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Separation of Polymers by Solvent Fractionation

Objectives:
1. To understand the concept of polymer solubility and fractionation and its related
parameters.
2. To expose to waste polymers which are also polluting agents, eg. Plastic and rubber.
Introduction
The dissolution of polymers depends not only on their physical properties but also on the
chemical structure, such as polarity, molecular weight, branching, crosslinking degree and
crystallinity. Solvent fractionation is that different solubility of polymers in different solvent will
precipitate the polymer from the polymer mixture. Polar macromolecules like poly(acrylic acid),
poly(acrylamide) and polyvinyl alcohol are soluble in water. On the other hand, non-polar
polymers or polymer showing low polarity such as polystyrene, poly(methyl methacrylate),
poly(vinyl chloride) and poly(isobutylene) are soluble in non-polar solvents.
A macromolecule becomes a single phase in solution according to the same
thermodynamics laws as the micromolecular solution substances. However, differences in
molecular size influence the solubility properties of both these substances. For example, a
macromolecule dissolves slowly due to its entangled constitution opposing the penetration of the
solvent, but most polymer-solvent pairs can mix in all of the proportions. On contrary, the
solubility of micromolecules is generally limited to saturated solution.
The solvent of a macromolecule can be considered good by one of these two standards
which are the kinetic standard or the thermodynamic standard. A good solvent from the kinetic
point of view is a solvent that easily dissolves the polymer in a short time. The solubility can be
made faster by decreasing the particle size of the polymer sample. From the thermodynamic
point of view, a good solvent has to be able to strongly interact with the solution substances.
Thus, a good solvent in terms of kinetics is fast while in terms of thermodynamics is efficient.
Generally, solubility of synthetic polymers increases as the molecular weight decreases.
However, properties such as viscosity, strength and flexibility are found to improve with
increasing molecular weight. The solubility of matrix and polymers in the same solvent is critical
for polymer analysis. Certain non-aqueous polymers can simply be dissolved in acetone or
methanol. Based on their solubility, synthetic polymers can be divided in four groups as follows:

Water-soluble polymers: poly(acrylic acid) and poly(ethylene glycol, PEG)


Polar organic-soluble polymers: acrylics and poly(methyl methacrylate, PMMA).
Non-polar organic-soluble polymers: polystyrene (PS), polyvinyl chloride and
polyethylene.
Low solubility polymers: cured polyimide.

Polymer fractionation is defined as the separation of polymers in order to obtain a


homogeneous fraction or component. Fractionation based on the solubility properties is done by
precipitating polymer from its solution through various methods such as:

Mixing solvent
Separating solvent by vapourisation
Temperature reduced

The solvent and precipitate should be chosen so that precipitation occurs over a wide range of
solvent composition, yet is complete before too high a ratio of precipitant to solvent is reached.
Other important considerations are the stability and volatility of the liquids and their ability to
form a highly swollen, mobile gel phase.
Apparatus:
Filter paper, beaker, boiling tube, glass rod, heater, Buchner funnel.
Materials:
Toluene, acetone, methanol, cyclohexanone, PVC [Poly (Vinyl Chloride)], LDPE [Low Density
Polyethylene], PMMA [Poly (Methyl Methacrylate)], PS [Polystyrene]
Result:
Table 1: Weight of polymers
Polymer

LDPE
PVC
PS
PMMA

Initial weight Final weight (g)


(g)
Filter paper +
watch
glass
product
0.5102
37.567
0.5012
37.5896
0.5100
37.5045
0.5035
37.3038

Calculation:
Percentage of yield of LDPE

=
= 97.90%

Percentage of yield of PVC

=
= 96.89%

Watch glass + Product


filter paper
37.0662
37.1040
37.0452
37.0969

0.4995
0.4856
0.4593
0.2069

Percentage of yield of PS

=
= 90.00%

Percentage of yield of PMMA

=
= 41.09%

Discussion:
Solvent extraction of polymer is using the basic principle of like dissolve like principle,
where the non-polar polymer will dissolve in non-polar solvent while polar polymer will dissolve
in the polar solvent. In this experiment, different solvents are used to extract a mixture of
polymers. Poly(methyl methacrylate), PMMA and polystyrene, PS can be dissolved in toluene
while low density polyethylene, LDPE and poly(vinyl chloride), PVC cannot be dissolved in
toluene. The diagrams below show the structures of LDPE, PVC, PS and PMMA polymers.

Diagram 1 Polymer Structure of LDPE, PVC, PS and PMMA (From left to right)

PMMA can be dissolved in toluene although it is a slight polar polymer. This is due to the
hydrophobic effect of the long chain hydrocarbon that form the back bone of the PMMA polymer
which make it more soluble in non-polar organic solvent.
According to the observations, LDPE remained undissolved in toluene after being stirred
for 30 minutes although it is a non-polar polymer, if we just look at its structure from the
diagram above. However, LDPE usually will become a slight polar polymer during the process
of manufacturing. Research has shown that when producing LDPE film, the LDPE film is
slightly polar as it comes out of the T-die. As the LDPE exits the T-die, oxidation occurs and
forms carbonyl groups. Since oxygen has greater affinity for electrons, it acquires a partial
negative charge, becoming electron-rich, while the carbon atom of the carbonyl group becomes
electron-deficient, acquiring a partial positive charge. This unique feature allows LDPE to bond
with polar substrates and makes LDPE a popular choice for many lamination applications.
The precipitate of LDPE and PVC was then dissolved in cyclohexanone to separate the
two components. This is because cyclohexanone is a more polar solvent, and PVC is more polar
than the LDPE, thus PVC can easily dissolve into the cyclohexanone while LDPE remain as

precipitate to be separated. The filtration product containing PVC dissolved in cyclohexanone


was poured into methanol to precipitate out PVC polymer. Since cyclohexanone has higher
polarity and smaller in size compared to the PVC polymer, thus it can easily dissolve into the
methanol and PVC polymer will be precipitated out.
On the other hand, the filtration product consist of PS and PMMA dissolved in toluene
was poured into methanol. Toluene can be dissolved into methanol up to a certain degree due to
the effect of entropy of mixing. When toluene dissolved into methanol, PS and PMMA will be
precipitated out due to the solubility of PS and PMMA in methanol is low. ThePS/PMMA
precipitate was then redissolved with acetone to separate PS and PMMA. This is because PS is
non-polar polymer while PMMA is a slight polar polymer and thus can be dissolved by the
acetone. Again, filtration product containing PMMA dissolved in acetone was poured into
methanol and the mixture of acetone-methanol was filtered. Less precipitate of PMMA obtained
with the filtration product remain in cloudy form, which could be due to the slight polar
properties of the PMMA that make it able to interact with the methanol used and partially
dissolve in methanol, thus causing the loss of PMMA polymer.

Conclusion
Mixture of polymers can be separated by mixing different solvent with different polarity.
A non-polar organic solvent can dissolve non-polar polymer while polar organic solvent can
dissolve polymer with higher polarity. LDPE is a slight polar polymer together with polar PVC
polymer can be separated from non-polar PS and PMMA at the early stage of experiment.
Further separation of polymers can be done by using different solvent system and the polymers
can be recovered easily. The percentage yield of recovery for LDPE, PVC, PS and PMMA are
97.90%, 96.89%, 90.00 % and 41.09 %, respectively.
Questions:
1. By using Smalls equation, calculate the polymer solubility parameter, 2, for PVC,

LDPE, PS and PMMA using the equation below, where the molar attraction
constant per unit for the functional groups are on the table as follows.
2 = E / V = E / M
Functional Group

E (J1/2 cm3/2 mol-1)

Functional Group

E (J1/2 cm3/2 mol-1)

-CH3

143

-COO-

326.5

-CH2

131.5

C=O

263

CH-

86

-CHO

293

32

-OH

226

-O- (ether, acetal)

115

-CN

354.5

-O- (epoxy)

176

-NH, -Cl

180

Molecular mass (M) of repeating unit for:


LDPE = 28 g mol-1
PVC = 62.5 g mol-1
PS = 104 g mol-1
PMMA = 100 g mol-1
Density () of:
LDPE = 0.85 g cm-3
PVC = 1.41 g cm-3
PS = 1.05g cm-3
PMMA = 1.17g cm-3
E of:
LDPE = 263 J1/2 cm3/2 mol-1
PVC = 397.5 J1/2 cm3/2 mol-1
PS = 1734.5 J1/2 cm3/2 mol-1
PMMA = 776 J1/2 cm3/2 mol-1

2 of LDPE = (0.85 g cm-3) (263 J1/2 cm3/2 mol-1) / (28 g mol-1)


= 7.98 J1/2 cm-3/2
2 of PVC = (1.41 g cm-3) (397.5 J1/2 cm3/2 mol-1) / (62.5 g mol-1)
= 8.97 J1/2 cm-3/2
2

of PS = (1.05 g cm-3) (1734.5 J1/2 cm3/2 mol-1) / (104 g mol-1)


= 17.51 J1/2 cm-3/2

2 of PMMA = (1.17 g cm-3) (776 J1/2 cm3/2 mol-1) / (100 g mol-1)


= 9.08 J1/2 cm-3/2

2. Explain how solubility is affected by polymer chain structure.

A polar polymer can be dissolved by polar solvent but not in non-polar solvent and vice
versa for the non-polar polymer. The higher degree of branching of polymer can enhances
the solubility of the polymer due to its smaller size. Crosslinking polymer will reduce the
solubility of the polymer significantly by inhibit the interaction between polymer chains
and solvent molecules, preventing those polymer chains from being transported into
solution.

3. Would processes resembling this experiment be suitable for treating plastic?


No. This is because plastic are made up of tens of thousands of repeating unit, and
dissolving the plastic in a solvent takes a very long time, which is not practical.
References
1. J. Raczkowskaet al. (2005). Effect of Diblock Copolymers on the Film Structure of Spin
Cast Polymer Blends. Journal of Nanostructured Polymers and Nanocomposites 1,
pp.023 033.
2. Mohammad Saleem Khan et al. (2008). Miscibility Studies of PVC/PMMA and
PS/PMMA Blends by Dilute Solution Viscometry and FTIR. African Journal of Pure and
Applied Chemistry, Volume 2 (4) , pp. 041 045.
3. Francesco La Mantia (2002). Handbook of Plastics Recylcing. Shawbury, Shrewsbury,
Shropshire, SY4 4NR, UK: Rapra Technology Limited. Chapter 1, pg. 13 14.