Atom Transfer Radical Polymerization of Acrylated Epoxidized Soybean Oil .

Rhys South and Adam Puderbaugh

Bioengineering Department, Summer RET, Iowa State University
INTRODUCTION
The limited availability of petroleum based polymers and the current emphasis on green
technologies has caused an increased interest in polymers derived from renewable biological
sources. Soybean and corn are the two predominant locally produced crops that can be
synthesized into bio-polymers. This project utilizes soybean oil since it is readily available
and cost-competitive with synthetic rubber feedstocks, e.g. butadiene, and is composed of
approximately 60% poly unsaturated fat, that when acrylated, brings the possibility of being
polymerized using different polymerization techniques, see Figure 3.
The goal of the project is to create a bio-polymer using Atom Transfer Radical
Polymerization (ATRP). In polymer chemistry , living polymerizations are used to gain control
over polymerization systems. Living polymerization is desirable because you can control or
eliminate chain breaking reaction such as termination and transfer. ATRP, see Figure 1, is a
living radical polymerization system that under the optimal parameters has the potential to
greatly reduce or even suppress the amount of chain breaking reactions. This occurs from
low radical concentrations that shift the equilibrium between active and dormant species Figure 3.- H-NMR spectrum for AESBO, reproduced from 4.
towards the dormant species, therefore controlling the rate of reaction. Remedying the
shortcomings of other living radical systems, ATRP is a robust system that provides control RESULTS
over polymer chain molecular weights and works with multiple classes of monomers such as Figure 5.- Glass transition temperature of the 0.6 toluene sample at 1440 minutes.
Samples from the cyclohexane run appeared to phase separate, indicating that constituents were not .
styrenes, acrylates, methacrylates, and acrylonitriles. 1
dissolving in this solvent, furthermore no further testing was conducted. Both the THF run and Toluene
run samples appear to dissolve and stay dissolved. CONCLUSIONS
Samples ran using THF were dried and their molecular weight was calculated using Gel
Permeation Chromatography (GPC) equipped with a light scattering and a refractive index detector. The Cyclohexane proved to be a poor choice for a solvent as phase separation of the
results were compared to that of the monomer and revealed that the THF samples did not polymerize, samples was evident. THF showed promise as solvent, but due to its low boiling point
likely due to the low reaction temperature. No further testing was done on the THF run samples. no evidence polymerization was observed. GPC testing of the toluene samples
Samples ran using toluene with low monomer to solvent concentration (0.2 and 0.5) did not show a revealed some polymerization at the lower solvent concentrations. Furthermore for
considerable changes in molecular weight in the 24 hours of reaction time. Samples with 0.6 monomer future experiments low solvent concentrations and longer reaction times will be
Figure 1.- Shows the ATRP mechanisms, where Pn-X is the initiator, Mt is the transition metal compound, L is concentration showed polymer chains of around 15 kilo-Daltons, see Figure 4a & 4b, that seemed to desirable.
the ligand, k is the reaction rate, and X is the halogen. Reproduced from 3. disappear as the reaction proceeded due to cross linking of the chains. . Samples with 0.8 monomer
concentration showed polymer chains of around 14 kilo-Daltons, see Figure 4c, but this chains seemed to FUTURE WORK
remain in that molecular weight for the complete 24 hours.
MATERIALS AND METHODS
Many more reactions will need to be completed and studied to determine the best
ATRP was used as the polymerization technique to synthesize poly-soybean oil. Acrylated Differential Scanning Calorimetry (DSC) tests were performed on the toluene samples and showed a glass parameters to reduce the amount of unreacted monomer and cross-linkage while
epoxidized soy bean oil (AESBO), was used as the monomer and used without any further transition (Tg) around -37.7°C, see Figure 5. b) having a relatively monodisperse polymer, see Figure 6.
purification, copper chloride (CuCl) used as the catalyst, benzyl chloride (Benzyl-Cl), as the
initiator, and pentamethyldiethylenetriamine (PMDETA) as the ligand.

All reactions were performed with oxygen-free techniques using an Argon

atmosphere. All samples were polymerized using same amounts of catalyst, ligand, and
initiator. Three control variables were changed for these experiments: type of solvent,
reaction temperature, and the ratio of solvent to monomer.

The first run was made using cyclohexane as a solvent at a temperature of 70°C, a)
the second run, tetrahydrofuran (THF) at 55°C, and the third, toluene at 100°C
(Experimental temperatures were decided according to the boiling points of each of the
solvents). For all the three runs five different ratios of solvent to monomer (by mass) were
reacted for 24 hours, aliquots were drawn at intervals of 30, 60, 90, 120, 150, 180, 240, 360,
480, 720, and 1440 minutes. Figure 2b & 2c show the color change as the reaction
progressed. All the samples were dried in the vacuum oven to remove the solvent. c) Figure 6.- GPC curves for the unreactive monomer and the polymerized molecule.
a) b) c)
ACKNOWLEDGEMENTS
Calvin Benson
Nacu Hernandez
Eric W Cochran

Figure 2.- a) Shows cross-linked samples of the cyclohexane run, sample were cross-linked due to high
temperatures in drying oven that reactivated the reaction. b) & c) Shows the reaction progress of the THF and
Toluene run respectively. Note color change is related to the oxidation progression of copper.
REFRENCES
1. How to Make Polymer Chains…ect. Gaynor, S. G. ;Matyjaszewski, K. Amer. Chem. Soc.,1998,
24,396
2. Tongurai, C. Thammasat Int .J. Sc. Tech., Vol.13, 2008
3. Matyjaszewski, K. “Development of ATRP”. Matyjaszewski Polymer Group. 2011. Carnegie
Mellon. 7/27/2011. http://www.cmu.edu/maty/development-atrp/index.html
Figure 4.- a) & b) GPC curves for the different reaction times of the 0.6 toluene samples. c) Shows the GPC curve for
4. New sheet molding compound resins from soybean oil.Jue Lu, Shrikant Khot, Richard P. Wool.
the 0.8 Toluene samples. Polymer 46 (2005) 71–80