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Vibrational Spectroscopy for Polymer Characterization

Iris Benardete S4619714
i.benardete@student.rug.nl
17 April 2023

Abstract
In this experiment, the rate of polymerization of BADGE-MA and styrene mixtures of different styrene and
cumene hydroperoxide concentrations were studied under different conditions. The mixtures were put into
different temperatures of 80, 100 and 120°C and the results were analyzed by Raman spectroscopy. The optimal
temperature for the samples A, D and G were found to be 120°C while the optimal polymerization temperature
for the mixtures B, C and F was concluded to be 100°C. For the kinetic analysis, the effect of an iron catalyst on
the time of curing was analyzed through Raman Spectroscopy. The highest conversion rate was given by mixture
G. No trend between the rate of polymerization and styrene concentration was determined.

Introduction
The polymerization of crosslinked polymers is initiated by radicals, which propagate to grow polymer chains,
and the chains are crosslinked to form a rigid solid (glass-like material). In this experiment, Raman spectroscopy
is used to monitor the extent of conversion of alkene monomers during and after curing. Two different methods
are used to initiate polymerization: thermal decomposition of alkyl peroxides and metal-catalyzed decomposition
of alkyl peroxides. The goal of this experiment is to study the rate of polymerization of a mixture of styrene and
BADGE-MA with an iron(II) catalyst and to analyze how the concentration of the catalyst, styrene, and cumene
hydroperoxide initiator affects the time profile for curing.

Theory
Raman Spectroscopy1:
Raman spectroscopy is an analytical technique used to study the vibrational modes of molecules. It involves the
interaction of a sample with monochromatic light, which causes the molecules to undergo scattering, resulting
in the emission of photons at different wavelengths. By measuring the intensity and frequency of these scattered
photons, valuable information about the sample's chemical composition and structure can be obtained. In this
experiment, Raman spectroscopy was used to monitor the extent of conversion of alkene monomers during and
after curing.
Mechanism:
The radical polymerization of the monomers styrene
and BADGE-MA is initiated by cumene
hydroperoxide, which forms free radicals through
either thermal decomposition or redox reaction with
iron (II) ions. First, cumene hydroperoxide is
homolytically cleaved into two free radicals, cumyl
peroxyl and hydroxyl radicals. These free radicals
react with the monomers, styrene and BADGE-MA,
to form the corresponding carbon-centered radicals.
The radical addition to the pi bond of the monomers
follows the anti-Markovnikov rule to form the most
stable carbon radical. This results in the formation
of a growing polymer chain with a new radical
active site that can react with more monomers,
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continuing the chain growth. Finally, termination occurs when two growing polymer chains combine, yielding
a higher molecular weight polymer that no
longer has a radical active site available for
further reaction. This stops the chain growth
and terminates the polymerization process.
Figure 1. Mechanism of the radical polymerization of the monomers styrene and BADGE-MA, with cumene hydroperoxide as the initiator

Experimental
A monomer mixture consisting of BADGE-MA (7.257 g, 21.9 mmol, 1 eq) and styrene (1.089 g, 9.7 mmol,
6.78 * 10-3 eq) was provided. Additional styrene (0.3624 g, 3.42 *10-3 mmol, 17.62*10-5 eq ) was added to the
mixture to reach the ratio of 1: 0.20. Lastly, cumene hydroperoxide (1006 mg) was added to the mixture and
the vial was mixed with the vortex mixer until the mixture was fully homogenous. Then, the mixture was put
into 4 different vials, each vial having approximately 1.5–2 mL of the monomer mixture obtained. Before
starting the experiments, the Raman spectrum of one of the vials were recorded. For the thermal
polymerization experiment, three vials were put into different sand baths with temperatures of 80, 100 and 120
o
C for 20 minutes. The caps of the vials were loosened to prevent pressure building up. After the 20 minutes
were completed, the vials were put into a cold sand bath to cool them down. The vials were analyzed by
Raman spectroscopy (λ=785nm). For the reaction progress monitoring experiment, a metal catalyst, Borch-
oxy-coat 1410 (19.6*10-6 mL), was added to the fourth vial. The vial was mixed in the vortex mixer and
analyzed by Raman spectroscopy (λ=785nm).

Analysis & Discussion

BADGE-MA : Styrene (g:g)
1 : 0.20 1 : 0.25 1 : 0.30
Milligrams of 10 A B C
Cumene
20 D E F
hydroperoxide per
gram of resin 30 G H I
Table 1. Analyzed mixture content’s

1. Thermal Analysis
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Figure 2. Alkene integral vs. temperature plots for different mixtures (A, B, C, D, F, G)

The plots in figure 3 shows the integral of the alkene peak against temperatures of 80, 100 and 120°C for different
mixtures (A, B, C, D, F, G). The data of the mixtures E, H and I were corrupted during the experiment which
may be caused by the breakage of the corresponding vials. When the vials are heated to 80, 100, and 120 degrees
Celsius, the temperature of the sample is increased, which leads to changes in the molecular environment of the
alkene functional groups in the sample. So, increased temperature can cause thermal degradation or reaction of
the alkene functional groups. Firstly, the integral of sample A and G decreases gradually as the temperature is
increased, which concludes that the sample goes through complete decomposition and the optimal temperature
is 120°C. The optimal polymerization temperature for sample B, C and F is 100°C as the integral value is the
lowest and the integral values for the other temperatures show a sharp increase when compared 100°C. Lastly,
sample D shows increased activity at 100 and 120°C which concludes that the optimal temperature for the
sample’s polymerization is 100 and 120°C. Since all mixtures contain different concentrations of the monomers,
the optimal temperature varies among the samples but it is mostly 100 or 120°C. This concludes that, as the
temperature increases, the alkene functional group’s activity increases and reacts more rapidly. So, if shorter
polymer chains are wanted to be synthesized, cooler temperatures should be used.
Kinetic Analysis:

Figure 3. Integral of the alkene peak against temperature graph for Figure 4. Conversion against time graph for different samples
different samples

Figure 3 displays the integral of the alkene peak over time graph for the mixtures A, B, D, F, G, H and I.
Sufficient uncorrupted data from samples C and E were not obtained and therefore is not included in the plot.
The data collected from mixture F was also corrupted and thus, cannot be analyzed. The graph shows changes
in the total amount of the alkene functional group present in the sample over a certain period of time. The alkene
peak is used to quantify the amount of the alkene functional group in the sample, which means that lower integral
values correspond to more monomers reacting and more double bonds being broken. Mixtures A and H reach
the glass formation phase the fastest but since H starts with a higher initial alkene amount, sample H has a higher
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degree of polymerization. Mixture G shows a gradual decrease, which indicates a slower reaction and
degradation process. The next mixture in the graph is sample B, which is almost a straight line indicating a low
degree of polymerization. Lastly, the slowest samples are I and D. Sample D displays a rapid decrease at first,
indicating that the alkene functional group is reacting quickly in the first seconds. Overall, no effect of cumene
hydroperoxide or styrene concentration on the integral alkene peak of the samples have been found.
Figure 4 shows the conversion over time graph for the samples A, B, D, F, G, H and I. The data collected from
sample F is corrupted and therefore is not suitable for analysis. The highest conversion belongs to mixture G
which is also verified from the integral graph since it shows the highest and slowest decrease. Samples A and H
come next, which is also seen from the integral graph as they reach the glass formation phase the fastest. Finally,
mixtures D, B and I have the lowest conversions, respectively. Once again, the styrene and cumene
hydroperoxide concentration has no effect on the conversion of the samples. It would have been expected that
the styrene concentration would increase the rate of polymerization due to increasing the viscosity of the mixture
and allowing the molecules to move and react faster, but this prediction is not confirmed from the results as the
highest conversion belongs to sample G with the lowest styrene concentration.

Conclusion
In conclusion, it was determined that the different styrene and cumene hydroperoxide concentrations has no
effect on the rate of polymerization. Repeating the experiment could have been more determining to understand
if there is a trend between them. As the temperature was increased from 80°C, the degree of polymerization was
optimized at 100°C for mixtures B, C and F, while it was optimized at 120°C for the mixtures A, D and G. The
highest conversion belonged to sample G indicating that the alkene functional groups reacted the most and
therefore had the highest degree of polymerization.

References

[1] Libretexts. “4.3: Raman Spectroscopy.” Chemistry LibreTexts, Libretexts, 28 Aug. 2022,
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Physical_Methods_in_Chemistry_and_N
ano_Science_(Barron)/04%3A_Chemical_Speciation/4.03%3A_Raman_Spectroscopy.

[2] Student manual practicum for Macromolecular Chemistry Practical. April 2023.