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13C NMR spectroscopic and light scattering studies have shown that the polyethylene produced with (a-diimine)palladium(II) catalysts is hyperbranched. See ref 9 and: Guan, Z.; Cotts, P. M.; McCord, E. F.; McLain, S. J. Science 1999, 283, 2059.
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Torn Dieck, H.1
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56
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33745572913
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Due to the high activity of these catalysts, even under conditions of high dilution and low catalyst loadings, the consumption of monomer is very rapid, and the catalyst rapidly becomes starved for monomer.
-
Due to the high activity of these catalysts, even under conditions of high dilution and low catalyst loadings, the consumption of monomer is very rapid, and the catalyst rapidly becomes starved for monomer.
-
-
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57
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33745572927
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Turnover frequency (TOF) is calculated as the moles of ethylene consumed per mole of catalyst used per unit of time (h).
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Turnover frequency (TOF) is calculated as the moles of ethylene consumed per mole of catalyst used per unit of time (h).
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58
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33745539991
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It is also possible that the 2,6-disubstituted aryl groups undergo slow rotation in solution, however on the time scale of the polymerization reactions, it is likely that these groups are fixed either in the Ci or C, conformations.
-
It is also possible that the 2,6-disubstituted aryl groups undergo slow rotation in solution, however on the time scale of the polymerization reactions, it is likely that these groups are fixed either in the Ci or C, conformations.
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-
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59
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33745566657
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Turnover frequencies given assume complete catalyst activation. Recent results suggest initial reaction with methylaluminoxane may produce some inactive nickel materials: Gates, D. P.; Brookhart, M. Unpublished results.
-
Turnover frequencies given assume complete catalyst activation. Recent results suggest initial reaction with methylaluminoxane may produce some inactive nickel materials: Gates, D. P.; Brookhart, M. Unpublished results.
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60
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33745524774
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Ph.D. Thesis, University of North Carolina at Chapel Hill
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Killian, C. M. Ph.D. Thesis, University of North Carolina at Chapel Hill, 1996.
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(1996)
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Killian, C.M.1
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note
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The branching numbers determined by 1H NMR give no information about the types of branches (i.e., methyl, ethyl, propyl), A series of multidimensional NMR experiments conducted by E. M. McCord on polyethylene produced from nickel diimine catalysts indicate the frequency of branching to be Me > Et > Pr > Bu, etc. See ref 9.
-
-
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62
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84982071317
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+ complexes in solution: Johnson, L. K.; Tempel, D. J.; Brookhart, M. Unpublished results.
-
+ complexes in solution: Johnson, L. K.; Tempel, D. J.; Brookhart, M. Unpublished results.
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(1976)
Chem. Ber.
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Torn Dieck, H.1
Svoboda, M.2
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63
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33745526623
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Monomer flow measurements using ortho alkyl-substituted catalysts 40 was attempted for comparative purposes; however, the data were unreliable because the polyethylene formed is not very soluble in the reaction solution. The reaction mixture becomes heterogeneous in less than 30 min and thus long-term flow data are inconsistent.
-
Monomer flow measurements using ortho alkyl-substituted catalysts (40 was attempted for comparative purposes; however, the data were unreliable because the polyethylene formed is not very soluble in the reaction solution. The reaction mixture becomes heterogeneous in less than 30 min and thus long-term flow data are inconsistent.
-
-
-
-
64
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33745522333
-
-
m's without also considering (i) the type of branching present and (ii) the shape of the melt endotherm. For example in Table 3 (entries 23 and 24), polymers prepared with catalyst 6 at 400 and 600 psig, respectively, show similar Tm's and branching numbers.
-
m's without also considering (i) the type of branching present and (ii) the shape of the melt endotherm. For example in Table 3 (entries 23 and 24), polymers prepared with catalyst 6 at 400 and 600 psig, respectively, show similar Tm's and branching numbers but inspection of the DSC thermograms show that the shapes of the melt transitions are quite different (entry 23 being much broader than entry 24). It becomes even more difficult to quantitatively compare branching vs Tm for polymers prepared using different catalysts. For example, catalyst 4f at 200 and 400 psig (35 °C) yields polymers with 13 and 12 branches respectively (Table 3 entries 13 and 14) and catalyst 5 at 400 and 600 psig (35 C) yields polymers with 11 branches (Table 5, entries 20 and 21), yet despite similar branching numbers, TVs are 128 and 126 C for polymers from catalyst 4f and 108 and 114 C for polymers from catalyst 5. Of course, the shapes of the melt curves are remarkably different. What is clear from the data is that, in general, the larger the branching number the lower the Tm and that the properties of the polyethylenes produced are highly sensitive to both the nature of the catalyst and the conditions under which the polymerizations are carried out.
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65
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0542386882
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Mark, H. F., Kroschwitz, J. I., Eds.; Wiley-Interscience: New York
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note
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Full details of the determination of the X-ray crystal structures of 4c and 4d have been deposited with the Cambridge Crystallographic Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K. (CCDC129234 and CCDC129234, respectively).
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