Mechanical degradation of high molecular weight polymers in dilute solution
โ Scribed by J. F. S. Yu; J. L. Zakin; G. K. Patterson
- Publisher
- John Wiley and Sons
- Year
- 1979
- Tongue
- English
- Weight
- 931 KB
- Volume
- 23
- Category
- Article
- ISSN
- 0021-8995
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โฆ Synopsis
The mechanical shear degradation of polydisperse polyisobutene and monodisperse polystyrene in oils of different viscosities in the concentration range of 0.1% to 1% was studied using a high-shear concentric cylinder viscometer under laminar and uniform well-defined shear field conditions. Molecular weight distributions (MWDs) were measured by gel permeation chromatography (GPC). Degradation of polydisperse polyisobutene solutions narrows the distributions principally through the breaking down of large molecules. Degradation of monodisperse polystyrene broadens the distributions a t lower shear stresses. At higher shear stresses, the distributions do not broaden as much but are still broader than those of the original polymer. The final MJM, ratios are considerably different from the value of 2 expected for random degradation. Hence, the degradation is likely a nonrandom process. It was found that the extent of degradation has a negative concentration dependence coefficient at relatively high molecular weight and a positive concentration dependence a t lower molecular weight. Competing mechanisms of "stretching" and "entanglements" for degradation were postulated to explain the results. The degradation data indicate that the shear stress is the controlling parameter, not the shear rate. The shear degradation is independent of initial molecular weight and viscosity of the solvent.
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