Substantially Conductive Polymers

Part 05

Mater ial-P35.cdx01/05/28

CF3F3CWCl6 / Me4Sn

CF3F3C

n

n+

CF3F3C

£G

WCl6 / R4SnnMetathesis

BallardROCO 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-HCl

CH CHn

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-HCl

CH CHn

I2, 50 S cm-1 (Stable)Unorientable Unstable Solution

Gel, Precipitation

OR

RO

OR

RO 200 - 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 nStable 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