Processes for correlating UV-VIS spectra of norbornene compound to polymerization processes using the same, and related purification methods and compositions
The invention provides a process of polymerizing ethylene and at least one α-olefin, said process comprises polymerizing the ethylene and the at least one α-olefin in the presence of 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances at the following wavelengths: 320 nm and 343 nm. The invention also provides a method of increasing the catalysts efficiency, and a method of determining the expected catalyst efficiency, each in a polymerization of ethylene and at least one α-olefin in the presence of the 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances at the above wavelengths. The invention further provides a method of purifying 5-ethylidene-2-norbornene to form a purified 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances of the above wavelengths.
1. A process of polymerizing a mixture comprising ethylene, at least one α-olefin and 5-ethylidene-2-norbornene, said process comprising polymerizing the ethylene and the at least one α-olefin in the presence of 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the UV absorbances at the following wavelengths: 320 nm and 343 nm, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter pathlength; and
wherein 5-ethylidene-2-norbornene is monitored by UV absorbance, and wherein the 5-ethylidene-2-norbornene having a sum of absorbances, at 320 nm and 343 nm, less than, or equal to, 0.31, is selected for polymerization.
2. The process of claim 1 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.25.
3. The process of claim 1 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.18.
4. The process of claim 1 , wherein the α-olefin is selected from the group consisting of C 3 -C 20 α-olefins, C 3 -C 12 α-olefins, and C 3 -C 8 α-olefins.
5. The process of claim 1 , wherein the α-olefin is selected from the group consisting of propylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene.
6. The process of claim 1 , wherein the polymerization takes place in solution.
7. The process of claim 1 , wherein the polymerization takes place in the gas phase.
8. The process of claim 1 , wherein the polymerization takes place in the presence of at least one constrained geometry catalyst.
9. A method of increasing a catalyst's efficiency in a polymerization of a mixture comprising ethylene, at least one α-olefin and 5-ethylidene-2-norbornene, said method comprising polymerizing the ethylene and the at least one α-olefin in the presence of the 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances at the following wavelengths: 320 nm and 343 nm, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter pathlength, and
wherein 5-ethylidene-2-norbornene is monitored by UV absorbance, and wherein the 5-ethylidene-2-norbornene having a sum of absorbances, at 320 nm and 343 nm, less than, or equal to, 0.31, is selected for polymerization.
10. The method of claim 9 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.25.
11. The method of claim 9 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.18.
12. The method of claim 9 , wherein the α-olefin is selected from the group consisting of C 3 -C 20 α-olefins, C 3 -C 12 α-olefins, and C 3 -C 8 α-olefins.
13. The method of claim 9 , wherein the α-olefin is selected from the group consisting of propylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene.
14. The method of claim 9 , wherein the polymerization takes place in solution.
15. The method of claim 9 , wherein the polymerization takes place in the gas phase.
16. The method of claim 9 , wherein the polymerization takes place in the presence of at least one constrained geometry catalyst.
17. A method of purifying 9-ethylidene-2-norbornene, said method comprising thermally treating said 5-ethylidene-2-norbornene, optionally under reduced pressure, to form a purified 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances at the following wavelengths: 320 nm and 343 nm, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter pathlength, and
wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.31.
18. The method of claim 17 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.25.
19. The method of claim 17 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.18.
20. A method for determining the “percent expected catalyst efficiency” for a polymerization of a mixture, said mixture comprising ethylene, propylene and 5-ethylidene-2-norbornene, said method comprising:
(1) measuring, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter pathlength, the level of impurities at the following UV absorbances: 320 nm and 343 nm, and determining the sum (SUM) of these two absorbances, and
(2) calculating the “percent expected catalyst efficiency (% Expected Cat. Eff.) according to the following equation: % Expected Cat. Eff.=100×(1.185−0.749×SUM).
21. The method of claim 20 , wherein the polymerization takes place in a batch reactor.
22. The method of claim 20 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.31.
23. The method of claim 20 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.25.
24. The method of claim 20 , wherein the polymerization takes place in solution.
25. The method of claim 20 , wherein the polymerization takes place in the gas phase.
26. The method of claim 20 , wherein the polymerization takes place in the presence of at least one constrained geometry catalyst.
27. A method for determining the “percent expected catalyst efficiency” for a polymerization of a mixture, said mixture comprising ethylene, an α-olefin and 5-ethylidene-2-norbornene, said method comprising:
(1) measuring, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter pathlength, the level of impurities at the following UV absorbances: 320 nm and 343 nm, and determining the sum (SUM) of these two absorbances, and
(2) determining the “percent expected catalyst efficiency (% Expected Cat. Eff.) according to the following equation: % Expected Cat. Eff.=100×(A−B×(SUM)), wherein the coefficients A and B are calculated from a linear regression of measured catalyst efficiencies from polymerization reactions, using 5-ethylidene-2-norbornene of varying summations (SUMS) of the UV absorbances at 320 nm and 343 nm.
28. The method of claim 27 , wherein the polymerization takes place in a batch reactor.
29. The method of claim 27 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.31.
30. The method of claim 27 , wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.25.
31. The method of claim 27 , wherein the polymerization takes place in solution.
32. The method of claim 27 , wherein the polymerization takes place in the gas phase.
33. The method of claim 27 , wherein the polymerization takes place in the presence of at least one constrained geometry catalyst.
34. A method of purifying 5-ethylidene-2-norbornene, said method comprising passing the 5-ethylidene-2-norbornene through a column, to form a purified 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances at the following wavelengths: 320 nm and 343 nm, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter path length, and wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.31.
35. A method of purifying 5-ethylidene-2-norbornene, said method comprising chemically treating the 5-ethylidene-2-norbornene, to form a purified 5-ethylidene-2-norbornene, which comprises low levels of impurities, as determined by the absorbances at the following wavelengths: 320 nm and 343 nm, in a neat sample of the 5-ethylidene-2-norbornene, contained in a quartz sample holder with a one centimeter pathlength, and wherein the sum of the absorbances at 320 nm and 343 nm is less than, or equal to, 0.31.
36. The process of claim 1 , wherein the polymerization takes place in the presence of at least one single-site catalyst.
37. The process of claim 1 , wherein the polymerization takes place in the presence of at least one multiple-site-site catalyst.
38. The method of claim 9 , wherein the polymerization takes place in the presence of at least one single-site catalyst.
39. The method of claim 9 , wherein the polymerization takes place in the presence of at least one multiple-site-site catalyst.
40. The method of claim 20 , wherein the polymerization takes place in the presence of at least one single-site catalyst.
41. The method of claim 20 , wherein the polymerization takes place in the presence of at least one multiple-site catalyst.
42. The method of claim 27 , wherein the polymerization takes place in the presence of at least one single-site catalyst.
43. The method of claim 27 , wherein the polymerization takes place in the presence of at least one multiple-site catalyst.