Makromol. Chem.

186, 71 - 75 (1985)

71

Interaction of poly(dially1dimethylammonium chloride) with ferro- and ferricyanide anions

Esen A . Bekturov*, Sarkyt E. Kudaibergenov, Valeri Zh. Ushanov, Saule S. Saltybaeva
Institute of Chemical Science, Academy of Sciences of the Kazakh SSR, Alma-Ata 480100, Krasin str. 106, USSR (Date of receipt: January 11, 1984) SUMMARY: The interaction of poly(1,l -dimethylpyrrolidinium-3 ,Cdiylethylene chloride) [poly(diallyldimethylammonium chloride)] (1) with ferro- and ferricyanide anions was investigated by conductometric titration, viscometry, IR and Raman spectroscopy. It could be shown that the binding of ferro- and ferricyanide anions with 1 proceeds by means of an ionic mechanism and is accompanied by a spectral shift of the cyanide bands.

Introduction

The interaction of polyelectrolytes with small ions and molecules is of considerable interest' -4). The ability of cationic polyelectrolytes to precipitate the cyanides of iron, copper, silver and gold is well k n o ~ n ~ Unfortunately the structure of the products ,~). remained more or less unknown. This paper reports on a study of the interaction of the cationic polyelectrolyte poly(diallyldimethylammonium chloride) *) (1)with ferro- and ferricyanide anions by means of viscometric, conductometric, Raman and IR spectroscopic measurements.

Experimental part
Poly(diallyldimethy1ammonium chloride) (1) with a molecular weight of 8. I d and 40.I d was used. The molecular weight was determined by means of an analytical ultracentrifuge 3 170/b type (MOM, Hungary) at 50000 r. p. m. and 298 k 0,l K in methanol using the FloryMandelkern equation7). Viscometric measurements were carried out with an Ubbelohde viscometer at 298 0,l K. Conductometric titration was performed with a conductometer of type

*)

Systematic name: poly( 1,l -dimethylpyrrolidinium-3 ,Cdiylethylene chloride).

0025-1 16X/85/$03.00

12

E. A. Bekturov, S. E. Kudaibergenov, V. Zh. Ushanov, S. S. Saltybaeva

OK-102/1 (Hungary) at room temperature. Raman spectra of K4 [Fe(CV6], K3 [Fe(CV6] and of the reaction products with 1 were recorded both in the solid and the liquid state, using the Raman spectrophotometer Ramanor HG.2S (France) at room temperature. An argon ion laser with I = 514,s nm was used for excitation. The intensity of radiation was 200 mW. The IR spectra of the samples were registered on the spectrophotometer UR-20 (DDR) with KCI pellets. Complexes of 1 with ferro- and ferricyanide anions were prepared by mixing concentrated (10 wt.-%) or diluted (1 wt.-%) aqueous solutions of the initial compounds. Reagentgrade salts % [Fe(CN6] .3H,O, K3 [Fe(CN)6], KC1, K,S04, and Na3P04. 1 2 H z0 were used.

Results and discussion Earlier8s9)we studied the influence of chloride, sulfate and phosphate anions on the hydrodynamic sizes of cationic polyelectrolytes. It was shown that the values of intrinsic viscosities of polycations decrease in the order: C1- < SOT, < PO,-3. This is attributed to the formation of intramolecular bridges which lead to a decrease of polyelectrolyte dimension. Fig. 1 represents the influence of C1-, S , , PO;3, [Fe(CN)6]-3 and [Fe(CN)6]-4 O, ions on the intrinsic viscosity [ q ] of 1. The effects of C1-, SO;, and P O r 3 ions are very similar, due to the high rigidity of the polyelectrolyte chain resistant to coiling because of the nonspecific binding of multivalent anions). A strong decrease of the intrinsic ViSCOSitY is observed in the presence of [Fe(CN)6]-4 and [Fc$CN)~]-~.This can be explained by a strong interaction between the complex anions and the quarternized nitrogen atoms of the polymer chain. It may be assumed that the interaction of 1 with ferro- and ferricyanide anions occurs both intramolecularly and intermolecularly resulting in crosslinking. Probably, the sharp decrease of [ q ] at the mol 1- ( = 0,005 -0,05 mol 1-I) is mainly p interval of C, = 5 . - 6 due to the intramolecular crosslinking as the system is water-soluble, whereas the intermolecular crosslinking takes place at C,> 6 . mol * 1- @ > 0,05 mol 1- ) leading to insolubility and consequently to phase separation of the system.

B
I -

Fig. 1. Plots of the intrinsic viscosity of 1 versus the ionic strength p in the presence of different salts. (A): KCl, (0): K,SO,, (V):Na3P04, ( 0 ) :K4[Fe(CV6] and ( ): K3 [Fe(CN)61

Interaction of poly(dially1dimethylammonium chloride) with. . .

13

Fig. 2. Conductimetric titration curves for systems [1]/[K4 [Fe(CN),]] (1) and Vl/[K3 [Fe(CN)611 (2)

I!!

Raman spectra of K4[Fe(CN),] and its complex with 1 ( - - -) in the solid state (a) and in aqueous solution (b) Fig. 3.
( )

(a)

(b)

2200 2100 2000 2200 2100 2000 Wave number in cm-'

m-

The conductometric curves in Fig. 2 show the mole ratio of [1]/[Fe(CN),]-4 and [l]/[Fe(CN),]-3 to be 5 : 1 and 3 :1, respectively. To elucidate the structure of the cyanide complexes incorporated in the polymer chain the Raman and IR spectra") were analyzed by comparing the C = N bands of & [Fe(CN),] and K3 [Fe(CN),] with those in their reaction products with 1.As seen in Fig. 3 the Raman spectrum of the solid & [Fe(CN),] shows 5 bands and that of the aqueous solution 2 bands for the C = N group. Upon interaction of K4 [Fe(CN),] with 1, the C = N bands at 2025, 2041, and 2073 cm-I disappear. The bands at 2063 and

74

E. A. Bekturov, S. E. Kudaibergenov, V. Zh. Ushanov, S. S. Saltybaeva

LOO

+ \
600

I " I

comp

2100 2300 W a v e number in cm-'

1900

2094 cm-' are shifted by 7 and 1 1 cm-' to a lower frequency, respectively. Besides, a new band at 2128 cm-' appears in the Raman spectrum (Fig. 3(a)). In aqueous solution the C = N bands of K4[Fe(CN),] (2059 and 2094 cm-'), as a result of interaction with 1, are shifted by 8 and 9 cm-' to a lower frequency, respectively. As well as in the solid state a new band appears at 2 126 cm-' (Fig. 3 (b)). The IR spectrum of & [Fe(CN),] shows 6 lines at 1992, 2038, 2055, 2070, 2080, and 2100 cm-', corresponding to the C = N group (Fig. 4). All bands with the exception of that at 2055 cm-' disappear upon interaction of K4[Fe(CN),] with 1. A new band at 2 110 cm-' appears in the IR spectrum. However, we did not observe an effect on the Fe-C bond in both the Raman and the IR spectra. Upon interaction of K3[Fe(CN),] with 1 the C E N band in the Raman spectrum (2 128 cm-' ) and in the IR spectrum (2 11 8 cm-' ) remain unchanged. Attention must be paid to the new CN bands in the Raman spectra (2 128 cm-I in the solid state and 2 126 cm-' in the liquid state) and in the IR spectra (2 110 cm-I in the solid state) which coincide with the CN bands in the Raman and IR spectra of K,[Fe(CN),]. This phenomenon is probably due to the attraction of 6- and n-electrons of the CN groups by the positive charges of the nitrogen atoms of 1. The deficit of these electrons is probably reinstated from the 6-and n-orbitals of the Fe+2 ion. An estimate by means of the intensity ratio of CN bands shows that about 25% of Fe+2ions in K4[Fe(CN),] are oxidized into Fe+, ions. Thus, the interaction of ferro- and ferricyanide anions with 1 proceeds by means of an ionic mechanism and is accompanied by a shift of the CN bands.

We would to thank Prof. G. Reinisch for the samples of poly(diallyldimethylammonium chloride).

')

E. A. Bekturov, R. E. Legkunetz, "Assotziatzya Polimerov s Malymi Molekulami" (Association of Polymers with Small Molecules), Nauka Kaz. SSR,Alma-Ata 1983 E. A. Bekturov, L. A. Bimendina, S. E. Kudaibergenov, "Polimernye Komplexy i Katalizatory" (Polymer Complexes and Catalysts), Nauka Kaz. SSR, Alma-Ata 1982

Interaction of poly(dial1yldimethylammonium chloride) with. . .

3 E. Tsuchida, H. Nishide, Adv. Polym. Sci. 24, 2 (1977)
4,

75

6,
) )

9,
lo)
I)

M. Kato, N. Oki, H. Ohno, E. Tsuchida, N. Oyama, Polymer 24, 846 (1983) L. N. Esenovskaya, L. Ya. Tzarik, Yu. M. Tshikin, Zh. Prikl. Khim. (Leningrad) 53, 1144 (1980); Chem. Abstr. 93, 115511e (1980) L. N. Esenovskaya, L. Ya. Tzarik, Yu. M. Tshikin, Zh. Prikl. Khim. (Leningrad) 54, 923 (1981); Chem. Abstr. 95, 191746s (1981) L. Mandelkern, P. J. Flory, J. Chem. Phys. 20, 212 (1952) Sh. Sh. Shajakhmetov, S. E. Kudaibergenov, E. A. Bekturov, Izv. Akad. Nauk Kaz. SSR, Ser. Khim. 29, 29 (1979); Chem. Abstr. 92, 7085q (1980) E. A. Bekturov, Sh. Sh. Shajakhmetov, S. E. Kudaibergenov, Polymer 21, 787 (1980) Ch. Wandrey, W. Yaeger, G. Reinisch, Acta Polymerica 33, 156 (1982) K. Nakamoto, Infrakrasnye Spektry Neorganisheskikh i Koordinatzionnykh Soedinenii (Infrared Spectra of Neorganic and Coordination Compounds), Mir, Moscow 1966