What is solubility and what it depends on?

It should be pointed out that not all polymers can be dissolved, and even though when they can, the
dissolution process may take up to several days or weeks. According to Rosen (1982), there is an assembly of
general rules for polymer solubility, based on experimental observations, from which interesting conclusions
can be obtained.

Thus, it is well known that the dissolution of polymers depends not only on their physical properties, but also
on their chemical structure, such as: polarity, molecular weight, branching, crosslinking degree, and
crystallinity. The general principle that states like dissolves like is also appropriate in the case of polymers.
Thus, polar macromolecules like poly (acrylic acid), poly (acrylamide) and polyvinyl alcohol, among others, are
soluble in water. Conversely, nonpolar polymers or polymer showing a low polarity such as polystyrene,
poly(methyl methacrylate), poly(vinyl chloride), and poly(isobutilene), are soluble in nonpolar solvents.

On the other hand, the molecular weight of polymers plays an important role in their solubility. In a given
solvent at a particular temperature, as molecular weight increases, the solubility of a polymer decreases. This
same behaviour is also noticed as crosslinking degree increases, since strongly cross-linked polymers will
inhibit the interaction between polymer chains and solvent molecules, preventing those polymer chains from
being transported into solution.

A similar situation occurs with crystalline macromolecules, although in such a case the dissolution can be
forced if an appropriate solvent is available, or warming the polymer up to temperatures slightly below its
crystalline melting point (Tm). For example, highly crystalline linear polyethylene (Tm = 135C) can be dissolved
in several solvents above 100C. Nylon 6.6 (Tm = 265C), a crystalline polymer which is more polar than
polyethylene, can be dissolved at room temperature in the presence of solvents with enough ability to interact
with its chains, through for example, hydrogen bonding. Branched polymer chains generally increase solubility,
although the rate at which this solubility occurs, depends on the particular type of branching. Chains
containing long branches, cause dense entanglements making difficult the penetration of solvent molecules.
Therefore the rate of dissolution in these cases becomes slower than if it was short branching, where the
interaction between chains is practically non-existent.

How a polymer gets dissolved?

As said earlier, the dissolution of a polymer is generally a slow process, which can take even several weeks,
depending on the structure and the molecular weight of a given polymer. When a low molecular weight solute
such as sucrose is added to water, the dissolution process takes place immediately. The sugar molecules leave
the crystal lattice progressively, disperse in water and form a solution. But polymer molecules are rather
different. They constitute long chains with a large number of segments, forming tightly folded coils which are
even entangled to each other. Numerous cohesive and attractive both intra and intermolecular forces hold
these coils together, such a dispersion, dipole-dipole interaction, induction, and hydrogen bonding (Figure 1a).

Based on these features, one may expect noticeable differences in the dissolution behaviour shown by
polymers. Due to their size, coiled shape, and the attraction forces between them, polymer molecules become
dissolved quite slowly than low molecular weight molecules. Billmeyer Jr. (1975) points out that there are two
stages involved in this process: in the first place, the polymer swelling and next the dissolution step itself.

When a polymer is added to a given solvent, attraction as well as dispersion forces begin acting between its
segments, according to their polarity, chemical characteristics, and solubility parameter. If the polymer-solvent
interactions are higher than the polymer-polymer attraction forces, the chain segment start to absorb solvent
molecules, increasing the volume of the polymer matrix, and loosening out from their coiled shape (Figure 1b).
We say the segments are now "solvated" instead of "aggregated", as they were in the solid state.
Figure 1. Schematic representation of the dissolution process for polymer molecules
The whole "solvation-unfolding-swelling" process takes a long time, and given it is influenced only by the
polymer-solvent interactions, stirring plays no role in this case. However, it is desirable to start with fine
powdered material, in order to expose more of their area for polymer-solvent interactions.

When crystalline, hydrogen bonded or highly cross-linked substances are involved, where polymer-polymer
interactions are strong enough, the process does stop at this first stage, giving a swollen gel as a result.

If on the contrary, the polymer-solvent interactions are still strongly enough, the "solvation-unfolding-
swelling" process will continue until all segments are solvated. Thus, the whole loosen coil will diffuse out of
the swollen polymer, dispersing into a solution. At this stage, the disintegration of the swollen mass can be
favoured by stirring, which increases the rate of dissolution.

However, once all the chain segments have been dispersed in the solvent phase, they still retain their coiled
conformation, yet they are now unfolded, fully solvated, and with solvent molecules filling the empty space
between the loosen segments. Hence, the polymer coil, along with solvent molecules held within, adopts a
spheric or ellipsoid form, occupying a volume known as hydrodynamic volume of the polymer coil (Figure 1c).

The particular behaviour shown by polymer molecules, explains the high viscosity of polymer solutions.
Solvent and low molecular weight solutes have comparable molecular size, and the solute does not swell when
dissolving. Since molecular mobility is not restricted, and therefore intermolecular friction does not increase
drastically, the viscosity of the solvent and the solution are similar. But the molecular size of polymer solutes is
much bigger than that of the solvent. In the dissolution process such molecules swell appreciably, restricting
their mobility, and consequently the intermolecular friction increases. The solution in these cases becomes
highly viscous.