End group measurement

Number-Average Molecular Weight of Polystyrenes Estimated by SEC and Calculated from End Groups Measured by Py-GC... 

Table 5.3 summarizes the results of variations of polymerization recipes and reaction conditions and their effects on melt viscosity, flex life, and end groups (measured by infrared spectroscopy). The strong effect of methanol on reducing the melt viscosity (i.e., molecular weight) can be observed from cases 3 and 5. Reaction time and pressure drive up molecular weight as reflected by the increase in melt viscosity. An increase in peroxide initiator lowers the molecular weight, thus lowering the melt viscosity. A comparison of the effectiveness of methanol and cyclohexane as chain transfer agents can be seen in Table 5.4. A small amount of either compound brings forth a drastic reduction in melt viscosity.

As with the rate of polymerization, we see from Eq. (6.37) that the kinetic chain length depends on the monomer and initiator concentrations and on the constants for the three different kinds of kinetic processes that constitute the mechanism. When the initial monomer and initiator concentrations are used, Eq. (6.37) describes the initial polymer formed. The initial degree of polymerization is a measurable quantity, so Eq. (6.37) provides a second functional relationship, different from Eq. (6.26), between experimentally available quantities-n, [M], and [1]-and theoretically important parameters—kp, k, and k. Note that the mode of termination which establishes the connection between u and hj, and the value of f are both accessible through end group characterization. Thus we have a second equation with three unknowns one more and the evaluation of the individual kinetic constants from experimental results will be feasible. 

Table 9.3 lists the intrinsic viscosity for a number of poly(caprolactam) samples of different molecular weight. The M values listed are number average figures based on both end group analysis and osmotic pressure experiments. Tlie values of [r ] were measured in w-cresol at 25°C. In the following example we consider the evaluation of the Mark-Houwink coefficients from these data. 

Hydroxyl number and molecular weight are normally determined by end-group analysis, by titration with acetic, phthaUc, or pyromellitic anhydride (264). Eor lower molecular weights (higher hydroxyl numbers), E- and C-nmr methods have been developed (265). Molecular weight deterrninations based on coUigative properties, eg, vapor-phase osmometry, or on molecular size, eg, size exclusion chromatography, are less useful because they do not measure the hydroxyl content. 

The molecular weight and molecular weight distribution may be determined by conventional techniques. As the resins are of comparatively low molecular weight it is possible to measure this by ebullioscopic and by end-group analysis techniques. 

At the end of the 1930s, the only generally available method for determining mean MWs of polymers was by chemical analysis of the concentration of chain end-groups this was not very accurate and not applicable to all polymers. The difficulty of applying well tried physical chemical methods to this problem has been well put in a reminiscence of early days in polymer science by Stockmayer and Zimm (1984). The determination of MWs of a solute in dilute solution depends on the ideal, Raoult s Law term (which diminishes as the reciprocal of the MW), but to eliminate the non-ideal terms which can be substantial for polymers and which are independent of MW, one has to go to ever lower concentrations, and eventually one runs out of measurement accuracy . The methods which were introduced in the 1940s and 1950s are analysed in Chapter 11 of Morawetz s book. 

The polymers initiated by BP amines were found to contain about one amino end group per molecular chain. It is reasonable to consider that the combination of BP and such polymers will initiate further polymerization of vinyl monomers. We investigated the photopolymerization of MMA with BP-PMMA bearing an anilino end group as the initiation system and found an increase of the molecular weight from GPC and viscometrical measurement [91]. This system can also initiate the photopolymerization of AN to form a block copolymer, which was characterized by GPC, elemental analysis, and IR spectra. The mechanism proposed is as follows ... 

Hjertberg et al. [72] have studied various PVC samples using Shimizu and Ohtsu s method [69]. They concluded that this method mainly gave a measure of the content of saturated 1,2-dichloroethyl chain end groups, the presence of which has been conclusively demonstrated [73]. With caution they contend there are 0-0.2 head-to-head structures per 1,000 monomer units. 

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