1.

1 Free-radical polymerization of styrene

In this work, the free radical polymerization of styrene is conducted in a dilatometer, which allows
observing the polymerization by volume change. The effect of either the temperature or the initiator
concentration on polymerization time is studied and compared to the theoretical calculations.
Polystyrene is typically an amorphous polymer with a glass transition temperature of 100 °C.1

1.1.1 Free radical radical polymerization in a dilatometer

The free radical initiated chain polymerization can usually be divided to three steps: initiation,
propagation and termination.2

In the initiation step, the initiator molecule dissociates into two radicals, which then combine with
monomer molecules, creating a new radicals, which begin the propagation step.

In the propagation step, new monomer molecules are added to the radical and thus the polymer
chain grows, until a termination reaction stops it. The termination of the radicals may occur either by
combination or disproportionation.

The reactions are presented in scheme 1.1.1.

Initiation
I 
kd
2R
R   M 
ki
M1 

Propagation
M n   M  M n 1 
p k

Termination
M n   M m  
k tc
M n m (Combination)
M n   M m   M n  M m (Disproportionation)
k td

Scheme 1.1.1 Steps of free radical chain polymerization

In free radical polymerization, the conversion (X) of monomer can be calculated using formula
1.1.1:

  f I 0  
0.5

X  1  exp  2k p   1  exp 0.5k d t  (1.1.1)

  k d kt  

where

kp is the chain propagation rate constant (dm3/(mol s))

kt is the chain termination rate constant (dm3/(mol s))
kd is the initiator dissociation rate constant (1/s)
f is the efficiency of the initiator

I0 is the initiator concentration

The values of constants kp ja kt are obtained from figure 1.1.1 and 1.1.2. The initiator dissociation
constant for 2,2´-azobisisobutyronitrile (AIBN) can be calculated using the Arrhenius equation
(1.1.2). The frequency factor and activation energy for AIBN are obtained according to Dixon. 3
 7.00

6.00 y = -4960x + 20,3

5.00

4.00
ln kp

3.00

2.00

1.00

0.00
0.0028 0.003 0.0032 0.0034 0.0036 0.0038
1/T (1/K)

Figure 1.1.1 Experimentally determined dependence of the chain propagation constant kp on the
reaction temperature. 4

20,0

18,0
ln kt

16,0

14,0
y = -4020x + 30

12,0
0,0028 0,0030 0,0032 0,0034 0,0036 0,0038
1/T (1/K)

Figure 1.1.2 Experimentally determined dependence of the chain termination constant kt on the
reaction temperature.4
Arrhenius equation:

 E 
k d  A exp  (1.1.2)
 RT 

where

kd is the reaction rate constant (1/s)

A is the AIBN frequency factor in styrene (1.29*1015 1/s)
E is the activation energy of AIBN in styrene (127.6 kJ 1/mol)
R is the universal gas constant (8.314 J 1/(mol K))
T is the temperature (K)
The efficiency (f) of AIBN for styrene polymerization is obtained from figure 1.1.3, where [M] is the
concentration of styrene.

Figure 1.1.3 The efficiency of AIBN for styrene polymerization.2

The rate of polymerization can be measured using density, refractive index, viscosity or light
absorption. The changes in density of a polymerization mixture can be measured precisely using a
dilatometer.

The conversion (X) of the monomer is directly proportional to the change in volume of the reaction
mixture, according to equation (1.1.3):

1 V0  V 
X  100 (1.1.3)
V V0

where

V is the relative shrinkage for complete polymerization (0<V<1)

V0 is the volume of the reaction mixture at time t = 0 (cm3)
V is the volume of the reaction mixture at time t

The volume of the polymerization mixture is read from the scale of the dilatometer during the
polymerization. The values of the scale are proportional to volume according to equation 1.1.4:

V0  V  ah0  h  (1.1.4)

where

a is the slope of the dilatometer calibration curve (a<0)

h0 is the dilatometer scale reading at time t = 0
h is the dilatometer scale reading at time t
By combining equations 1.1.3 and 1.1.4, the conversion X can be presented using the dilatometer
readings according to equation 1.1.5:

a h0  h 
X  100 (1.1.5)
V V0

The calibration curve of the dilatometer used in this laboratory work is presented in figure 1.1.4. The
relative shrinkage for complete polymerization (V) is dependent on the temperature, according to
figure 1.1.5. The dependence of the density of styrene on the temperature is presented in figure
1.1.6.

17.00
16.50
16.00
tilavuus (ml)

15.50
15.00
14.50
14.00
13.50
13.00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
dilatom etrin lukem a

Figure 1.1.4 The calibration curve for the dilatometer.

20.0
19.5
19.0
18.5
V (%)

18.0
T (°C)  V (%)
17.5
60 17,0
17.0
80 18,37
16.5 90 20,0
16.0
60 65 70 75 80 85 90
T (°C)

Figure 1.1.5 The effect of temperature on the relative shrinkage for complete polymerization (V)
for the polymerization of styrene.5
 0.94

0.92
0.90

tiheys (g/ml)
0.88
0.86

0.84
0.82

0.80
0.78
0 20 40 60 80 100 120 140 160
T (°C)

Figure 1.1.6 The effect of temperature on the density of styrene. 6

 
1.1.2 Work procedure

In this work, two polymerizations are conducted using either two different temperatures or initiator
concentrations. A diagram of the dilatometer apparatus is presented in figure 1.1.7. Styrene and
AIBN are stored in the fridge and denatured technical ethanol can be found in the work place. The
material safety data sheets of each chemical must be read before performing the work and protective
gloves and goggles are mandatory when handling the chemicals. A respirator must be used when
handling styrene.

Typpi

2
3

4 1
1-3 Kaksitiehana
4 Kolmitiehana 7
5 Suukappale 5
6 Päärynäkolvi
7 Dilatometri

Figure 1.1.7 Dilatometer apparatus.

The polymerization is conducted to reach a 10 % conversion, so the time needed for this has to be
calculated beforehand.

First, a thermostated water bath is adjusted to the polymerization temperature. Before performing
the polymerization, the operation of the dilatometer is practiced with acetone, then the apparatus is
dried.

Before operating the valves of the apparatus, make sure that the nitrogen gas is closed.
1. Practicing/rinsing with acetone

 The flask containing fresh acetone is connected.

 Close the cap 5.

 Valve 2 is closed, valve 3 is opened and the three way valve 4 is turned to open position.

 Open the nitrogen flow adjustment valve slowly to push the monomer/initiator solution into the
dilatometer.

 When the dilatometer is adequately filled, the nitrogen flow is stopped, the valve 2 is opened and
the three way valve 4 is turned to recycle. The liquid on both sides of the dilatometer are now at
the same level.

 The cap 5 is removed.

 Valves 2 and 3 are closed and the tree-way valve is turned to recycle.

 Acetone is driven back to pear-shaped flask using small nitrogen flow. The flask is removed and
emptied into waste bottle reserved for the lab work.

 Practicing is repeated until the use of dilatometer is approved by the instructor. The dilatometer
is rinsed three times with acetone (fresh acetone each time) between each polymerization and at
the end of the work.

The proper amount of initiator is weighed in the pear-shaped two-neck flask and connected to the
dilatometer. The weighed amount of styrene is then added and initiator is allowed to dissolve during
nitrogen bubbling.

Since oxygen inhibits the polymerization, the reaction mixture is bubbled with nitrogen gas for 10 –
15 minutes before starting.

2. Nitrogen purging of the apparatus and the monomer:

 The flask is connected.

 The three-way valve number 4 is turned to recycle.

 The cap 5 is removed, valves 1 and 2 are opened and valve 3 is closed.

 Check that the nitrogen flow adjustment valve is closed.

 Open the nitrogen main valve completely.

 Open the nitrogen flow adjustment valve slowly until bubbling begins.

3. Filling of the dilatometer

 Close the cap 5.

 Valve 2 is closed, valve 3 is opened and the three way valve 4 is turned to open position.

 Open the nitrogen flow adjustment valve slowly to push the monomer/initiator solution into the
dilatometer.

 When the dilatometer is adequately filled, the nitrogen flow is stopped, the valve 2 is opened and
the three way valve 4 is turned to recycle. The liquid on both sides of the dilatometer are now at
the same level.

 If the dilatometer contains bubbles, it has to be emptied and filled again.

4. Polymerization

 When the filling procedure is succesfully completed, the dilatometer is put in the water bath.

 Due to heat expansion, the liquid levels will rise for few minutes.

 Take note on the reading from the dilatometer scale when the heat expansion has stopped.

 The volume of the liquid will decrease during polymerization and dilatometer readings are written
down during suitable intervals; the conversion of the monomer is calculated using equation 1.1.5.

5. Emptying of the dilatometer

 The cap 5 is removed.

 Valves 2 and 3 are closed and the tree-way valve is turned to recycle.

 The reaction mixture is now driven to an empty, clean pear-shaped flask using small nitrogen
flow. Two samples for 1H-NMR and GPC are taken from this mixture using a pipette (3-5 drops
for each analysis) The 1H-NMR sample is collected to disposable capped vial and deuterated
 chloroform (1ml) is added. The GPC sample is put in a test tube and 5 ml of normal chloroform is
added.

6. Precipitation of polystyrene

 The contents of the pear-shaped flask is emptied to 200 ml of technical ethanol while stirring.

 The obtained precipitate is filtrated, rinsed with a small amount of ethanol and finally dried
overnight at 50 °C.

 The conversion is calculated gravimetrically from the weight of the precipitate and the result is
compared to the results obtained using the dilatometer and to the theoretical conversion.

7. Cleaning of the dilatometer

 The dilatometer is rinsed three times with acetone (fresh acetone each time) between each
polymerization and at the end of the work (see 1. Practicing/rinsing with acetone).

 The boiling point of acetone is 56 °C, so the dilatometer has to be out of the heated water bath
when cleaning.

 The apparatus is allowed to dry using nitrogen flow.

Anything containing styrene, acetone or ethanol shall not be poured to the sewer. Waste chemicals
are collected into waste bottles reserved for the lab work.

1.1.3 Laboratory report

The laboratory report should be written according to “the guide to writing literature and lab reports”
(http://chemat.tkk.fi/en/studies/study_programme/degree_programme_of_chemical_technology/kirj
aopas_eng_1.pdf)

The conversions (X) calculated from dilatometer readings and polymerization rates (dX/dt) are
presented. The results are compared to the theoretical calculations and to the gravimetric results as
well as 1H-NMR results. The effect of reaction conditions to the obtained molecular weights (obtained
from GPC results) is discussed.
The success of the polymerization is evaluated and possible interfering factors are estimated. In
addition, the equation 1.1.1 is deduced and the structure of polystyrene is presented. Examples of
other polymers are sought from the literature that can be synthesized in the same manner.

To the report belongs also short essays (1-2 pages) about two (2) articles about free-radical
polymerization of styrene. Find as new article as possible. The essays are added to the report as
appendices.

                                                            
1.  Miller, R.L., Crystallographic Data and Melting Point for Various Polymers. Teoksessa Polymer Handbook, toim. 
J. Brandrup, E.H. Immergut ja E.A. Grulke, 4. painos, John Wiley & Sons, USA 1999, s. VI/211.  
2.  Odian, G., Principles of polymerization, 4. painos, John & Wiley Sons, USA 2004, ss. 198‐349.  
3.  Dixon, K.W., Decomposition Rates of Organic Free Radical Initiators. Teoksessa Polymer Handbook, toim. J. 
Brandrup, E.H. Immergut ja E.A. Grulke, 4. painos, John Wiley & Sons, USA 1999, s. II/4. 
4.  Eastmond, G.C., Kinetic Data for Homogeneous Free‐Radical Polymerizations of Various Monomers. Teoksessa 
Comprehensive Chemical Kinetics, toim. C.H. Bamford ja C.F.H. Tipper, vol 14A, Elsevier Scientific Publishing 
Company, Amsterdam 1976, ss. 157‐161. 
5.  Braun, D. ja Disselhoff, G., Kinetics of Copolymerizations: 1. Dilatometric Investigation of the Copolymerizations 
of Benzyl Methacrylate, Styrene and Methyl Methacrylate, Polymer 8 (1977) 963‐966. 
6.  Coulter, K.E. ja Kehde, H., Styrene Polymers (Monomers). Teoksessa Encyclopedia of Polymer Science and 
Technology, toim. N.M. Bikales, H.F. Mark ja N.G. Gaylord, vol 13, John Wiley & Sons, New York 1970, ss. 135‐
155.