Special Topics on Materials Chemistry

材 化 特 論
Part III
Conducting polymers

國 立 清 華 大 學 化 學 系
 
韓 建 中 教 授 授課

1
2000 Nobel Prize : Conducting Polymers (Since 1977)
Profs. MacDiarmid / Shirakawa / Heeger
(Chemist / Polymer Chemist / Physicist)

2
Conducting Polymers

Polyacetylene
Polyaromatics ( )n
( CH CH )n (aromatic + vinyl)
Polyphenylene Polyphenylene Vinylene
Polyheteroaromatics ( S
)n (
S
CH CH )
n
Polythiophene Polythienylene Vinylene

( )n ( CH CH )
N N n
R R
Polypyrrole Polypyrylene Vinylene

( )n ( CH CH)n
O O
Polyfuran Polyfurylene Vinylene
( NH)
n
Polyaniline
( VersiconTM ) (aromatic + lone pair e) 3
Key Features of Intrinsically
Conductive Polymers
I. Highly Conjugated Backbones
II. Polymer Backbones need to be ionized (doped) to be conductive
Doping Reaction

- e, X
(Charge carriers)
n +e n Cations
(oxidation) X p-type
Insulator Conductor

+ e, M
Anions
n -e n
(reduction) n-type
M
Insulator Conductor
Oxidant : FeCl3, Fe(OTs)3, AsF5, I2, Br2, Cl2 Reductant : RLi, Naph-Li+
Anode : Oxidation Cathode : Reduction
p-type and n-type conductors
Doping by Chemical, Electrochemical, Photochemical means
Doping is Reversible ( 10-11 - 10+3 S/cm )
4
SPECTRUM
SPECTRUM OF
OF CONDUCTIVIES
CONDUCTIVIES

Copper
(S/cm)
105 ohm-1 cm-1 Fully doped
c
o
n
Doped 100 d

Partially doped
u
Silicon c
t
i
10-5 n
g

Water p
o
l
10-10 y
m
Diamond e
r
Nylon s

10-15 Undoped
Quartz • With a very broad conductivity range
Teflon • Tunable by the degree of doping
10-20
5
Conductivity Spectrum
Surface
Conductivity Applications
Conductive Materials (S/cm)
Resistance
(electrical) (Ω/Sq)

Metals 10+5 High Current (Ω/□)

Conductive EMI Shielding

100
Polymers (Low Current)

Electrostatic
Conductive 10-5 Dissipation 106-109
Carbons (ESD)

Antistats 109-1011
Ionic Salts 10-10

Conventional
Polymers 10-15 Insulation
6
(Nylon, ABS, PC)
Important Potential Applications of Conducting Polymers
Electrical conduction Sensors
• Anti-static • Chemical sensor
• ESD • Bio-sensor
• EMI shielding Electronic devices
Electrical field protection • Smart window
• Cable shielding • Solar cell
• Radar shielding • Light emitting diode
Chemical potential protection • Electrochromic display
• Anti-corrosion • Field effect transistor
Charge storage • NLO
• Capacitor Miscellaneous application
• Rechargeable battery • Gas separation membrane
Semiconductor • Plastic welding
• Lithography • Conductive adhesive
7
• Via-hole electroplating • Conductive gasket
Application/Property Relationships of Conducting Polymers
Conductivity (charge transport) Hydrogen bonding (Doped/Some undoped)
EMI; ESD; Antistat Microwave/Radar absorbing shield;
Plastic welding
Charge storage capability
(doping/dedoping) Strong intermolecular interactions
Battery; Capacitor High strength fiber; Reinforcement materials
Color change (doping/oxidation degree) Conjugation
Smart window; Electrochromic display. NLO; Photoconductor; Photoswitch;
LED; Thermochromic; Liquid Crystalline
Charge transfer bands (UV-vis-NIR)
Solar energy control window; UV-vis stabilizer

Dimension change (doping/dedoping)

Electromechanical actuator; Micro-mechanical device

High ionic characteristic (Doped)

Exchange/Separation membrane; Virus cleaner

Redox/chemical activity (doping/dedoping/oxidation/reduction) 8

Chemical sensor, Biosensor; Anti-corrosion
Preparation of the First Polyacetylene (PA) Film
Preparation of PA powder (insoluble) had been reported as early as 1958.
Natta, Mazzanti, and Corradini
Atti Accad. Naz. Lincei, Cl. Sci. Fis. Mat. Nat.,
Rend. 1958, 25, 3

Preparation of first PA film (insoluble) was reported only after 1971.

Ti(OBu)4 / AlEt 3 ( 1 : 3.3 )
HC CH
n
Toluene / Anisole ( 1 : 3 ) , -78oC
( 100 um )
Shirakawa and Ikeda PA film
Polymer J. 1971, 2, 231

Chlorination reaction of PA had been studied by Shirakawa

 Observing metallic shining in some cases
 But did not recognize the connection to its novel conducting behavior
9
Discovery of the First Conducting Polymer

Ti(OBu)4 + AlEt3 ect. X2 Doped Polyacetylene

HC CH etc.
Polyacetylene

Dopant Conductivity (S/cm)

Cl2 < 0.05

Br2 0.4 - 0.5

30 - 38
I2
Shirakawa, MacDiarmid, Heeger, et. al.
J. Chem. Soc. Chem. Commun., 578 (1977)

10
Important Historical Aspects and Developments
of Conducting Polymers
• Processibility Improvement
(New synthetic routes; New processing concepts)

• Conducting Mechanism
 (Intrachain transport vs Interchain hoping)

• Doping Mechanism
 (Redox reaction / Non-oxidative protonic acid doping)

• New Functional Dopants

 (Dopant moiety provides the means for color and solubility modifications)

• Lower Bandgap Polymers

 (RO-substituted poly(thienylene vinylene); became transparent after doping)
 
• New Properties  New Applications
(PLED / FET / Solar Cells)

• Superconducting Polymers? 11
Why π-Conjugated Polymer is a Better Conductor

Polyacetylene Polyethylene

*
* *


Smaller E  Larger E
 


Low energy
 bond
High energy 
resonance
bond-breaking
process
process
-bonding frame keep
the resonance  orbitals
to remain within the effective The escape of the vinyl
chemical bonding distance fragments make the reverse
12
etc. transport process impossible
Possible HC CH
WCl6 / Bu4Sn

Polymerization acetylene
Bu4Sn Bu3SnCl
polyacetylene

Mechanism WCl6 CH3CH2CH 2CH2 WCl5

of Acetylene Bu4Sn

(via the metal-carbene "Metal carbene"

Bu3SnCl
intermediate) H
CH3CH2CH2CH3
H
C WCl4 CH3 CH2CH2 C
CH3CH2CH 2 H WCl 4

H3CH2CH2CH2C
HC CH

HC CH HC CH HC CH
H
C WLn CH C WLn
WLn
H
H7C 3 H7C 3 C3H7

metal-carbene metallocycle
HC CH
H
H
C C3H7 C C3H7 H C 3H7
C H C
H C
C C
HC H HC C H CH
H H
H C WLn WLn
HC WLn C
C 3H 7
C
H
HC CH
Insoluble
termination
WLn Polyacetylene
Infusible 13
etc.
H Intractable
Solubility Improvement of Polyacetylenes
(via incorporation of substituents)
WCl6 etc.
RC CH etc.
R R R R R
T. Masuda et. al. with improved solubility

+ C6H5C CH + etc. etc.

WCl6
1 x 200 Ph Ph Ph

C. C. Han & T. J. Katz Olefin Metathesis

Organometallics 1982, 1, 1093 ring-opening polymerization
Organometallics 1985, 4, 2186
WCl6 + PhC CH etc. WLx
Ph Ph Ph

W
Lx
etc. W
Ph Ph Ph
Ph Ph Ph

H
etc. WLx etc. WLx 14
Ph Ph Ph Ph Ph Ph
Substituent Effects: R R R R R
Solubility doped with I 2 R = Me, Br, Cl ......... etc.
Conductivity doped with I 2; < 0.001 S/cm
> 10 S/cm

Steric hindrance effect of substituent is very important

Because,
R group destroy the coplanarity of the conjugation system
Reduce electron mobility of intrachain and interchain

Coplanarity gives best overlaping

between  orbitals
Coplanarity full overlaping
is the key for
Distortion from coplanarity
gaining high reduces the electron mobility
conductivity partial overlaping

90o distortion lead to conjugation defects

15
no overlaping
A Molecular Orbital Description of Stability

• Bonding MO: constructive (in-phase) overlap

• Antibonding MO: destructive (out-of-phase) overlap 16
Consider the  molecular orbitals of 1,4-pentadiene:

2 x *

4 x 2p
2x

This compound has 4  e, which forming 2  bonds

that are completely separated from one another

17
The Molecular Orbitals of 1,3-Butadiene
CH2 CH CH CH2 CH2 CH CH CH2 CH2 CH CH CH2

resonance contributors

CH2 CH CH CH2
resonance hybrid

HOMO = the highest

LUMO
occupied MO

LUMO = the lowest

HOMO unoccupied MO
4 x 2p

18
The Molecular Orbitals of 1,3,5-Hexatriene
CH2 CH CH CH CH CH2 CH2 CH CH CH CH CH2
1,3,5-hexatriene resonance hybrid of
1,3,5-hexatriene

19
Summary of Energy Diagram

h h h

20
Conjugation / Wavelength / Molar Absorptivity

21
Bands and Bandgaps

Metal
1 1 2 2 n's n's

Interaction between Formation of an

two orbitals that have orbital band
the same symmetry and
energy level

Conducting band
£k*
(empty orbitals) Semiconductor/
¡µEg
£k Valence band
Insulator
band gap (filled orbitals)

Element Solids
¡µEg smaller , Conductivity higher
C : insulator
(5.5 eV)
Si : semiconductive
(1.1 eV)
Ge : semiconductive
(0.7 eV)
Sn : metal
(0.1 eV) 22
Metal Semiconductor Insulator
(No bandgap) (Narrow bandgap) (Wide bandgap )
Pb : metal
Energy diagram for a H-H bond formation

increased repulsion increased attraction

(nucleus  nucleus) (nucleus  e cloud)
• Bond dissociation energy (bond strength) :
23
energy required to break a bond or energy released to form a bond
Bonding in Hydrogen Halides

24
Typical Charge Carriers (via doping)
soliton trans-polyacetylene

antisoliton

positive soliton

negative soliton

hole polaron cis-polyacetylene

hole polaron N N N N polypyrrole

N N N N
H H

electron polaron polyphenylene

R
R R R
hole polaron R polydiacetylene
R
R R R
R

S S S S
positive bipolaron S S S polythiophene 25
S
π* band
Energy diagrams hv1

of charge carriers hv1

π band

neutral positive negative

soliton soliton soliton
S0 S+ S-

hv2 hv3
No. of charge carrier hv1
absorption bands:
Soliton: 1
neutral positive negative
Polaron: 3 polaron polaron polaron
Bipolaron: 2 P0 P+ P-

positive negative
bipolaron bipolaron 26
B++ B--
Alternative Methods for Making Polyacetylenes
Dehydrochlorination
Cl Cl Cl Cl Cl - HCl
¡µ
PVC pyrolytic elimination
poly(vinylchloride) C. S. Marvel et. al. JACS, 61, 3241 ( 1939 )

Cl Cl
Cl2 - HCl

poly(1,4-butadiene) Cl Cl KNH2 / NH3 (liq)

East German patent 50, 954 ( 1966 )

CA 66 : 86117 r

Both approaches yield poorly conductive polyacetylenes

Cl
Cl Cl Cl Cl Cl

27
conjugation defects
Durham Route (via a processable precursor)
X X X X X X
Ring-opening I2
olefin metahesis doping
polymerization retro-cyclization 10 S/cm

n
n
t1/2 ¡Ü 20 h at 20 oC
10-7 S/cm
Cyclization very unstable ¡î too much " stability gain "
difficult in handling both products form
conjugated systems
+ XC CX
(X = -CF 3, -COOMe) Feast et. al.
1. Polymer, 21, 595 ( 1980 )
Cyclooctatetraene 2. J. Phys. Colloq. C3, Suppl. 6, 44 : C3 -148 ( 1983 )
3. Polymer, 25, 395 ( 1984 )

X
X
28
8.8
The Diels–Alder Reaction
(1,4-addition reaction; concerted reaction)

7-45.ppt
new  bond

diene dienophile new  bond

transition
state
3   2σ+ 1 
29
a pericyclic reaction; a [4+2] cycloaddition reaction
Strategy : Stabilize the prepolymer by reducing the stability gain in the conversion step

ROMP
£G
70 oC Resonance
Energy (Kcal/mol)
n
stable at RT
n For the 2nd ring:
easier in handling " less stability gain " 24 kcal/mol
36
X X 60
X X
retro-cyclization

n
t1/2 20 h at 20 o C) n

unstable at RT

30
Syntheses of Poly(p-phenylene) (PPP)
Reductive polymerization (step-reaction)
Cl Cl + Na + NaCl Wurtz -Fittig Reaction
n

G. Gold finger et. al. J. Polym. Sci., 4, 93 ( 1949 )

J. Polym. Sci.,16, 589 ( 1955 )
R R

I I + Cu Ullmann reaction
n

S. Ozasa et. al. Bull. Chem. Soc. Jpn., 53, 2610 ( 1980 )
• Had very low molecular weights or irregular structures
Cl Cl + Na Cl Cl + Na

Cl
Cl Cl Cl + NaCl

Cl Cl
Na
Cl

or Cl Cl
31
Cl
R Oxidative R
addition
I I + Cu I CuI

I CuI

Reductive
R R R R
elimination
I I I Cu I + CuI2

R R R R R

etc. etc.

32
Oxidative polymerization (step-reaction)
+ CuCl2 / AlCl3
n
P. Kovacic et. al. JACS 85, 454 ( 1963 )
Most successful and economical
Oxidizing agent : CuCl2, MnO2, MoCl5, FeCl3
Lewis acid catalyst : AlCl3, AlBr3
CuCl2 Cl
Cl Al Cl + CuCl
AlCl3 Cl
Radical
cation

AlCl3
CuCl2 H
CuCl + 2 HAlCl 4 + AlCl4
- 2H H

Use of AlCl3 help reduce the following side-reaction

H CuCl2
+ Cl Cl Cl + CuCl + Cl
-H 33
Catalyzed Chain polymerization
Ziegler catalyst - H2 450 ¢J
n chloranil £G n
xylene aromatization

MW = 5000 - 10,000 C. S. Marvel et. al.

JACS 81, 448 ( 1959 )
poly(1,3-cyclohexadiene)
J. Polym. Sci. A3,1553 ( 1965 )

O
Cl Cl p-chloranil

Cl Cl Oxidant
O
( tetrachloro-1,4-benzoquinone )
X X
X2 300 - 380 ¢J

n ( Cl2, Br2 ) n £G n
- 2 HX
- H2
-2 HX

- H2

n 34
Lower the aromatization temperature via the decarboxylation

pseudomonas putida
HO OH HO OH

Base
highly soluble ; easily processible O
DP = 600-1000 ( degree of polymerization ) Cl C R
R = OCH3, CH3, Ph
( for improving solubility )
n O O
radical chain
R C O O C R polymerization R C O O C R
O O

220 ℃ Ballard et. al. JCS, CC 954 ( 1983 )

 n
( t1/2 = 30 sec for R = OMe)

X X
300 - 380 ℃
- H2 450 ℃
  n
n chloranil n n

xylene aromatization - 2 HX 35
- H2
Free Radical Chain Reaction

OR RO
ROCO OCOR ROCO OCOR ROCO OCOR

Initiation step
Propagation steps
ROOR

RO X RO
n
R' R' R' R' R' R' Termination R' R' R' R'

(X = radical terminator) ( R' = OCOR)

36
Initiation RO OR 2 RO

RO
Propagation RO +
X
X
RO
Radical Chain X
+
X
RO
X X

Polymerization
Mechanism RO
X X +
X
RO
X X X

X X X
RO

Termination X X X X X X
RO + RO RO
OR
n n

X X X X X X OR X X X X X X OR
RO + RO
n n n n

X X X X X X
Chain transfer RO + ZR' RO + R'
Z
n n
( Z = H, I, Br, Cl )
X X X X X X
RO RO + H
n
37
n
Radical Initiators
ROOR 2 RO


CH3 CH3 CH3

100 - 120oC
H3C C O O C CH3 2 H 3C C O

CH3 CH3 CH3
t-Butyl peroxide

O O O
60 - 80oC O
C O O C 2 C O C O

more stable
Benzoyl peroxide radical

O CH3 CH3
H 3C O
C O OH
H C O C O O C O C H
H3C CH3 CH3
Diisopropyl peroxydicarbonate Cumyl hydroperoxide

H2O 2 (Hydrogen peroxide)

K2S2O8 (Potassium persulfate)

(H3C)2C N N C(CH3)2 2 C(CH3)2 + N N


CN CN CN
AIBN 38
Azo bis(isobutyronitrile)
Chain Transfer
HC CH2 CH2 CH CH2 CH
a Radical stability : 3o > 2o > 1o > methyl
stablized by
Allylic
Benzylic
polystyrene chain
Styrene
O OR NR2
O CH2 CH CH2 CH Other
destablized by OAc ROOH, R S H, R C H, R CH, R' CH2
O C CH3 a activated - H
O O (more reactive)
H3C C H3C C R
O O
TABLE 2.2 Chain Transfer Constants for Selected Solvents at 60oC with Respect
to Polystyrene and Poly(vinyl acetate)

Cs X 104
Solvet Polystyrene Poly(vinyl acetate)

Benzene 0.18 2.2

Toluene 1.25 21
Ethylbenzene 6.7 55
Isopropylbenzene 8.2 90
n-Heptane 0.42 17
Acetone 4.1 (80 oC ) 11
Butanone 5.0 (80 oC ) 65
Ethyl acetate 2.3
Ethyl butyrate 17 (50 oC )
Phenol 220 (40 o )
C
Anilin 210
n-Butyl chloride 0.04 10
n-Butyl bromide 0.06 50
n-Butyl iodide 1.85 800
Methylene chloride 0.15 4
Chloroform 0.5 140
Carbon tetrachloride 920
Carbon tetrabromide 92 39
13,600 39,000
Syntheses of Polyphenylene Vinylene (PPV)
H (CH3)3C O K G. Kossmehl et. al.
H3C C CH CH Makromol. Chem. 182,3419 ( 1981 )
O n
DMF

B
H
H H
H2C C H2C C
O O

- H2O H H
CH CH C C
n
H OH n

Nu H H H H
H H H H
C C C C Nu C C C C etc.
H OH H OH
H OH H OH
or

H H H H H H
C C C C C C
H OH H OH H OH

H H H
etc. C C C etc. 40
H OH H
Witting Condensation
H O
Ph3P CH CH PPh3 + C C CH CH
O H n

R. N. McDonald et. al. JACS 82,4669 ( 1960 )

G. E. Wnek et. al. Polymer 20,1441 ( 1979 )

H H O
Ph3P CH CH PPh3 Ph3P CH C C C
PPh3 O H

H H O H H O
Ph3P CH C C C Ph3P CH C C C
H H
PPh3 OH
Ph3P O

H H O
Ph3P CH C C C etc. CH C CH C CH C etc.
H H H
H

Br Br

Ph3P BrH2C CH2Br Ph3P H2C CH2 PPh3

Base (like LiBu)

triphenyl phosphine
Ph3P HC
41 CH PPh
Ph3P CH CH PPh3 3
Phosphorus ylide (phosphorus-stabilized carbanion)
Dehalogenation
Cl Cl Cl Cl
- Cl2
Cl3C CCl3 CCl CCl
n
Cl Cl Cl Cl

M. Ballester et. al. JACS 88, 957 ( 1966 )

McMurry Condensation (TiCl3/LiAlH4)

- "O2"
OHC CHO CH CH
n

L. Rajaraman et. al. Curr. Sci. 49 (3), 101 ( 1980 )

O O - "O2"
C C C C
n

Feast et. al. Polymer Commum. 24,102 ( 1983 )

42
Dehydrohalogenation of Benzyl Halides
R R
NaH/DMF
ClH2C CH2 Cl CH CH
-HCl n
R R

( R = H, CH3, OCH3 )

H. H. Horhold et. al. Makromol. Chem. 131, 165 ( 1970 )

H
H H H H
Cl C C Cl C C
Cl H
H H

-HCl H H H
CH CH etc. CH2 C CH2 C CH2 C
n
Cl Cl Cl

From Bis(diazobenzylic) Compounds

Ph Ph Ph Ph Ph Ph

N2
C C
N2
- N2 C C C C
n
43
carbene intermediate
Via Sulfonium Polyeletrolyte Precursor
ClH2C CH2Cl + SMe2 Me2S H2C CH2 SMe2

Cl Cl
bissulfonium salt

NaOH
- SMe2
Casting H
- HCl CH2 C + NaCl
CH CH
n £G n
SMe2
Cl
R. A. Wessling et.al. sulfonium polyelectrolyte
J. Polym. Sci. Polym. Symp.,72, 55( 1986 )
U. S. Patent 3,706, 677 ( 1972 ) dialysis
Casting
U. S. Patent 3,401, 152 ( 1968 )
-NaCl
£G - low MW molecules
NaOH

H H H
Me2S C C SMe2 Me2S C C SMe2
H H H H
Cl Cl

H SMe2 Cl H SMe2 Cl
C C C C
H H H H
diradical
quinone dimethane 44
Initiates the polymerization of quinone dimethane
H SMe2 Cl H SMe2 H Cl
SMe2
Nu
C C H C C C C
H H Nu H H H

Other possible mechanism :

H
CH2 C
n
SMe2
Cl

H2 NaOH dialysis H
Me2 S C CH2 SMe2 CH 2 C
Cl Cl n
SMe2
Cl
Acid titration : > 90 - 95 % NaOH has been consumed.
(25 - 35 % yield)
Why ?

a
Me
H2
Me2 S C CH2 S NaOH
Cl Cl Me b
May be : a
b
Me
Me H2
H2 Me2 S C CH2 S + MeOH
Me2 S C CH S
Cl Cl
Me
non-productive pathway
sulfonium polyelectrolyte 45
10.9

A good nucleophile is required Does not require a good nucleophile

A good leaving group is required A good leaving group is required

Polar solvent is not required Polar ionizing solvent is usually required

46
A possible solution : SMe2 SEt2

CH2CH3
Et 2S H 2C CH2 S
Cl Cl CH2CH3
2o C is more hindered, which
reduce the SN2 side reaction
But a new problem was created ,
a
Et
H2
Et2S C CH2 S H H NaOH
Cl Cl C C H b
a H H
b
Et Et
H2 H2
Et2S C CH S Et2 S C CH 2 S + H2C CH2
Cl Et Cl
non-productive pathway

47
sulfonium polyelectrolyte
Relative stabilities of radicals

Relative stabilities of carbocations

R R H H

most R C > R C > R C > H C least

stable stable
R H H H
tertiary secondary primary methyl
carbocation carbocation carbocation carbocation

Relative stabilities of carbanions

least : : : : most
stable stable
48
carbanion carbanion carbanion anion
A possible solution : SEt2 SPr 2

Pr
Pr2S H2C CH2 S
Cl CH 2CH2CH3
Cl
2o C, disfavor
-H abstraction
New problems appeared,
2o C, disfavor SN2
SR 2 yield
ClH2C CH 2Cl + SR2 price
SMe2 80 %

SEt 2 60 %
increase
R2S H2C CH2 SR2 SPr 2 30 % dramatically
Cl Cl
Why ? and How ? H H H
H H H
H C H C C H
H
C H C H H C H
H
Nucleophilicity : S < S < S
C H H C H
C H H
H
H C H C C H
H H H H H
H
49
even worse !
A possible solution :
1
2 3'
S S contains only 2o C, which will
disfavor all possible side reactions
3 2'
1'
also a stronger Nu

ClH2C CH2Cl + S S H 2C CH2 S

> 80% yd
cheap ! Cl Cl

C. C. Han et. al. Polymer Communications 28, 261 ( 1987 ) NaOH

J. of Polym. Sci., Polym. Chem. 26, 3241 ( 1988 )

H
CH CH CH2 C > 80% yd
n  n
S
best quality
Cl

S works equally well

C. C. Han et. al. J. of Polym. Sci., Polym. Chem. 26, 3241 ( 1988 ) 50
H
CH2 C CH CH + SMe2 + HCl
n n
SMe2 £G

Cl

doped with AsF5

CH2 CH CH CH 10 S/cm
x n-x
SMe
a conjugation defect

H
CH2 C CH CH + S + HCl
n n
S £G

Cl with less conjugation defect

doped with AsF5

all 2o C, disfavor SN 2
50 S/cm

doped with AsF5

H
CH2 C CH CH 180 S/cm
n n
S £G
even better
Cl

C. C. Han et. al. J. of Polym. Sci., Polym. Chem. 26, 3241 ( 1988 ) 51
Effects of Sulfides on the Synthesis of PPV Material-P38.cdx
01/05/38

“nucleophilicity” “side reactions” “defects”

-SR2
NaOH H -HCl
ClH2C CH2Cl R2SH2C CH2SR2 CH2 C CH CH
n n
yield yield SR2 £G
Cl Cl 
Cl
1 2 3

yield of 1 SMe2 ~ S ~ S > SEt2 >> SPr2

yield of 2 SMe2 < SEt2 < S

Conductivity of 3 SMe2 < SEt2 < S < S

(doped with AsF5) 7 15 44 180 S/cm

R.W. Lenz, C.C. Han, J. Stenger-Smith, F.E. Karasz

J. Polym. Sci., Polym. Chem. (1988), 26, 3241-3249
52
Conjugation Length Effects
on ionization potential

53
Conjugation Length Effects
on ionization / oxidation potentials

54
Conjugation Length Effects
on ionization potential and electron affinity

HOMO Oxidation Potential

level
4.4 eV

LUMO
Reduction Potential
level

55
Conjugation Length Effects
on band gap

56
Conjugation Length Effects
on absorption wavelength

57
Substituent Effects on the Ionization Potential (eV)
(Small Molecules)
Me F F F6

F F
8.80 9.25 9.30 9.64 10.12

Me F

F5

CN CN CN CN

9.38 9.71 9.74 10.45

PhC CPh < PhC CMe < PhC CH

8.00 (+0.05) 8.42 8.82

58
6.97
Substituent Effects on the Ionization Potential (eV)

59
Precursor routes for conducting polymers
Material-P35.cdx
01/05/28

F3C CF3 F3C CF3 F3C CF3

WCl6 / Me4Sn
Durham +
£G n

Ring opening metathesis polymerization (ROMP)

(Olefin metathesis polymerization)

WCl6 / R4Sn
Metathesis n

+ 2RCO2H
Ballard n n
ROCO OCOR ROCO OCOR £G

Radical chain polymerization

60
PPV via Wessling Route
(Dow Chemical route)
Materia-P36.cdx
01/05/28

Poly(phenylene vinylene)

bissulfonium salt
NaOH
ClH2C CH2Cl R2SH2C CH2SR2 R2SH2C CHSR2

Cl Cl Cl

Anionic chain polymerization NaOH

-SR2
-HCl H
CH CH CH2 C H2C CH
n n
£G SR2
SR2

AsF5, FeCl3 (unstable), 10 S cm-1 Cl Cl

Orientable, 103 S cm-1 Stable Solution
require strong oxidant sulfonium polyeletrolyte

61
Poly(dialkoxyphenylene vinylene)

OR CH2O OR OR
HCl SR2
ClH2C CH2Cl R2SH2C CH2SR2 SR2 = SMe2 , SEt2

RO RO RO
Cl Cl S S
,
(OR = OMe, OEt, OBu)
RX
NaOH NaOH
bissulfonium salt
OH

OR -SR2 OR
HO
-HCl H
CH CH CH2 C
n n
£G
SR2 sulfonium
RO RO
200 - 250oC polyeletrolyte
I2, 50 S cm-1 (Stable) Cl
Unorientable Unstable Solution
mild oxidant work fine Gel, Precipitation

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
62
3. steric hindrance: chain conformation, packing morphology, e-transport
Material-P39.cdx
01/05/28

Processible Copolymers

OR

S H2C CH2 S + r S H2C CH2 S

RO
Cl Cl Cl Cl

OR
(1+r) NaOH/H2O
CH2 CH CH2 CH Stable Solution
0oC, N2 1-x x n
S RO S

Cl Cl

OR
1.Dialysis
I2 Dopable
CH CH CH CH
2.Casting 1-x x Orientable
n
3. £G RO Stable

good electroluminescent materials

Polymer Communciations 261, 28 (1987)

C.C. Han, R.W. Lenz, and F.E. Karasz

+ + +
63
Orientable Copolymers
R

CH CH CH CH
1-x x
n
R

Draw Ratio Conductivity (Scm-1)

Polymer X (L/Lo) (Doped with I2)

Homopolymers

PPV 0% 1 < 10-5

PDMPV 100% 1 51

Copolymers

1 27
(R = OMe) 13%
4 428

1 12
(R = OEt) 12%
10 500

1 8.3
13%
13 694

Polymer Communciations 261, 28 (1987)

C.C. Han, R.W. Lenz, and F.E. Karasz 64
R

CH CH CH CH
1-x x
n
R

 Polymer, 30, 1041 (1989)

R. W. Lenz, C. C. Han and M. Lux

+ + +
65
Material-P42.cdx
01/05/28

Scheme 1
e

Fig A

R' R'
R' O R' H O
O O

O
R'
O Electron transport: e
O
R'
H OH

R' R' Interchain hopping

Fig B vs
Intrachain moving

H C
C H

C C H
C H C

66
Fig C
R

CH CH CH CH
1-x x
n
R

Conductivity (Scm-1)
Polymer X (Doped with I2)

PPV 0 < 10-5

PDMPV 1 < 10-5

(R = Me)

Copolymers 0.1 0.3

(R = Me)

67
Gel or Precipitate

H
CH2 C 3 - 6 Months
n
S

Cl

OMe
H
CH2 C 1 -3 Days
n
S
MeO

Cl

OBu
H
CH2 C 1 - 5 Hours
n
S
BuO

Cl

H
CH2 C 1 - 5 Hours
S n
S

68
Cl
Electron Donating Groups Promote Elimination

OR OR Cl
CH CH2 CH CH2 + SR2

RO SR2 RO
Cl

OR

CH CH + SR2 + HCl

RO

CH CH2 CH CH2
S n O n
SR2 SR2
Cl Cl 69
Proposed Mechanism For Precipitation

OMe OMe

¡ì¡ì CH2 CH ¡ì¡ì ¡ì¡ì CH CH ¡ì¡ì + HCl + SR2

MeO SR2 MeO

Cl

OMe Crossing Linking

Aggregation
CH2 CH Low Aqueous Solubility
MeO Cl

Low Aqueous Solubility

70
Stabilization of Polyelectrolyte
OMe
H2O Precipitates
CH2 CH in 1 - 3 Days
n
MeO SR2
H2 O Stable Solution
Cl
for 14 + Months
Py

Conductivity (S cm-1)

PDMPV I2-Doped FeCl3-Doped

Pyridine-Stabilized 500 300

Unstabilized 50 30

C. C. Han, R. L. Elsenbaumer
Synth. Met. 1991, 41-43, 849

71
Relative Stabilizing Ability of Amines

H3C CH3
N
N OH
> NMe3 ~ >> > NEt3 ~
N N N OH N

> ~ > > ~

N Me N Me N
N N
Me Me

OH OH
N N
~ ~ ~ > ~
N N
N Br N HO N
OH

N N OH
> ~
N OH N OH

72
73
Stabilization of Polyelectrolyte

CH3CN/H2O OBu CH3CN/H2O/Py

Precipitates Stable solution
BuOH CH2 CH
in 5 hours n
BuOH/Py for + 14 months
BuO S

Cl

Precipitates H2O H2 O/Py Stable solution

CH2 CH
in 5 hours S n for + 14 months
S

Cl

74
Stabilization of Polyelectrolyte
OMe OMe
Py/H2O
CH2 CH CH2 CH
n n
MeO SR2 small amount MeO SR2
Cl Cl

Stable Solution
Unstable Film (insoluble)

OMe OMe
Py/H2O
CH2 CH CH2 CH
larger amount SR2
x
N
y
MeO MeO
Cl Cl

Stable Solution
Stable Film
Soluble (H2 O, DMF, DMSO, MeOH, EtOH)
1
HNMR, TGA

75
Non-Ionic Precursor Polymer

OBu OBu
BuOH/Pyridine
CH2 CH CH2 CH
n Room Temperature n
BuO S BuO OBu
Cl
Soluble, Stable
Elastomer, Tg = 2.6oC
1
C. C. Han, R. L. Elsenbaumer HNMR, TGA, GPC
Mol. Cryst. Liq. Cryst. 1990, 189, 183

76
Thermal Elimination

OBu OBu
250 - 300oC
CH2 CH CH CH
n n
OBu £G
BuO BuO

I2, 1 Scm-1
Insoluble

77
Non-Thermal Elimination
OBu OBu
H
¡ì¡ì CH2 CH ¡ì¡ì ¡ì¡ì CH CH ¡ì¡ì + BuOH + H
n
BuO OBu BuO

Butanol Scavengers
Butanol Scavengers

Me3SiCl
Me3SiBr OBu
Me3SiI ¡ì¡ì CH CH ¡ì¡ì + Butanol Adducts
Me2SiCl2
(CH3CO)2O BuO
(CF3CO)2O
Soluble
I2, 14 Scm-1

C. C. Han, R. L. Elsenbaumer
Mol. Cryst. Liq. Cryst. 1990, 189, 183

78
Simultaneous Elimination and Doping

OBu
H+, Solvent
CH CH
n
Weak Acid
OBu BuO
CH2 CH
n
Neutral Polymer Solution
BuO OBu
H+ , Solvent
Doped Polymer Solution
Strong Acid

C. C. Han, R. L. Elsenbaumer
Mol. Cryst. Liq. Cryst. 1990, 189, 183

79
Simultaneous Elimination and Doping
Weak Acid
CH2 CH Neutral Polymer
S n
OMe Strong Acid
Doped Polymer

OMe
Weak Acid
CH2 CH Neutral Polymer
n Strong Acid
MeO OMe
Doped Polymer

80
Protonic Acid-Doping of Various Conducting Polymers
Conductong Polymers Dopants Conditions Conductivity Dopong Level
S/cm mol %

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

_
CF3COOH neat, 1 day < 10-4

FeCl3¡E6H2O in CH3NO2, 20h 5.3 31.2 %

Poly(phenylene vinylene- CH3SO3H 44.1 19.7 %

in CH3NO3, 2h
co-dimethoxyphenylene
vinylene) (90:10) _
CF3 COOH neat < 10-7

FeCl3¡E6H2 O in CH3NO2, 50h 31.5 19.7 %

Poly(phenylene vinylene) CH3 SO3H in CH3NO2, 3 h 15 min 10.7 10.9 %

_
CF3COOH neat < 10-7

FeCl3¡E6H2O in CH3NO2 _
< 10-7

81
C. C. Han, R. L. Elsenbaumer
Synth. Met. 1989, 30, 123
Protonic Acid-Doping of Poly(dimethoxyphenylene vinylene)
Acids Conditions Conductivity Doping Level
S/cm mol %
CH3SO3H in CH3NO2, 15 min 36.8 46.1

C6H5SO3H in CH3NO2, 1 hr 40 min 42 54.0

CF3SO3H in CH3NO2, 28 min 24

HBF4 in CH3NO2, 16 hr 25 min 69.4

CF3COOH Neat & in vacuo, 1.5 hr 46 9.3

CF3CF2COOH in CH3NO2, 23 hr 32

CF3(CF2)2COOH in CH3NO2, 23.5 hr 42

CF3(CF2)6COOH in CH3NO2, 26 hr 71

CH3COOH in CH3NO2 < 10-7

CH2ClCOOH in CH3NO2, > 100 hr < 10-3

CHCl2COOH in CH3NO2, 23 hr 12.1 20.7

CCl3COOH in CH3NO2, 8 hr 18.8 13.1

¡E in CH3NO2, 36 min 105 4.4

C. C. Han, R. L. Elsenbaumer
Synth. Met. 1989, 30, 123 82
83
Proposed Doping Mechanism

OMe OMe OMe

OMe H OMe H OMe
H H

MeO H MeO H H Disproportionation MeO H H

MeO MeO MeO
OMe OMe OMe
OMe OMe OMe

MeO MeO MeO

MeO MeO MeO

Bipolaron Two Polarons

13 C NMR ESR
UV-vis-NIR

C. C. Han, R. L. Elsenbaumer
Synth. Met. 1989, 30, 123

84
Non-thermal Elimination

OBu OBu OBu

CH2 CH CH CH CH2 CH
n Partial m n-m
BuO OBu BuO BuO OBu
Elimination

Soluble, Orientable
Liquid Crystalline

C. C. Han, R. L. Elsenbaumer
Mol. Cryst. Liq. Cryst. 1990, 189, 183

85
1. Conventional Liquid Crystalline Polymers

etc. etc.

Flexible
Rigid
Non-Planar
Planar

2. Partially Eliminated Precursor Polymers

etc. etc.

OR OR

CH CH CH2 CH
i j
RO RO OR

86
OR X H OR
+ HX
CH CH CH CH
n
n
RO RO

Doping is very time-consuming, and sometimes almost impossible.

87
Potential Approach for a Doping Free Process
OR

CH CH2 + Latent Dopant

RO SR2
Cl
Processing

Non-conductive Articles

Processing

Conductive Articles

Criterions :

¡E High aqueous solubility

¡E No chemical reactivity

¡E Similar solubility

¡E Remains homogeneous distribution

¡E Maintains mechanical strength

88
Concurrent Elimination and Doping
R R
- R2S, - HCl
CH2 CH
n
£G
R SR2 R n

Cl

Precursor polymer Intermediate Conductive Polymer

R R H R
- R2S
CH2 CH CH CH
n
£G n
R SR2 R n R
B HB + R2S B

Protonic Acid-Doped

Ion Exchange B = Halogen, BF4 , PF6 , SbF6 , RSO3 , etc.

CH2 CH C.C. Han and R.L. Elsenbaumer

n Synthetic Metals, 30, 123-131 (1989)
R SR2

Cl 89
Interconversion between Various Redox Forms of Polyaniline

H H H H
Leucoemeraldine Base N N N N Fully Reduced
n

(+2e ; +2H+ ) [ Red ] [ Ox ] ( -2e ; -2H+ )

H H
Emeraldine Base N N N N Half Oxidized
n

( +2e ; +2H+ ) [ Red ] [ Ox ] ( -2e ; -2H+ )

Pernigraniline N N N N Fully Oxidized

n

90
Protonic Acid Doping of Pani

H H
N N N N

HX

H H
H H
N N N N

X X

H H H H
H H H H
N N N N N N N N

X X

H H H H
H H H H
N N N N N N N N

X X

91