Interchain attraction

There are two principal forces that govern the abdity of a polymer to crystallise the interchain attractive forces, which are a function of the chain stmcture, and the countervailing kinetic energy of the chain segments, which is a function of the temperature. The fact that polymers consist of long-chain molecules also iatroduces a third parameter, ie, the imposition of a mechanical force, eg, stretching, which can also enhance interchain orientation and favor crystallisation. 

The glass transition temperature of a random copolymer usually falls between those of the corresponding homopolymers since the copolymers will tend to have intermediate chain stiffness and interchain attraction. Where these are the only important factors to be considered a linear relationship between Tg and copolymer composition is both reasonable to postulate and experimentally verifiable. One form of this relationship is given by the equation... 

Poly(methyl isopropenyl ketone) + 114 +243 Interchain attraction... 

The regular structure of the alternating copolymer with its absence of side chains enables the polymer to crystallise with close molecular packing and with interchain attraction augmented by the carbonyl groups. As a result these polymers exhibit the following characteristics ... 

In spite of possessing a flexible backbone and low interchain attraction polyethylene is not a rubber. This is because its chain regularity enables a measure of crystallinity which does not disappear until temperatures of the order of 100°C are reached. It therefore follows that if crystallinity can be substantially reduced it should be possible to obtain an ethylene-based polymer which is rubbery. The means by which this objective has been achieved on a commercial scale may be classified into three categories ... 

As a class the aliphatic polyalkenamers have low values due to a combination of low chain stiffness and low interchain attraction. The presence of double bonds has the effect of increasing the flexibility of adjacent single bonds (see Chapter 4) and overall this leads to a reduction in. Thus in the sequence from polydecenamer down to polypentenamer an increase in the double bond concentration leads to a lowering of Tg. On the other hand the Tg of polybutenamer, i.e. poly butadiene, is somewhat higher than that of polypentenamer, presumably because the proportion of stiff links, i.e. double bonds, becomes sufficiently high to override the flexibilising effect on adjacent chains. Consequently the polypentenamers have the lowest Tg values known for hydrocarbon polymers (cis- -114°C, trans- -97°C). 

A -Substitution. Replacement of the hydrogen atom in the —CONH— group by such groups as CH3 and -CH20CH3 will cause a reduction in the interchain attraction and a consequent decrease in softening point. Rubbery products may be obtained from methoxymethyl nylons. These materials are considered in more detail in Section 18.9. 

Polyamides such as nylon 6, nylon 66, nylon 610, nylon 11 and nylon 12 exhibit properties which are largely due to their high molecular order and the high degree of interchain attraction which is a result of their ability to undergo hydrogen bonding. 

It is particularly interesting to consider the influence of the substituents R and Rj in diphenylol alkanes of the type shown in Figure 20.12. Such variations will influence properties because they affect the flexibility of the molecule about the central C-atom, the spatial symmetry of the molecule and also the interchain attraction, the three principal factors determining the physical nature of a high polymer. 

The ester link appears to enhance chain flexibility of an otherwise polymethylenic chain. At the same time it generally increases interchain attraction and in terms of the effects on melting points and rigidity the effects appear largely self-cancelling. 

It is reasonable to consider that in an ester group the in-chain ether link —C—O—C— increases the chain flexibility compared with a polymethylene chain to decrease the heat of fusion. At the same time there will be some increase in interchain attraction via the carbonyl group which will decrease the entropy of fusion. Since these two effects almost cancel each other out there is almost no change in melting point with change in ester group concentration. 

The range of high-temperature rubbers is very small and limited to the silicones, already considered in this chapter, and certain fluororubbers. With both classes it is possible to produce polymers with lower interchain attraction and high backbone flexibility and at the same time produce polymers in which all the bonds have high dissociation energies and good resistance to oxidation. 

Since a variation of the counterion implies a corresponding variation in interchain attraction, can the glass transition be correlated with various parameters of the counterion by simple electrostatic considerations ... 

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