2 Workshop on Fats and Oils as Renewable Feedstock for ... - abiosus

L22
New approaches to polymers and composites from plant oils
Selim Küsefoglu, Bogazici University Chemistry Department, Istanbul, Turkey
kusef@boun.edu.tr
Almost all commercially successful polymers and plastics are now synthesized from
petroleum based raw materials. Manufacture of useful polymers from plant oils would
present a number of advantages such as the renewability of the raw materials, fast
biodegradability of the polymers and cheaper prices. Synthesis of polymers from plant oils
is not new: ancient Egyptians used flax oil to protect the wood in their ships. However
synthesis of rigid, load bearing polymers that are suitable for fiber reinforcement is a new
and very active research field.
When an organic chemist looks at a triglyceride the double bonds, the allylic
positions, the carbonyl group and the alfa position to the carbonyl group are noticed as the
only useful positions for derivatization. So the task of the polymer chemist is to synthesize
new monomers from plant oils using these functional groups. The following are some
examples from our efforts in this field.
Epoxidation of the soybean oil double bonds followed by opening of the epoxy ring
with acrylic acid gave acrylated epoxidized soybean oil (AESO) which is a plant oil based
analog of vinyl ester resins. When this monomer is mixed with styrene reactive diluent, a
liquid molding resin is obtained which can be reinforced with glass fiber and can be cured
free radically to give laminates with a tensile strength of 450Mpa (1)
O
O
O
O
O
O
O
O
O
O
O
O
ESO
AESO
COOH
O
O
OH
O
Plant oils can be brominated at the allylic positions easily . Reaction of allylic bromide with
silver isocyanate gives the isocyanate substituted triglyceride. This molecule can be easily
converted to polyurethanes with various diols and polyols and particularly, with hydroxyl
bearing oils such as castor oil. Thus the first example of a polyurethane where both of the
monomers are plant oil based are obtained. The polymer is suitable for the production of
flexible foams. (2)
Acrylated epoxidized soybean oil can be reacted with furylamine in a Michael reaction.
When the amine is the limiting reagent a desired fraction of the acrylate groups can be
preserved for future manipulations. The resulting amine can be easily quaternized with
methyl iodide and the product turns out to be an excellent exfoliating agent for
montmorillonite clay. XRD analysis indicated an increase in intergallery distance from 12
O
O
O
O
O
O
O
O
O
O
O
O
Br
Alilik Bromine SO
AgNCO in THF
R.T.
NCO
Isosiyanatlanmis SO
35