ELSEVIER SyntheticMetds84(1997) 117-118

Conducting blends of polyaniline with conventional polymers

J Laska” K. .&l? and A. Prince
aAcademy of Mining and Metallurgy, Dept. of Material Sciences and Ceramics, ul. Mickiewicza 30,30059 Krakow (Poland)
bwarsaw Technical University, Dept. of Chemistry, ul. Noakowskiego 3,00664 Warszawa (Poland)

Abstract
Phosphoric acid diesters effectively protonate polyaniline and simultaneously plasticize it. This plasticized polyaniline can be processed
either by thermal methods or from solution. It can serve, therefore, as a conducting additive to common polymers, such as poly(viny1
chloride), polystyrene, poly(methy1 methacrylate) and cellulose derivatives. In each case only few wt. % of polyaniline is needed to
render a conductive blend. Microprobe studies and scanning electron microscopy show uniform distribution of polyanilinefdiester in the
polymer matrix. The conductivity of the blends ranges between 10.‘and 10 S/cm, and the mechanical properties are those of the non-
conducting matrix. Thermally processable blends of PVC, having very good mechanical properties, were prepared by mechanical mixing
with plasticized polyaniline, while those of PMMA, PS or cellulose derivatives were cast from solutions.

Kqwords: polyaniline, processing, conducting blends

important application of the conducting blends is their use as

1. Introduction
Technological uses of neat conducting polymers are not very
likely because of their poor mechanical properties which rarely
meet teclmological expectations. However, the unique
combination of electronic and mechanical properties of blends of
conducting polymers with conventional polymers seems to have
great promise for many applications. Such polymeric blends
appear to be much better solutions than the carbon black- or
metal-loaded polymers. Although mechanical properties of
conducting polymers are inferior to those of nonconjugated ones,
they are much better than those of carbon black. Furthermore, the
percolation threshold for conductivity can be reached at much
lower loading than, for example, in the case of metal.
The percolation threshold depends greatly on the size of the
particles as well as on the efficiency of mixing and uniformity of
size. These criteria seem to be met since solubility and
processability of conducting polymers have been improved. In
blends of doped polyaniline [l] and also in blends of derivatives
of some substituted polythiophenes [2] in conventional insulating
polymers, very low (~5%) percolation thresholds were observed.
It is believed that percolation is reached at a very low level since
the continuous conducting polymer forms a network within the
host polymer, thus forming a fme continuous conducting matrix
throughout the bulk material.
The most important domain in applications of conducting
blends are antistatic materials. Conductivities for antistatic
applications need not to be high (10e6 - 10” S/cm ranges are
sufficient). Some materials using polythiophene or doped
polyaniline were already introduced for packaging of electronic
items. Another very important application seems to be
electromagnetic shielding which requires higher conductivities
( 10m3- 10-l S/cm typically in antiradar protection). Blends of
conducting polymers in conventional polymers are very
promising materials for this purpose. The third potentially
membranes for gas separation of high selectivity.
2. Conductivity of blends
Phosphoric acid diesters are known to protonate and
simultaneously plasticize polyaniline (PANI) [3]. Such doped
polyaniline can be processed thermally up to 220°C or corn
solution. For our experiments we used polyaniline doped with,
both, aliphatic and aromatic phosphates. The following blends
were investigated:
* polyaniline/diisooctyl phosphate (DiOHP) - PVC
* polyaniline/di(m-tolyl) phosphate (DmTHP) - PVC
* polyaniline/diphenyl phosphate (DPHP) - PVC
* polyaniline/diisooctyl phosphate - poly(methy1
methacrylate)
* polyaniline/diisooctyl phosphate - polystyrene
* polyaniline/diisooctyl phosphate - cellulose acetate-butyrate
* polyaniliue/diisooctyl phosphate - cellulose propionate.
Blends of PVC were prepared by extended mixing of
plasticized PANI/diester with the plasticized PVC in a mortar
and then hot pressing of thin films. Plasticized PVC was
obtained by mixing PVC powder with a plasticizer, for instance,
diisooctyl phthalate, tricresyl phosphate, or triphenyl phosphate.
The conductivity of the blends depends on several factors,
namely, a processing temperature, content of the doping agent, or
a content of the conducting phase in the nonconducting matrix, as
well as the quantities of the PVC plasticizer. The conductivity of
the blends pressed at 160°C vs. content of doped polyaniline is
shown in Fig. 1. As can be seen, the percolation threshold for all
PVC blends commences at a loading 5 - 7wt% of doped
polyaniline. In the region of the contents of 7 - 2Owt% the
conductivities of all samples are high enough for most
technological applications. On the other hand, these contents are
low enough not to change significantly mechanical properties of
nonconducting matrix.

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0 PAMDmTHP n PAIWDiOHP APANUDPHP does not have significant influence on the macroscopic properties
of the blend. When the percolation threshold is reached, though,
a three-dimensional network of conducting globular aggregates
in the insulating matrix is created. This network is responsible
for a blend being conductive, but at the same time the
mechanical properties have to be ascribed to by the so called
parallel model and are the combination of the mechanical
3 l.OE-8 < properties of both phases.
0 10 20 30 40 50 However, the Young modulus of PVC blends pressed at
Content of PANIidiester [wt%] 160°C does not depend strongly on the PANUDiOHP content and
the value of the modulus remains between 100-300 MPa for
Fig. 1. Conductivity of PVC blends pressed at 160°C vs. content PANIIDiOHP-PVCldiisooctylphthalate and 15-25 MPa for
of the conducting phase. Molar ratio of PANI to diester: 110.3. PANI/DmTHP-PVCltriphenyl phosphate blends which is only
Our systematic studies show that the content of the slightly higher than that of neat plasticized PVC.
phosphoric acid diester has no influence on the conductivity. For
example, the conductivity of the PVC blend co&ining 15% of 0 PANIDnTHP o PANUDiOHP
PANUDiOHP, for the PANI:DiOHP molar ratio of 1:0.27 is Yg
- 200
9*10e5 S/cm, while for 1:0.36 molar ratio it is 1.5*1U5 S/cm.
Similarly, the conductivity slightly depends on the time of the hot e2 150 lo
pressing at a given temperature. We found that the optimum +i 0
100
time for hot pressing is 20 min. After that time conductivity of z8 50 i 0
%
blends containing 7 - 15% of the conducting phase increases one
order in magnitude comparing to these pressed during 1 min. s3 03
and reaches IOe6- 1Oe4 S/cm depending on the PANI content. 0 20 40 60 80 100
The conductivity of the blends containing greater amounts of the Content of PANI/diester [wt%]
conducting phase remains the same or insignificantly decreases.
Polyaniline doped with aliphatic or alkyl-substituted- Fig. 2. Elongation at break of PVC blends pressed at 160°C vs.
aromatic phosphates shows the highest conductivity at the content of the conducting phase. Molar ratio of PANI to diester:
pressing temperature of 100°C and decreases one or two orders 1 I 0.3.
of magnitude at 160°C. However, the temperature usually
applied in PVC processing is 150-170°C. Hence most of the The tensile strength of PVC decreasesfrom 40 MPa
measurements was performed for the films pressed at 160°C. (plasticizedPVC) to 25 MPa uponmixing with PANIl DmTHP
Blends of PANI doped with DiOHP with poly(methyl (8 MPa when PANUDiOHP is used), and remainsrelatively
methacrylate) were cast as thin films from chloroform solutions. unchanged up to 45% of the conductingphasein theblend.
The conductivity of the blends is in the range of 10” - 10’ S/cm. It is worthy to mentionthat stress-strain
behavior of PVC-
Transparent films showing the conductivity of 10s3 -IO-’ S/cm PANUDmTHPblendsdiffers for variouscontentsof polyaniline.
were obtained by casting from m-cresol. The solutions were The stress-straincurves obtainedfor samplescontainingless
stirred during 6-7 hrs and then centrifuged in order to remove than 5% of PANUDmTHPis characteristicof neckingand cold-
fine insoluble particles. Similarly, transparent films of cellulose drawingpolymers,samples containinglo-20% of PANUDrnTHP
derivatives and polystyrene were obtained. The conductivity of behavelike ductile polymers,while samplescontainingmore
the cellulose blends containing 5% of polyaniline is 10” S/cm. than 25 % of the conductingphaseare brittle. This behavior,
Scanning electron microscopy shows very homogenous however,can be “controlled” by addingdifferent amountsof a
distribution of all components of the blends. Only the transparent PVC plasticizer.
films of polystyrene blends cast from m-cresol solutions are not
homogenous on a microscopic scale. Nonconducting regions of 4. Conclusions
polystyrene are scattered in the continuous conducting phase as
separated islands. Blendsof polyanilinedopedwith phosphoricacid diestersin
conventionalpolymershave beenfabricated.They appearto be
3. Mechanical properties particularly attractive by combiningrelatively high conductivity
Mechanical properties of composites or blends are with goodmechanicalproperties.
profoundly influenced by their composition and morphology.
Addition of the doped polyaniline to the conventional polymers 5. References
slightly impairs their mechanical properties. Elongation at break
of the plasticized PVC reaches cu. 210% and adding 5wt”/o of [I] Y. Cao, P. Smith, A. J. Heeger,SyntheticMetals, 48
the conducting phase it decreases to ca. 150%. It depends (1992)91.
strongly on the content of the conducting phase and is [2] A. J. Heeger,Science and Applications of Conducting
contentedly high for low contents but decreases abruptly above Polymers, W. R. Salaneck,D. T. Clark and E. J.
the percolation threshold (Fig. 2). It can be explained, that below Samuelson, Eds.,IOPPublishingLtd., Bristol, UK, 1990.
the percolation threshold the conducting phase is dispersed in the [3] J. Laska,A. Pro& S. Lefiant, J. Polymer Sci.: Part A:
form of separated islands in the continuous PVC matrix and it Polymer Chemise, 33 (1995) 1437.