Conductive Polymers Based on Thiophene and

Pyrrole Groups and Their Applications as Smart

Corrosion-Inhibiting Coatings
February 22, 2019

Presenter: Dr. Peter Zarras

NAWCWD Code 4F0000D
1900 N. Knox Road (Stop 6303)
China Lake, CA 93555-6106
(P) 760-939-1396
(F) 760-939-1617
peter.zarras@navy.mil

2019 Smart Coatings Conference

February 20-22, 2019, Orlando, Florida

FOR OFFICIAL USE ONLY Distribution Statement A- Approved for Public Release
 Acknowledgements
• Financial support gratefully acknowledged - Dr. A. Perez, ONR Code 333

Synthesis Support:
• Drs. John Stenger-Smith, William Lai, Mathew Davis, Jeff Bottaro, Mr. Andrew Chafin, Mr. Todd
Dames (NAWCWD-ESDP), Ms. Shelly Vang (NAWCWD-ESDP), Ms. Alicia M . Hughes
(NAWCWD - ESDP), Mr. Jacob Letcher (NAWCWD- ESDP), Mr. Matthew Watrous (ONR NREIP)
• FTIR Analysis:
• Dr. Lee Cambrea (NAWCWD)
NMR Analysis:
• Dr. Lawrence Baldwin (NAWCWD)
GC-MS Analysis:
• Ms. Roxanne L. Quintana, Alicia M. Hughes (NAWCWD)
• Film/Pellet Fabrication/Characterization:
• Dr. Alfred Baca, Dr. Paul Goodman, Mr. Daniel Connor, and Mr. Joshua Baca (NAWCWD)
Conductivity Measurements:
• Dr. Paul Goodman, Dr. Mark Moran, Dr. Linda Johnson (NAWCWD)
Electrochemical Analysis of Precursor- Polymer Corrosion Properties:
• Dr. Paul Goodman (NAWCWD)

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Corrosion Environment for DON

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 Types of Corrosion
Definition of Corrosion:
“An attack on a metallic material by reaction
with its environment”
Corrosion and Protection, Einar Bardal, Springer-Verlag, London, 2004

There are three main types of corrosion:

a) wet corrosion: corrosive environment is an aq. sol. w/dissolved species
liquid is an electrolyte
process is electrochemical
b) corrosion in other fluids:
fused salts
molten metals
c) dry corrosion: corrosive environment is a dry gas
also known as chemical corrosion
example is high temperature corrosion

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 EAPs as Corrosion Protective Coatings
Proposed Mechanism on Steel alloys
Introduction:
EAPs (polyaniline, polypyrrole, polythiophene) as corrosion protective coatings
first suggested by A. G. MacDiarmid Short Course on Electrically
Conductive Polymers, New Paltz, New York 1985

EAPs potentially offer a new generation of environmentally-benign corrosion

protective coatings for DoD and commercial use

Proposed EAP mechanism for corrosion protection:

• Barrier protection

• Passivation of metal surface/released dopant ions

• Formation of an electric field at metal surface, electronically restricting

flow of electrons from metal to oxidant

McAndrew T. P., TRIP, 5(1), 7 (1994); Tallman et al., Journal of the

Electrochemical Society, 156(10), C360 (2009)

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 History of Corrosion-inhibition w/EAPs

• Benicewicz (LANL) and Thompson (KSC) first demonstrated corrosion

prevention on steel substrates using processable Polyaniline (PANI)
coatings (1994, NASA study)
PANI corrosion protection is limited:
• pH dependent for conductive form-works in acidic media.
• Effective for NASA space shuttle support structure/Polyaniline
dispersions in epoxy coatings to prevent corrosion commercialized
• Corrosion protection is limited in marine environment/“double-strand”
PANI has shown corrosion inhibition in sea water
• Polythiophene and polypyrrole has shown corrosion protection on
steel alloys

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 Corrosion Inhibition Utilizing Idea of
“Smart Coatings” for Navy Applications

 Smart Coatings can play an active role in corrosion prevention for Navy
systems and infrastructure

 A “smart coating” is defined as a coating that can sense and

respond to a stimulus in its environment (pressure, light, heat,
corrosion, etc.) and react in a predictable and possibly reversible
fashion

 Comprehensive corrosion strategy that incorporates

“smart functions” need to include the following capabilities:
 warning or detection for corrosion
 corrosion inhibition
 self-healing

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 Smart Corrosion Strategy
In order to have smart coatings one must
start with smart materials!

Key Elements to make Smart Materials

into Smart Coatings:
 Readily available and cheap starting
materials
 Easy synthetic route to desired
product
 Simple processing conditions to
obtain smart coatings
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 Omniconjugated Polymers: Design
Approach: Synthesis of Omniconjugated Polymers
Omniconjugation, therefore, refers to certain molecules that have more than
three terminals that are truly p-conjugated
Z

X Y
X Y

Scientists have spent the past two decades devising synthetic strategies to produce CPs with low
bandgaps Eg <1.5 eV(e.g. PEDOT, poly(ethylenedioxythiophene,
Eg = 1.6 eV)). Since small or zero bandgaps would produce greater electron mobility
in CPs there would be a concurrent increase in their electrical conduction.
Omniconjugated polymers represent a step in this direction. By reducing the bandgap,
through a 2-D network of conjugated pathways, electron mobility would increase
producing higher electrical conductivities in the polymer.

Van der Veen, M. H., Rispens, M. T., Jonkman, H. T., Hummelen, J. C., Adv. Funct. Mater., 14, 215-223 (2004).
Zarras, P., Baca, A., Stenger-Smith, J. D., Chafin, A., and Lai, W., US Patent 9,058,915 B1 June 16, 2015.

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 Synthesis of Intermediates leading to
(1E,3E)-1,4-bis(1-methyl-1H-pyrrol-2-yl)
buta-1,3-diene Intermediate
Avg Yield = 60-65%, clear liquid
b.p. = 58-60oC (4.0 mm Hg)

Avg Yield = 90-95%, white powder

m.p. = 145.7oC

Avg Yield = 90-95%, off-white powder

m.p = 211.3oC (dec.)

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Synthesis of (1E,3E)-1,4-bis(1-methyl-
1H-pyrrol-2-yl)buta-1,3-diene

Avg Yield = 40-45%, m.p. = 97oC

Cryst. from 40/60 (v/v)CHCl3/pet ether,
Further purification sublimed (0.02 Torr, 120oC),
bright yellow powder

Avg Yield = 40-45%, m.p = 148.5oC (dec.)

Purified via sublimation (0.05 Torr, 150oC), bright yellow powder

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 Polymerization of Monomer
Poly[1,4-bis(1-methyl-1H-pyrrol-2-yl)buta-1,3-
diene

Avg Yield = 40-60%, dark blue powder

Polymerization methods employed to polymerize

(1E,3E)-1,4-bis(1-methyl-1H-pyrrol-2-yl)buta-1,3-diene:

 Oxidative/chemical polymerization in THF using 0.20-0.25 equivalents or catalytic

quantities FeCl3 (~10 mg) at 0oC 30 seconds -2 minutes reaction time

 Electrochemical polymerization only on Pt electrodes , corrosion evident on 1010 steel

alloys using (1E,3E)-1,4-bis(1-methyl-1H-pyrrol-2-yl)buta-1,3-diene monomer via
electrochemical polymerization technique

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 Electropolymerization of
(1E,3E)-1,4-bis-(1-methyl-1H-pyrrol-2-
yl)buta-1,3-diene

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 Synthesis of (1E, 3E) -1,4-di(thiophen-2-
yl)-buta-1,3-diene Monomer
Synthesis via one-step Perkin Reaction

Product purified via recystallization from

toluene, sublimed at 125oC(0.05Torr)
mp = 170.9oC (DSC), brilliant yellow powder

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 Electropolymerization of (1E, 3E)-1,4-
di(thiophen-2-yl) buta-1,3-diene monomer

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 Oxidative polymerization of monomer to
Poly[1,4-di(thiophen-2-yl)-buta-1,3-diene]

 Polymer was extracted with de-ionized water for 168 hours under reflux to
remove the FeCl3 impurity
 A black solid polymer was obtained in 20-30% yield
 Total Fe analysis showed 1.95 ppm (0.12 wt.% residual Fe in polymer compound)

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 Conductivity and Bandgap of
Heretocyclic butadiene Conductive
Polymers

 Polymer powder was pressed under mechanical stress

(20,000 lbs) with a hand press into pellets and measured
for resistivity
 The results below show the values for the conductivities
and bandgap
Polymer Bandgap Conductivity (S/cm)
Poly[(1E,3E)-1,4-bis-(1-methyl-1H-pyrrol-2- 2.23 eV 7.44 x 10-4 S/cm
yl)buta-1,3-diene

Poly[(1E, 3E) -1,4-di(thiophen-2-yl) buta- 2.00 eV 1.64 x 10-3 S/cm

1,3-diene

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Synthetic Method to Improve Polythiophene-
butadiene derivative Solubility

Only 7% product obtained (GC/MS) not able to duplicate results from

Syn. Met., 217, 172 (2016) ~92%

Yield = 65%, clear liquid,

b.p. = 63-75oC (0.02 mmHg)
JACS, 135, 13695 (2013)
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Synthetic Method to Improve Polythiophene
derivative Solubility

Yield = 53%, b.p. = 92-99oC, (0.05 mmHg)

Light yellow oil, Chem Mater., 25(21), 4239 (2013)

Yield = 10%, red oil, purified by col. chromatography,

GC/MS purity = 97%
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Synthetic Method to Improve Polythiophene-
butadiene derivative Solubility

Yield = 70%, clear liquid, bp = 65-105oC (0.05 mmHg)

Org. Lett., 4(11), 1889 (2002)

Yield = 40%, light yellow liquid,

bp = 100-105oC (0.05 mmHg)
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 Synthetic Method to Improve
Polythiophene derivative Solubility via
Perkin Reaction

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 Synthetic Method to Improve
Polythiophene derivative Solubility via
TMS removal (Monomer Formation)

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 Conclusions
• Polymerized via electrochemical, chemical, novel 1D conductive polymers
based on pyrrole and thiophene derivatives

• Characterized 1D conductive polymer(s) for bandgap and

conductivities using 4-point probe technique

• Synthesis/characterization of several intermediates for the n-hexyl

derivatives of thiophene

Future Plans:

• Complete synthesis leading to (1E, 3E)-1,4-bis(3-hexylthiophen-2-yl)

buta-1,3-diene
• Complete synthesis leading to (1E,3E)-1,4-bis(4-hexylthiophen-2-yl)
buta-1,3-diene
• Determine corrosion-inhibiting properties of CP films
• Test smart coating hypothesis
• Polymerize 1,4-di(thiophen-2-yl)buta-2,3-diol to form epoxy compounds
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