Claims
- 1. A liquid phase polymerization process for preparing a polyolefin product having preselected properties, said process comprising:
providing a liquid feedstock comprising at least one olefinic component; providing a catalyst composition comprising a stable complex of BF3 and a complexing agent therefor; introducing said feedstock and said catalyst composition into a residual reaction mixture in a loop reactor reaction zone; recirculating the residual reaction mixture in said zone at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the feedstock and the catalyst composition to thereby present a recirculating, intimately intermixed reaction admixture in said reaction zone; maintaining the recirculating intimately intermixed reaction admixture in its intimately intermixed condition and removing heat of reaction from the reaction admixture at a rate calculated to provide a substantially constant reaction temperature in the reaction admixture while the same is recirculating in said reaction zone, said constant reaction temperature being at a level appropriate for causing olefinic components introduced in said feedstock to undergo polymerization to form said polyolefin product in the presence of said catalyst composition; withdrawing a product stream comprising said polyolefin product from said reaction zone; and controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence time of the olefinic components undergoing polymerization in the reaction zone is appropriate for production of said polyolefin product.
- 2. A process as set forth in claim 1, wherein the reaction zone comprises a tube side of a shell-and-tube heat exchanger and said heat of reaction is removed simultaneously with its generation by circulation of a coolant in the shell side of the exchanger.
- 3. A process as set forth in claim 1, wherein said residence time is no greater than about 3 minutes.
- 4. A process as set forth in claim 1, wherein said residence time is no greater than about 2 minutes.
- 5. A process as set forth in claim 1, wherein said residence time is no greater than about 1 minute.
- 6. A process as set forth in claim 1, wherein said residence time is less than 1 minute.
- 7. A process as set forth in claim 1, where said complexing agent comprises an alcohol.
- 8. A process as set forth in claim 7, where said complexing agent comprises a primary alcohol.
- 9. A process as set forth in claim 8, where said complexing agent comprises a C1-C8 primary alcohol.
- 10. A process as set forth in claim 7, where said alcohol has no hydrogen atom on a β carbon.
- 11. A process as set forth in claim 10, where said alcohol comprises methanol.
- 12. A process as set forth in claim 10, where said alcohol comprises neopentanol.
- 13. A process as set forth in claim 1, where said complexing agent provides a complex with BF3 which is stable at temperatures needed to produce oligomeric olefinic products.
- 14. A process as set forth in claim 1, where said complexing agent comprises a glycol.
- 15. A process as set forth in claim 14, where said complexing agent comprises ethylene glycol.
- 16. A process as set forth in claim 1, wherein the molar ratio of BF3 to complexing agent in said complex ranges from approximately 0.5:1 to approximately 5:1.
- 17. A process as set forth in claim 1, wherein the molar ratio of BF3 to complexing agent in said complex ranges from approximately 0.5:1 to approximately 2:1.
- 18. A process as set forth in claim 1, wherein the molar ratio of BF3 to complexing agent in said complex ranges from approximately 0.5:1 to approximately 1:1.
- 19. A process as set forth in claim 1, wherein the molar ratio of BF3 to complexing agent in said complex is approximately 1:1.
- 20. A process as set forth in claim 1, wherein from about 0.1 to about 10 millimoles of BF3 are introduced into said reaction admixture with said catalyst composition for each mole of olefinic component introduced into said admixture in said feedstock.
- 21. A process as set forth in claim 1, wherein from about 0.5 to about 2 millimoles of BF3 are introduced into said reaction admixture with said catalyst composition for each mole of olefinic component introduced into said admixture in said feedstock.
- 22. A process as set forth in claim 1, wherein the reaction admixture is recirculated at a first volumetric flow rate, and said feedstock and said catalyst composition are introduced at a combined second volumetric flow rate.
- 23. A process as set forth in claim 22, wherein the ratio of said first volumetric flow rate to said second volumetric flow rate is such that the concentrations of ingredients in the reaction admixture remain essentially constant.
- 24. A process as set forth in claim 22, wherein the ratio of said first volumetric flow rate to said second volumetric flow rate is such that essentially isothermal conditions are established and maintained in said reaction admixture.
- 25. A process as set forth in claim 22, wherein said feedstock and said catalyst composition are premixed and introduced into the reaction zone together as a single stream at said second volumetric flow rate.
- 26. A process as set forth in claim 22, wherein said feedstock and said catalyst composition are introduced into the reaction zone separately as two streams, the flow rates of which together add up to said second volumetric flow rate.
- 27. A process as set forth in claim 22, wherein the reactor configuration, the properties of the reaction mixture, and the first volumetric flow rate are such that turbulent flow is maintained in said reaction zone.
- 28. A process as set forth in claim 27, wherein the reaction zone is a tube side of a shell-and-tube heat exchanger.
- 29. A process as set forth in claim 28, wherein a U of at least about 50 Btu/min ft2 ° F. is maintained in said reaction zone.
- 30. A process as set forth in claim 1, wherein said feed stock comprises at least about 30% by weight of said olefinic component.
- 31. A process as set forth in claim 1, wherein said feed stock comprises non-reactive hydrocarbon diluents.
- 32. A process as set forth in claim 31, wherein said feed stock comprises at least about 30% by weight of said olefinic component with the remainder being said diluents.
- 33. A process as set forth in claim 22, wherein said reaction zone is the tube side of a shell-and-tube heat exchanger.
- 34. A process as set forth in claim 1, wherein the molar ratio of BF3 to complexing agent in said complex is approximately 0.75:1.
- 35. A process as set forth in claim 1, wherein the polymerization process is a cationic process.
- 36. A process as set forth in claim 1, wherein the polymerization process is a covalent process.
- 37. A process as set forth in claim 1, wherein said polyolefin product has a molecular weight no more than about 5000.
- 38. A process as set forth in claim 37, wherein said polyolefin product has a molecular weight of at least about 350.
- 39. A process as set forth in claim 38, wherein the olefinic component comprises isobutylene and the polyolefin product comprises polyisobutylene.
- 40. A process as set forth in claim 39, wherein said polyisobutylene has a vinylidene content of at least about 50%.
- 41. A process as set forth in claim 10, wherein the olefinic component comprises a C3 to C15 linear alpha olefin.
- 42. A process as set forth in claim 14, wherein the olefinic component comprises a C3 to C15 linear alpha olefin.
- 43. A process as set forth in claim 10, wherein the olefinic component comprises a C4 to C15 reactive non-alpha olefin.
- 44. A process as set forth in claim 43 wherein the olefinic component is 2-butene.
- 45. A process as set forth in claim 14, wherein the olefinic component comprises a C4 to C15 reactive non-alpha olefin.
- 46. A process as set forth in claim 45 wherein the olefinic component is 2-butene.
- 47. A process as set forth in claim 37, wherein said polyolefin product has a molecular weight of at least about 250.
- 48. A process as set forth in claim 1, wherein said liquid feedstock comprises a raff-1 stream.
- 49. A process as set forth in claim 48, wherein the olefinic component comprises isobutylene and the polyolefin product comprises polyisobutylene.
- 50. A process as set forth in claim 39, wherein said liquid feedstock comprises a raff-1 stream.
- 51. A liquid phase polymerization process for preparing a polyolefin product having preselected properties, said process comprising:
providing a liquid feedstock comprising at least one olefinic component; providing a catalyst composition comprising a stable complex of BF3 and a complexing agent therefor; introducing said feedstock and said catalyst composition into a residual reaction mixture in a loop reactor reaction zone; recirculating the residual reaction mixture in said zone at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the feedstock and the catalyst composition to thereby present a recirculating, intimately intermixed reaction admixture in said reaction zone; maintaining the recirculating intimately intermixed reaction admixture in its intimately intermixed condition and removing heat of reaction from the reaction admixture at a rate calculated to provide a substantially constant reaction temperature in the reaction admixture while the same is recirculating in said reaction zone, said constant reaction temperature being at a level appropriate for causing olefinic components introduced in said feedstock to undergo polymerization to form said polyolefin product in the presence of said catalyst composition; withdrawing a product stream comprising said polyolefin product from said reaction zone; and controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence time of the olefinic components undergoing polymerization in the reaction zone is appropriate for production of said polyolefin product, wherein the reaction admixture is recirculated at a first volumetric flow rate, and said feedstock and said catalyst composition are introduced at a combined second volumetric flow rate, and wherein the ratio of said first volumetric flow rate to said second volumetric flow rate ranges from about 20:1 to about 50:1.
- 52. A process as set forth in claim 51, wherein the ratio of said first volumetric flow rate to said second volumetric flow rate ranges from about 25:1 to about 40:1.
- 53. A process as set forth in claim 52, wherein the ratio of said first volumetric flow rate to said second volumetric flow rate ranges from about 28:1 to about 35:1.
- 54. A liquid phase polymerization process for preparing a polyolefin product having preselected properties, said process comprising:
providing a liquid feedstock comprising at least one olefinic component; providing a catalyst composition comprising a stable complex of BF3 and a complexing agent therefor; introducing said feedstock and said catalyst composition into a residual reaction mixture in a loop reactor reaction zone; recirculating the residual reaction mixture in said zone at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the feedstock and the catalyst composition to thereby present a recirculating, intimately intermixed reaction admixture in said reaction zone; maintaining the recirculating intimately intermixed reaction admixture in its intimately intermixed condition and removing heat of reaction from the reaction admixture at a rate calculated to provide a substantially constant reaction temperature in the reaction admixture while the same is recirculating in said reaction zone, said constant reaction temperature being at a level appropriate for causing olefinic components introduced in said feedstock to undergo polymerization to form said polyolefin product in the presence of said catalyst composition; withdrawing a product stream comprising said polyolefin product from said reaction zone; and controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence time of the olefinic components undergoing polymerization in the reaction zone is appropriate for production of said polyolefin product, wherein the reaction admixture is recirculated at a first volumetric flow rate, wherein the reactor configuration, the properties of the reaction mixture, and the first volumetric flow rate are such that turbulent flow is maintained in said reaction zone, and wherein a Reynolds number of at least about 2000 is maintained in said reaction zone.
- 55. A process as set forth in claim 54, wherein the reactor is a tube side of a shell-and-tube heat exchanger, and a heat transfer coefficient of at least about 50 Btu/min f2 ° F. is maintained in said reaction zone.
- 56. A liquid phase polymerization process for preparing a polyolefin product having preselected properties, said process comprising:
providing a liquid feedstock comprising at least one olefinic component; providing a catalyst composition comprising a stable complex of BF3 and methanol; introducing said feedstock and said catalyst composition into a residual reaction mixture in a loop reactor reaction zone; recirculating the residual reaction mixture in said zone at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the feedstock and the catalyst composition to thereby present a recirculating, intimately intermixed reaction admixture in said reaction zone; maintaining the recirculating intimately intermixed reaction admixture in its intimately intermixed condition and removing heat of reaction from the reaction admixture at a rate calculated to provide a substantially constant reaction temperature in the reaction admixture while the same is recirculating in said reaction zone, said constant reaction temperature being at a level appropriate for causing olefinic components introduced in said feedstock to undergo polymerization to form said polyolefin product in the presence of said catalyst composition; withdrawing a product stream comprising said polyolefin product from said reaction zone; and controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence time of the olefinic components undergoing polymerization in the reaction zone is appropriate for production of said polyolefin product.
- 57. A single stage liquid phase polymerization process for preparing a polyolefin product having preselected properties, said process comprising:
providing a liquid feedstock comprising at least one olefinic component; providing a catalyst composition comprising a stable complex of BF3 and a complexing agent therefor; introducing said feedstock and said catalyst composition into a residual reaction mixture in a loop reactor reaction zone, said reaction zone being the only stage of the process where substantial polymerization occurs; recirculating the residual reaction mixture in said zone at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the feedstock and the catalyst composition to thereby present a recirculating, intimately intermixed reaction admixture in said reaction zone; maintaining the recirculating intimately intermixed reaction admixture in its intimately intermixed condition and removing heat of reaction from the reaction admixture at a rate calculated to provide a substantially constant reaction temperature in the reaction admixture while the same is recirculating in said reaction zone, said constant reaction temperature being at a level appropriate for causing olefinic components introduced in said feedstock to undergo polymerization to form said polyolefin product in the presence of said catalyst composition; withdrawing a product stream comprising said polyolefin product from said reaction zone; and controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence time of the olefinic components undergoing polymerization in the reaction zone is appropriate for production of said polyolefin product.
- 58. A process as set forth in claim 57, wherein said complexing agent comprises methanol.
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of copending utility application Ser. No. 09/655,084 filed on Sep. 20, 2000, which in turn is a continuation-in-part of copending utility application Ser. No. 09/515,790 filed on Feb. 29, 2000. Priority from each of said copending utility applications is claimed herein pursuant to 35 U.S.C. §120. In addition, priority benefits under 35 U.S.C. §119(e) are claimed in this application from provisional application Serial No. 60/160,357, filed on Oct. 19, 1999. The entireties of the disclosures of said prior applications are hereby specifically incorporated herein by reference.
Provisional Applications (1)
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Date |
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60160357 |
Oct 1999 |
US |
Continuations (1)
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Number |
Date |
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Parent |
09665084 |
Sep 2000 |
US |
Child |
10208234 |
Jul 2002 |
US |
Continuation in Parts (1)
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Number |
Date |
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09515790 |
Feb 2000 |
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09665084 |
Sep 2000 |
US |