Substantially Conductive Polymers

Part 06

Non-Ionic Precursor Polymer

8

CH2

OBu

BuO

CH

S

Cl

nCH2

OBu

BuO

CH

OBun

BuOH/Pyridine

Room Temperature

Soluble, StableElastomer, Tg = 2.6oC1HNMR, TGA, GPCC. C. Han, R. L. Elsenbaumer

Mol. Cryst. Liq. Cryst. 1990, 189, 183

Thermal Elimination

CH2

OBu

BuO

CH

OBun

CH

OBu

BuO

CHn£G

250 - 300oC

I2, 1 Scm-1 Insoluble

9

Non-Thermal Elimination

CH2

OBu

BuO

CH

OBun

CH

OBu

BuO

CH

SolubleI2, 14 Scm-1

H+ BuOH + H

Butanol Scavengers

CH

OBu

BuO

CH + Butanol Adducts

Butanol Scavengers

Me3SiClMe3SiBrMe3SiIMe2SiCl2(CH3CO)2O(CF3CO)2O

¡ì¡ì ¡ì¡ì ¡ì¡ì ¡ì¡ì

¡ì¡ì ¡ì¡ì

C. C. Han, R. L. ElsenbaumerMol. Cryst. Liq. Cryst. 1990, 189, 183

10

Simultaneous Elimination and Doping

CH2

OBu

BuO

CH

OBun

CH

OBu

BuO

CHn

H+, Solvent

Weak Acid

H+, Solvent

Strong Acid

Neutral Polymer Solution

Doped Polymer Solution

C. C. Han, R. L. ElsenbaumerMol. Cryst. Liq. Cryst. 1990, 189, 183

11

Simultaneous Elimination and Doping

CH2

OMe

MeO

CH

OMen

CH2 CH

OMenS

Weak Acid

Strong AcidNeutral Polymer

Doped Polymer

Weak Acid

Strong AcidNeutral Polymer

Doped Polymer

12

Protonic Acid-Doping of Various Conducting PolymersConductong Polymers Dopants Conditions Conductivity Dopong Level

S/cm mol %

Poly(thienylene vinylene) CH3SO3H in CH3NO2, 20h 2.4 8.7 %

_< 10-4neat, 1 day

31.2 %5.3in CH3NO2, 20h¡E

19.7 %44.1 in CH3NO3, 2hCH3SO3HPoly(phenylene vinylene- co-dimethoxyphenylenevinylene) (90:10) _< 10-7neat

19.7 %31.5in CH3NO2, 50h¡E

10.9 %10.7 in CH3NO2, 3 h 15 minCH3SO3HPoly(phenylene vinylene)

_< 10-7neat

_< 10-7 in CH3NO2¡E

C. C. Han, R. L. ElsenbaumerSynth. Met. 1989, 30, 123

CF3COOH

FeCl3 6H2O

CF3COOH

FeCl3 6H2O

CF3COOH

FeCl3 6H2O

13

Proposed Doping Mechanism

OMe

MeO

OMe

MeO

OMe

MeO

OMe

MeO

H

OMe

MeO

OMe

MeO

OMe

MeO

OMe

MeO

H H

H HDisproportionation

OMe

MeO

OMe

MeO

H H

H H

OMe

MeO

OMe

MeO

Bipolaron13C NMR

Two PolaronsESRUV-vis-NIR

C. C. Han, R. L. ElsenbaumerSynth. Met. 1989, 30, 123

16

Non-thermal Elimination

CH2

OBu

BuO

CH

OBun Partial

Elimination

CH

OBu

BuO

CHm

CH2

OBu

BuO

CH

OBun-m

Soluble, OrientableLiquid Crystalline

C. C. Han, R. L. ElsenbaumerMol. Cryst. Liq. Cryst. 1990, 189, 183

17

1. Conventional Liquid Crystalline Polymers

etc. etc.

etc. etc.

RigidPlanar

FlexibleNon-Planar

2. Partially Eliminated Precursor Polymers

CH2

OR

RO

CH

ORj

CH

OR

RO

CHi

18