Method of polymerization and polymer produced therefrom

{
  "publication_number": "US6417304B1",
  "country": "US",
  "kind": "B1",
  "title": "Method of polymerization and polymer produced therefrom",
  "abstract": "This invention relates to a polymerization process comprising combining an olefin in the gas or slurry phase with a liquid carrier comprising an activator and a compound represented by the following formula: wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, each X is independently a leaving group, y is 0 or 1 (when y is 0 group L′ is absent), n is the oxidation state of M, m is 0, −1, −2 or −3, L is a Group 15 or 16 element, L′ is a Group 15 or 16 element or Group 14 containing group, Y is a Group 15 element, Z is a Group 15 element, R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, R 3 is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatom containing group, R 4 and R 5 are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or multiple ring system, preferably having up to 20 carbon atoms, R 1 and R 2 may be interconnected to each other, and/or R 4 and R 5 may be interconnected to each other, R 6 and R 7 are independently absent, or hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably absent, and R* is absent, or is hydrogen, a Group 14 atom containing group, a halogen, a heteroatom containing group. This invention further relates to the polymer produced from the above process.",
  "claims": [
    "1. A polymerization process comprising introducing a liquid carrier into a gas or slurry phase reactor wherein the carrier comprises an activator and a compound represented by the following formula: wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, each X is independently a leaving group, y is 0 or 1, n is the oxidation state of M, m is 0, −1, −2 or −3, L is a Group 15 or 16 element, Y is a Group 15 element, Z is a Group 15 element, R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, R 3 is a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group, R 4 and R 5 are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multiple ring system, R 1 and R 2 may be interconnected to each other, and/or R 4 and R 5 may be interconnected to each other, and R 6 and R 7 are independently absent, hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group.",
    "2. The process of claim 1 wherein M is a group 4, 5 or 6 transition metal.",
    "3. The process of claim 1 wherein M is zirconium or hafnium.",
    "4. The process of claim 1 wherein each X is independently hydrogen, halogen or hydrocarbyl group.",
    "5. The process of claim 1 wherein R 1 and R 2 are independently a C 1 to C 6 hydrocarbon group.",
    "6. The process of claim 1 wherein R 1 and R 2 are a C 1 to C 20 alkyl, aryl or aralkyl group.",
    "7. The process of claim 1 wherein m is 0, −1, −2, or −3 and n is +3, +4 or +5.",
    "8. The process of claim 1 wherein R 3 is hydrogen or methyl.",
    "9. The process of claim 1 wherein R 4 and R 5 are independently a C 1 to C 20 hydrocarbon group.",
    "10. The process of claim 1 wherein R 4 and R 5 are independently a C 1 to C 20 aryl group or a C 1 to C 20 aralkyl group.",
    "11. The process of claim 1 wherein R 4 and R 5 are independently a cyclic aralkyl group.",
    "12. The process of claim 1 wherein R 4 and R 5 are independently a group represented by the following formula: wherein each R 8 to R 12 are independently hydrogen, or a C 1 to C 20 alkyl group, a heteroatom, or a heteroatom containing group having up to 40 carbon atoms, and any two R groups can combine to form a cyclic group or a heterocyclic group.",
    "13. The process of claim 12 wherein R 8 is methyl, ethyl, propyl or butyl and/or R 9 is methyl, ethyl, propyl or butyl, and/or R 10 is methyl, ethyl, propyl or butyl, and/or R 11 is methyl, ethyl, propyl or butyl and/or R 12 is methyl, ethyl, propyl or butyl.",
    "14. The process of claim 13 wherein R 9, R 10 and R 12 are methyl and R 8 and R 11 are hydrogen.",
    "15. The process of claim 1 wherein the activator comprises alkyl aluminum compounds, alumoxanes, modified alumoxanes, non-coordinating anions, boranes, borates and/or ionizing compounds.",
    "16. The process of claim 1 wherein the olefin comprises ethylene.",
    "17. The process of claim 1 wherein the olefin comprises ethylene and a C 3 to C 20 alpha olefin.",
    "18. The process of claim 1, wherein the olefin comprises ethylene and hexene and/or butene.",
    "19. The process of claim 1, wherein the polymer produced has a molecular weight 200,000 Daltons or more.",
    "20. The process of claim 1 wherein the transition metal compound and/or the activator are combined before being placed in the liquid carrier.",
    "21. The process of claim 1 wherein the carrier is an alkane.",
    "22. The process of claim 21 wherein the carrier is pentane, hexane, and/or isopentane.",
    "23. The process of claim 1 wherein metal stearate is also introduced into the reactor.",
    "24. The process of claim 1 wherein a metal stearate is combined with the transition metal compound and/or the activator and/or the liquid carrier prior to entering the reactor.",
    "25. A process to produce a film comprising extruding, blowing or casting a film from polymer produced by a polymerization process comprising combining an olefin in the gas or slurry phase with a liquid carrier comprising an activator and a compound represented by the following formula: wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, each X is independently a leaving group, y is 0 or 1, n is the oxidation state of M, m is 0, −1, −2 or −3, L is a Group 15 or 16 element, Y is a Group 15 element, Z is a Group 15 element, R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, R 3 is a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group, R 4 and R 5 are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multiple ring system, R 1 and R 2 may be interconnected to each other, and/or R 4 and R 5 may be interconnected to each other, and R 6 and R 7 are independently absent, hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group.",
    "26. The method of claim 25 wherein the film is a blown film.",
    "27. A polymerization process comprising introducing a liquid carrier into a gas or slurry phase reactor wherein the carrier comprises an activator and a compound represented by the following formula: wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, each X is independently a leaving group, y is 0 or 1, n is the oxidation state of M, m is 0, −1, −2 or −3, L′ is a Group 15 or 16 element, Y is a Group 15 element, Z is a Group 15 element, R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, R 3 is absent, a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group, R 4 and R 5 are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multiple ring system, R 1 and R 2 may be interconnected to each other, and/or R 4 and R 5 may be interconnected to each other, R 6 and R 7 are independently absent, hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, and R* is absent, hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group.",
    "28. A process to produce a film comprising extruding, blowing or casting a film from polymer produced by a polymerization process comprising combining an olefin in the gas or slurry phase with a liquid carrier comprising an activator and a compound represented by the following formula: wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 main group metal, each X is independently a leaving group, y is 0 or 1, n is the oxidation state of M, m is 0, −1, −2 or −3, L′ is a Group 15 or 16 element, Y is a Group 15 element, Z is a Group 15 element, R 1 and R 2 are independently a C 1 to C 20 hydrocarbon group, a heteroatom containing group having up to twenty carbon atoms, silicon, germanium, tin, lead, or phosphorus, R 3 is absent, a hydrocarbon group, hydrogen, a halogen, or a heteroatom containing group, R 4 and R 5 are independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multiple ring system, R 1 and R 2 may be interconnected to each other, and/or R 4 and R 5 may be interconnected to each other, R 6 and R 7 are independently absent, hydrogen, an alkyl group, halogen, heteroatom or a hydrocarbyl group, and R* is absent, hydrogen, a Group 14 atom containing group, a halogen, or a heteroatom containing group."
  ],
  "description_excerpt": "This invention relates to olefin polymerization catalysts containing a metal atom bound to at least two group 15 atoms fed in solution or slurry into a gas phase or slurry phase reactor to produce polyolefins and the polyolefins produced therefrom.\n\nMetallocene polymerization catalysts (i.e. transition metals, typically groups 4, 5 or 6, having at least one pi bonded ligand, preferably a cyclopentadienyl, indenyl or fluorenyl group) have recently been used to produce resins having a desirable product properties.\n\nFurthermore, there is always a need in the art for a method to introduce catalysts into a gas or slurry phase reactor in such a way as to reduce fouling and/or increase activity. Catalysts used in the gas phase are typically supported because in the past liquid catalysts severely fouled the reactor. Some supported catalysts however have the disadvantages of reduced activity. Thus there is a need in the art of gas or slurry phase processes to find efficient, cost effective reduced fouling means to feed catalysts into a gas or slurry phase reactor. For more information on the disadvantages of using liquid catalysts in a gas phase reactor see the background sections of U.S. Pat. Nos. 5,317,036 and 5,693,727 which relates to introducing unsupported catalysts into a gas phase reactor.\n\nSchrock et al in U.S. Pat. No. 5,889,128 discloses a process for the living polymerization of olefins in solution using initiators having a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms.",
  "cpc": [
    "C08F 10/02",
    "C08F 10/00",
    "C08F 210/16",
    "C08F 2410/03",
    "C08F 4/65912",
    "C08F 4/65916",
    "C08F 4/6592",
    "C08L 2205/02",
    "C08L 23/0815",
    "C08L 23/16",
    "C08L 2314/06",
    "Y10S 526/901"
  ],
  "ipc": [
    "C08F 10/02",
    "C08F 210/16",
    "C08F 4/44",
    "C08F 4/64",
    "C08L 23/08",
    "C08L 23/16"
  ],
  "assignees": [
    "Univation Technologies LLC"
  ],
  "inventors": [
    "David H. McConville",
    "John F. Szul",
    "Donald R. Loveday"
  ],
  "filing_date": "1999-11-18",
  "publication_date": "2002-07-09",
  "grant_date": "2002-07-09",
  "priority_date": "1999-11-18",
  "application_number": "US-44281399-A",
  "family_id": "23758255",
  "cited_by_count": 46,
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}