الفهرس 
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Abstract
Due to the essential importance of conductive polymers and its
entrance in many vital industrial applications such as antistatic coatings,
shielding materials against electromagnetic interference (EMI), materials for
rechargeable batteries, capacitors and super capacitors, electrochromic devices
(smart windows), and a variety of electrochemical sensors. Semiconducting
polymers and oligomers can be used in more high-tech devices such as lightemitting
diodes (LEDs), field-effect transistors FETs, photovoltaic solar cells,
and solid-state injection lasers.
So in this work we try to reach to a series of polymers and copolymers
of p- phenylenediamine can obey these vital applications and improve their
properties by using waste product which also eco-friendly material (Egg
Shell). Egg Shell was added to polymers and copolymers of pphenylenediamine
in two forms in nano scale 50-100nm (ESN) and in micro
scale 0.2μ (ESG) with different concentrations (1%) 0.02gm and (2%)
0.04gm, furthermore egg shell in two forms combined to Carbon nano tubes
(CNT+ESG) and ( CNT+ESN) and added to polymers and copolymers of pphenylenediamine.
This work divided to three categories
(1) Preparation of polyp-phenylenediamine (PpPDA) with additives ESG,
ESN, CNT, (CNT+ESG) and (CNT+ESN)) and comparing their results
with the other copolymers of p-phenylenediamine with Ethylene Glycol
and Glycerol with the same additives.
(2) Preparation of copolymers p-phenylenediamine with ethylene glycol
(poly(pPDA/EG) with different ratios (1:1), (1:2) and (2:1) and studying
effect of additive of ES and CNT with different concentrations on the
prepared copolymers.
(3) Preparation of copolymers p-phenylenediamine with glycerol
(poly(pPDA/Gl) with different ratios (1:1), (1:2) and (2:1) and studying
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effect of additive of ES and CNT with different concentrations on the
prepared copolymers.
Firstly, Polyp-phenylenediamine (PpPDA) was prepared by
Oxidative polymerization with molecular weight 14500. The structure was
confirmed by IR, H1NMR and Raman spectroscopy. In IR spectroscopy the
two characteristic peaks of quinonoid and benzenoid structure of PpPDA
appears at 1300 cm-1 and 1500 cm-1 respectively. The peak at 3450 cm-1
appears due to N-H deformation vibrations. The H1 NMR spectrum
displayed the strongest doublet peak at 5.6 ppm due to —NH2 protons; four
doublets centered at 6.9–7.2 ppm due to —NH— protons; and broad weak
peaks at 7.7–7.9 ppm due to the protons on 1,2,4,5-tetrasubstituted benzene
rings. While two characteristic bands of PpPDA were detected at 1528 cm-1
for the C–C benzenoid rings and 1395 cm-1 for quinoid rings deformation
appears in Raman spectroscopy.
Addition of additives influence clearly on morphology of PpPDA
that’s appears clearly in X-ray which improve the crystanility of net polymer.
TEM shows good dispersion of additives in polymer matrix. While the effect
of addition of additives with different concentrations (1%) 0.02 gm and (2%)
0.04 gm to PpPDA is also studied according to thermal, electrical and
mechanical properties. It was found that addition of ES both nano and ground
form with CNT of concentration 0.04 gm(2%) gives better thermal stability,
electrical and hardness values than the 0.02 gm (1%) concentration. Where
the residue at 800 0C of 0.04gm PpPDA/ (CNT+ESG) is 95.92% and 0.04 gm
PpPDA/ (CNT+ESN) reaches to 99.39%. While electrical conductivity of the
nanocomposites are also increased reaches to 10-6 Ohm-1 Cm-1 and 10-5
Ohm-1 cm-1 respectively compared with PpPDA which consider insulator
material this differed and increased is due to the electron mobility on the
conjugated polymer that increased by the presence of CNT and ES which fill
the interface of polymer matrix. The hardness appears a moderate values of
PpPDA and its nanocomposites at 0.04 gm (ESN+CNT) with different values
of pressure at 1Kg and 5Kg and it was observed that as the pressure increase,
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the hardness values also increased that is attributed to the compression
pressure which used for preparation of pellets effect on physical properties and
on the residual porosity that greatly influence on the mechanical properties of
the polymer.
Copolymerization of Poly p phenylenediamine with ethylene glycol
(Poly(pPDA/EG)) was carried out by condensation polymerization with
different ratios (1:1), (1:2) and (2:1) with molecular weights13680, 17266 and
21600 respectively. The chemical structures of prepared copolymers of
Poly(pPDA/EG) were confirmed by IR spectroscopy where a broad band at
3332,3127 and 3445 cm-1 of N-H group stretching vibrations and 1600,1684
and 1643 cm-1 band for N-H group bending as respectively of (1:1), (1:2) and
(2:1) ratios. 1301, 1307 and 1308 cm-1 peaks were attributed to the C-N
stretching in the benzenoid unit. The beaks at 1462, 1403 and 1390 cm-1 were
attributed to C-H bending of CH2 of EG unit, also the clear peak at 1500 cm-1
for all ratio related to the benzenoid ring. The peaks at 830, 826 and 833 cm-1
for ring substituted, while existence of peaks of C-O stretching at 1110, 1135
and 1133cm-1 respectively. On the other hand, the peaks at 1640-1690 cm-1 of
C=NH and 3500 cm-1 of free NH2 were disappeared which confirmed that the
PpPDA not formed but the copolymer occurred. Also, the peak at 3590 cm-1 of
-OH alcoholic of ethylene glycol was disappeared which confirmed the
formation of copolymer in ratio (2:1). At the same time, the peak at 2592 cm-1
proved the duplicated of the-[NH-CH2CH2-O]- in the repeated unit in the ratio
1:2 only. On the other hand the structures also confirmed by H1NMR, peaks at
6.92-7.1 ppm due to —NH— protons adjacent to alkane chain and peak at
6.58-6.66 ppm for -NH- terminal in the repeating unit. While the peak for
proton -OH terminal at 3.39 ppm and proton for -CH2CH2 at 3.81 ppm
confirmed the presence of copolymer with ratio 1:1 while the absence of the
terminal amino group at 6.58-6.66 ppm and presence of the duplicated peaks
at 3.39- 3.44 ppm for second hydroxyl group confirmed the copolymer with
ratio (1:2). On contrast, the disappear of two -OH terminal and the presence
of two terminal amino group at 6.58-6.66 ppm which confirmed the
copolymer with ratio (2:1).
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It was found that all prepared copolymers of (Poly(pPDA/EG) of
different ratios shows good performance in thermal stability, electrical
properties and hardness values compared to PpPDA due to presence of EG
unit that have ability to form H bond that improve the physical properties of
the copolymer than that polymer itself.
All prepared copolymers of (Poly (pPDA/EG) were treated with
different concentration 1% (0.02 gm) and 2% (0.04gm) of ESG, ESN, CNT,
(CNT+ESG) and (CNT+ESN) and the entrance of this fillers are confirmed by
the characteristic peak of CaCo3 at 712 cm-1 in IR spectra. While the
morphology of the prepared copolymers affected clearly due to this additions
that’s appears in XRD which influence in the crystallinity of copolymers. The
spread of ESN and CNT in the copolymer matrix show clearly in TEM
pictures that show a good dispersion of this fillers in the copolymer matrix. It
was found that physical properties of composite and nanocomposite of
poly(pPDA/EG) affects seriously with addition of this fillers of ES and CNT
with different concentrations 1% (0.02 gm) and 2% (0.04gm) .We found that
thermal stability was enhanced with high concentration of fillers, the residues
at 600 0C of 0.04gm (2%) Poly(PpDA/EG)+(CNT+ESN) of ratios (1:1),
(1:2)and (2:1) are 61.77% , 58.80% and 62.20% respectively. While electrical
measurements of nanocomposite increased due to such addition which reaches
to 8x10-5, 1.58x 10-4 and 2.5x 10-5 Ohm-1 Cm-1 at 0.04gm (2%) CNT+ESN.
This increase in conductivity attributed to increasing of charge carriers.
On the other hand higher values of mechanical properties represented
in hardness of Poly (pPDA/EG) is due to presence of ethylene glycol units that
effect on the compatibility of the polymer. As the compression pressure
increase, the hardness increase. It was found that increasing the ratio of
ethylene glycol monomer, hardness also increase this is due to hydrogen bond
which cause compatibility of the copolymer. Egg shell reinforced the
copolymers nanocomposite this may be attributed to the fact that the eggshell
particles contains high percentage of CaCO3 and that increase the resistance of
the copolymer to deformation so the hardness value of the ESN reinforced the
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copolymers nanocomposite is more than that of neat copolymers, then the
hardness value increases in the 0.04gm (2%) (CNT+ESN) more than 0.02
gm(1%) for all ratio of the copolymers.
Finally Copolymerization of Poly p phenylenediamine with Glycerol
(Poly (pPDA/Gl)) was synthetized by condensation polymerization with
different ratios (1:1), (1:2) and (2:1) the average molecular weight 16560,
20160 and 24030 respectively. The chemical structures of all prepared
copolymers of Poly (pPDA/Gl) were characterized by IR spectroscopy, their
structures confirmed by the presence of bands of NH stretching and bending,
CN stretching, CO stretching, CH of CH2 bending, benzenoid ring and ring
substituted. The peak belong alcoholic -OH of the glycerol at 3304, 3724 and
3633 cm-1 respectively with the ratio 1:1, 1:2 and 2:1. On the other hand the
structures also confirmed by H1NMR, where the structures of the three
expected copolymers (Poly pPDA /Gl 1:1), (Poly pPDA/Gl 1:2) and (Poly
pPDA/Gl 2:1) have special peaks for each one. Peaks at 3.22- 3.35 ppm
attributed to the third hydroxy group of the glycerol. While raman
spectroscopy also confirm the structure of the three copolymers.
The results show that the copolymerization of p phenylenediamine
with glycerol give satisfied thermal stability, high performance in electrical
measurements and high resistance for deformation represented in hardness
values than the PpPDA itself.
Copolymers of Poly (pPDA/Gl) were treated with different concentration 1%
(0.02 gm) and 2% (0.04 gm) of ESG, ESN, CNT, (CNT+ESG) and
(CNT+ESN). The morphology of the prepared copolymers affected clearly
due to this additions that’s appears in XRD where it is increase crystanility of
copolymers. The spread of ESN and CNT in the copolymer matrix shows
clearly in TEM pictures where there is good dispersion of fillers in the
copolymer matrix. As a result of this addition of fillers to the copolymers of
Poly(pPDA/Gl), physical properties of composite and nanocomposite clearly
change. We found that thermal stability was enhanced with high concentration
of fillers, the residues at 800 0c of 0.04 gm Poly(pPDA/Gl) + (CNT+ESN) of
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ratios (1:1), (1:2) and (2:1) are 43.3%, 39.1 and 39.5% respectively. While the
electrical conductivity of the three copolymers of (polypPDA/Gl) with
different ratio give the same behavior of (polyp PDA/EG), with increasing the
ratio of glycerol (1:2), the conductivity was increased, The conductivity of
(PpPDA/Gl) 1:2 was 8.46x 10-6 which the highest value than that of
(PpPDA/Gl) 1:1 = 4.0x10-6 and (PpPDA/Gl) 2:1 =2.9x10-6. With increasing
the ratio of glycerol in (PpPDA/Gl) 1:2, the electron density is higher than the
other ratio. Due to the effective dispersion of filler in the copolymers, the
electrical conductivity for the copolymers was enhanced. Depending on the
result, the best enhancement was for 0.04gm (2%) of (ESN+CNT) for the ratio
1:1, 1:2 and 2:1 which reaches to 5.46x 10-4, 1.2x 10-3 and 1.8x10-5.
Poly(pPDA/Gl) copolymer with different ratios and their
nanocomposites shows higher values of the hardness at ratio 2:1, this is
attributed to presence of (CH2OH) of glycerol units that increase the hydrogen
bond which cause the cross linked that greatly influence the physical
properties of the copolymer. In the nanocomposites with different
concentration 1% (0.02 gm) and 2% (0.04 gm) of (CNT+ESN) show higher
values, this is attributed to presence of CNT and ESN that increase the
resistance of copolymer to the higher loads that is illustrate disappear of
hardness values at low load 1Kg.