Aliena Mari P.

Miranda September 30, 2016

MSE 122
Experiment 3: Free-Radical Polymerization of Styrene in Bulk

I. Introduction

Free-radical polymerization can be achieved through several processes but bulk

polymerization is commonly used in the industry as it is cost-efficient. Bulk polymerization
involves dissolving an initiator in a pure monomer in liquid state. The reaction is then
initiated by heating or exposure to radiation2.
Bulk polymerization is advantageous as it doesnt involve any contaminant and allows
for the production of high molecular weight polymer. The disadvantages of bulk
polymerization are difficulty in heat transfer and a broad distribution of molecular weight.
Polystyrene, an aromatic polymer commonly found in protective packaging and
containers as molded plastic or foam, is produced through addition polymerization 3. PS is
used for these applications because it can be molded easily to suit the needed application and
it is economical to produce.
This experiment is on the production of polystyrene through bulk polymerization, a
method of addition polymerization. In this experiment, styrene monomer was mixed with
benzoyl peroxide and heated for two hours at a temperature range of 75-80C.

Figure 1: Reaction of an initiator and a propragating polystyrene

chain with styrene monomer.4

II. Materials and Set-Up

1. Equipment

Round bottom flask Analytical Balance

Iron stands and clamps Heating mantle
Magnetic stir bars Septum cap
Stirring Rod Buchner funnel
Beakers Thermometer
2. Reagents

Name/Formula Structure Use

Styrene Styrene monomer is
(C8H8) polymerized into
From Sigma- polystyrene
Aldrich
Benzoyl Peroxide Benzoyl peroxide is
used to produce radical
initiators.

Dichloromethane Dichloromethane is used

to dissolve the polymer.

Silicone Oil Oil bath for round

bottom flask during
heating

III. Methodology

7 mL of styrene monomer and 0.5 g of benzoyl peroxide were poured into a round
bottom flask. A magnetic stir bar was added and the round bottom flask was covered with a
rubber septum. The rubber septum was pierced with a syringe head to prevent gases from
building up in the round bottom flask.
The round bottom flask was then placed in a silicon oil bath which was maintained at
a temperature range of 75-80C. A magnetic stirrer was used so that the mixture could be
heated and stirred for a duration of two hours. At the end of the two hours of heating and
stirring, the flask was removed from the silicon oil bath and it was allowed to cool for five
minutes. Approximately 1 mL of dichloromethane was added to dissolve the mixture so that it
could easily pour out of the round bottom flask.
The solution was poured into 200 mL of methanol in a 400 mL beaker. The precipitate
formed was collected using a Buchner funnel. The precipitate was washed with 50 mL
methanol and then removed from the Buchner funnel. The filter paper containing the
precipitate was placed on a watch glass and set aside to dry. In the succeeding days, the
weight of the watch glass was measured to determine the weight of the polymer.
IV. Results

3.5

2.5

2
Mass (g)

1.5

0.5

0
0 20 40 60 80 100 120 140
Time since extraction (hrs)

Figure 2: Chart of precipitate mass measured over time

ExperimentalYield 0.48 g
yield= 100 %= 100 %=7.55 %
TheoreticalYield 6.363 g

V. Discussion

(a) (b) (c)

Figure 2: The styrene solution (a) initially and after (b) five minutes and (c) ten minutes of
heating and stirring.

It was observed that initially the solution was clear before it was heated, but five
minutes into the heating process, the solution turned yellow. Five minutes later, the solution
returned to its initial clear color. Some condensation also formed inside the round bottom
flask. When the solution was removed from the silicon oil bath, the viscosity notably
increased from when it was not heated. The solution was thick, but since polystyrene is
soluble in dichloromethane, dichloromethane was used to dissolve the polystyrene so it
would be easier to pour into the beaker containing the methanol. Unlike dichloromethane,
methanol cannot dissolve polystyrene but it allows the polymer to clump together.
The yield product is significantly low because of the polymerization time.
Polymerization was only carried out for two hours, but literature has shown that at least six
hours is needed to fully polymerize all the styrene monomers used.
Answers to Questions:

1. Free-radical polymerization has to be performed in an oxygen free environment because

oxygen can turn into free radicals which could then interfere with the polymerization by
terminating the polymer growth or by competing with the monomers for the initiator radicals.
Polymerization cannot start until the monomers can compete efficiently for the initiator
radicals1.

2. Solution polymerization is expected to give polymer of equal molecular weight while bulk
polymerization is expected to give a polymer of broad distribution of molecular weight when
conversion rate increases2. Bulk polymerization is expected to give a higher molecular weight
polymer because contaminants are not used in the process, while low molecular weight
polymer is possible in solution polymerization through solvent chain transfer.

3. Literature2 has shown that it takes at least

six hours to fully polymerize styrene, while
the experiment has shown that two hours of
polymerization only converts 7.55% of the
styrene. The data is graphed in Fig. 3.

Figure 3: Graph of conversion vs. time for bulk

polymerization.

References:

[1]C. Wiberg, "Effects of Oxygen Inhibition in Acrylic and Non-Acrylic Free Radical
Systems | Radtech Europe: the European association for the promotion of UV and EB curing
technology", Radtech-europe.com, 1997. [Online]. Available: http://www.radtech-
europe.com/knowledge-center/articles/other/effects-oxygen-inhibition-acrylic-and-non-
acrylic-free-radical. [Accessed: 29- Sep- 2016].
[2]J. Qin, W. Guo and Z. Zhang, "A kinetic study on bulk thermal polymerization of styrene",
Polymer, vol. 43, no. 26, pp. 7521-7527, 2002.
[3] J. Maul, B. G. Frushour, J. R. Kontoff, H. Eichenauer and K.-H. a. S. C. Ott, "Polystyrene
and Styrene Copolymers," in Ullmann's Encyclopedia of Industrial Chemistry, Weinheim,
Wiley, 2007.
[4] M. P. Stevens, Polymer Chemistry: An Introduction, New York: Oxford University Press
Inc., 1999.