Polymer Gels and Networks 6 (1998) 233245

Polypyrrole/poly(2-methoxyaniline-5-sulfonic acid) polymer composite

Huijun Zhao, Gordon George Wallace*
Intelligent Polymer Research Institute, University of Wollongong, Northelds Avenue, Wollongong, NSW 2522 Australia Received 8 June 1998; received in revised form 9 July 1998; accepted 9 July 1998

Abstract The incorporation of an electronically conducting polyelectrolyte (poly(2-methoxyaniline-5sulfonic acid)[PMAS]) as the dopant in polypyrrole results in the formation of a new class of materials. The resultant polymer structure has high water content ('90%), reasonable electronic conductivity (58 S cm\) and multiple switching capabilities. The latter arises from the fact that both the polypyrrole and the PMAS are redox active. 1998 Elsevier Science Ltd. All rights reserved.

1. Introduction It is well known that conducting polymers such as polypyrrole are readily synthesised electrochemically according to

(1)

*Corresponding author. Present address: School of Applied Science, Grith University, Gold Coast Campus, PMB 50, Gold Coast Mail Centre, Queensland 9726, Australia 0966-7822/98/$ see front matter 1998 Elsevier Science Ltd. All rights reserved. PII: S 0 9 6 6 - 7 8 2 2 ( 9 8 ) 0 0 0 1 6 - 1

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The counteranion incorporated during synthesis may be a simple anion [1] such as chloride or nitrate or may itself contain some functionality, e.g. metal complexing agents [25], enzymes [69], antibodies [10, 11] and even living cells have been incorporated [1214]. Recently both ourselves [14, 15] and others [16] have advocated the use of polyelectrolytes (PEs) as the counteranion in electronically conducting polymer systems. This approach results in production of more chemically stable systems since it is dicult for large (polyelectrolyte) counterions to leach out of the polymer, even when the latter is reduced. The incorporation of immobile dopants during synthesis ensures that cation exchange processes predominate upon reduction/oxidation (Eq. (2)):

(2)

Furthermore, the introduction of polyelectrolytes introduces some unique properties to the resultant conducting polymer structure including a high water content, sometimes as much as 90% (w/w). These conducting polymerpolyelectrolyte composites can be dehydrated and rehydrated making them electronically conducting hydrogels. Finally, the use of polyelectrolytes as dopants provides a convenient route for introducing predetermined functional groups that are part of the polyelectrolyte chain. This can be used to introduce redox activity (e.g. ferrocene groups) [19] metal complexing groups [20] or groups that render the resultant material biocompatible [21, 22]. The use of appropriate polyelectrolytes can also result in improved mechanical properties [23, 24]. Previously reported work in this area has considered the introduction of non (electronically) conductive polyelectrolytes into the polymer networks. We report here the incorporation of conductive electroactive polyelectrolytes as the counterion system. In the course of this work, an electrically conductive polyelectrolyte, POLY(2METHOXYANILINE 5-SULFONIC ACID) was incorporated into polypyrrole as the dopant during growth. The eect of incorporating such a dopant on the electropolymerisation process as well as on the properties of the polymer produced has been investigated. 2. Experimental 2.1. Chemicals All reagents used were of AR grade purity unless otherwise stated. Pyrrole was obtained from Merck and was distilled prior to use. Poly(2-methoxyaniline-5-sulfonic acid) [PMAS] and p-toluenesulfonate sodium salt (PTS) were obtaianed from

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NITTO Chemical Industry Co., LTD and Merck respectively. All solutions were prepared with deionized Milli-Q water (18 M cm). 2.2. Instrumentation A princeton applied research (PAR) model 363 Potentiostat/Galvanostat was employed for the electropolymerisation. When the PAR-363 was used for application of pulsed potentials, it was combined with a home made signal generator (Science Faculty workshop in University of Wollongong, Australia). Cyclic voltammetric experiments were performed using a BAS CV-27 (Bioanalytical System Inc, USA). All electrochemical data were recorded using a MacLab interfaced with a Macintosh computer. All electrochemical experiments were carried out using a single compartment cell with a three electrode system. In the case of lm synthesis, a stainless steel plate (10.0;6.0 cm, mirror nish surface), a platinum coated PVDF membrane (0.22 m, d"6.5 cm) or an ITO-coated glass slide (4.0;1.0;0.5 cm) were employed as the working electrodes and a reticulated vitreous carbon plate (10;7;1 cm) auxiliary electrode was used. All electrode potentials were measured relative to a Ag/AgCl (BAS, 3 M NaCl) reference electrode. A standard fourpoint probe (made at the University of Technology, Sydney, Australia) was used to obtain the DC-conductivities of lms. Studies of the mechanical tensile strength of the membranes were carried out using an Instron Dynamic Analyser model 4303. 2.3. Polymer lm preparation All lms used for physical property tests were prepared electrochemically using either galvanostatic or potentiostatic polymerisation techniques. The composition of the polymerisation solutions and the electrochemical conditions used for lm preparation are shown in Tables 14. The lms for conductivity and tensile strength measurements were deposited onto a stainless-steel substrate electrode. For water content measurements lms were deposited on platinum-coated PVDF substrate. For capacitance/surface area measurements, the lms were electrochemically deposited on a platinum disc electrode. Films used for measuring optical properties were electrochemically deposited onto ITO glass unless otherwise stated. A solution containing 0.2 M pyrrole and 0.5%. PAS and a current density of 4.0 mA cm\ was employed.
Table 1 Conductivity and tensile strength data for PP/PMAS lms Sample number Composition of polymerisation solution 0.5 M Py#0.8% PMAS 0.2 M Py#0.5% PMAS 0.5 M Py#0.1% PMAS Conductivity  (S cm\) 5.4$2.3 7.9$1.8 8.5#1.7 Tensile strength (MPa) 89$35 97$41 111$47

1 2 3

Note: All lms were prepared galvanostatically at the charge density of 4.8C cm\. The current density used for samples 1 and 2 was 2.0 mA cm\ and, for sample 3 was 0.4 mA cm\.

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Table 2 Elemental analysis data of PP/PMAS polymer composite Specications (%) C H N S Amount 46.61 3.91 11.09 6.87 N/S ratio PP/PMAS ratio

3.69

1.84

Note: Polymerisation was carried out in a solution containing 0.2 M Py and 0.5% PMAS at current density of 2 mA cm\ for 4 h.

Table 3 The change of dimension of the polymer composite during dehydration Specications Diameter (cm) Thickness (cm) Volume (cm ) Wet polymer 4.0 0.35 4.4 Dried polymer 2.1 0.08 0.3

Note: Polymerisation was carried out in a solution containing 0.2 M Py and 0.5% PMAS at current density of 2 mA cm\ for 4 h. Volume" /4D2 h, where D"diameter, h"thickness.

Table 4 Surface area data of PP/PMAS lm SPECIFICATIONS C ( f cm\) & Capacitance ( f ) Surface area (cm) PP/PTS Film 20 70 000 3 500 670 000 33 500 PP/PMAS lm

Note: Polymerisation was carried out in a 0.5 M Pyrrole solution containing 0.5% PMAS or 0.1 M PTS at current density of 10 mA cm\ for 30 s. The measurements were carried out eloectrochemically using a triangular potential waveform with a potentil range 0.150.20 V (vs Ag/AgCl) and scan rate of 0.1 mV s\.

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3. Results and discussion 3.1. Electropolymerisation of pyrrole in the presence of PMAS The polymerisation of pyrrole in the presence of PMAS (1) shown below was investigated:

The polymerisation process can be described, according to:

(4)

Initially, polymerisation was carried out using a potentiodynamic method by application of a potential sweep (Fig. 1). It was found that the current increased with

Fig. 1. Cyclic voltammogram of 0.2 M pyrrole in 0.5% PMAS at a Pt disc electrode. Scan rate"20 mV s\.

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Fig. 2. Chronoamperometric responses at dierent potentials for oxidation of 0.2 M pyrrole in 0.5% PMAS at a Pt disc electrode.

increasing potential cycles indicating polymer deposition. The current response observed within the negative potential range (#0.2 V to !0.6 V) was due to the reduction and re-oxidation of the polymer formed and deposited on the electrode surface. The large increase in current in this potential range suggests high polymer deposition

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eciency and/or formation of a polymer with a large electroactive surface area. The results also indicate that the polymer can be formed at potentials as low as #0.40 V vs Ag/AgCl. Results obtained from potentiostatic polymerisation show an increasing current transient at potentials as low as #0.45 V vs AgAgCl (Fig. 2) conrming that this polymer can be formed and deposited at much lower potentials than polypyrroles containing other dopants. The low polymer deposition potential and high deposition eciency can be explained by considering the unique role of an electronically conductive polyelectrolyte such as PMAS. Upon application of a positive potential, oxidation of the pyrrole monomer will occur. Polypyrrole will then deposit on the electrode incorporating PMAS as dopant. Since this counterion system is itseslf a conducting polymer, electron transfer during subsequent polymerisation can be achieved not just through the polypyrrole network but also via the PMAS chain (Schematic 1). Since the eective electrode surface area continues to increase with polymer deposition time the rate of polymerisation is accelerated. Application of this positive potential is also sucient to oxidise PMAS [25] creating potential electrocatalytic sites for subsequent pyrrole oxidation. Chronopotentiograms recorded during growth using current densities in the range 0.42.0 mA cm\ showed a potential that was constant (varying between #0.40 and #0.45 V depending on current density) throughout the polymer growth period indicating that a conducting polymer was deposited.

Schematic 1. Schematic representation of the conducting polymer composite formation.

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Fig. 3. AFM imgae of dried PP/PMAS polymer.

3.2. Physical properties of the PP/PMAS polymer composite Conductivities of approximately 5 S cm\ and tensile strengths of about 100 Mpa were obtained for stand alone lms grown galvanostatically using current densities in the range of 0.42.0 mA cm\. The eect of the polymerisation solution composition on both the conductivity and tensile strength was investigated (see Table 1). The results indicate that lms with higher conductivity were obtained when a lower concentration of PMAS solution was employed. In contrast, an increase in the PMAS concentration up to 0.8% (w/w) results in an increase in the tensile strength. The surface image of a dried polymer composite was obtained using AFM (Fig. 3). It reveals a nodular morphology with the largest nodular size less than 100 nm. Note that the polymer sample used in this study was 4 mm thick (when grown wet). Drying of the polymer resulted in shrinkage of more than 90% of its volume and a very smooth surface was obtained. Attempts to compare surface morphology of the wet polymer composite and the dried polymer failed because high quality surface images of the wet polymer could not be obtained. Table 2 shows the results of elemental analysis. It was found that the ratio between the pyrrole and MSA units was 1.81.0. This ratio is much lower than polypyrroles prepared using conventional counterions where this value is normally between 3 and 4. This result indicates that excess sulfonate groups are present in the polymer

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Fig. 4. Dehydration of PP/PMAS as a function of time.

material, a result consistent with the high-water contents observed. The water content of the polymer composites formed were found to be greater than 90%. It was found that variations of the polymerisation had no marked eect on the water content of the resultant polymer composite. It should be noted that this polymer composite can be quite easily dehydrated in air but cannot be rehydrated if totally dried. Fig. 4 shows the change in mass due to dehydration of the polymer composite as a function of time. The polymer composite loses 70% of its weight in the rst 10 h (drying in air, at 25C). The dehydration of the polymer composite was accompanied by dimensional changes (see Table 3 and Fig. 5). The sample volume changed between the wet and dried state by a factor of approxiamately 15. The solubility of the polymer composite in other solvents was investigated. Immersion experiments revealed that only trace amounts of the polymer composite could be dissolved in water. The polymer was insoluble in all common organic solvents such as alcohol, DMF and ether. The optical properties of the polymer composite lm were characterised using UVVis spectrophotometry (Fig. 6). Samples were prepared by electrodeposition of PP/PMAS lm onto a conducting ITO glass plate. The results indicate that a doped (conducting) polymer was obtained. This is evidenced by the strong absorbance band observed at wavelengths greater than 620 nm. The surface area and capacitance of the polymer composite were measured electrochemically. It was found that the surface area/capacitance of the PP/PMAS polymer

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Fig. 5. A photograph of wet and dried PP/PMAS polymers. The original sample sizes of wet and dried polymer were 4.0 cm\ and 2.1 cm in diameter, respectively.

Fig. 6. UV/Vis spectrum of a PP/PAMS lm electrochemically deposited on a ITO glass plate.

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Fig. 7. Cyclic voltammogram of (a) PP/PMAS and (b) PP/PTS-coated Pt disc electrode in a solution containing 0.2 M KCl. Scan rate"20 mV s\.

composite obtained was about 10 times larger than that obtained for PP/PTS (Table 4). 3.3. Electrochemical properties of the PP/PMAS polymer composite Cyclic voltammograms recorded in a 0.2 M KCl solution reveal that the polymer obtained was electroactive (Fig. 7a) and similar to a polypyrrole coated electrode prepared using normal counterions such as Cl\, NO\ or PTS (e.g. Fig. 7b). When  a larger cation (Mg>) was employed, the cation incorporation/expulsion responses observed were even more pronounced than that observed in K> case (see Fig. 8).

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Fig. 8. Cyclic voltammogram of a PP/PMAS coated Pt disc electrode in a solution containing 0.2 M MgCl . Scan rate"20 mV s\. 

Fig. 9. Cyclic voltammogram of a PP/PMAS coated Pt disc electrode in a solution containing 0.2 M NaCOOC H . Scan rate"20 mV s\.  

When a large organic anion was used, the cyclic voltammogram clearly shows a pair of redox peak at about #0.3 V. This response is presumably due to the aniline based polyelectrolyte (see Fig. 9).

4. Conclusions A novel conducting polymer polyelectrolyte composite has been developed. The structure has good conductivity and mechanical properties. It also has high water content and an open porous, high surface area, structure in the wet state. Multiple electrochemical switches are available but apparently only in the presence of selected species. These properties should be usseful for membrane transport, controlled release

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and sensing applications. Perhaps most facinating is the apparent electrocatalytic growth of this polymer that occurs at low potentials. This will assist in incorporation of species such as proteins or living cells that are denatured at more extreme potentials.

Acknowledgements Professor Gordon Wallace acknowledges the continued support of the Australian Research Council. We are grateful to Nitto Chemicals for the supply of PMAS.

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