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Material-P35.cdx01/05/28
CF3F3CWCl6 / Me4Sn
CF3F3C
n
n+
CF3F3C
£G
WCl6 / R4Sn
nMetathesis
Ballard
ROCO OCOR ROCO OCOR
n n+ 2RCO2H
£G
Durham
7
Precursor routes for conducting polymers
Ring opening metathesis polymerization (ROMP)(Olefin metathesis polymerization)
Radical chain polymerization
Poly(phenylene vinylene)
ClH2C CH2Cl R2SH2C CH2SR2
Cl Cl
Materia-P36.cdx01/05/28
R2SH2C CHSR2
Cl
NaOH
NaOH
CHH2C
SR2
Cl
CH2
Cl
HC
SR2
n£G
-SR2
-HClCH CH
n
AsF5, FeCl3 (unstable), 10 S cm-1
Orientable, 103 S cm-1Stable Solution
8
PPV via Wessling Route
require strong oxidant
(Dow Chemical route)
Anionic chain polymerization
bissulfonium salt
sulfonium polyeletrolyte
Material-P37.cdx01/05/28
Poly(dialkoxyphenylene vinylene)
OR
RO
OR
RO
ClH2C CH2Cl
OR
RO
R2SH2C CH2SR2
Cl Cl
OH
HO
(OR = OMe, OEt, OBu)
NaOH
SR2 = SMe2 , SEt2
SS
CH2
Cl
HC
SR2
n£G
-SR2
-HClCH CH
n
I2, 50 S cm-1 (Stable)Unorientable Unstable Solution
Gel, Precipitation
OR
RO
OR
RO200 - 250oC
,
9
mild oxidant work fine
Substituent effects: 1. solubility: procesibility, quality of film/coating, application potentials 2. e-effect (donating/withdrawing): HOMO/LUMO, bandgap, coloring, redox, e-density, e-polarizability 3. steric hindrance: chain conformation, packing morphology, e-transport
bissulfonium salt
sulfonium polyeletrolyte
RXNaOH
CH2OHCl SR2
Material-P39.cdx01/05/28
Processible Copolymers
H2C CH2 SS
ClCl
+ r
OR
RO
H2C CH2 SS
ClCl
(1+r) NaOH/H2O
0oC, N2
CH2 CH
S
OR
RO
CH2 CH
S
ClCl
1-x x n
Stable Solution
1.Dialysis
2.Casting3. £G
I2 DopableOrientableStable
CH CH
OR
RO
CH CH1-x x
n
Polymer Communciations 261, 28 (1987)C.C. Han, R.W. Lenz, and F.E. Karasz
good electroluminescent materials
10
Orientable Copolymers
CH CH
R
R
CH CH1-x x
n
Polymer XDraw Ratio (L/Lo)
Conductivity (Scm-1)
(Doped with I2)
Homopolymers
PPV
PDMPV
Copolymers
(R = OMe)
(R = OEt)
0%
100%
13%
12%
13%
1
14
110
113
1
< 10-5
51
27428
12500
8.3694
Polymer Communciations 261, 28 (1987)C.C. Han, R.W. Lenz, and F.E. Karasz 11