Radiation Polymerization of 4(Acryloylamido)benzonitrile: Zinc and Copper Complexes
857
drochloride and transition metal nitrates such as Cu(NO3)2 ꢅ
Electron Spin Resonance (ESR)
3H2O and ZnNO3 (Hopkin and Williams Ltd, England) were
used as received. Other chemicals were reagent grade and
used without further purification.
ESR measurements were carried out at room temperature with
a Bruker spectrometer, model ECS 106 in the x-band range
(9.4GHz). The g-values were estimated using the Varian-stan-
dard ‘‘strong-pitch’’ with g ¼ 2.0028. The polymer powder
was placed in the sample tubes. The stretching direction of
the polymer was either parallel or perpendicular to the axis of
the magnetic field.
Monomer Synthesis
The reaction between acryloyl chloride with 4-aminobenzo-
nitrile was carried out in dry acetone, for about 1 h. Saturated
ammonium carbonate solution was added to neutralize the
evolved hydrochloric acid. The solid monomer 4-(acryl-
oylamido)benzonitrile (AMBN) was filtered off, washed
thoroughly with water, and recrystallized from ethanol (m.p.
168ꢁC). Elemental analysis: found C 67.7, H 4.7, N 16.3%,
calcd. C 70.2, H 4.1, N 16.4%.
Atomic Absorption Spectroscopy (AAS)
AAS measurements were carried out with a Perkin-Elmer
5000pc (USA).
Scanning Electron Microscopy (SEM)
The polymer complexed with ZnII, CuII, and ZnII=CuII ions at
room temperature were examined in a model JSM-6300 JEOL
scanning electron microscope (Japan) at 20kV.
Polymerization
The polymer was prepared by radiation-induced polymeriza-
tion of the monomer. The monomer powder was immersed in
dimetylformamide (DMF) in glass ampoules. The mixture in
the glass ampoules was sealed and then subjected to ꢀ-radia-
tion from 60Co with 0.0–2.5 Gy at a dose rate of 0.3 kGy=h
with modulus stress at 50% elongation (M50) as a function
of irradiation dose in atmosphere using a gamma type 4000
from energy authourity of Egypt. The ampoules contents were
poured into a large excess of ethanol and the polymer poly(4-
(acryloylamido)benzonitrile) (PAMBN) was filtered off and
reprecipitated from DMF solution into ethanol. Finally, it
was dried in a vacuum oven till constant weight and analyzed.
Elemental analysis: found C 68.4, H 3.8, N 15.6%, calcd.
C 70.0, H 4.4, N 16.3%.
Thermogravimetry Analysis (TG)
TG was carried out in a dynamic atmosphere of pure nitrogen
gas using a Shimadzu DSC 50 analyzer (Japan) set at a heat-
ing rate of 20ꢁC=min.
References
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Preparation of Amidoxime Polymer
The PAMBN was reacted with 0.25 M hydroxylamine hydro-
chloride (NH2OHꢅ HCl) in ethanol=NaOH at 60 ꢁC for 12h.
The amidoxime polymer (PAMBN-AO) was dried and the
conversion to amidoxime structure was determined by the
disappearance of the cyano groups band from its FTIR spectra.
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Synthesis of Amidoxime Polymer-Metal Complexes
The PAMBN-AO was immersed in 3 M NaOH in a water bath
at 60ꢁC for overnight. The sodium salt of amidoxime polymer
was washed with distilled water and then dried in a vacuum
oven at 50ꢁC. The sodium salt of amidoxime polymer was
reacted with 1.0 wt% Cu(NO3)2 ꢅ 3H2O, ZnNO3, and a mixture
of ZnII=CuII (1:1 mole). The complex was formed immedi-
ately at room temperature. The complexed-metal powder was
characterized using different techniques.
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Nuclear Magnetic Resonance Spectrocopy (NMR)
1H and 13C nuclear magnetic resonance (NMR) spectra
were recorded using a Brucker AVANCE DPX400 MHz
spectrometer.
IR Spectra
IR spectra were measured for the monomer, polymer, and
amidoximated polymer using a Shimadzu 5000 FTIR spec-
trometer. The test samples were used without diluents or
supports.
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