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408

GLASSRUBBER TRANSITION BEHAVIOR

8.10

DEPENDENCE OF Tg ON CHEMICAL STRUCTURE

In Section 8.9 some effects of crystallinity and hydrogen bonding on Tg were considered. The effect of molecular weight was discussed in Section 8.7, and the effect of copolymerization was discussed in Section 8.8. This section discusses the effect of chemical structure in homopolymers. Boyer (135) suggested a number of general factors that affect Tg (see Table 8.11). In general, factors that increase the energy required for the onset of molecular motion increase Tg; those that decrease the energy requirements lower Tg. 8.10.1 Effect of Aliphatic Side Groups on Tg

In monosubstituted vinyl polymers and at least some other classes of polymers, exible pendant groups reduce the glass transition of the polymer by acting as internal diluents, lowering the frictional interaction between chains. The total effect is to reduce the rotational energy requirements of the backbone. The aliphatic esters of poly(acrylic acid) (136), poly(methacrylic acid) (137), and other polymers (138) (see Figure 8.32) (139) show a decline in Tg as the number of CH2 units in the side group increases. At still longer aliphatic side groups, Tg increases as side-chain crystallization sets in, impeding chain motion. In this latter composition range the materials feel waxy. In the ultimate case, of course, the polymer would behave like slightly diluted polyethylene. For cellulose triesters (37) the minimum in Tg is observed at the triheptanoate, probably because of the increased basic backbone stiffness. 8.10.2 Effect of Tacticity on Tg

The discussion so far in this chapter has assumed atactic polymers, which with a few exceptions are amorphous. Other stereo isomers include isotactic and syndiotactic polymers (see Section 2.3). The effect of tacticity on Tg may be signicant, as illustrated in Table 8.12 (140,141). Karasz and MacKnight (141) noted that the effect of tacticity on Tg is expected in view of the GibbsDiMarzio theory (Section 8.6.3.1). In disubstituted vinyl polymers, the energy difference between the two predominant rotational isomers is greater for the syndiotactic conguration than for the isoTable 8.11 Factors affecting Tg (135)

Increase Tg Intermolecular forces High CED Intrachain steric hindrance Bulky, stiff side groups

Decrease Tg In-chain groups promoting exibility (double-bonds and ether linkages) Flexible side groups Symmetrical substitution

8.10 DEPENDENCE OF Tg ON CHEMICAL STRUCTURE

409

Figure 8.32 Effect of side-chain lengths on the glass transition temperatures of polymethacrylates [ (S. S. Rogers and L. Mandelkern, J. Phys. Chem., 61, 985, 1957)]; poly-palkyl styrenes [ (W. G. Bard, J. Polym. Sci., 37, 515, 1959)]; poly-a-olens [ (M. L. Dannis, J. Appl. Polym. Sci., 1, 121, 1959; K. R. Dunham, J. Vandenbergh, J. W. H. Farber, and L. E. Contois., J. Polym. Sci., 1A, 751, 1963)]; and polyacrylates [ (J. A. Shetter, Polym. Lett., 1, 209, 1963)] (139). Table 8.12 Effect of tacticity on the glass transition temperatures of polyacrylates and polymethacrylates (141)

Tg (C) Polyacrylates Side Chain Methyl Ethyl n-Propyl Iso-Propyl n-Butyl Iso-Butyl Sec-Butyl Cyclo-Hexyl Isotactic 10 -25 -11 -23 12 Dominantly Syndiotactic 8 -24 -44 -6 -49 -24 -22 19 Isotactic 43 (50)* 8 27 -24 8 51 Polymethacrylates Dominantly Syndiotactic 105 (123)* 65 35 81 20 53 60 104 100% Syndiotactic 160 120 139 88 120 163

* Tg (M = ), K. Ute, N. Miyatake, and K. Hatada, Polymer, 36, 1415 (1995).

410

GLASSRUBBER TRANSITION BEHAVIOR

tactic conguration. In monosubstituted vinyl polymers, where the other substituent is hydrogen, the energy difference between the rotational states of the two pairs of isomers is the same. Thus the acrylates in Table 8.12 have the same Tg for the two isomers, whereas the methacrylates show distinctly different Tgs, with the isotactic form always having a lower Tg than the syndiotactic form. 8.11 EFFECT OF PRESSURE ON Tg The discussion above has assumed constant pressure at 1 atm (1 bar). Since an increased pressure causes a decrease in the total volume [see equation (8.8)], an increase in Tg is expected based on the prediction of decreased free volume. Tamman and Jellinghaus (142) showed that a plot of volume versus pressure at a temperature near the transition shows an elbow reminiscent of the volumetemperature plot (see Figure 8.9). If the temperature is raised at elevated pressures, Tg will in fact show a corresponding increase (see Figure 8.33) (143).

Figure 8.33 Glass transition versus pressure for various substances (143).

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