Polystyrene glass transition, effect

DeMaggio, W.E. Frieze, D.W. Gidley, M. Zhu, H.A. Hristov, and A.F. Yee, Interface and surface effects on the glass transition in thin polystyrene films, Phys. Rev. Lett. 78, 1524 (1997). " D.B. Hall, J.C. Hooker, and J.M. Torkelson, Ultrathin polymer films near the glass transition Effect on the distribution of a relaxation times as measured by second harmonic generation, Macro molecules 30, 667 (1997). 

In contrast to the applications previously described in which alkanesulfonates are used in polymers with a high glass transition temperature (PVC, polystyrene, and ABS), in antistatic-modified polyethylene articles the antistatic agent is able to continue migrating to the surface over a long period of time. Thus, a more permanent antistatic effect is achieved. 

A third factor influencing the value of Tg is backbone symmetry, which affects the shape of the potential wells for bond rotations. This effect is illustrated by the pairs of polymers polypropylene (Tg=10 C) and polyisobutylene (Tg = -70 C), and poly(vinyi chloride) (Tg=87 C) and poly(vinylidene chloride) (Tg =- 19°C). The symmetrical polymers have lower glass transition temperatures than the unsymmetrical polymers despite the extra side group, although polystyrene (100 C) and poly(a-meth-ylstyrene) are illustrative exceptions. However, tacticity plays a very important role (54) in unsymmetrical polymers. Thus syndiotactic and isoitactic poly( methyl methacrylate) have Tg values of 115 and 45 C respectively. 

PVA Particles. Dispersions were prepared in order to examine stabilization for a core polymer having a glass transition temperature below the dispersion polymerization temperature. PVA particles prepared with a block copolymer having M PS) x 10000 showed a tendency to flocculate at ambient temperature during redispersion cycles to remove excess block copolymer, particularly if the dispersion polymerization had not proceeded to 100 conversion of monomer. It is well documented that on mixing solutions of polystyrene and poly(vinyl acetate) homopolymers phase separation tends to occur (10,11), and solubility studies (12) of PS in n-heptane suggest that PS blocks with Mn(PS) 10000 will be close to dissolution when dispersion polymerizations are performed at 3 +3 K. Consequently, we may postulate that for soft polymer particles the block copolymer is rejected from the particle because of an incompatibility effect and is adsorbed at the particle surface. If the block copolymer desorbs from the particle surface, then particle agglomeration will occur unless rapid adsorption of other copolymer molecules occurs from a reservoir of excess block copolymer. 

Thus the quantum yield for acid production from triphenylsulfonium salts is 0.8 in solution and about 0.3 in the polymer 2 matrix. The difference between acid generating efficiencies in solution and film may be due in part to the large component of resin absorption. Resin excited state energy may not be efficiently transferred to the sulfonium salt. Furthermore a reduction in quantum yield is generally expected for a radical process carried out in a polymer matrix due to cage effects which prevent the escape of initially formed radicals and result in recombination (IS). However there are cases where little or no difference in quantum efficiency is noted for radical reactions in various media. Photodissociation of diacylperoxides is nearly as efficient in polystyrene below the glass transition point as in fluid solution (12). This case is similar to that of the present study since the dissociation involves a small molecule dispersed in a glassy polymer. 

In most cases when the temperature of measurement is above the glass transition, the effect of temperature leads to very complicated spectral effects since structural changes and temperature-induced spectroscopic changes are occuring simultaneously 201,322) jn some the structural changes are well defined as in the case of polystyrene 322). 

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