Synthesis of poly(3,4-ethylenedioxythiohene), polyaniline and their metal-composite nano-objects by dispersion polymerization

Muhammad Mumtaz

Description

Sous la direction de Henri Cramail
Thèse soutenue le 26 octobre 2009: Bordeaux 1
Dans l'objectif d'améliorer la mise en forme des polymères semi-conducteurs tels que le poly (3,4-éthylènedioxythiophène) et la polyaniline, nous avons développé leur synthèse par polymérisation en dispersion de leurs monomères respectifs en utilisant le poly(oxyde d'éthylène), le poly (vinyl alcool), le poly [(N-vinylpyrrolidone)-co-(vinyl alcool)] et le poly [(N-vinylpyrrolidone)-b-(vinyl alcool)] comme stabilisants réactifs dans des milieux dispersants aqueux. Des nano-objets de nature et de structure bien définis ont été obtenus. Afin de moduler la conductivité et les propriétés opto-électroniques de ces nano-objets, leurs composites avec des métaux tels que l'or, l'argent et le cuivre ont été préparés en utilisant les sels métalliques correspondants comme co-oxydants au cours de la polymérisation en dispersion. La morphologie des nano-objets a notamment été évaluée par Microscopie Electronique en Transmission, Microscopie Electronique à Balayage, et Microscopie à Force Atomique. Le nature cœur-écorce de ces nano-objets, le niveau de dopage et la présence de métaux dans les nano-composites ont été examinés par spectrométrie de photoélectrons induits par rayons X.
-Poly (34-éthylènedioxythiophène)
-Polymérisation en milieu dispersé
-Stabilisants polymères réactifs
-Poly (oxyde d'éthylène)
-Poly (vinyl alcool)
-Nanocomposites de PEDOT
With the objective to improve the processability of “stiff” semi-conducting polymers, well defined poly(3,4-ethylenedioxythiophene) and polyaniline core-shell nano-objects were synthesized by dispersion polymerization of their respective monomers using poly(ethylene oxide), poly(vinyl alcohol), poly[(N-vinylpyrrolidone)-co-(vinyl alcohol)] and poly[(N-vinylpyrrolidone)-b-(vinyl alcohol)]-based reactive stabilizers in aqueous dispersant media. In order to improve the conductivity and opto-electronic properties of these nano-objects, their composite with gold, silver and copper were prepared using the metal salts as co-oxidants during dispersion polymerization. The morphology of the nano-objects was observed by microscopy analyses such as Transmission Electron Microscopy, Scanning Electron Microscopy, and Atomic Force Microscopy. The core-shell nature of these nano-objects, doping level and the presence of metals in the nano-composites were examined by X-rays Photoelectron Spectroscopy.
Source: http://www.theses.fr/2009BOR13854/document

Informations

• Publié par: Thesee
• Nombre de lectures: 104
• Langue: English
• Poids de l'ouvrage: 12 Mo

Extrait

Nºd`ordre: 3854 THÈSE
Manuscrit provisoire
L’UNIVERSITÉ BORDEAUX-1
ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES
Par MUHAMMAD MUMTAZ
Pour obtenir le grade de
DOCTEUR
SPÉCIALITÉ : POLYMÈRE
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SYNTHESIS OF POLY(3,4-ETHYLENEDIOXYTHIOPHENE),
POLYANILINE AND THEIR METAL-COMPOSITE NANO-
OBJECTS BY DISPERSION POLYMERIZATION
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Date de soutenance: 26 octobre 2009






Jury :

M. Claude CHEVROT, Professeur, Université de Cergy-Pontoise Rapporteur
M. David MECERREYES, Research Head, CIDETEC, Espagne
M. Jaroslav STEJSKAL, Professeur, IMC, Czech Republic Examinateur
M. Georges HADZIIOANNOU, Professeur, Université Bordeaux 1
M. Henry CRAMAIL, Professeur, Université Bordeaux 1 Directeur de thèse
M. Eric CLOUTET, Chargé de Recherche, CNRS, LCPO Invité PUBLICATIONS


M. Mumtaz, C. Labrugere, E. Cloutet, H. Cramail, “Water-borne dispersions of PEDOT
using PNVP-based reactive stabilizers” Macromolecules (submitted)

M. Mumtaz, C. Labrugere, E. Cloutet, H. Cramail, “Synthesis of PEDOT- and PANI-
metal composites particles in aqueous dispersion media” Chemistry of Materials
(submitted)

M. Mumtaz, C. Labrugere, E. Cloutet, H. Cramail, “Synthesis of polyaniline nano-
objects using poly(vinyl alcohol), poly(ethylene oxide), and poly[(N-vinyl pyrrolidone)-co-
(vinyl alcohol)] based reactive Stabilizers” Langmuir, 2009 (accepted)

E. Cloutet, M. Mumtaz, H. Cramail, Synthesis of PEDOT latexes by dispersion
polymerization in aqueous media. Materials Science & Engineering, C: Materials for
Biological Applications 2009), 29, 377-382

M. Mumtaz, E. Ibarboure, C. Labrugere, E. Cloutet, H. Cramail, “Synthesis of PEDOT
Nano-objects Using Poly(vinyl alcohol)-Based Reactive Stabilizers in Aqueous Dispersion”
Macromolecules, 2008, 41, 8964-8970

M. Mumtaz, S. Lecommandoux, E. Cloutet, H. Cramail, “Synthesis of Calibrated
Poly(3,4-ethylenedioxythiophene) Latexes in Aqueous Dispersant Media” Langmuir, 2008,
24, 11911-11920.

M. Mumtaz; A. de Cuendias,; J.-L. Putaux,; Cloutet, Eric; H. Cramail, “Synthesis of
PEDOT nanoparticles and vesicles by dispersion polymerization in alcoholic media”
Macromolecular Rapid Communications. 2006, 27, 1446-1453.


CONFERENCES


M. Mumtaz, E. Cloutet, H. Cramail, “Synthesis of PEDOT nano-objects by dispersion
polymerization in aqueous media (poster)”  International conference ELECMOL’08,
December 8–12, 2008 (Grenoble – HMMNT/Minatec, France)

M. Mumtaz, E. Cloutet, H. Cramail, “Synthesis of π-congugated polylers latexes (poster)”
The 1st Aquitaine Conference on Polymers, October 16-19, 2007,(Arcachon, France)

????????? Acknowledgements


Firstly, I would like to thank Prof. Yves GANANOU and Prof. Henri CRAMAIL to allow me to
work as a PhD student in LCPO. I am really grateful to Prof. Henri CRAMAIL and Dr. Eric
CLOUTET for giving me the chance to do my PhD under their very watchful eye and very kind
supervision in LCPO. They always encouraged me and gave lot of suggestions whenever I
presented my before them. They were very helpful and gave me lot of freedom while doing my
research work and helped me whenever it was needed. They gave me a plenty of their precious
time for discussions during research, writing publications and thesis.
I am indeed thankful to my other colleagues in LCPO particularly Rachid MATMOUR, Anne de
CUENDIAS, Cécile BOUILHAC for their initial support to handle the instruments etc at the
beginning of my PhD work. I would like to thankful to my collaborators without whom my
research would have been considerably more difficult: Christine Labrugere for XPS analysis
discussions about them; Emmanuel IBARBOURE, Jean-Luc PUTAUX and Sabrina LACOMME
for their help in AFM and TEM analysis respectively; Sebastian LECOMMANOUX for SANS
and important discussions about DLS results and Nicolas GUIDOLIN for teaching how to use
DLS and GPC instruments.
I am grateful to Catherine ROULINAT, Corine GONCALVES de CARVALHO, Bernadette
GUILLABERT and Nicole GABRIEL for their help in administrative works. I cannot forget
their ever smiling faces. They treat me like their family member whenever I visited them and feel
them like my mother.
Without a doubt, the best part of my D.Phil was being able to spend my days working alongside,
so many great people like Rachid MATMOUR (Expert in anionic polymerization); Anne de
CUENDIAS (Conducting polymers); Yougang LI and Suresh Kumar (Expert in RAFT and
ATRP and I never forget the time when we use to go to have a cup of coffee every afternoon)
etc.
I am equally thankful to all members of LCPO for their lot of help and moral support. I really grateful to the Pakistani student community in Bordeaux with home I passed excellent
time during my PhD studies. I cannot forget the time we passed together during trips, dinner and
lunch parties, EID celebrations and other occasions. I am also thankful for their services and
contribution for preparing some delicious Pakistani food on the day of my thesis defense
Finally, of course, thanks to my mother, father, wife (Misbah Batool), sister, brothers and friends
for lot of their moral supports and prayers.



Dedications

I feel pleasure to dedicate this thesis to my dear and sweet parents and wife as
without their help, moral support and prayers it was not possible to achieve this
goal.




Muhammad Mumtaz

List of abbreviations

AFM : Atomic Force Microscopy
AlCl : Aluminum chloride 3
AIBN : Azo bis-isobutyro Nitrile
AsF : Arsenic pentafluoride 5
BEDOT : Bis(ethylenedioxythiophene)
Br : Bromine 2
BF : Boron trifloride 3
n-BuLi : n-butyl lithium
CuBr : Copper(II) bromide 2
CuCl : Copper(II) chloride 2
CB : Conduction Band
CMRP : Cobalt Mediated controlled Radical Polymerization
2+Cu : Cupric ion
DBSA : Dodecylbenzene sulfonic acid
DLVO : Derjaguin and Landau, Verwey and Overbeek
DLS : Dynamic Light Scattering
DMSO : Dimethyl sulfoxide
DMF : N,N’-dimethylformamide
DMAEMA : 2-(dimethylamino)ethyl methacrylate
DPMK : Diphenyl methyl potassium
DPTS : 4-(dimethylamino)pyridinium 4-toluenesulfonate
DPn  : Average degree of polymerization
DSC : Differential Scanning Calorimetry
EA : Electronic Affinity
EAP : Electrically Active Polymer
EDOT : ethylenedioxythiophene
EHEC : Ethylhydroxycellulose
2+Fe : Ferrous ion
3+Fe : Ferric ion
FeCl : Ferric chloride 3
Fe(OTs) : Iron (p-toluenesulfonate) 3GPC : Gel Permeation Chromatography
HBr : Hydrobromic acid
HCSA : Camphorsulfonic acid
HFIP : 1,1,1,3,3,3-hexafluoro-2-propanol
H O : Hydrogen peroxide 2 2
H SO : Sulfuric acid 2 4
HOMO : Highest Occupied Molecular Orbital
HCl : Hydrochloric acid
I : Iodine 2
IR : Infra Red
IP : Ionization potential
ITO : Indium tin oxide
KMnO : Potassium permanganate 4
LUMO : Lowest Unoccupied Molecular Orbital
Mn  : Number average molecular weight
M w : Mass average molecular weight
NMP : N-methyl pyrrolidone
(NH ) S O : Ammonium persulfate 4 2 2 8
OCPs : Organic Conducting Polymers
OEGMA : Oligo(ethylene oxide) methacrylate
PAA : Poly(acrylic acid)
PEO : Poly(ethylene oxide)
PNVP : Poly(N-vinylpyrrolidone)
PS : Polystyrene
PPP : Poly(para-phenylene)
PT : Polythiophene
PPy : Polypyrrole
PU : Polyurethane
PANI : Polyaniline
PEDOT : Poly(3,4-ethylenedioxythiophene)
PIL : Polymeric Ionic Liquid
PPV : Poly(p-phenylenevinylene)
PLED : Polymer Light Emitting Diode