Crosslink Density in Polymers

E. Asmussen, A. Peutzfeldt, Influence of selected components on crosslink density in polymer structures, Eur. J. Oral Sci. 109 (2001) 282-285. 

For example, increased crosslink density in polymer network I in an IPN clearly decreases the domain size of polymer II.This is illustrated by comparison of Figure 2.3, bottom left and bottom right. This effect appears reasonable because a tighter initial network must restrict the size of the regions in which polymer II can phase separate. However, the role of crosslinks in merely diminishing phase domain size, and in increasing compatibility in a thermodynamic sense, needs to be carefully distinguished. 

The activation volume of the three polymers turned out to be v 2 nm3, independent of their crosslink density. In the crosslinked polymer A the strands are short and about five of them fit into the activation volume. In contrast, one strand of polymer E requires a volume five times larger than the activation volume ... 

Table II shows Tgs obtained from DSC traces. (Footnotes a and b in Table II show T s values of three reference polymers two PIBs, whose Mns are similar to the Mns of MA-PIB-MA used in the network synthesis, and a PDMAAm the difference in the Tg for the Mn=4,000 and 9,300 PIBs is due to the dependence of Tg on Mn(72)). The DSC traces of the networks exhibited two Tgs, one in the range of -63 to -52 °C (PIB domains) and another in the range of 90 to 115 °C (PDMAAm domains) indicating microphase separated structures. The Tgs associated with the PIB phase in the PDMAAm-1-PIB networks were higher than those of the reference homoPIBs which may be due to PIB chain-ends embedded in the glassy PDMAAm phase restricting segmental mobility. The Tg of the PIB phase in the PDMAAm-1-PIB increases by increasing the PIB content which may be due to an increase in crosslink density. In contrast, the Tg for the PDMAAm phase in the network decreases upon increasing the PIB content. Interaction of the (-CH2-CH-) moiety of the PDMAAm with the flexible PIB and thus the formation of a more flexible structure may explain this phenomenon.

DC Harsh, SH Gehrke. Characterization of ionic water absorbent polymers Determination of ionic content and effective crosslink density. In L Brannon-Peppas, RS Harland, eds. Absorbent Polymer Technology. Amsterdam Elsevier, 1990, pp 103-124. 

If we accept the model proposed for these mixed monofunctional/ difunctional systems, we can draw some conclusions about the network structure in polymers based on I alone. For example, Fig. 7 shows how the Tg varied with the relative crosslink density in the mixed systems. The abcissa represents the probability that a monomer chosen at random is linked to the network at both ends. At moderate degrees of crosslinking, the expected relationship between Tg and crosslink density is linear, so the data were approximated by a straight line (10). From the extrapolation in Fig. 7, one concludes that a typical bis-phthalonitrile cured to a Tg of 280 0 has a relative crosslink density of 0.5, or about 70% reaction of nitrile groups. 

Thus the factor (Mc — M )/(Mn — M ) may be thought of as the sieving term mentioned in the theory of Yasuda et al. [150], In the Peppas-Reinhart theory, the sieving mechanism takes an understandable form which is a function of the structure of the network. It must be noted that the presence of semicrystalline regions in the polymer membrane leads to deviations from the predicted dependencies in this theory. These researchers found that as the crosslinking density in the polymer membrane increased, the solute diffusion coefficient decreased, further illustrating the importance of structural parameters of the polymer network in predicting the solute diffusion coefficient [156],... 

When plasticized polymers are in contact with the mother polymers, plasticizers are likely to migrate to mother polymers and the extent of their migration depends on a number of factors such as polymer-plasticizer system, polarity of polymer and plasticizer, crosslink density of polymer, molecular weight of plasticizer etc. 

Generally speaking, these properties are almost independent of the crosslink density in the same way as they are almost independent of the chain length in linear polymers. Thus, there are no fundamental differences between thermosets and amorphous thermoplastics in the glassy state, although certain second-order effects linked to crosslinking can be observed, sometimes, on packing density and local mobility. 

One of the most characteristic properties of crosslinked rubbers is the ability to swell in appropriate solvents to a constant volume. Not only is this property exploited for estimation of parameters such as crosslink densities and polymer-solvent interaction parameters, but the resultant change in nuclear magnetic resonance (NMR) parameters allows a large number of new and interesting NMR experiments. It is the aim of this chapter to introduce some simple concepts of polymer swelling and to examine the information obtainable for the range of NMR experiments possible on swollen gels. 

The fractions of protons decaying according to relaxation functions Rx and R2 are given by fj and f2. In molten polymers this relationship has long been exploited to provide a measure of the crosslink density in many polymer systems [64-83]. The form of the decay functions has been the subject of much discussion, however, it is often observed that Rj and R2 can be approximated by simple exponential decay functions. It is generally accepted that the protons with short relaxation times are those directly attached to or adjacent to crosslink points. As an example Figure 13.4 shows the decays of transverse... 

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