Research Article Structure and Electrical Study of New ...OMe OMe 4-Methoxyaniline, KI (a) (b) S :...

Research ArticleStructure and Electrical Study of New ChemicallyModified Poly(vinyl chloride)

F Ammari1 M Dardouri1 M Kahlaoui2 and F Meganem1

1Laboratory of Organic Synthesis Faculty of Sciences of Bizerte University of Carthage Jarzouna 7021 Bizerte Tunisia2Laboratory of Materials Physics Faculty of Sciences of Bizerte University of Carthage Jarzouna 7021 Bizerte Tunisia

Correspondence should be addressed to M Kahlaoui kahlaouimessaoudyahoofr

Received 12 March 2015 Revised 20 May 2015 Accepted 26 May 2015

Academic Editor Jose Ramon Leiza

Copyright copy 2015 F Ammari et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The aim of this work was to study the structural and electrical properties of a new polymer obtained by functionalization of acommercial poly(vinyl chloride) (PVC) (Mw= 48000) by grafting aminoalkyl and aminoaryl groupsModified poly(vinyl chloride)was prepared in two steps The structural properties of the polymer were systematically investigated by varieties of techniques asdifferential scanning calorimetric (DSC) thermogravimetry analysis (TG) X-ray diffraction (XRD) and Fourier transform infrared(FTIR) spectroscopy The electrical properties of the polymer were studied by electrochemical impedance spectroscopy (EIS)

1 Introduction

Taking into account its excellent miscibility compatibilityproperties good mechanical strength low energy consump-tion and its low cost [1ndash5] poly(vinyl chloride) (PVC) hasbeen considered as a good candidate polymer for use in agreat variety of electrochemical devices such as high energydensity batteries fuel cells sensors and electrochromicdevices [6ndash8] The development of PVC polymer with highionic conductivity is one of the main objectives in polymerresearch In fact various approaches have been made tomodify the structure of PVC polymer in order to improvetheir electrical electrochemical and mechanical propertiesAmong the modified PVC we found those cited in manyliteratures [9ndash11] In the present work differential scanningcalorimetric (DSC) studies thermogravimetry analysis (TG)X-ray diffraction (XRD) Fourier transform infrared (FTIR)and temperature dependent conductivity were performed ona new polymer obtained by functionalization in two steps of acommercial poly(vinyl chloride) by grafting aminoalkyl andaminoaryl groups

2 Experimental

21 Chemicals The commercial poly(vinyl chloride) Mw =48000 (packed in Switzerland) was purchased from Fluka

diethylenetriamine and 4-methoxyaniline were purchasedfrom Aldrich-Chemistry 7924 Steinheim Germany anddioxane and THF were purchased from Prolabo (GroupsRone Poulenc)

22 Instrumentation Electrochemical Impedance Spectra(EIS) were obtained using a Hewlett-Packard HP 4192 ana-lyzer (99 Washington Street Melrose MA 02176-6024) IRThermo Scientific Nicolet IR 2000 (Verona Road MadisonWI 53711-4495 USA) DSC Setaram DSC 131 (7 LrsquoOratoryStreet 69300 Caluire France) TG Setaram B60 (7 LrsquoOratoryStreet 69300 Caluire France) and XR XrsquoPert Pro darPanalytical min voltage 40 kV and current 30mA (OestlicheRheinbruckenstraszlige 49 76187 Karlsruhe Germany)

23 Structure of Amino-p-anisidine-PVC (P2) Synthesis is

described in our precedent work [11] as shown in Scheme 1

3 Results and Discussion

31 DSC Analysis The DSC diagram (Figure 1) of the com-mercial PVC shows a melting point at 279∘CThe diagram ofthe material (P

2) shows an exothermic peak at 177∘C and an

endothermic transformation at 185∘C

Hindawi Publishing CorporationInternational Journal of Polymer ScienceVolume 2015 Article ID 280325 5 pageshttpdxdoiorg1011552015280325

2 International Journal of Polymer Science

PVCDiethylenetriamine KI

THF 3h 160∘C

NH

NH

NHNHNH

NH

NH

NH

NH

NH NH

NH

NH

NH

NH

NH

NH

NHNH

NH

NH

NH

NH

NH

NH NH

NH

NHII

II Cl

Cl ClCl Cl

Cl

NH2

NH2NH2

NH2

(P1) (P1) (P2)

THF 3h 150∘C

OMeOMe

4-Methoxyaniline KI

(a) (b)

Scheme 1 Structures of (a) amino-PVC (P1) and (b) amino-p-anisidine-PVC (P

2)

100 200 300 400 500

PVCExo

Temperature (∘C)

P2

Figure 1 DSC diagrams of commercial PVC and polymer (P2)

32 TG Analysis In order to study the thermal stabilityof polymer (P

2) TG analysis has been done from room

temperature to 800∘C as shown in Figure 2 It can be seen thatwhen (P

2) is heated at 156ndash169∘C theweight loss is about 3mg

and 38mg while heated at 572ndash577∘C It is due to two factorsincluding the elimination ofHCl andHI groups and completedecomposition of the polymer

33 Analysis byXRD TheX-ray diffraction pattern shows theamorphous nature of the commercial PVC and the studiedpolymer (P

2) (Figure 3)

34 IR Spectroscopy Figure 4 shows the IR spectra of thepowder form of the studied polymer The spectrum of thecommercial PVC shows a high intensity band assigned tothe stretching vibration ]CndashCl at 690 cm

minus1 The spectrum ofP2shows two broad peaks around 338297 and 330942 cmminus1

attributed to the stretching vibration of NH primary aminessome bands of stretching vibration ]C=C (arom) at 1617 1513and 1437 cmminus1 ]CndashO at 1244 and bending vibration bands

100 200 300 400 500 600 700 8000

10

20

30

40

50

60

70

80

Wei

ght l

oss (

mg)

Temperature (∘C)

Figure 2 TG curves of polymer (P2)

10 20 30 40 50 60 70 80 900

50100150200250300350400450500550600

I (au

)

(a)

(b)

2120579 (∘)

(a) Commercial PVC(b) Polymer P2

Figure 3 XRD of commercial PVC and polymer (P2)

International Journal of Polymer Science 3

4000 3500 3000 2500 2000 1500 1000 500

(PVC)

Tran

smiss

ion

()

(P2)

Wave number (cmminus1)

(a)

4000 3500 3000 2500 2000 1500 1000 500

Tran

smiss

ion

()

(P2)


(P2 heated at 190∘C)

(b)

Figure 4 IR spectra of (a) PVC and (P2) and (b) (P

2) and (P

2) heated at 190∘C

12

8

4

0

12840

minusZ

998400998400(Ω

)

Z998400 (Ω)

160∘C170∘C180∘C

200∘C

190∘C

210∘C220∘C

times105

times105

Figure 5 Complex plane impedance plots of polymer (P2) at different temperatures

120575Ct etndashH (Me) at 1332 and 120575Ct etndashH (aromp-sub) at 828 cmminus1 we also

note that the band ]CndashCl at 690 cmminus1 becomes very lowcompared to that corresponding to the PVC as a consequenceto the increase of the number of chlorine atoms substituted bydiethylenetriamine groups The IR spectrum of the polymer(P2) heated at 190∘C shows the appearance of a band of

vibration ]C=C = 1605 cmminus1 and the disappearance of the band

]CndashCl at 690 cmminus1 which indicates the removal of HCl and HI

groups giving rise to a conjugated system having an alternateof single and double bonds

35 Electrical Study

351 Electrical Measurements The powders were ground inan agate mortar and then pressed at 4 tons into cylindricalpellets with 118mm in diameter and 27mm in thicknessElectrochemical Impedance Spectra (EIS) were obtained

using a Hewlett-Packard HP 4192 analyzer The impedancemeasurements were taken in an open circuit using twoelectrode configurations with signal amplitude of 50mVand a frequency band ranging from 5Hz to 13MHz Bothpellet surfaces were coated with silver pastes electrodes whilethe platinum wires attached to the electrodes were used ascurrent collectors All these measurements were performedat equilibrium potential at a temperature ranging between160∘C and 220∘C

352 Electrochemical Characterization Figure 5 shows theNyquist diagram obtained from pellet of amino-p-anisidine-PVC (P

2) between 160∘C and 220∘Cwhich appears as a semi-

circle and the amplitude of this arc is thermally dependentThe impedance spectra plotted in Figure 5 were analyzed byfitting the data with the equivalent circuit shown in Figure 6In this figure119871 corresponds to an inductancewhich is usually


RsL R

CPE

Figure 6 Equivalent circuit used for fitting the impedance data

Ea2 = minus021 eV

Ea1 = 057 eV

minus94

minus96

minus98

minus100

minus102

minus104

minus106

200 205 210 215 220 225 230 235

Arrhenius plot1000T(Kminus1)

ln(120590

T(S

middotcmminus1

K))

Figure 7 Arrhenius plots of the conductivity of polymer (P2) solid

solutions

associated with the platinum current-voltage probes 119877119904is

the ohmic resistance of the amino-p-anisidine-PVC (P2)119877 is

resistance and CPE is a constant phase element representingtime-dependent capacitive elements

(1) dc Conductivity Study For a pellet with thickness 119889 andsection area 119878 the dc conductivity was calculated using thefollowing relation

120590 =1119877times119889

119878 (1)

Activation energies (119864119886) were obtained by fitting the

conductivity data to the Arrhenius relation for thermallyactivated conduction which is calculated using the followingequation

120590 =1198600119879

exp(minus119864119886

119896119879) (2)

where 120590 1198600 119864119886 119896 and 119879 are respectively the conduc-tivity preexponential factor activation energy Boltzmannconstant and absolute temperature

Figure 7 shows the Arrhenius plot of the dc electricalconductivity for the sample named amino-p-anisidine-PVC(P2) in the temperature range 160ndash220∘C As can be seen in

Figure 7 the Arrhenius plot shows a significant curve whichmay be interpreted as a transition behavior of the polymerThis curvature is observed at around 190ndash200∘C and arisesfrom the differences in the conduction mechanism due tothe changes in the behaviors of the polymer at 160ndash190∘Cand 200ndash220∘C temperatures On the other hand most likelythe transport of ions must occur via indirect motion along aconvoluted path restricted to the plasticizer-phase which isresponsible for low conductivity at PVC polymer [4]

The increase in conductivity may be explained by theformation of a conjugate system with the elimination of

ln[120590

(Smiddotcm

minus1)]

ln[f (Hz)]

170∘C180∘C190∘C

200∘C210∘C220∘C

minus115

minus120

minus125

minus130

minus135

120 125 130 135 140

Figure 8 ln(120590) versus ln(119891) for amino-p-anisidine-PVC (P2)

HCl and HI groups as shown in the TG analysis describedpreviously

The observed conductivity of this polymer was equal to216 10minus7 Scm at 190∘C which was higher than 10minus8 Scmfound for the polyacene quinone radical (PAQR) [12] andalso higher than that reported in literature [13] for the poly-mer poly-2-[(4-mercaptophenyl) iminomethyl] phenol (P-4-MPIMP) and polymer-metal complex compounds which isbetween 10minus11 and 10minus10 Scm

(2) FrequencyDependence of acConductivityThedependenceof 120590ac with frequency at different temperature is shown inFigure 8 Its value is related to frequency by the followingrelation [14]

120590ac = 119860 sdot 120596119904 (3)

where 119860 is a temperature dependent constant and 119904 is thepower exponent The evolution of 119904 with temperature istributary to the conduction mechanism

The estimated power exponent 119904 values are shown inTable 1 in terms of temperature This power exponent fluctu-ates with temperature between 084 and 095 in 170∘Cndash220∘Cdomain

Variations of the power exponent 119904 with the tempera-ture do not meet any of the known models such as thequantum mechanical tunneling (QMT) model [15ndash17] theoverlapping-large-polaron tunneling (OLPT) model [16ndash18]and correlated barrier hopping (CBH) model developed byElliott [19 20]

4 Conclusion

This work allowed for studying the new material amino-p-anisidine-PVC (P

2) obtained by functionalization of a PVC

(Mw = 48000) XRD result shows amorphous nature ofP2 The endothermic transformations were confirmed by


Table 1 Power exponent of the polymer (P2) for different tempera-tures

Temperature (∘C) Power exponent 119904170 088180 091190 089200 084210 095220 094

electrical properties These results show that the polymer(P2) may be useful in a great variety of electrochemical

devices such as rechargeable batteries super-capacitors andgas sensors

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

The authors wish to thank the officials of Organic SynthesisLaboratory and Materials Physics Laboratory

References

[1] Z Ahmad N A Al-Awadi and F Al-Sagheer ldquoMorphologythermal stability and visco-elastic properties of polystyrene-poly(vinyl chloride) blendsrdquo Polymer Degradation and Stabilityvol 92 no 6 pp 1025ndash1033 2007

[2] M Tang and W-R Liau ldquoSolvent effect on the miscibilityof poly(4-hydroxystyrene)-poly(ethylene oxide) blendsrdquo Euro-pean Polymer Journal vol 36 no 12 pp 2597ndash2603 2000

[3] K Pielichowski and I Hamerton ldquoCompatible poly(vinyl chlo-ride)chlorinated polyurethane blends thermal characteristicsrdquoEuropean Polymer Journal vol 36 no 1 pp 171ndash181 2000

[4] A M Stephan T P Kumar N G Renganathan S PitchumaniR Thirunakaran and N Muniyandi ldquoIonic conductivity andFT-IR studies on plasticized PVCPMMA blend polymer elec-trolytesrdquo Journal of Power Sources vol 89 no 1 pp 80ndash87 2000

[5] M Alamgir and KM Abraham ldquoLi ion conductive electrolytesbased on poly(vinyl chloride)rdquo Journal of the ElectrochemicalSociety vol 140 no 6 pp L96ndashL97 1993

[6] T Uma T Mahalingam and U Stimming ldquoSolid polymer elec-trolytes based on poly(vinylchloride)-lithium sulfaterdquoMaterialsChemistry and Physics vol 90 no 2-3 pp 239ndash244 2005

[7] S Ramesh and M F Chai ldquoConductivity dielectric behaviorand FTIR studies of highmolecular weight poly(vinylchloride)-lithium triflate polymer electrolytesrdquo Materials Science andEngineering B Solid-State Materials for Advanced Technologyvol 139 no 2-3 pp 240ndash245 2007

[8] S Ramesh A H Yahaya and A K Arof ldquoDielectric behaviourof PVC-based polymer electrolytesrdquo Solid State Ionics vol 152-153 pp 291ndash294 2002

[9] R Vinodh A Ilakkiya S Elamathi and D Sangeetha ldquoA novelanion exchange membrane from polystyrene (ethylene buty-lene) polystyrene Synthesis and characterizationrdquo Materials

Science and Engineering B Solid-State Materials for AdvancedTechnology vol 167 no 1 pp 43ndash50 2010

[10] S Moulay ldquoChemical modification of poly (vinyl chloride)-Stillon the runrdquo Progress in Polymer Science vol 35 no 3 pp 303ndash331 2010

[11] F Ammari and F Meganem ldquoPoly(vinyl chloride) function-alization by aliphatic and aromatic amines application to theextraction of somemetal cationsrdquo Turkish Journal of Chemistryvol 38 pp 638ndash649 2014

[12] B Wang L Ma C Hao and Q Lei ldquoSynthesis of polyacenequinone radical polymers with controllable conductivity andtheir smart electrorheological behaviorrdquo Synthetic Metals vol182 pp 28ndash32 2013

[13] I Kaya and F Baycan ldquoSynthesis characterization con-ductivity band gap and thermal analysis of poly-2-[(4-mercaptophenyl) imino methyl] phenol and some of itspolymerndashmetal complexesrdquo Synthetic Metals vol 157 no 16-17pp 659ndash669 2007

[14] A K Jonscher ldquoThe lsquouniversalrsquo dielectric responserdquoNature vol267 no 5613 pp 673ndash679 1977

[15] I G Austin and N F Mott ldquoPolarons in crystalline and non-crystalline materialsrdquoAdvances in Physics vol 18 no 71 pp 41ndash102 1969

[16] A R Long ldquoFrequency-dependent loss in amorphous semicon-ductorsrdquo Advances in Physics vol 31 no 5 pp 553ndash637 1982

[17] A Ghosh andD Chakravorty ldquoAC conduction in semiconduct-ing CuO-Bi

2O3-P2O5glassesrdquo Journal of Physics Condensed

Matter vol 2 no 24 pp 5365ndash5372 1990[18] M Pollak ldquoTemperature dependence of ac hopping conductiv-

ityrdquo Physical Review vol 138 no 6 pp 1822ndash1826 1965[19] S R Elliott ldquoAc conduction in amorphous chalcogenide and

pnictide semiconductorsrdquoAdvances in Physics vol 36 no 2 pp135ndash217 1987

[20] S R Elliott ldquoA theory of ac conduction in chalcogenideglassesrdquo Philosophical Magazine vol 36 no 6 pp 1291ndash13041977

Submit your manuscripts athttpwwwhindawicom

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


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MaterialsJournal of


Nano

materials


Journal ofNanomaterials


PVCDiethylenetriamine KI

THF 3h 160∘C

NH

NH

NHNHNH

NH

NH

NH

NH

NH NH

NH

NH

NH

NH

NH

NH

NHNH

NH

NH

NH

NH

NH

NH NH

NH

NHII

II Cl

Cl ClCl Cl

Cl

NH2

NH2NH2

NH2

(P1) (P1) (P2)

THF 3h 150∘C

OMeOMe

4-Methoxyaniline KI

(a) (b)

Scheme 1 Structures of (a) amino-PVC (P1) and (b) amino-p-anisidine-PVC (P

2)

100 200 300 400 500

PVCExo

Temperature (∘C)

P2

Figure 1 DSC diagrams of commercial PVC and polymer (P2)

32 TG Analysis In order to study the thermal stabilityof polymer (P

2) TG analysis has been done from room

temperature to 800∘C as shown in Figure 2 It can be seen thatwhen (P

2) is heated at 156ndash169∘C theweight loss is about 3mg

and 38mg while heated at 572ndash577∘C It is due to two factorsincluding the elimination ofHCl andHI groups and completedecomposition of the polymer

33 Analysis byXRD TheX-ray diffraction pattern shows theamorphous nature of the commercial PVC and the studiedpolymer (P

2) (Figure 3)

34 IR Spectroscopy Figure 4 shows the IR spectra of thepowder form of the studied polymer The spectrum of thecommercial PVC shows a high intensity band assigned tothe stretching vibration ]CndashCl at 690 cm

minus1 The spectrum ofP2shows two broad peaks around 338297 and 330942 cmminus1

attributed to the stretching vibration of NH primary aminessome bands of stretching vibration ]C=C (arom) at 1617 1513and 1437 cmminus1 ]CndashO at 1244 and bending vibration bands

100 200 300 400 500 600 700 8000

10

20

30

40

50

60

70

80

Wei

ght l

oss (

mg)

Temperature (∘C)

Figure 2 TG curves of polymer (P2)

10 20 30 40 50 60 70 80 900

50100150200250300350400450500550600

I (au

)

(a)

(b)

2120579 (∘)

(a) Commercial PVC(b) Polymer P2

Figure 3 XRD of commercial PVC and polymer (P2)


4000 3500 3000 2500 2000 1500 1000 500

(PVC)

Tran

smiss

ion

()

(P2)


(a)

4000 3500 3000 2500 2000 1500 1000 500

Tran

smiss

ion

()

(P2)



(b)


2) and (P


12

8

4

0

12840

minusZ

998400998400(Ω

)

Z998400 (Ω)

160∘C170∘C180∘C

200∘C

190∘C

210∘C220∘C

times105

times105







35 Electrical Study







RsL R

CPE


Ea2 = minus021 eV

Ea1 = 057 eV

minus94

minus96

minus98

minus100

minus102

minus104

minus106

200 205 210 215 220 225 230 235


ln(120590

T(S

middotcmminus1

K))


solutions





120590 =1119877times119889

119878 (1)



120590 =1198600119879

exp(minus119864119886

119896119879) (2)





ln[120590

(Smiddotcm

minus1)]

ln[f (Hz)]

170∘C180∘C190∘C

200∘C210∘C220∘C

minus115

minus120

minus125

minus130

minus135

120 125 130 135 140





120590ac = 119860 sdot 120596119904 (3)




4 Conclusion











Acknowledgments


References































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




4000 3500 3000 2500 2000 1500 1000 500

(PVC)

Tran

smiss

ion

()

(P2)


(a)

4000 3500 3000 2500 2000 1500 1000 500

Tran

smiss

ion

()

(P2)



(b)


2) and (P


12

8

4

0

12840

minusZ

998400998400(Ω

)

Z998400 (Ω)

160∘C170∘C180∘C

200∘C

190∘C

210∘C220∘C

times105

times105







35 Electrical Study







RsL R

CPE


Ea2 = minus021 eV

Ea1 = 057 eV

minus94

minus96

minus98

minus100

minus102

minus104

minus106

200 205 210 215 220 225 230 235


ln(120590

T(S

middotcmminus1

K))


solutions





120590 =1119877times119889

119878 (1)



120590 =1198600119879

exp(minus119864119886

119896119879) (2)





ln[120590

(Smiddotcm

minus1)]

ln[f (Hz)]

170∘C180∘C190∘C

200∘C210∘C220∘C

minus115

minus120

minus125

minus130

minus135

120 125 130 135 140





120590ac = 119860 sdot 120596119904 (3)




4 Conclusion











Acknowledgments


References































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




RsL R

CPE


Ea2 = minus021 eV

Ea1 = 057 eV

minus94

minus96

minus98

minus100

minus102

minus104

minus106

200 205 210 215 220 225 230 235


ln(120590

T(S

middotcmminus1

K))


solutions





120590 =1119877times119889

119878 (1)



120590 =1198600119879

exp(minus119864119886

119896119879) (2)





ln[120590

(Smiddotcm

minus1)]

ln[f (Hz)]

170∘C180∘C190∘C

200∘C210∘C220∘C

minus115

minus120

minus125

minus130

minus135

120 125 130 135 140





120590ac = 119860 sdot 120596119904 (3)




4 Conclusion











Acknowledgments


References































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










Acknowledgments


References































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Research Article Structure and Electrical Study of New ...OMe OMe 4-Methoxyaniline, KI (a) (b) S :...

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Transcript of Research Article Structure and Electrical Study of New ...OMe OMe 4-Methoxyaniline, KI (a) (b) S :...