Claims
- 1. A process for the polymerization of a polymerizable monomer, comprising,
- (a) contacting ethylene, a norbornene or a styrene, and a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV), and a first compound selected from the group consisting of: ##STR150## and wherein: X is a noncoordinating anion;
- Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl;
- each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ;
- R.sup.43 is hydrogen or alkyl;
- n is 1 or 2;
- E is 2-thienyl or 2-furyl;
- each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
- each R.sup.9 is independently hydrogen or hydrocarbyl; and
- each R.sup.3 is independently a monovalent aromatic moiety;
- m is 1, 2 or 3;
- each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
- each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- Ar.sup.2 is an aryl moiety;
- R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or less;
- each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar.sup.3 is an aryl moiety;
- R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl;
- Ar.sup.4 is an aryl moiety;
- Ar.sup.5 and Ar.sup.6 are each independently hydrocarbyl;
- Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety;
- Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
- Ar.sup.11 is an aryl moiety;
- R.sup.41 is hydrogen or hydrocarbyl;
- R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ;
- R.sup.44 is aryl;
- R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and
- R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety.
- 2. A process for the polymerization of a polymerizable monomers, comprising, contacting ethylene, a norbornene, or a styrene with a nickel �II! complex of a first compound selected from the group consisting of: ##STR151## and wherein: X is a noncoordinating anion;
- Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl;
- each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ;
- R.sup.43 is hydrogen or alkyl
- n is 1 or 2;
- E is 2-thienyl or 2-furyl;
- each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
- each R.sup.3 is independently a monovalent aromatic moiety;
- each R.sup.9 is independently hydrogen or hydrocarbyl; m is 1, 2 or 3;
- each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
- each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- Ar.sup.2 is an aryl moiety;
- R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or less;
- each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar.sup.3 is an aryl moiety;
- R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl;
- Ar.sup.4 is an aryl moiety;
- Ar.sup.5 and Ar.sup.6 are each independently hydrocarby;
- Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety;
- Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety, --CO.sub.2 R.sup.25, or Ar.sup.7 and Ar.sup.8 taken together are a divalent aromatic moiety and wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
- Ar.sup.11 is an aryl moiety;
- R.sup.41 is hydrogen or hydrocarbyl;
- R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ;
- R.sup.44 is aryl;
- R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms, and
- R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety.
- 3. A process for the polymerization of polymerizable monomers, comprising, contacting ethylene, a norbornene or a styrene with a nickel containing first compound of the formula �L.sup.1.sub.q L.sup.2.sub.r L.sup.3.sub.s L.sup.4.sub.t Ni!.sup.+ X.sup.- (XXXIII), wherein:
- L.sup.1 is a first monodentate neutral ligand coordinated to said nickel, L.sup.2 is a second monodentate neutral ligand coordinated to said nickel which may be said first monodentate neutral ligand and r is 0 or 1, or L.sup.1 and L.sup.2 taken together are a first bidentate neutral ligand coordinated to said nickel and r is 1;
- L.sup.3 and L.sup.4 taken together are a .pi.-allyl ligand coordinated to said nickel, L.sup.3 and L.sup.4 taken together are ##STR152## coordinated to said nickel, or L.sup.3 is a third neutral monodentate ligand selected from the group consisting of ethylene, a norbornene and a styrene or a neutral monodentate ligand which can be displaced by an olefin, and L.sup.4 is R.sup.38 ;
- q, s and t are each 1;
- X is a relatively non-coordinating anion;
- said first monodentate neutral ligand and said first bidentate neutral ligand are selected from the group consisting of ##STR153## Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ;
- R.sup.43 is hydrogen or alkyl
- n is 1 or 2;
- E is 2-thienyl or 2-furyl;
- each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl;
- each R.sup.9 is independently hydrogen or hydrocarbyl; and
- each R.sup.3 is independently a monovalent aromatic moiety;
- m is 1, 2 or 3;
- each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms;
- each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
- Ar.sup.2 is an aryl moiety;
- R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group;
- R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or less;
- each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms;
- Ar.sup.3 is an aryl moiety;
- R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl;
- Ar.sup.4 is an aryl moiety;
- Ar.sup.5 and Ar.sup.6 are each independently hydrocarbyl;
- Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety;
- Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
- Ar.sup.11 is an aryl moiety;
- R.sup.41 is hydrogen or hydrocarbyl;
- R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ;
- R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and
- R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety;
- R.sup.35 is hydrocarbylene;
- R.sup.36 is hydrogen, alkyl, or --C(O)R.sup.39 ;
- each R.sup.37 is hydrocarbyl or both of R.sup.37 taken together are hydrocarbylene to form a carbocyclic ring;
- R.sup.38 is hydride, alkyl or --C(O)R.sup.39 ;
- R.sup.39 is hydrocarbyl; and
- R.sup.44 is aryl.
- 4. The process as recited in claim 1 or 2 wherein the molar ratio of (III):(II) is about 0.5 to 5, and the molar ratio of (IV):(II) is about 0.5 to about 10.
- 5. The process as recited in claim 1, 2 or 3 wherein X is BF.sub.4.sup.-, PF.sub.6.sup.-, BAF.sup.-, or SbF.sub.6.sup.-.
- 6. The process as recited in claim 1, or 2 wherein (II) is bis(.eta..sup.4 -1,5-cyclooctadienyl)nickel�0!.
- 7. The process as recited in claim 1, 2 or 3 wherein an olefin is ethylene.
- 8. The process as recited in claim 1, 2 or 3 wherein an olefin is norbornene.
- 9. The process as recited in claim 1, 2 or 3 wherein an olefin is styrene.
- 10. The process as recited in claim 1, 2 or 3 wherein an olefin is a combination of styrene and norbornene, and a copolymer of styrene and norbornene is produced.
- 11. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (III).
- 12. The process as recited in claim 11 wherein:
- n is 1, Q is --CR.sup.9= NR.sup.3, R.sup.9 is hydrogen, Ar.sup.1 is 9-anthracenyl, and R.sup.3 is 2-carbamoylphenyl or 2,6-diisopropylphenyl;
- n is 2 and Q is --CR.sup.9 =NR.sup.3, R.sup.3 is 2,6-disubstituted phenyl in which substitutents are halo, alkyl, or halo and alkyl, Ar.sup.1 is p-phenylene, and R.sup.9 is hydrogen;
- n is 1, Q is --CR.sup.9 =NR.sup.3, R.sup.9 is hydrogen, R.sup.3 is 2,6-dimethylphenyl, and Ar.sup.1 is pentafluorophenyl; or
- n is 1, Q is --CR.sup.9 =NR.sup.3, R.sup.9 is hydrogen, R.sup.3 is 2,6-diisopropylphenyl, and Ar.sup.1 is 2-hydroxy-1-naphthyl.
- 13. The process as recited in claim 11 wherein:
- n is 1, Q is --NR.sup.2 R.sup.43, R.sup.2 is --CH=CPh.sub.2, R.sup.43 is hydrogen, and Ar.sup.1 is 2,6-diisopropylphenyl;
- n is 1, Q is --NR.sup.2 R.sup.43, R.sup.2 is --CH=CPh.sub.2, R.sup.43 is hydrogen and Ar.sup.1 is 2-carbamoylphenyl;
- n is 2, Q is --NR.sup.2 R.sup.43, R.sup.2 is hydrogen, R.sup.43 is hydrogen, and Ar.sup.1 is 1,8-napthylylene;
- n is 1, Q is --NR.sup.2 R.sup.43, R.sup.2 is --CH=CPh.sub.2, R.sup.43 is hydrogen, and Ar.sup.1 is 2-methoxycarbonylphenyl;
- n is 1, Q is --NR.sup.2 R.sup.43, R.sup.2 is hydrogen, R.sup.43 is hydrogen, and Ar.sup.1 is 2-carboxyphenyl;
- n is 1, Q is --NR.sup.2 R.sup.43, R.sup.2 is --CH=CPh.sub.2, R.sup.43 is hydrogen, and Ar.sup.1 is 1-anthraquinonyl;
- n is 1, Q is NR.sup.2 R.sup.43, R.sup.2 is --CH=CPh.sub.2, R.sup.43 is hydrogen, and Ar.sup.1 is ##STR154## wherein (III) is ##STR155##
- 14. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (V).
- 15. The process as recited in claim 14 wherein:
- m is 1, all of R.sup.8, R.sup.4, R.sup.5, R.sup.6 an R.sup.7 are hydrogen, and both of R.sup.10 are 2,6-diisopropylphenyl; or
- m is 1, all of R.sup.8, R.sup.4, R.sup.5, R.sup.6 an R.sup.7 are hydrogen, and both of R.sup.10 are cyclohexyl.
- 16. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XVI).
- 17. The process as recited in claim 16 wherein:
- Ar.sup.2 is 2-(N-2,2-diphenylethenylamino)phenyl and R.sup.10 is hydrogen;
- Ar.sup.2 is phenyl and R.sup.10 is 2,6-diisopropylphenyl;
- Ar.sup.2 is 2-pyridyl and R.sup.10 is hydrogen; or
- Ar.sup.2 is 3-hydroxy-2-pyridyl and R.sup.10 is hydrogen.
- 18. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XVII).
- 19. The process as recited in claim 18 wherein:
- R.sup.11 and R.sup.15 are t-butyl and R.sup.12, R.sup.13 and R.sup.14 are hydrogen;
- R.sup.11, R.sup.13 and R.sup.15 are t-butyl and R.sup.12 and R.sup.14 are hydrogen;
- R.sup.11 and R.sup.15 are phenyl and R.sup.12, R.sup.13 and R.sup.14 are hydrogen; or
- R.sup.11 is t-butyl and R.sup.12 and R.sup.14 are hydrogen, R.sup.13 is methoxy, and R.sup.15 is 2-hydroxy-3-t-butyl-5-methoxyphenyl.
- 20. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XVIII).
- 21. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XIX).
- 22. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XX) both of R.sup.44 are phenyl.
- 23. The process as recited in claim 22 wherein:
- both of R.sup.16 and R.sup.17 are hydrogen; or
- both of R.sup.16 and R.sup.17 are acetyl.
- 24. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXI).
- 25. The process as recited in claim 24 wherein Ar.sup.3 is 2-aminophenyl.
- 26. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXII).
- 27. The process as recited in claim 26 wherein R.sup.18 and R.sup.19 are both methyl or both hydrogen.
- 28. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXIII).
- 29. The process as recited in claim 28 wherein Ar.sup.4 is phenyl.
- 30. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXIV).
- 31. The process as recited in claim 30 wherein both of Ar.sup.5 and Ar.sup.6 are phenyl or wherein both of Ar.sup.5 and Ar.sup.6 are cyclohexyl.
- 32. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXV).
- 33. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXVI).
- 34. The process as recited in claim 33 wherein Ar.sup.7 is p-tolyl or phenyl and Ar.sup.8 is 2,6-diisopropylphenyl.
- 35. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXVII).
- 36. The process as recited in claim 35 wherein:
- Ar.sup.9 and Ar.sup.10 taken together are 1,8-naphthylylene; or
- Ar.sup.9 is --CO.sub.2 CH.sub.3 and Ar.sup.10 is ##STR156##
- 37. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXVIII).
- 38. The process as recited in claim 37 wherein:
- all of R.sup.22, R.sup.23 and R.sup.24 are 2,4,6-trimethoxyphenyl;
- both of R.sup.22 and R.sup.23 are 2,3,6-trimethoxyphenyl and R.sup.24 is ethyl;
- all of R.sup.22, R.sup.23 and R.sup.24 are 2,6-dimethoxyphenyl; or
- both of R.sup.22 and R.sup.23 are 2,3,6-trimethoxyphenyl and R.sup.24 is isopropyl.
- 39. The process as recited in claim 38 wherein at least one of R.sup.22, R.sup.23 and R.sup.24 is substituted and that a sum of .sigma. and .sigma.* constants for at least one of R.sup.22, R.sup.23 and R.sup.24 is about -0.50 or less.
- 40. The process as recited in claim 39 wherein R.sup.24 is an aryl moiety, all of R.sup.22, R.sup.23 and R.sup.24 are substituted, and said sum of said .sigma. and .sigma.* constants for each of R.sup.22, R.sup.23 and R.sup.24 is about -0.50 or less.
- 41. The process as recited in claim 2 or 3 carried out in a solvent.
- 42. The process as recited in claim 1, 2 or 3 carried out at a temperature of about -20.degree. C. to about 100.degree. C.
- 43. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXXVI).
- 44. The process as recited in claim 1, 2 or 3 wherein (XXXVI) is ##STR157##
- 45. The process as recited in claim 1, 2 or 3 wherein said first compound or said first monodentate neutral ligand is (XXXVII).
- 46. The process as recited in claim 45 wherein both of R.sup.8 are aryl moieties and all of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are hydrogen.
- 47. The process as recited in claim 46 wherein both of R.sup.8 are 2,6-dimethylphenyl.
- 48. The process as recited in claim 1, 2 or 3 wherein X is BAF.
- 49. The process as recited in claim 3 wherein r is 1.
- 50. The process as recited in claim 3 wherein r is 0.
- 51. The process as recited in claim 50 wherein (XXXIII) is a dimer with bridging L.sup.1 ligands.
- 52. The process as recited in claim 11 wherein:
- n is 2
- Q is --CR.sup.9 =NR.sup.3 ;
- Ar.sup.1 is diphenylmethyl; R.sup.9 is hydrogen
- and R.sup.3 is selected from the group consisting of 2,6-diisopropylphenyl, 2-carbamoylphenyl, 2-methoxycarbonylphenyl, 1-anthraquinolyl, 2,6-dimethylphenyl and 1-fluoren-9-onyl.
- 53. The process as recited in claim 2 wherein said nickel �II! complex is a .pi.-allyl complex.
- 54. The process as recited in claim 3 wherein L.sup.3 and L.sup.4 taken together are a .pi.-allyl group.
- 55. The process as recited in claim 53 or 54 wherein a Lewis acid is also present.
- 56. The process as recited in claim 1, 2 or 3 wherein at least 2 or more norbornenes are present, to form a copolymer.
- 57. The process as recited in claim 1, 2 or 3 wherein at least 2 or more styrenes are present to form a copolymer.
- 58. The process as recited in claim 1, 2 or 3 wherein at least one styrene and at least norbornene are present to form a copolymer.
- 59. The process as recited in claim 56 wherein a nobornene present is 5-ethylidene-2-norbonene.
Parent Case Info
This application is a continuation-in-part of U.S. application Ser. No. 60/000,747, filed Jun. 30, 1995.
US Referenced Citations (12)
Foreign Referenced Citations (1)
Number |
Date |
Country |
0 454 231 A2 |
Apr 1991 |
EPX |