Molecular weight, measurement

This suggests that polymerizations should be conducted at different ratios of [SX]/[M] and the molecular weight measured for each. Equation (6.89) shows that a plot of l/E j. versus [SX]/[M] should be a straight line of slope sx Figure 6.8 shows this type of plot for the polymerization of styrene at 100°C in the presence of four different solvents. The fact that all show a common intercept as required by Eq. (6.89) shows that the rate of initiation is unaffected by the nature of the solvent. The following example examines chain transfer constants evaluated in this situation. 

Molecular Weight. Measurement of intrinsic viscosity in water is the most commonly used method to determine the molecular weight of poly(ethylene oxide) resins. However, there are several problems associated with these measurements (86,87). The dissolved polymer is susceptible to oxidative and shear degradation, which is accelerated by filtration or dialysis. If the solution is purified by centrifiigation, precipitation of the highest molecular weight polymers can occur and the presence of residual catalyst by-products, which remain as dispersed, insoluble soHds, further compHcates purification. 

The molecular stmcture of the copolymers is also important. Molecular-weight measurements (osmometry, gpc) and functional group analysis are useful. Block copolymers require supermolecular (morphological) stmctural information as well. A listing of typical copolymer characterization tools and methods is shown in Table 6. 

Select the detector. To acquire molecular weight distribution data, use a general detector such as a refractive index detector. To acquire structural or compositional information, employ a more selective detector such as an ultraviolet (UV) or infrared (IR) detector. Viscometric and light-scattering detectors facilitate more accurate molecular weight measurement when appropriate standards are not available. 

FIGURE 3.6 Small differences in flow rate can have a significant effect on the molecular weight measurement. 

Thus, the slope of a plot of ln[T] vs ln[M] will yield the transfer constant. This method does not rely on molecular weight measurements. 

Many solvents and additives have measurable transfer constants (Table 6.5). The accuracy of much of the transfer constant data in the literature is questionable with values for a given system often spanning an order of magnitude. In some cases the discrepancies may be real and reflect differences in experimental conditions. In other cases they are less dear and may be due to difficulties in molecular weight measurements or other problems. 

Gel permeation chromatography (GPC) or size exclusion chromatography (SEC) has been routinely used to estimate die molecular weight of die polymers. The molecular weight measured by GPC is relative to a polymer standard, typically polystyrene GPC is dius a relative method rather than an absolute one. For those polymers whose structure is very different from polystyrene, GPC molecular weight values could significantly differ from the real ones. In those cases, GPC values should only be regarded as a reference. 

The number of branches of star molecules made this way cannot be precisely predicted. Accurate molecular weight measurements are necessary to determine the average... 

Conversely, if we know the molecular weight we can make inferences about the conformation of polysaccharides in solution using Eq. 13 and other power-law relations. We will consider this in more detail after we have considered further molecular weight measurement by absolute (i.e. without assumptions concerning conformation) procedures. 

In SEC/LALLS, the molecular weight measured at any instant is (M ). Thus the sample M can be calculated by the standard definition... 

Table 6.30 lists the main characteristics of quadrupole mass spectrometers. QMS is a relatively simple and robust analyser which does not need such a high vacuum as a sector instrument. The maximum admissible pressure at the source of the spectrometer is 10 6mbar in continuous regime and 10-5—10 4 mbar during short time intervals. Quadrupole technology assures reproducible and accurate molecular weight measurements day in and day out. For figures of merit, see Table 6.27. 

Table II. Molecular weight measurements on copolymer films undergoing irradiation. (9)...

H2 + CH4, D2, P2 + Tetralin, GO + H2O were selected and reduction was conducted by varying the reaction time. Each isolated fraction was subjected to ultimate analysis, H-NMR, C-13 NMR, molecular weight measurement and the structural parameters were calculated. The results of the study of these structural parameters in the course of the reactions were evaluated and the reaction mechanisms thereof are discussed below. 

A highly reactive form of titanocene could be obtained when a suspension of the gray-green hydride 14 was stirred in ethyl ether for 2 hours at room temperature. The solid gradually disappeared concurrent with the evolution of 0.5 equivalent of H2 per equivalent of Ti. Molecular weight measurements showed this metastable form of titanocene (15) to be dimeric. Treatment of a cold ethereal solution of (Cp2Ti)2 (15) with CO resulted in a quantitative yield of Cp2Ti(CO)2 (1) (24,36). 

Molecular weight measurements agreed with the difructose anhydride composition. The matter of the anomeric structures of the D-fructoste units is left undecided because there is no evidence now known which relates to this question. 

The reasons behind this accelerated rate behavior have been attributed to a decrease in chain transfer processes (28,29) and a decreased termination rate (24,25) indicated by molecular weight measurements (26). Recently, direct evidence of decreases in the termination rate have been shown (27) and in these studies both the termination and propagation kinetic constants were determined for polymerizations exhibiting enhanced rates in a smectic phase. The propagation constant, kp, decreases slightly in the ordered phase from the isotropic polymerization. Such a decrease would be expected because of the lower temperature in the smectic phase. The termination kinetic constant, kt, however, decreases almost two orders of magnitude for the ordered polymerization, indicating a dramatically suppressed termination rate. 

Molecular weight measurements were determined by size exclusion chromatography on a high pressure liquid chromatograph equipped with a differential refracto-meter. A Waters Styragel HR 5 i column set (106 104 500 A) was employed and calibrated with PS standards. THF was used as solvent at a flow rate of 1 ml/min. 

These isomers resulted from the non-stereoselectivity of the initial coupling process typical of the aza-ACE reactions of the 7-isopropylidene-bridged dipolarophile 38, while molecular weight measurements and the presence of an isopropenyl group in the H NMR of each product supported C,A-methano-bridge formation. Such products were considered to arise via the bond reorganisation depicted by the arrows in adduct 156 in which one of the isopropylidene rc-bonds acted as the nucleophile to attack the methylene carbon of the adjacent A-methoxymethyl group. 

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