Functionalization of Polybutadiene Using Potassium Peroxymonosulfate (OXONE®) in
the Presence of Phase Transfer Catalyst
M.M.Alavi Nikje*,A.Rafiee.(E-mail:rafiee_28@yahoo.com)Department of chemistry ,faculty
of sciences,Imam Khomeini International University,Qazvin,Iran,P.O.Box:288
There are various methods for the epoxidation of polybutadiene that all of them have their
merits and drowbacks [1 ]. One advantage of modifying polybutadiene by epoxidation of the
double bonds to prepare functional resins is that only a one-step modification of a
commercially available matrix is needed [2 ]. Polymers contain epoxy groups are of interest
as adhesives and composite matrices due to their good shelf life, case of processability and
excellent network mechanical properties[ 3]. Resulting networks also show good slovent and
corrosion resistance and are extremly versatile. Properties of the resin and cured network can
be tailored for specific applications by varying both the epoxy chemistry and the crosslinking
agent used to cure the epoxy[4 ]. Oxone® is a convenient stable source of potassium
peroxymonosulfate and has been used as an oxidizing agent for a number of functional
groups, including alkenes , arenes , amines , imines , sulfides and used for the preparation of
dioxiranes[5].
Epoxidation of polybutadiene is performed in dichloromethane using potassium
peroxymonosulfate (OXONE®) as oxidant and tetra-n-butyl ammonium bromide as phase
transfer catalyst. Various conditions and reaction times are examined in detail . The
epoxidation of varios microstructural polybutadiene was studied by spectroscopic methods
(FT-IR, 1HNMR and 13CNMR). In the 1HNMR the peak at 5.3 ppm , which is attributed to
vinylic protons is shifted to about 2.8-3.0 ppm in the polyepoxide and the peak at about 2.00
ppm , which is attributed to -CH2- protons is shifted to about 1.70 in the polyepoxide .In the
13
CNMR the peak at 130 ppm , which is attributed to vinylic carbon is shifted to about 57
ppm in the polyepoxide . The above results are consistent with the FT-IR data.All ring bonds
, stretching and contracting in phase , were observed at about 1272 cm –1 .
In our experiments was found that reactivity depends on chain microstructure in the following
way : 1,4-cis polybutadiene > 1,4- cis-trans polybutadiene > 1,4- cis and trans and 1,2-vinyl
polybutadiene .The reaction conditions are straight forward and purfication of the modifide
resin is simple . These results render this system promising for the epoxidation of polyene
polymers in a more general way .
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