POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 10, 8285 (1999)

Preparation and Characterization of Polyacrylic AcidAlkali Metal Salt Complex

PeiXin Xu1*, ZhiZhong Chen2 and WenMing Xie3
1 2

Department of Chemistry, Zhejiang University, Hangzhou 310027, China Department of Physics, Zhejiang University, Hangzhou 310027, China 3 P O Box, 353, Zhejiang University, Hangzhou 310027, China

ABSTRACT W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
Polymeric solid ionic conductor is a new class in functional materials. Its study has grown vigorously in recent years. The polymerization of polyacrylic acid alkali metal salt complex is studied for the first time. Some important factors and reaction conditions, such as polymerization temperature, concentration of initiator and amount of alkali metal salt, have been discussed. The results, show that the polymerization temperature should be controlled at about 60C and the best initiator's amount is 0.040.05% of the whole weight of materials. The complex has been characterized with infrared spectroscopy, differential scanning calorimetry, conductance ratio and adhesion strength determinations, acute toxicity and skin allergy reaction. This complex is a kind of multifunctional medical conductive adhesive with good performances in medicine, conductive adhesiveness and pressure sensitivity. 1999 John Wiley & Sons, Ltd.
KEYWORDS: polymeric solid ionic conductor; polyacrylic acidalkali metal salt complex; medical conductive adhesive; molecular design; conductivity

INTRODUCTION W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
The early study of polymeric solid ionic conductors (PSIC) is focused on polyethylene glycol oxide alkali metal salt complex system [1, 2]. Compared with inorganic solid ionic conductor, PSIC has the following advantages: (1) good viscoelasticity, adhering tightly to electrodes; (2) good forming capability, easily formed into all kinds of different shapes according to different requirements; (3) high chemical and electrochemical stabilities; (4) good organism ion-conduction property. The ionconduction of PSIC is very similar to that of an organism, therefore PSIC can be used as solid electrolyte in the preparation of biological electrodes. There is a growing interest about appliances of PSIC in cell, electrochromic display, sensor, high capacity electric condenser, solid photoelectric chemical pool, electrochemical transistor, molecular circuit, memory meterials, auto-filter, solid-state microelectro chemical transistor and new field for chemical reaction, etc. [3]. But there is no report about PSIC used as a biomedical electrode adhesive. Based on the molecular design principle of traditional medical adhesive and the conductive mechanism of PSIC, a molecular structure design for medical conductive adhesive is described. A new kind of PSIC, medical conductive adhesive, is
Received 12 August 1997 Revised 21 October 1997 Accepted 10 November 1997

* Correspondence to: PeiXin Xu, Department of Chemistry, Zhejiang University, Hangzhou 310027, China. Contract grant sponsor: Natural Science Fund of Zhejiang Province.

CCC 10427147/99/01008204 $17.50 1999 John Wiley & Sons, Ltd.

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obtained by solution polymerization using acrylic acid as the first monomer, and acrylamide derivant with hydroxy, amido, etc., functional group as the second monomer, then the polymer complexes with alkali metal salt. This adhesive has such advantages as good adhesiveness, low resistance, difficulty in drying, no residue, is nontoxic and produces no skin allergies.

RESULTS AND DISCUSSION W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W

Selection of Polymerization Formulation Ideal of Molecular Design. According to the functions and properties of our required medical conductive adhesive, the design target should be a polymer that has moderate adhesiveness, can dissociate alkali metal salt and impel ions to transfer quickly. This polymer has not only adhesiveness ingredients, but also the heteroatom with solvation capability so that it can complex alkali metal salt with low lattice energy to form polymeric viscoelastic ionic conductor. The major factors that affect the complex's conductivity are the number and transfer speed of charged ionic carriers. In the polymer the carrier's production accords with the following equation: ni no exp Ea2kT 2 where ni is the number of carriers, E the dissociation energy of alkali metal salt, e the dielectric constant, T the thermodynamic temperature, and n0 and k are constants. From eq. (2) we know that the number of carrier produced is more if e is big and E is low. But the major factor that affects the carrier mobility is the thermal motion of the polymer's segment, which dominates the ionic transference in the amorphous regions of the polymer. The relationship of temperature and its conductivity follows the WilliamsLandelFerry (WLF) equation: ! C1 T Tg 'T log 3 'Tg C2 T Tg where C1 and C2 are parameters of the equation, Tg glass transition temperature, T thermodynamic temperature and ' is conductivity. It shows that the conductivity is good if Tg is small. Traditional acrylic ester pressure-sensitive ad-

EXPERIMENTAL W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
Materials and Standards Acrylic acid, acrylamide derivant, ammonium persulfate, alkali metal salt (LiCl, NaCl, KCl) and emollient were used. Acrylamide derivant is selfmade and other materials are analytical reagent grade. Polymerization and Treatment of Polymer A four-necked flask with mechanical agitator, condenser, thermometer and dropping funnel was used for the polymerization. After replacing the air in the flask by nitrogen, materials were added to the flask in a specific sequence. As the agitator and heater were turned on, ammonium persulfate was added. The temperature was controlled at about 60C for 23 hr. Finally alkali metal salt and emollient were added and the pH value of the liquid in the flask was adjusted to 7.0. After the heater was turned off and the temperature decreased to room temperature, the target polymer was obtained. Analysis and Test For the conversion 23 g of reaction liquid was taken from the flask and put into a weighing bottle that had been weighed and dried. Two or three drops of hydroquinone solution were added, and it was then dried, to constant weight and the conversion was calculated according to the following formula: G1 G0 W C7 1007 1 G0 M where G0 is the weight of reaction liquid, G1 the weight of reaction liquid that has been dried to constant weight, W the weight percentage of nonvolatile components in polymerization formulation, M the weight percentage of monomers in polymerization formulation, and C% is the conversion. The complex's structure was analysed with IR and differential scanning calorimetry (DSC) methods. The adhesion strength was determined according to GB532-82 [4]. The toxicity and allergy to skin were tested according to GB7919-87 [5].
1999 John Wiley & Sons, Ltd.

FIGURE 1. Effect of polymerization temperature on conversion. Polym. Adv. Technol. 10, 8285 (1999)

84 / Xu et al.

lattice energy. In this course moderate emollient must be added. Polymerization Conditions Effect of Polymerization Temperature. Figure 1 shows that the change of conversion is rapid and then slow when the polymerization temperature rises. The polymerization temperature should be controlled at about 60C. If the temperature is lower, the speed of polymerization is slow. When the temperature is lowered to 40C, the conversion may be only 96% after more than 10 hr. The reason is that under low temperature the decomposition rate of the initiator descends, the produced free radical reduces and induction period prolongs. All these lead to the polymerization rate descent. If the temperature is too high, the polymerization is severe and the heat dispersion is difcult: the reaction is not easy to control and it results in explosive polymerization. Effect of Initiator's Concentration. Figure 2 shows the relationship between the amount of initiator and the conversion in this polymerization system. When the polymerization temperature is kept at 60C, polymerization time is 2 hr and other conditions are controlled as before. The conversion increases with the increase in the initiator's concentration. The result shows that the best initiator's amount is 0.040.05% of the whole weight of materials. If the amount is too small, the polymerization is not complete, the conversion is low and the post-treatment process is difficult. If the amount exceeds 0.05%, the conversion is high, but the molecular weight is low and the adhesiveness is worse. Effect of Amount of Alkali Metal Salt on Conductivity. Figure 3 shows that the conductivity of the complex increases linearly with the increase in the amount of alkali metal salt at rst, then declines sharply

FIGURE 2. Effect of amount of initiator on conversion.

hesive is obtained using acrylic ester with low Tg as the first monomer. Its main function is adhesion. The introduction of polar groups usually enhances its cohesion and adhesion. Since the medical conductive adhesive studied in this paper is used to prepare electrocardioelectrodes whose use is to measure the biopotential of a human body's surface, it needs only moderate adhesiveness. Component of Materials. In order to improve the conductivity of the complex and to obtain moderate adhesiveness, the best way is to increase the carrier's number and decrease the Tg. The copolymer is obtained with little branching and crosslinking using acrylic acid as the rst monomer and acrylic amide derivant as the second monomer. Then it complexes alkali metal salt with a low

FIGURE 3. Effect of amount of alkali metal salt on conductivity. 1999 John Wiley & Sons, Ltd.

FIGURE 4. DSC curves of different complexes containing different amounts of alkali metal salt: ZA1, 0 wt% of alkali metal salt; ZA2, 1.57 wt% of alkali metal salt; ZA3, 2.20 wt% of alkali metal salt. Polym. Adv. Technol. 10, 8285 (1999)

Polyacrylic AcidAlkali Metal Salt Complex / 85

peak. But there is no clear peak in the DSC curve during the course of lowering the temperature or the second rising temperature after quenching, which means there is no crystal phase in the complex. This is helpful to ionic mobility, and hence this system has excellent conductivity. The endothermal peak is because of further high crosslinking of the polymer at high temperature. After this test, the sample becomes hard, fragile and swelling in water. This proves its high crosslinking. Conductance Ratio Determination. After dehydration, the complex is made into slices, and its conductance ratio is 8.2 104 S/cm determined by 7150 Digital Multimeter at room temperature.
FIGURE 5. DSC curves of different methods of temperature rise; A, the course of temperature rise in normal way; B, the course of the second rising temperature after quenching; C, the course of lowering temperature.

Adhesion Strength Determination. Referring to GB532 -82, the adhesion strength is 6. 5 N/25 mm using adhesive-bonded fabric at a speed of 200 mm/min. Acute Toxicity and Skin Allergy Reaction. According to GB7919-87, the complex is proved to be nontoxic and non-allergenic.

after it reaches the highest point. The reason is that when the salt's concentration is low, the number of carrier's increases linearly with the increase of the amount of salt, therefore the conductivity increases. But if too much salt is added, its dissociation is not full. The salt will separate out when the complex takes shape, which will result in the appearance of a crystalline phase in the complex. Accordingly the resistance of the ion's transference increases and the conductivity declines sharply. Characterization and Performance Test IR Spectroscopy of the Complex. IR spectroscopy of the complex is obtained by using Nicolet 5DX Fourier Transform IR spectrograph while the sample is made into slice. The gure shows 35003200 cm1, 1670 cm1, 1610 cm1 and 15601539 cm1 are the absorption peaks of amidogen and carboxylic salt. The absorption peak at 650 cm1 proves the existence of imide in the complex system. DSC Analysis. DSC analysis is measured with a Perkin Elmer DSC-7 differential scanning calorimeter at a heating rate of 10C/min. Figure 4 shows different DSC curves of samples with different amounts of alkali metal salt. The amount of alkali metal salt has a great influence on the Tg of complexes. The addition of alkali metal salt compels the interaction of intramolecular and intermolecular forces to change, and increases the action between alkali metal ion, acid ion and polymer chain. The result is that polymer chain becomes rigid and the Tg increases. Figure 5 shows that there is an endothermal peak at about 220C. It is perhaps a crystal fusion

CONCLUSIONS W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
Unlike the traditionally used polyether or polyester as taxogen, a polyacrylic acidalkali metal salt complex synthesized by solution polymerization has good adhesiveness, high chemical and electrochemical stabilities, and excellent conductivity. As a new class of PSIC, it has such advantages as rapid response, high stability, good repeatability, is not toxic and is nonallergenic to skin when used in preparing biomedical electrodes. The comprehensive properties of the complex meet the requirements of actual appliances.

ACKNOWLEDGMENTS W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
We appreciate the financial support provided for this work by the Natural Science Fund of Zhejiang Province.

REFERENCES W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
1. D. E. Fenton, J. M. Parker and P. V. Wright, Polymer, 14, 589, (1973). 2. M. B. Armand, Solid State Ionics, 9 & 10, 745, (1983). 3. Q. C. Gu, W. Z. Xu and T. L. Mo, J. Functional Mater., 22(1), 21, (1991). 4. A Collection of National Standard of the People's Republic of China, GB 53282, 4, 36, (1983). 5. A Collection of National Standard of the People's Republic of China, GB 791987, 93, 359, (1991).

1999 John Wiley & Sons, Ltd.

Polym. Adv. Technol. 10, 8285 (1999)