A compound according to claim 19 or 20, wherein R<4> and R<5> are each hydrogen or methyl. 25. A compound according to claim 19 or 20, wherein: R<1>, R<2>, R<3>, R<9>, R<11>, R<14> and R<16> are hydrogen, and R<4>, R<5>, R<8>, R<10>, R<12>, R<13>, R<15> and R<17> are methyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<14>, R<15> and R<16> are hydrogen, R<4> and R<5> are methylthio and R<8>, R<12>, R<13> and R<17> are i-propyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<12>, R<14>, R<15>, R<16> and R<17> are hydrogen, R<4> and R<5> are 1-imidazolyl, and R<8>, R<12>, R<13> and R<17> are i-propyl; R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<12>, R<14>, R<15>, R<16> and R<17> are hydrogen, R<8> and R<13> are chloro, and R<4>, R<5>, R<12> and R<17> are methyl; or R<1>, R<2>, R<3>, R<9>, R<10>, R<11>, R<12>, R<14>, R<15>, R<16> and R<17> are hydrogen, R<4> and R<5> are methyl, and R<8>, R<12>, R<13> and R<17> are i-propyl.