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Basic Chemistry of Polystyrene 57

A plot of log [rj]0 vs. log (M) for each solvent gives a

straight line in which a is the slope and K is the intercept on

the log [rj]0 axis. Such plots are an easy means of estimating

molecular weight from intrinsic viscosity.

The physical properties of polystyrene are greatly dependent

on its average molecular weight. Low molecular weight poly-

mer is very brittle and has a low softening temperature. Fox

and Flory 1 have shown that the second-order transition tem-

perature increases with an increasing number average molecu-

lar weight according to the following relationship:

The limiting value of 100°C is reached approximately at

a molecular weight of 30,00Q. The tensile strength of low

molecular weight polystyrene is very low; it increases rapidly,

however, as molecular weight increases. For molecular weights

above approximately 100,000 the tensile strength is essen-

tially constant at 7000 to 8000 psi, and the polymer is less


The melt viscosity of polystyrene increases rapidly as the

weight average molecular weight increases. If it is too high

the polymer is very difficult to mold, therefore the average

molecular weight should be kept as low as possible without

tensile strength, softening point or impact strength being de-

creased. Molecular weight distribution has been shown, to

iafluence physical properties; the,CQndusionJs_that extremes

in distribution are detrimental to strength_and. mold^bility^f

1 Fox and Flory, /. Appl. Physics, 21, 581 (1950).

2 Merz, Nielson, and Buchdahl, lnd. Eng. Chem., 43, 1396 (1951).

a McCormick, /. Polymer Sci., 39, 87 (1959).

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