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Polymer Dissolution
What is solubility and what it depends on?
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
spherical or ellipsoid form, occupying a volume known as
hydrodynamic volume of the polymer coil (Figure 1c).
(1)
where ∆Gm is the Gibbs free energy change on mixing, ∆Hm is the
enthalpy change on mixing, T is the absolute temperature, and
∆Sm is the entropy change on mixing. A negative value of the free
energy change on mixing means that the mixing process will
occur spontaneously. Otherwise, two or more phases result from
the mixing process. Since the dissolution of a high molecular
weight polymer is always associated with a very small positive
entropy change, the enthalpy term is the crucial factor in
determining the sign of the Gibbs free energy change. Solubility
parameters were developed to describe the enthalpy of mixing.
(2)
(3)
(4)
Eq. (2) can be rewritten to give the heat of mixing per unit volume
for a binary mixture:
(5)
The heat of mixing must be smaller than the entropic term in Eq.
(1) for polymer–solvent miscibility (∆Gm ≤0): Therefore, the
difference in solubility parameters (δ1 - δ2) must be small for
miscibility or dissolution over the entire volume fraction range.
However, these predictions with the Hildebrand solubility
parameters are made with the absence of any specific
interactions, especially hydrogen bonds. They also do not account
for the effects of morphology (crystallinity) and cross-linking. In
addition, there may be (non-ideal) changes with changes in
temperature and, in many cases, with changes in concentration.
(6)
Boltzmann Equation
According to the Boltzmann equation the number of ways the
solids and solvent molecules can be arranged is given by the
equation.
∆Sm = K ln W (1)
where
K = Boltzmann constant
φs = (3)
φp = (4)
Where
denotes the number of solvent molecules
∆Em = K T [χ Ns φp + Ns ln φs + ln φ p] (5)
The Flory Huggins theory arrives at the equation for total free
energy of dilution based on the following train of thought. There
are two entropy factors which contribute to the free energy of
dilution: one arising from contact between the polymer segments
and solvent molecules, and the other is called conformational
entropy. Thus the overall free energy of dilution will be the sum of
the two terms as follows :
From thermodynamics
χ c = n+ +½
(11)
(φ p)c = 1+
(12)
Here (φ p)c represents the critical composition (i.e. critical volume
fraction of the polymer), corresponding to the critical value χ c
∆E contact = R T [χ φp2 ]
(13)
or
When the experimental osmotic pressure data is extrapolatde to
zero concentration the higher power concentration terms can be
neglected and the eqn gets reduced to
Let's assume C1, C2, and C3 are carbon atoms in the same plane.
According to this, the atom C4 can occupy any place throughout
the circle, which represents the base of a cone originated by the
rotation of the bond E3. The angles of such bonds are symbolized
by w, whereas the location of atom C4 is specified by the internal
angle of rotation l.
For a macromolecule in the solid state, the angle l has a fixed
value due to the restrictions of the network packing. That is why
the possible rotational isomers do not occur. Nevertheless when
this macromolecule is dissolved, the packing disappears and the
angle l can vary widely, originating maximums and minimums of
energy. Thus, the probability of reaching diverse stable
conformations with each minimum of energy is high. On the other
hand, the variation of the internal angle of rotation is associated
to an energy change that, at minimums, is small. Hence, the
chains can move freely to adopt such stable conformations. The
fact that the chains are changing from one conformation to
another is also favored, due to the low potential energy of the
system. All these factors define, therefore, a flexible
macromolecule and from these concepts, the typical random coil
form arises.
q temperature
Polymer Solvent(s) (oC)
Polyethylene n-Hexane 133
n-Hexanol / Xylene (70:30) 170
n-Octane 210
Polypropylene n-Butanol / Carbon Tetrachloride
(atactic) (33:67) 25
n-Butanol / n-Hexane (32:68) 25
Cyclohexanone 92
Polystyrene Benzene / n-Butanol (58:42) 35
Cyclohexane 34-35
Cyclohexanol 79-87
Poly (vinyl acetate) Ethanol 19
Ethanol / Methanol (40:60) 36
Poly (vinyl alcohol) Ethanol / Water (41.5-58.5) 25
Water 97
Poly (vinyl chloride) Cyclohexanone 22
Dimethylformamide 36.5
Polyacrylamide Methanol / Water (2:3) 20
Polymethylmethacry
late Acetone -126
Cyclohexanol 77.6
Toluene -65
Dioxane / Water (85:15) 25
Table 2. q solvents for selected polymers.
[4]
Statistical Parameter
According to what we have been studying so far, dissolved
polymer molecules do not remain fully extended in a stationary
state; instead they adopt a typical random coil form in continuous
motion, changing readily from one conformation to another. When
rotation around C-C simple bonds is hindered, the random coil
conformation is reached only at high temperatures, due to the
thermal energy conferred to the segments.
Figure 6. Maximum value (left) and minimum value (right) for the
end-to-end distance r
(6)
(7)
(8)
Where a is the linear expansion factor, and (r)2o the end-to-end
distance of the unperturbed dimension.
Radius of Gyration
In the case of branched chains, with a large number of ends, it
turns out more appropriate to talk about the square-mean radius
of gyration instead of the end-to-end distance, which is more
applicable to linear polymers. Represented as (s)2, the radius of
gyration is the square mean radius of each one of the elements of
the chain measured from its center of gravity. Although (s)2 is
defined according to:
(9)
(10)
(11)
(12)
(13)
Theta Solvent
Physical Interpretation
Theta Temperature
Reference
1. POLYMER SCIENCE
By V.R.Gowariker, N.V.Viswanathan, Jayadev Sreedhar
2. POLYMER SOLUTIONS
by IWAO TERAOKA
BY Fred W. Billmeyer