Molecular weight distribution viscosity measurement

Studies of melt flow properties of polypropylene indicate that it is more non-Newtonian than polyethylene in that the apparent viscosity declines more rapidly with increase in shear rate. The melt viscosity is also more sensitive to temperature. Van der Wegt has shown that if the log (apparent viscosity) is plotted against log (shear stress) for a number of polypropylene grades differing in molecular weight, molecular weight distribution and measured at different temperatures the curves obtained have practically the same shape and differ only in position. 

The sizes determined in this work are the apparent molecular sizes and not necessarily the sizes of the asphaltene and maltene molecules at process conditions. Association efforts for asphaltene molecules have been observed for both vapor-phase osmometry molecular weight and viscosity measurements (14, 15). The sizes reported here were measured at 0.1 wt % in tetrahydrofuran at room temperature. Other solvent systems (chloroform, 5% methanol-chloroform, and 10% trichlorobenzene-chloroform) gave similar size distributions. Under these conditions, association effects should be minimized but may still be present. At process conditions (650-850°F and 5-30% asphaltene concentration in a maltene solvent), the asphaltene sizes may be smaller. However, for this work the apparent sizes determined can be meaningfully correlated with catalyst pore size distributions to give reasonable explanations of the observed differences in asphaltene and maltene process-abilities (vide infra). In addition, the relative size distributions of the six residua are useful in explaining the different processing severities required for the various stocks. Therefore, the apparent sizes determined here have some physical significance and will be referred to just as sizes. 

APHA color (269) is usually one of the specifications of PTMEG, sometimes viscosity is another (270). Melt viscosity at 40°C is often used as a rough measure of the molecular weight distribution within a narrow molecular weight range. Sometimes an empirical molecular weight ratio,... 

Molecular weights of PVDC can be determined directly by dilute solution measurements in good solvents (62). Viscosity studies indicate that polymers having degrees of polymerization from 100 to more than 10,000 are easily obtained. Dimers and polymers having DP < 100 can be prepared by special procedures (40). Copolymers can be more easily studied because of thek solubiUty in common solvents. Gel-permeation chromatography studies indicate that molecular weight distributions are typical of vinyl copolymers. 

These data for typical properties of EP polymers are either as measured or as advertised by respective manufacturers. This table is not intended to be definitive either in terms of the total grade slate or the specific data reported for each producer. Note that the molecular weight distribution data are based on a qualitative comparison of GPC curves. Mooney viscosities are repotted for final product form (i.e.. in the case of oil-extended rubbers, the viscosity is that of the EP plus oil. 

When the full distribution is needed, it is measured by size-exclusion chromatography (also called gel permeation chromatography). This is a solution technique that requires dissolution of the polymer in a reasonable solvent such as tetrahydrofuran or tetrachlorlobenzene. For polymers that require exotic solvents or solution temperatures above about 150°C, a simple measurement of solution viscosity can be a useful surrogate for the actual molecular weight. The viscosity of the pure polymer (i.e., a polymer melt viscosity) can also be used. Such simplified techniques are often satisfactory for routine quality control, particularly for condensation polymers such as PET that vary in average molecular weight but usually have a polydispersity of 2. 

It is well known that LCB has a pronounced effect on the flow behavior of polymers under shear and extensional flow. Increasing LCB will increase elasticity and the shear rate sensitivity of the melt viscosity ( ). Environmental stress cracking and low-temperature brittleness can be strongly influenced by the LCB. Thus, the ability to measure long chain branching and its molecular weight distribution is critical in order to tailor product performance. 

There are commercially available in-line or on-line viscometer devices. In-line devices are installed directly in the process while on-line devices are used to analyze a side stream of the process. Most devices are based on measuring the pressure drop and flow rate through a capillary. The viscosity is either determined at a single shear rate or, at most, a few shear rates. Complex fluids, on the other hand, exhibit a viscosity that cannot be so easily characterized. In order to capture enough information that allows, for example, a molecular weight distribution to be inferred, it is necessary to determine the shear viscosity over reasonably wide ranges of shear rates. 

Figure 11 Molecular weight distribution obtained from viscosity (o) and GPC (solid curve) measurements from the studies of Wood-Adams and Dealy [84]. Reprinted with permission from Wood-Adams and Dealy [84]. Copyright 2000, American Chemical Society.

Materials. Four samples of sodium poly(styrenesulfonate) (NaPSS) prepared by sulfonation of polystyrenes with narrow molecular weight distribution were purchased from Pressure Chemical Co. The characteristics of the samples, according to the manufacturer, are listed in Table I. The intrinsic viscosities of NaPSS in aqueous NaCl solution were measured using an Ubbelhode viscometer at 25 °C. 

GPC measurements were used to demonstrate that a monomodal molecular weight distribution with a polydispersity of approximately 2 was obtained. The glass transition temperature was determined on a Perkin-Elmer DSC-2 using a heating rate of 10 C/min and the intrinsic viscosity was determined in NMP at 25°C. These data are summarized in Table I. 

Solution viscosity measurements for Mn are calibrated from the flow characteristics of linear molecules of the equilibrium molecular weight distribution. Branched polymers have a lower radius of gyration for their molar mass than the corresponding linear molecule. One, therefore, expects different flow properties as branching increases, hence causing the viscosity numbers to become less and less accurate and so should only be used for trends - not exact calculations. 

Measures taken to minimise the amount of unadsorbed polymer in solution have been shown to improve the viscosity performance of both kaolin and calcium carbonate slurries. These include adjustment of the pH or initial neutralisation of the polymer to increase its affinity to the surface and fractionation of the polymer to reduce the width of its molecular weight distribution. 

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