CA2285523A1 - Group 8, 9 or 10 olefin copolymerization catalyst - Google Patents
Group 8, 9 or 10 olefin copolymerization catalyst Download PDFInfo
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- CA2285523A1 CA2285523A1 CA002285523A CA2285523A CA2285523A1 CA 2285523 A1 CA2285523 A1 CA 2285523A1 CA 002285523 A CA002285523 A CA 002285523A CA 2285523 A CA2285523 A CA 2285523A CA 2285523 A1 CA2285523 A1 CA 2285523A1
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- 239000003054 catalyst Substances 0.000 title claims 4
- 150000001336 alkenes Chemical class 0.000 title claims 3
- 238000007334 copolymerization reaction Methods 0.000 title 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract 11
- 239000002184 metal Substances 0.000 claims abstract 11
- 238000000034 method Methods 0.000 claims 65
- -1 hydrocarbyl radical Chemical class 0.000 claims 57
- 239000012190 activator Substances 0.000 claims 29
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 12
- 229910052782 aluminium Inorganic materials 0.000 claims 12
- 229910052796 boron Inorganic materials 0.000 claims 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 12
- 239000003446 ligand Substances 0.000 claims 12
- 125000000524 functional group Chemical group 0.000 claims 10
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims 8
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims 7
- 229920000098 polyolefin Polymers 0.000 claims 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 6
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 6
- 125000005843 halogen group Chemical group 0.000 claims 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- 229910052731 fluorine Inorganic materials 0.000 claims 4
- 125000001153 fluoro group Chemical group F* 0.000 claims 4
- 125000004665 trialkylsilyl group Chemical group 0.000 claims 4
- 229910052742 iron Inorganic materials 0.000 claims 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 3
- 239000000178 monomer Substances 0.000 claims 3
- 125000001424 substituent group Chemical group 0.000 claims 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 239000002168 alkylating agent Substances 0.000 claims 2
- 229940100198 alkylating agent Drugs 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 2
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 claims 2
- 239000004711 α-olefin Substances 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 239000007818 Grignard reagent Substances 0.000 claims 1
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000004795 grignard reagents Chemical class 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000002516 radical scavenger Substances 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract 1
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 125000004076 pyridyl group Chemical group 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Olefin co- or homopolymers having a good molecular weight and short chain branching may be prepared in the presence of a pyridyl bridged bisphosphinimine complex of a Group 8, 9 or 10 metal.
Claims (13)
1. A ligand of formula I:
wherein R2, R3, R4 and R5 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted, further substituted or an inert functional group; R6 and R7 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted, trialkyl silyl radical and an inert functional group; and R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom, a hydrocarbyl radical which is unsubstituted or further substituted and an inert functional group.
wherein R2, R3, R4 and R5 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted, further substituted or an inert functional group; R6 and R7 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted, trialkyl silyl radical and an inert functional group; and R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom, a hydrocarbyl radical which is unsubstituted or further substituted and an inert functional group.
2. The ligand according to claim 1, wherein R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical.
3. The ligand according to claim 2, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a C1-10 alkyl or aryl radical.
4. The ligand according to claim 3, wherein R6 and R7 are independently selected from the group consisting of tri C1-6 alkyl silyl radicals and phenyl radicals which are unsubstituted or substituted by up to five substituents independently selected from the group consisting of a C1-10 hydrocarbyl radical or two hydrocarbyl radicals taken together may form a ring.
5. The ligand according to claim 4, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
6. The ligand according to claim 5, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
7. The ligand according to claim 6, wherein R8, R9 and R10 are a hydrogen atom.
8. The ligand according to claim 6, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
9. The ligand according to claim 8, wherein R8, R9 and R10 are the same.
10. A process for the polymerization of one or more C2-12 alpha olefins in the presence of:
(a) a complex comprising a Group 8, 9 or 10 metal and ligand of formula I:
wherein R2, R3, R4 and R5 are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl or an inert functional group; R6 and R7 are each independently selected from hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or unsubstituted aryl;
and R8, R9 and R10 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group; and (b) an activator at a temperature from 20 to 250°C and at a pressure from 15 to 15000 psi.
(a) a complex comprising a Group 8, 9 or 10 metal and ligand of formula I:
wherein R2, R3, R4 and R5 are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl or an inert functional group; R6 and R7 are each independently selected from hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or unsubstituted aryl;
and R8, R9 and R10 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group; and (b) an activator at a temperature from 20 to 250°C and at a pressure from 15 to 15000 psi.
11. The process according to claim 10, wherein the activator is selected from the group consisting of:
(i) aluminoxane compounds R20 2AlO(R20AlO)m AlR20 2 wherein each R20 is independently selected form the group consisting of C1-20 hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of aluminum to Group 8, 9 or 10 metal from 20:1 to 1000:1;
(ii) anions of the formula [B(R18)4]- wherein each R18 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted by up to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom and a silyl radical of the formula -Si(R19)3; wherein each R'9 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and an activator of the formula [B(R19)3] wherein R18 is as defined above and to provide a molar ratio of Group 8, 9 or 10 metal to boron from 1:1 to 1:3;
and (iii) a mixture of activators (i) and (ii) and an aluminum compound selected from the group consisting of aluminum alkyls of the formula AIR3-n X n in which R is independently selected from the group consisting of a C1-8 alkyl radical, X is a halogen atom and n is 0, 1, 2 or 3 to provide a ratio of Group 8, 9 or 10 metal to aluminum to boron from 1:1:1 to 1:100:5.
(i) aluminoxane compounds R20 2AlO(R20AlO)m AlR20 2 wherein each R20 is independently selected form the group consisting of C1-20 hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of aluminum to Group 8, 9 or 10 metal from 20:1 to 1000:1;
(ii) anions of the formula [B(R18)4]- wherein each R18 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted by up to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom and a silyl radical of the formula -Si(R19)3; wherein each R'9 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and an activator of the formula [B(R19)3] wherein R18 is as defined above and to provide a molar ratio of Group 8, 9 or 10 metal to boron from 1:1 to 1:3;
and (iii) a mixture of activators (i) and (ii) and an aluminum compound selected from the group consisting of aluminum alkyls of the formula AIR3-n X n in which R is independently selected from the group consisting of a C1-8 alkyl radical, X is a halogen atom and n is 0, 1, 2 or 3 to provide a ratio of Group 8, 9 or 10 metal to aluminum to boron from 1:1:1 to 1:100:5.
12. The process according to claim 11, wherein said one or more olefins are selected from the group consisting of ethylene, propylene, butene, hexene and octene.
13. The process according to claim 12, wherein R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical.
20. The process according to claim 19, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
21. The process according to claim 20, wherein R8, R9 and R10 are a hydrogen atom.
22. The process according to claim 21, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
23. The process according to claim 22, wherein R8, R9 and R10 are the same.
24. The process according to claim 16, wherein the temperature is from 20 to 120°C, the pressure is from 15 to 4,500 psig, the activator is an aluminoxane in which each R20 is selected from the group consisting of C1-4 alkyl radicals and m is from 5 to 30.
25. The process according to claim 24, wherein R20 is a methyl radical.
26. The process according to claim 25, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
27. The process according to claim 26, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
28. The process according to claim 27, wherein R8, R9 and R10 are a hydrogen atom.
29. The process according to claim 27, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
30. The process according to claim 29, wherein R8, R9 and R10 are the same.
31. The process according to claim 16, wherein the temperature is from 120 to 250°C, the pressure is from 100 to 4,500 psig and the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
32. The process according to claim 31, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
33. The process according to claim 32, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
34. The process according to claim 33, wherein R8, R9 and R10 are a hydrogen atom.
35. The process according to claim 33, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
36. The process according to claim 35, wherein R8, R9 and R10 are the same.
37. The process according to claim 16, wherein the temperature is from 20 to 120°C, the pressure is from 15 to 4,500 psig and the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
38. The process according to claim 37, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
39. The process according to claim 38, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
40. The process according to claim 39, wherein R8, R9 and R10 are a hydrogen atom.
41. The process according to claim 39, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
42. The process according to claim 41, wherein R8, R9 and R10 are the same.
43. The process according to claim 16, wherein the temperature is from 120 to 250°C, the pressure is from 15 to 4,500 psig and the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl compound.
44. The process according to claim 43, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
45. The process according to claim 44, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
46. The process according to claim 45, wherein R8, R9 and R10 are a hydrogen atom.
47. The process according to claim 45, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
48. The process according to claim 47, wherein R8, R9 and R10 are the same.
49. The process according to claim 16, wherein the temperature is from 20 to 120°C, the pressure is from 15 to 4,500 psig and the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl compound.
50. The process according to claim 49, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
51. The process according to claim 50, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
52. The process according to claim 51, wherein R8, R9 and R10 are a hydrogen atom.
53. The process according to claim 51, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
54. The process according to claim 53, wherein R8, R9 and R10 are the same.
55. A process comprising reacting a compound of formula II:
wherein R2, R3, R4 and R5 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted and an inert functional group; R6 and R7 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted, a trialkyl silyl radical and an inert functional group; and R8, R9 and R10 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted, further substituted, or an inert functional group; M is a Group 8, 9 or 10 metal; X is a halogen atom or a C1-10 alkoxy radical; and n is an integer from 1 to 3;
with an alkylating agent at a temperature from -50 to 200°C.
56. The process according to claim 55, wherein the alkylating agent is selected from the group consisting of a Grignard reagent of the formula RMgX wherein R is a C1-10 alkyl radical and X is a halide; LiR wherein R is a C1-10 alkyl agent; and alkyl aluminum reagents.
57. A process for reacting one or more C2-12 alpha olefins in the presence of a catalyst of formula III:
wherein R2, R3, R4 and R5 are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl or an inert functional group; R6 and R7 are each independently selected from hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or unsubstituted aryl;
R8, R9 and R10 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group and an activator; M is a Group 8, 9, or 10 metal; L1 is a neutral monodenate ligand which is displaced by one or more of an activator, a scavenger, or a monomer; L2 is an activatable ligand; x is from 0 to 12; and y is equal to the oxidation state of the metal; with an activator at a temperature from 20 to 250°C and at a pressure from 15 to 15000 psi.
58. The process according to claim 57, wherein the activator is selected from the group consisting of:
(i) aluminoxane compounds R20 2AlO(R20AlO)m AlR20 2 wherein each R20 is independently selected form the group consisting of C1-20 hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of aluminum to Group 8, 9 or 10 metal from 20:1 to 1000:1;
(ii) anions of the formula [B(R18)4]- wherein each R18 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted by up to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom and a silyl radical of the formula -Si(R19)3 wherein each R19 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and an activator of the formula [B(R18)3] wherein R18 is as defined above and to provide a molar ratio of Group 8, 9 or 10 metal to boron from 1:1 to 1:3;
and (iii) a mixture of activators (i) and (ii) and an aluminum compound selected from the group consisting of aluminum alkyls of the formula AlR3-n-X n in which R is independently selected from the group consisting of a C1-8 alkyl radical and a C1-8 alkoxy radical, X is a halogen atom and n is 0, 1, 2 or 3 to provide a ratio of Group 8, 9 or 10 metal to aluminum to boron from 1:1:1 to 1:100:5.
59. The process according to claim 58, wherein L1 is selected from the group consisting of a water and tetrahydrofuran.
60. The process according to claim 59, wherein L2 is selected from the group consisting of C1-4 alkyl radical, C1-4 alkoxy radical and a halogen atom.
61. The process according to claim 60, wherein y is 2 or 3.
62. The process according to claim 61, wherein said one or more olefins are selected from the group consisting of ethylene, propylene, butene, hexene and octene.
63. The process according to claim 62, wherein the temperature is from 120 to 250°C and the pressure is from 100 to 4,500 psig.
64. The process according to claim 63, wherein R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical.
65. The process according to claim 64, wherein in R2, R3, R4 and R5 are phenyl radicals.
66. The process according to claim 65, wherein in the precursor R6 and R7 are selected from the group consisting of 2,6-di-isopropyl phenyl radicals and trimethyl silyl radicals.
67. The process according to claim 66, wherein M is selected from the group consisting of Fe, Co, Ni and Pd.
68. The process according to claim 67, wherein the activator is an aluminoxane in which each R20 is selected from the group consisting of C1-4 alkyl radicals and m is from 5 to 30.
69. The process according to claim 68, wherein R20 is a methyl radical.
70. The process according to claim 69, wherein the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
71. The process according to claim 67, wherein the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl.
72. The process according to claim 67, wherein the temperature is from 20 to 120°C and the pressure is from 15 to 4,500 psig.
73. The process according to claim 72, wherein R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical.
74. The process according to claim 73, wherein R2, R3, R4 and R5 are phenyl radicals.
75. The process according to claim 74, wherein R6 and R7 are selected from the group consisting of 2,6-di-isopropyl phenyl radicals and trimethyl silyl radicals.
76. The process according to claim 75, wherein the activator is an aluminoxane in which each R20 is selected from the group consisting of C1-4 alkyl radicals and m is from 5 to 30.
77. The process according to claim 76, wherein R20 is a methyl radical.
78. The process according to claim 75, wherein the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
79. The process according to claim 75, wherein the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl.
80. A polyolefin having a weight average molecular weight (Mw) from 5 x 10 4 to 10 7 and a degree of short chain branching from 1-30 per 1000 carbon atoms when prepared by a process according to claim 10.
81. The polyolefin according to claim 80, having a weight average molecular weight (Mw) from 10 5 to 10 7.
82. The polyolefin according to claim 81, having a degree of short chain branching from 1-20 per 1000 carbon atoms.
83. The polyolefin according to claim 82, comprises at least 80 weight of ethylene and up to 20 weight % of one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
84. A polyolefin having a weight average molecular weight (Mw) from 5 x 10 4 to 10 7 and a degree of short chain branching from 1-30 per 1000 carbon atoms when prepared using an iron based catalyst.
85. A polyolefin having a molecular weight from 5 x 10 4 to 10 7 and a degree of short chain branching from 1-20 per 1000 carbon atoms prepared in the presence of an iron or cobalt containing catalyst.
86. The polyolefin according to claim 85 comprising at least 80 weight of ethylene and up to 20 weight % of one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
20. The process according to claim 19, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
21. The process according to claim 20, wherein R8, R9 and R10 are a hydrogen atom.
22. The process according to claim 21, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
23. The process according to claim 22, wherein R8, R9 and R10 are the same.
24. The process according to claim 16, wherein the temperature is from 20 to 120°C, the pressure is from 15 to 4,500 psig, the activator is an aluminoxane in which each R20 is selected from the group consisting of C1-4 alkyl radicals and m is from 5 to 30.
25. The process according to claim 24, wherein R20 is a methyl radical.
26. The process according to claim 25, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
27. The process according to claim 26, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
28. The process according to claim 27, wherein R8, R9 and R10 are a hydrogen atom.
29. The process according to claim 27, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
30. The process according to claim 29, wherein R8, R9 and R10 are the same.
31. The process according to claim 16, wherein the temperature is from 120 to 250°C, the pressure is from 100 to 4,500 psig and the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
32. The process according to claim 31, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
33. The process according to claim 32, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
34. The process according to claim 33, wherein R8, R9 and R10 are a hydrogen atom.
35. The process according to claim 33, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
36. The process according to claim 35, wherein R8, R9 and R10 are the same.
37. The process according to claim 16, wherein the temperature is from 20 to 120°C, the pressure is from 15 to 4,500 psig and the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
38. The process according to claim 37, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
39. The process according to claim 38, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
40. The process according to claim 39, wherein R8, R9 and R10 are a hydrogen atom.
41. The process according to claim 39, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
42. The process according to claim 41, wherein R8, R9 and R10 are the same.
43. The process according to claim 16, wherein the temperature is from 120 to 250°C, the pressure is from 15 to 4,500 psig and the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl compound.
44. The process according to claim 43, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
45. The process according to claim 44, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
46. The process according to claim 45, wherein R8, R9 and R10 are a hydrogen atom.
47. The process according to claim 45, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
48. The process according to claim 47, wherein R8, R9 and R10 are the same.
49. The process according to claim 16, wherein the temperature is from 20 to 120°C, the pressure is from 15 to 4,500 psig and the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl compound.
50. The process according to claim 49, wherein R2, R3, R4 and R5 are independently selected from the group consisting of a t-butyl radical or a phenyl radical.
51. The process according to claim 50, wherein R6 and R7 are independently selected from the group consisting of a trimethyl silyl radical and a 2,6-di-isopropyl phenyl radical.
52. The process according to claim 51, wherein R8, R9 and R10 are a hydrogen atom.
53. The process according to claim 51, wherein R8, R9 and R10 are independently selected from the group consisting of C1-4 alkyl radicals.
54. The process according to claim 53, wherein R8, R9 and R10 are the same.
55. A process comprising reacting a compound of formula II:
wherein R2, R3, R4 and R5 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted and an inert functional group; R6 and R7 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted or further substituted, a trialkyl silyl radical and an inert functional group; and R8, R9 and R10 are independently selected from the group consisting of a hydrocarbyl radical which is unsubstituted, further substituted, or an inert functional group; M is a Group 8, 9 or 10 metal; X is a halogen atom or a C1-10 alkoxy radical; and n is an integer from 1 to 3;
with an alkylating agent at a temperature from -50 to 200°C.
56. The process according to claim 55, wherein the alkylating agent is selected from the group consisting of a Grignard reagent of the formula RMgX wherein R is a C1-10 alkyl radical and X is a halide; LiR wherein R is a C1-10 alkyl agent; and alkyl aluminum reagents.
57. A process for reacting one or more C2-12 alpha olefins in the presence of a catalyst of formula III:
wherein R2, R3, R4 and R5 are each independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl or an inert functional group; R6 and R7 are each independently selected from hydrocarbyl, substituted hydrocarbyl, trialkyl silyl and substituted or unsubstituted aryl;
R8, R9 and R10 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, an inert functional group and an activator; M is a Group 8, 9, or 10 metal; L1 is a neutral monodenate ligand which is displaced by one or more of an activator, a scavenger, or a monomer; L2 is an activatable ligand; x is from 0 to 12; and y is equal to the oxidation state of the metal; with an activator at a temperature from 20 to 250°C and at a pressure from 15 to 15000 psi.
58. The process according to claim 57, wherein the activator is selected from the group consisting of:
(i) aluminoxane compounds R20 2AlO(R20AlO)m AlR20 2 wherein each R20 is independently selected form the group consisting of C1-20 hydrocarbyl radical and m is from 5 to 30 to provide a molar ratio of aluminum to Group 8, 9 or 10 metal from 20:1 to 1000:1;
(ii) anions of the formula [B(R18)4]- wherein each R18 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted by up to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom and a silyl radical of the formula -Si(R19)3 wherein each R19 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and an activator of the formula [B(R18)3] wherein R18 is as defined above and to provide a molar ratio of Group 8, 9 or 10 metal to boron from 1:1 to 1:3;
and (iii) a mixture of activators (i) and (ii) and an aluminum compound selected from the group consisting of aluminum alkyls of the formula AlR3-n-X n in which R is independently selected from the group consisting of a C1-8 alkyl radical and a C1-8 alkoxy radical, X is a halogen atom and n is 0, 1, 2 or 3 to provide a ratio of Group 8, 9 or 10 metal to aluminum to boron from 1:1:1 to 1:100:5.
59. The process according to claim 58, wherein L1 is selected from the group consisting of a water and tetrahydrofuran.
60. The process according to claim 59, wherein L2 is selected from the group consisting of C1-4 alkyl radical, C1-4 alkoxy radical and a halogen atom.
61. The process according to claim 60, wherein y is 2 or 3.
62. The process according to claim 61, wherein said one or more olefins are selected from the group consisting of ethylene, propylene, butene, hexene and octene.
63. The process according to claim 62, wherein the temperature is from 120 to 250°C and the pressure is from 100 to 4,500 psig.
64. The process according to claim 63, wherein R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical.
65. The process according to claim 64, wherein in R2, R3, R4 and R5 are phenyl radicals.
66. The process according to claim 65, wherein in the precursor R6 and R7 are selected from the group consisting of 2,6-di-isopropyl phenyl radicals and trimethyl silyl radicals.
67. The process according to claim 66, wherein M is selected from the group consisting of Fe, Co, Ni and Pd.
68. The process according to claim 67, wherein the activator is an aluminoxane in which each R20 is selected from the group consisting of C1-4 alkyl radicals and m is from 5 to 30.
69. The process according to claim 68, wherein R20 is a methyl radical.
70. The process according to claim 69, wherein the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
71. The process according to claim 67, wherein the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl.
72. The process according to claim 67, wherein the temperature is from 20 to 120°C and the pressure is from 15 to 4,500 psig.
73. The process according to claim 72, wherein R8, R9 and R10 are independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical.
74. The process according to claim 73, wherein R2, R3, R4 and R5 are phenyl radicals.
75. The process according to claim 74, wherein R6 and R7 are selected from the group consisting of 2,6-di-isopropyl phenyl radicals and trimethyl silyl radicals.
76. The process according to claim 75, wherein the activator is an aluminoxane in which each R20 is selected from the group consisting of C1-4 alkyl radicals and m is from 5 to 30.
77. The process according to claim 76, wherein R20 is a methyl radical.
78. The process according to claim 75, wherein the activator is an ionic activator selected from the group consisting of N,N-dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron.
79. The process according to claim 75, wherein the activator is a combination of an ionic activator selected from the group consisting of N,N- dimethylaniliniumtetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate and trispentafluorophenyl boron and an aluminum alkyl.
80. A polyolefin having a weight average molecular weight (Mw) from 5 x 10 4 to 10 7 and a degree of short chain branching from 1-30 per 1000 carbon atoms when prepared by a process according to claim 10.
81. The polyolefin according to claim 80, having a weight average molecular weight (Mw) from 10 5 to 10 7.
82. The polyolefin according to claim 81, having a degree of short chain branching from 1-20 per 1000 carbon atoms.
83. The polyolefin according to claim 82, comprises at least 80 weight of ethylene and up to 20 weight % of one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
84. A polyolefin having a weight average molecular weight (Mw) from 5 x 10 4 to 10 7 and a degree of short chain branching from 1-30 per 1000 carbon atoms when prepared using an iron based catalyst.
85. A polyolefin having a molecular weight from 5 x 10 4 to 10 7 and a degree of short chain branching from 1-20 per 1000 carbon atoms prepared in the presence of an iron or cobalt containing catalyst.
86. The polyolefin according to claim 85 comprising at least 80 weight of ethylene and up to 20 weight % of one or more monomers selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002285523A CA2285523C (en) | 1999-10-01 | 1999-10-01 | Group 8, 9 or 10 olefin copolymerization catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002285523A CA2285523C (en) | 1999-10-01 | 1999-10-01 | Group 8, 9 or 10 olefin copolymerization catalyst |
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| CA2285523C CA2285523C (en) | 2010-03-09 |
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