INDUSTRIAL POLYMER CHEMISTRY

EXPERIMENT 1
IDENTIFICATION OF POLYMERS FROM SOLUBILITY
TESTS

1
Objective

To identify polymer using solubility test

Introduction

Solubility parameters were initially developed to guide solvent selection in the paint and
coatings industry. Today, they are widely used in in many other fields to predict miscibility and
solubility of polymers, chemical resistance, and permeation rates. Solubility parameters are also
often used in industry to predict compatibility of polymers, chemical resistance, swelling of
cured elastomers by solvents, permeation rates of solvents, and even to
characterize the surfaces of pigments, fibers, and fillers

One of the most important application of solubility parameters is the prediction of polymer
solubility in solvents. The closer the solubility parameters of the solute and the solvent are, the
more likely the solubility of the solute in the given solvent.
In the case of polymers, there are several rules of thumb for selecting suitable solvents:
1. Using Hildebrand solubility parameters, if the polymer (p) and the solvent (s) have
similar polar and hydrogen bonding parameter, following simple rule applies: 

|δs - δp| ≤ 3.6 MPa1/2

2. Using Hansen solubility parameters, an approximate spherical "volume" of solubility

with radius R can be drawn up for each solute. Only solvents that have Hansen solubility
parameters within this volume are likely to dissolve the polymer in question:

[4(δd2 - δd1)2 + (δp2 - δp1)2 + (δh2 - δh1)2]1/2 ≤ R

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Methodology

Materials and Apparatus

1. Small test -tubes (13 mm x 100 mm), measuring cylinder, glass stirring rod and water
bath.
2. Unknown polymer samples, different type of solvents (refer flow chart 1.1)

Polymer Identification

2 unknown polymer samples was provided for identification. 0.001 g of the polymer sample
was placed in small test-tube and 5 ml of solvent was added for the test. The test-tube was
stirred with a glass rod. The dissolution process can be made faster by heating the test tube in a
hot water bath in the fume cupboard.
A soluble polymer will form a homogeneous solution with the solvent (solvent category), while
an insoluble polymer will remain as a separate phase from the solvent (non-solvent category).
The solubility test is considered negative if i) the two phases still remain after stirring with a
glass rod or ii) two phases are formed again after the solution temperature reduced to room
temperature.
The following flow-chart must be used as a guide to identify the unknown polymers. Use the
solvent indicated down the chart. If the polymer is soluble in the solvent or the test result is
positive, move towards the right arm of the chart. However, if the polymer is insoluble (test
result is negative), move towards the left arm of the chart Continue the solubility test until the
type of polymer is discovered.

Flowchart 1.1 : Polymer identification from solubility test

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Result & Calculation

Sample Code : Z10 Sample Code : H10

Structure

Poly(methyl methacrylate) Poly (vinyl chloride)

Polymer Solubility Parameter 19.0715 J 1 /2 cm3/ 2 19.2456 J 1 /2 cm3/ 2

Polymer : Poly(methyl methacrylate)

Density : 1.17 g cm−3

Molecular mass of repeating unit : 100.12 g/mol.

Group G( J 1 /2 cm3/ 2 mol−1)

2-CH 3 840
1-CH 2 280
1-C- 0
O=C-O 512
ΣG 1632

δ p= ( density x ΣG )/(molecular mass of repeating unit)

= (1.17 g cm−3 x 1632 J 1 /2 cm3/ 2 mol−1)/ 100.12 g/mol

= 19.0715 J 1 /2 cm3/ 2

δ s(Acetone) = 20.0 ( J cm¿¿−3)1/ 2 ¿

Polymer : Poly(vinyl chloride)

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Density : 1.35 g cm−3

Molecular mass of repeating unit : 62.50 g/mol.

Group G( J 1 /2 cm3/ 2 mol−1)

1-CH 2 280
1-CH 140
1-CI 471
ΣG 891

δ p= ( density x ΣG )/(molecular mass of repeating unit)

= (1.35 g cm−3 x 891 J 1 /2 cm3/ 2 mol−1)/ 62.50 g/mol

= 19.2456 J 1 /2 cm3/ 2

δ s(Cyclohexanone) = 19.5 ( J cm¿¿−3)1/ 2 ¿

Discussion

For poly(methyl methacrylate), the solvent used to dissolve the polymer is acetone. The
polymer is in crystalline state. The polymer solubility parameter, δ p for poly(methyl
methacrylate) is 19.0715 J 1 /2 cm3/ 2 while the solvent solubility parameter, δ s is 20.0
( J cm¿¿−3)1/ 2 ¿. As we can see, the value between δ p and δ s is quite similar. The closer the
solubility parameters of the solute and the solvent are, the more likely the solubility of the
solute in the given solvent.

For poly(vinyl chloride), the solvent used to dissolve the polymer is cyclohexanone. The polymer
is in amorphous state. The polymer solubility parameter,δ p for poly(vinyl chloride) is 19.2456
J 1 /2 cm3/ 2 while the solvent solubility parameter, δ s is 19.5( J cm¿¿−3) ¿. As we can see, the
1/ 2

value betweenδ p and δ s is quite similar. When the solubility parameter for polymer and solvent
are closer to each other , the higher the solubility of the polymer in the solvent.

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. We say the segments are now
"solvated" instead of "aggregated", as they were in the solid state.

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

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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 crosslinked 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 favored 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.

Conclusion

The unknown polymers was identified.

Poly(methyl methacrylate)

δ p= 19.0715 J 1 /2 cm3/ 2

δ s(Acetone) = 20.0 ( J cm¿¿−3)1/ 2 ¿

Poly(vinyl chloride)

δ p = 19.2456 J 1 /2 cm3/ 2

δ s(Cyclohexanone) = 19.5 ( J cm¿¿−3)1/ 2 ¿

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References

1. Miller-Chou, B. A., & Koenig, J. L. (2003). A review of polymer dissolution. Progress in Polymer

Science, 28(8), 1223-1270.

2. Koenhen, D. M., & Smolders, C. A. (1975). The determination of solubility parameters of solvents
and polymers by means of correlations with other physical quantities. Journal of Applied Polymer
Science, 19(4), 1163-1179.