LAB REPORT # 4

The Polymerization of Polyethylacrylate from Ethyl Acrylate

Monomer

Damir Karimov
Lab instructor: Eugene Douglass

Nazarbayev University
2015

Purpose:

to understand the mechanism of solution and emulsion polymerization processes

to perform solution and emulsion polymerization of different monomers

Instruments and Tools:

300mL Erlenmeyer flask, 50mL beakers, 200mL beakers

Materials and Reagents:

ethyl acrylate, 0.1 M potassium bromate, KBrO 3, 0.45 M sodium hydrogen sulfite,
NaHSO3, 5 M NaCl, acetone, CH3COCH3,
Introduction:
In this lab experiment, two different methods of polymerization were performed. Firstly,
acrylic acid was used to make a solution polymerization of polyacrylic acid. Also, ethyl acrylate
was used to prepare an emulsion polymerization of polyethyl acrylate. The procedure method
was almost identical for both monomers.

Ethyl acrylate

Acrylic acid

Today, emulsion polymerization is widely used in industrial and commercial process for
water-insoluble monomers. The system of emulsion polymerization consists of three types of
particles: monomer droplets, inactive micelles in which polymerization is not occurring and
active micelles in which polymerization is occurring. Emulsion may be defined as a stable
colloidal suspension, consisting of an immiscible liquid dispersed and held in another liquid by
an emulsifier (Parrish, 2015). Overall, emulsion polymerization occurs in three steps. Firstly,
polymer particles formed by the decomposition of initiator. Then they form short oligomers for
futher polymerization. Oligomers are brought together surfactants, creating micelles in the
polymer chain. These surfactants stabilize the nature of oligomers, which further stimulate the
development of free radicals. In second step, particles increase their size by oligomer free
radicals. Finally, the solution is free of monomers and rate of polymerization decreases.

(Douglass, 2015).
From picture above, it is clear seen that emulsion polymerization shows different rate
behavior depending on relative rates of initiation, propagation and termination. In interval I,
particle nucleation occurs and polymerization rate increases with time as particle number
increases. Interval I is the shortest and takes about 10-15% conversion. In interval II, the
polymerization rate is constant or slightly increases with time. In this interval, the polymer
particles increase their size and monomer droplets decrease. As the monomer droplets disappear,
II interval would be ended. After interval II, almost 70% conversion is finished. In interval III,
the monomer concentration decreases with time and polymerization rate steadily decreases.
Finally, 100% conversion is achieved.
In order to initiate emulsion polymerization, a water soluble initiator is used. Due to the
fact that initiator is water soluble and monomer is insoluble, the rate of polymerization is lower

comparing other polymerization methods. Thus, emulsion polymerization forms higher

molecular weight polymers. However, there are some limitations in emulsion polymerizations.
For instance, cationic, anionic, condensation or ring-opening polymerizations are not compatible
with water. Thus, only free-radical polymerization is used for emulsion.

Procedure:

30 ml of 5% ethyl acrylate was placed in a 250mL Erlenmeyer flask.

5 ml of 0.1 M potassium bromate solution was added to 250mL Erlenmeyer
flask.
5 ml of 0.45 M sodium hydrogen sulfite solution was also added to solution
The flask was swirled to mix the contents thoroughly
The reaction proceeded for about 15 minutes and at this time the flask was
shaken occasionally during this time.
The emulsion was poured into 30 ml of 5 M sodium chloride solution to
coagulate the polymer.
The polymer was removed with tweezers.
Results:
Mass of obtained polyethyl acrylate = 0.43711g
Density of ethyl acrylate = 0.9405 g/mL;

%yield = ((0.43711g) / (0.9406g/ml * 30ml)) * 100% = 1.5%

Discussion:

The low percent yield of final polymer result in different procedural errors that were
made during experiment. In the part, when initiator should react with monomer for 15minutes,
the flask should be shaken properly and well enough for the reaction to proceed. In addition, this
mistake lead to the fact that not all monomer did not react fully with initiator, it resulted that
monomer did not convert into polymer.
In this experiment, free radical emulsion polymerization of ethyl acrylate was performed.
The overall mechanism of how reaction proceeds is shown below:

Conclusion:
In this lab experiment, the nature of emulsion polymerization of polystyrene was
examined. Students became familiar with the mechanism of free radical emulsion polymerization
in practice. However, not all polymerization reactions proceed successfully and in this lab
experiment we observed one of these cases.

References:

Douglass E. 2015. Emulsion polymerization, lecture slides distributed in Polymer

Chemisty II, January 2015, Nazarbayev University.
Odian, George G., and George Odian. Principles of polymerization. Vol. 3. New York:
Wiley-Interscience, 2004.
Parrish D. 2015. Emulsion polymerization. Retrieved 31 January, 2015 from
http://pslc.ws/macrog/emulsion.htm