SID2002

INDUSTRIAL POLYMER CHEMISTRY I

LABORATORY REPORT

EXPERIMENT 1:
IDENTIFICATION OF POLYMERS FROM SOLUBILITY TESTS

NAME: NUR ERMA FARISHA BINTI MOHD HALIM SHAH

MATRIC NUMBER: 17174204 / IIV180053
OCCURRENCE: 01
DATE OF EXPERIMENT: 1ST NOVEMBER 2021
DATE OF SUBMISSION: 8TH NOVEMBER 2021
LECTURER: DR DESMOND ANG TECK CHYE
 OBJECTIVE:
To identify two unknown polymer samples using simple solubility test

RESULT AND DISCUSSION

In this experiment two unknown polymer samples were given: A25 and B25 in
amorphous and crystalline form respectively. Both sample were determined by using
simple solubility test based on the flow chart in Figure 1. There are a few general
rules can be apply to identify the polymer using a solubility tests:1
1) Like dissolve like
2) The crystallinity will decrease the solubility
3) The solubility rate increases with short branches molecules which allow the
solvent to penetrate more easily
4) The solubility rate decreases with longer branches since the molecule
entanglement make it harder to be separated

Figure 1: Polymer identification from solubility test

The dissolution of unknown polymers in the given solvent also depends on the
thermodynamic factors: Gibbs free energy, ΔG and the solubility parameters of
solvent, 𝛿𝑠 and solubility parameter of polymer 𝛿𝑝 .

1
Chapter 7: Polymer Solubility and Solutions. Accessed on 2021 Nov 7. Retrieved from
https://www.cheric.org/files/education/cyberlecture/e200201/e200201-701.pdf
 The unknown polymer was dissolved in solvents with different polarities in a small
test tube. The mixing of unknown polymer and solvents gave the Gibbs free energy of
the solution which given by Equation (1):
∆G = ∆H − T∆S …. (Eqn. 1)
∆H: The change in enthalpy of mixing
T: Absolute temperature in the process (in Kelvin)
∆𝑆: The change in entropy of mixing

The dissolution will only took place if ∆G has negative sign which indicates the
spontaneous reaction represent the physical and chemical changes. Absolute
temperature usually have positive value. Meanwhile ∆𝑆 is significantly small and have
positive value when polymer solution is formed. However, ∆H may be either in positive
sign indicates the polymer and solvent are in their lower energy state or negative sign
indicates the solution in its lower energy state which showed the hydrogen bonding
interaction established between polymer and solvent molecules but it must be smaller
than T∆S to obtain negative ∆G to make the polymer be soluble.2

The dissolution observation for both unknown polymers were shown in Table 1 and
Table 2.
Table 1: The solubility test observation for sample A25
Solvent Solubility Test
Water Insoluble
Toluene Insoluble
Cyclohexanone Insoluble
Cresol Insoluble
DMF Insoluble
Xylene Insoluble
Chloroform Insoluble

2
Thermodynamic considerations for polymer solubility. Accessed on 2021, Nov 7. Retrieved from
https://pslc.ws/macrog/property/solpol/ps4.htm
 Table 2: The solubility test observation for sample B25
Solvent Solubility Test
Water Insoluble
Toluene Soluble
Methanol Insoluble
Ethyl acetate Soluble
Acetone Insoluble

In this experiment, the amorphous unknown polymer A25 does not soluble in all the
solvent tested even after it has been warmed in water bath. They neither dissolve nor
became rubber-like structure. Amorphous polymer does not have melting point but they
have a glass transition temperature. The amorphous polymer entangled chain only can
rotate or move in space if temperature reach above the glass transition temperature to
produce a rubbery state.3

Meanwhile, the crystalline unknown polymer B25 took a longer observation period.
The crystalline polymer slowly change into a swollen gel, and became soft after being
stirred in the water bath. The process is slower because the solvent cannot penetrate
into the polymer molecule easily due to the crystallinity, crosslinking and hydrogen
bonding of the polymer. The gel will gradually disintegrates into a true solution and
based on my observation the solution will became a bit cloudy.4

Solubility parameters is important to predict the polymer solubility in the solvent. The
closer the solubility parameters of the solute and the solvent, the more likely the
solubility of the solute in the given solvent. Based on Hildebrand solubility parameters,
if the polymer and solvent have similar polar and hydrogen bonding the rule in Equation
(2) is applied.5
|δs ̶ δp | < 3.6 MPa1/2 ….. Eqn. (2)

3
Amorphous vs. Crystalline Polymers. (2020, Nov 10). Retrieved from
https://www.mcpolymers.com/library/amorphous-vs-crystalline-polymers
4
Ariadne L. Juwono, (2006), Chapter 7: Polymer Solutions. Retrieved from
http://www.ggdckalna1.in/wp-content/uploads/2020/05/polymer-solution.pdf
5
Polymer Solubility and Solubility Parameter. Accessed on 2021, Nov 8. Retrieved from
https://polymerdatabase.com/polymer%20physics/Polymer%20Solubility.html
The polymer sample A25 is Polytetrafluoroethylene which is a synthetic
fluoropolymer. It consist a chain of carbon atoms with two fluorine bonded to each
carbon. The fluorine act as a protective sheath creating a chemically inert and
relatively dense molecule with very strong carbon-fluorine bonds. It is inert to most
chemical and does not melt below 327℃. Based on the calculation using Equation (2)
for one of the insoluble solvent using in Table 1, we will found that:

δs Chloroform = 18.9 J1/2 cm−3/2

𝛿𝑝 PTFE = 13.12 J1/2 cm3/2
|δs ̶ 𝛿𝑝 | = |18.9 ̶ 13.12| J1/2 cm3/2
= 5.78 J1/2 cm3/2 > 3.6 MPa1/2

The calculation proved that PTFE is insoluble in the chloroform. The amorphous PTFE will
not dissolved in any solvent and only a very low molecular weight PTFE may
dissolved to a small degree in perfluorinated high boiling solvents.

In this experiment the most important precaution steps are:

1) Ensure no water get inside the test tube when it being immersed in the water bath
2) Point away the face of test tube during heating it in the water bath to avoid any
incident
3) Do not forget to wear glove during handling the experiment

CONCLUSION
1. Sample 1 (A25)- PTFE (polytetrafluoroethylene)
2. Sample 2 (B25)- PS (polystyrene)
ANSWERS:
1. Calculate the polymer solubility parameter (𝛿𝑝 ) for the polymers that have been
identified
𝛿𝑝 = d’ ΣG/M’

Sample A25:
Polymer: Polytetrafluoroethylene = -[-CF2 CF2 -]𝑛 -
Density: 2.00 g cm−3 (Amorphous)
Molecular mass of repeating unit = 100.02 g mol−1

Group G (J1/2 cm3/2 mol−1 )

2 - CF2 656
ΣG 656

𝛿𝑝 = (density × ΣG) / (molecular mass of repeating unit)

= (2.00 g cm−3 × 656 J1/2 cm3/2 mol−1 ) / 100.02 g mol−1
= 13.12 J1/2 cm3/2

Sample B25:
Polymer: Polystyrene = -[-CH(C6 H5 )CH2 -]-
Density: 1.12 g cm−3 (Crystalline)
Molecular mass of repeating unit = 104.1 g mol−1
Group G (J1/2 cm3/2 mol−1 )
1 - 𝐶𝐻2 280
1 - CH 140
1 - C6 H5 1517
ΣG 1937

𝛿𝑝 = (density × ΣG) / (molecular mass of repeating unit)

= (1.12 g cm−3 × 1937 J1/2 cm3/2 mol−1 ) / 104.1 g mol−1
= 20.84 J1/2 cm3/2
2. Calculate the solvent solubility parameter (𝛿𝑠 ) for one solvent under each of the
following category for the unknown polymer:
δs = [(∆Hv ̶ RT) / (M/d)]1/2

∆Hv : The molar heat of vaporization

M: Molecular mass of solvent
d: Density of solvent

Table 3: Solvent solubility parameters

Note: s = strong hydrogen bonding

m = moderate hydrogen bonding
p = poor hydrogen bonding

i. Solvent for the unknown polymer B25, Polystyrene = Ethyl acetate

δs = 18.6 J1/2 cm−3/2
ii. Non solvent for the unknown polymer B25, Polystyrene = Methanol
δs = 29.5 J1/2 cm−3/2

3.Based on value measured in 1 and 2, comment about the polymer relative solubility
in solvent of both categories (solvent and non-solvent)

Polystyrene and its solvent, Ethyl acetate (moderate hydrogen bonding)

δs = 18.6 J1/2 cm−3/2

𝛿𝑝 = 20.84 J1/2 cm3/2

c = |18.6 ̶ 20.84| J1/2 cm3/2

= 2.24 J1/2 cm3/2

Polystyrene and its non-solvent, Methanol (strong hydrogen bonding)

δs = 29.5 J1/2 cm−3/2

𝛿𝑝 = 20.84 J1/2 cm3/2
 |δs ̶ 𝛿𝑝 | = |29.5 ̶ 20.84| J1/2 cm3/2

= 8.66 J1/2 cm3/2

Normally without strong interaction like hydrogen bonds, the solubility of polymer can be
predicted if |δs ̶ 𝛿𝑝 | < 1. However differences between amorphous and crystalline
polystyrene might influence the polymer density and affect its solubility parameters. The
crystalline polystyrene has entangled constitution oppose the penetration of solvent from
interact with polymer chain easily. Thus cross-linked polymers do not dissolve completely but
they only swell when the solvent diffuse into the polymers.6

In addition the explanation for non-solvent can be clearly shown via the Scathard-Hildebrand
equation: ΔH / VΦs Φ p = (δs ̶ 𝛿𝑝 )2 . From this equation the larger difference value between
polymer and solvent solubility parameter will give higher enthalpy of the solution. Higher
enthalpy give the possibilities for getting a positive sign ∆G which is a non-spontaneous
reaction. Thus the polymer is not soluble in methanol.

4.Discuss on how polymer dissolved in solvent?

Polymer do not dissolve instantaneously. The dissolution involve the disentanglement

of the polymer chains process and the diffusion of the chains through a boundary
layer adjacent to the polymer-solvent interface.7

When an uncross-linked, amorphous, glassy polymer is in contact with a

thermodynamically compatible solvent, the solvent will diffuse into the polymer.8 The
polymer network will swell and form a gel-like swollen layer due to the osmotic activity
of the solvent thus increase the segmental motion along with two separate interfaces,
one between the glassy polymer and gel layer and the other between the gel layer and
the solvent. Further penetration of the solvent, the polymer will continue to expand and
increase its freedom to move. When the solvation process has sufficiently advanced to
allow transitional movement to the chains the substance will separate out to form a
solution.

6
One Part of Chemistry, (2013). Retrieved from https://1chemistry.blogspot.com/2013/04/polymer-solubility-
parameter-and.html
7
Beth A. Miller-Chou, Jack L. Koenig, A review of polymer dissolution, 28: 8, (2003), pp 1223-1270, Retrieved
from https://doi.org/10.1016/S0079-6700(03)00045-5.
8
Beth A. Miller-Chou, Jack L. Koening, A review of polymer dissolution, Prog. Polym. Sci. 28 (2003) 1223–1270.
DOI:10.1016/S0079-6700(03)00045-5