Melt flow molecular weight distribution

Molecular Weight Distribution. In industry, the MWD of PE resins is often represented by the value of the melt flow ratio (MER) as defined in Table 2. The MER value of PE is primarilly a function of catalyst type. Phillips catalysts produce PE resins with a broad MWD and their MER usually exceeds 100 Ziegler catalysts provide resins with a MWD of a medium width (MFR = 25-50) and metallocene catalysts produce PE resins with a narrow MWD (MFR = 15-25). IfPE resins with especially broad molecular weight distributions are needed, they can be produced either by using special mixed catalysts or in a series of coimected polymerization reactors operating under different reaction conditions. 

The width of molecular weight distribution (MWD) is usually represented by the ratio of the weight—average and the number—average molecular weights, MJM. In iadustry, MWD is often represented by the value of the melt flow ratio (MER), which is calculated as a ratio of two melt indexes measured at two melt pressures that differ by a factor of 10. Most commodity-grade LLDPE resias have a narrow MWD, with the MJM ratios of 2.5—4.5 and MER values in the 20—35 range. However, LLDPE resias produced with chromium oxide-based catalysts have a broad MWD, with M.Jof 10—35 and MER of 80-200. 

The molecular weight distribution of LLDPE resins is usually characterized in industry by the ratios of melt indexes measured in the same apparatus using different loads (2.16, 10.16, and 21.6 kg). The commonly used ratios are melt flow ratio, MFR) and I q/I2. Both of these ratios... 

Only a limited amount of information is available concerning the effects of molecular weight distribution. There is, however, evidence that the narrower the distribution the more Newtonian are the melt flow properties. It has been noted... 

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. 

Fig. 8-6 Melt flow rates as a function of molecular weight distribution.

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. 

Resins with a significant low molecular weight tail, as shown in Fig. 5.3 c), exhibit similar melt flow characteristics to the most probable molecular weight distribution, but may be more flexible in the solid state due to the plasticizing effect of the shorter chains. 

In practice, product developers often blend two or more resins together in order to obtain a product that has the required melt flow and solid-state characteristics. Thus, we frequently combine metallocene catalyzed linear low density polyethylene, having a most probable molecular weight distribution, with low density polyethylene, having a broad molecular weight distribution. The linear low density polyethylene provides good impact resistance, while the low density polyethylene improves melt flow characteristics. 

The z average molecular weight has been found to correlate with the shear viscosity of polymer melts when the molecular weight distribution is very broad and where very large molecules appear to dominate the resistance to fluid flow. 

Disclosed is a crossUnked ethylenic polymer foam structure of an ethylenic polymer material of a crosslinked, substantially linear ethylenic polymer. The ethylenic polymer in an uncrossUnked state has (a) a melt flow ratio greater than or equal to 5.63 (b) a molecular weight distribution defined by a given equation and (c) a critical shear rate at onset of surface melt fracture of at least 50% greater than the critical shear rate at the onset of surface melt fracture of a linear ethylenic polymer having about the same melt flow ratio and molecular weight distribution. Further disclosed is a process for making the above foam structure. 

Tu, as a function of Newtonian wall shear rate, F, for a number of common polymers. Consider the melt spinning of PS at a volumetric flow rate of 4.06 x 10 cm /s through a spinneret that contains 100 identical holes of radius 1.73 X 10 cm and length 3.46 x 10 cm. Assume that the molecular weight distribution is broad. 

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