European Polymer Journal 37 (2001) 865867

Short communication

On the hydrolysis of cellulose acetate in toluene/acetic acid/ water system

Niculae Olaru *, Adrian Andriescu, Liliana Olaru
``Petru Poni'' Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda nr. 41A, Iasi 6600, Romania Received 15 June 1999; received in revised form 2 May 2000; accepted 23 August 2000

Abstract This paper deals with the inuence of the toluene presence in the reaction medium on the distribution of substituents and the degradation of macromolecular chains during the partial hydrolysis of cellulose acetate in toluene/acetic acid/ water media, using sulfuric acid as a catalyst. Products with a low degree of substitution were obtained in shorter times than in the conventional procedure (acetic acid/water system). The presence of toluene in the hydrolysis bath leads to products with a higher amount of primary hydroxyls than in those obtained in the conventional process. The degradation of the polymeric chain during hydrolysis is lower in the rst period of reaction and higher in the last one in comparison with that produced in a toluene-free system. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Cellulose acetate; Hydrolysis; Substituent distribution; Chain degradation

1. Introduction It is well known that soluble cellulose acetates with low substitution are usually prepared starting from highly acetylated cellulose by its hydrolysis in an aqueous solution of acetic acid in the presence of sulfuric acid as a catalyst. The rate of hydrolysis is controlled by the temperature, the concentration of sulfuric acid and the percentage of water in the hydrolysis bath [1]. In these conditions, the deacetylation process is rather slow. The reaction medium also inuences other fundamental properties of the polymer: the distribution of acetyl groups among the three reactive positions of the anhydroglucose unit (AGU), namely C6 , C2 and C3 , and the degree of polymerization. On the other hand, some organic solvents like toluene or benzene are used either in the cellulose acetate synthesis or for the recovery of acetic acid from the precipitation medium [2,3].

In a previous paper [4] we studied the homogeneous hydrolysis of cellulose acetate in toluene-containing systems in order to obtain hydrolyzed products with a degree of substitution (DS) of about 1.70, useful for further derivatization. This alternative hydrolysis procedure was studied by us from the point of view of deacetylation kinetics. It was observed that the presence of toluene in this hydrolysis system leads to the increase of the reaction rate and the decrease of catalyst and water amounts used in the process. These eects were explained by the modication of composition of the solvation shell around cellulose acetate chains due to the presence of toluene in the hydrolysis bath. In this article we discuss the eect of toluene presence on the distribution of substituents among the C6 , C2 and C3 positions and on the degradation of macromolecular chains of hydrolyzed acetates.

2. Experimental
*

Corresponding author. Fax: +40-32-211299. E-mail address: nolaru@poni.ichpp.tuiasi.ro (N. Olaru).

The starting cellulose was cotton linters, activated overnight with glacial acetic acid. The acetylation was

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N. Olaru et al. / European Polymer Journal 37 (2001) 865867

Table 1 Conditions of hydrolysis in toluene/acetic acid/water systems at 60C Reaction system I II III IV V Composition (wt.%) Toluene 0 20 20 34 34 Acetic acid 92 72 67 63 58 Water 8 8 13 3 8

accomplished with an excess of acetic anhydride in acetic acid medium using sulfuric acid as a catalyst (10 wt.% with respect to the starting cellulose), then partial hydrolysis was performed without isolation of the product and the procedure described in the previous paper [4] was used. For the study of the inuence of toluene presence in the hydrolysis bath, ve experimental systems were selected whose compositions are presented in Table 1. The hydrolysis was carried out with continuous stirring at 60C and samples were removed after 8, 16, 24 and 32 h of reaction, respectively. DS determination was performed using the alkali saponication method [5]. Viscosity measurements were carried out at 25C using an Ubbelohde viscometer. Reduced viscosity, gsp ac, of cellulose acetate solutions in glacial acetic acid was performed at a concentration of 0.0952 g/dl for samples with DS 2X70, and corrections of concentration were applied for the others, so as to consider the variation of the monomer molecular weight which occurs because of the dierent DS values. Intrinsic viscosities of regenerated celluloses in ``cuen'' solutions were also performed. The regeneration of cellulose from cellulose acetate samples was realized in a diluted solution of sodium hydroxide. The distribution of substituents was evaluated by means of 1 H-NMR method proposed by Goodlett et al. [6], using a JEOL NMR apparatus operating at 60 MHz and room temperature.

Fig. 1. 1 H-NMR spectra of cellulose acetates obtained in the hydrolysis systems I spectrum a, II spectra b and d, and III spectra c and e (cf. Table 1).

3. Results and discussion It is known that in the conventional hydrolysis of cellulose acetate, a low percentage of water favors re-esterication and, since this reaction occurs preferentially at the C6 position, products of low primary hydroxyl content are then obtained [7]. Besides the water content, the presence of toluene in the hydrolysis bath may also inuence the distribution of acetyl groups in hydrolyzed cellulose acetates, as compared with those performed in acetic acidwater system.

In Fig. 1, 1 H-NMR spectra of ve samples of cellulose acetate obtained in three dierent reaction media are presented. A qualitative discussion on the inuence of toluene presence may be performed on the basis of the relative heights of the peaks assigned as C6 , C2 and C3 , which correspond to the acetyl groups bonded at 6primary, 2- and 3-secondary carbon atoms, respectively. Thus, for cellulose acetates with DS higher than 2.00, an increase of the primary hydroxyl content is observed for the samples obtained in toluene-containing system II (spectrum b), in comparison with those obtained in the absence of toluene (spectrum a). A further increase of the primary hydroxyl content is observed if the water content in the hydrolysis bath is increased from 8% (spectrum b) up to 13% (spectrum c), for the same content of toluene (20%) and for DS values slightly above 2.00. As the hydrolysis proceeds (for DS values below 2.00), the distribution of the substituents seems to be no more modied when using toluene or changing water content in the system (spectra d and e, as compared with a).

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Another important property of cellulose acetate which is signicantly inuenced by the hydrolysis medium is the degree of polymerization. For an evaluation of macromolecular chain degradation during hydrolysis, which could occur by both acetolysis and hydrolysis, the reduced viscosity (gsp ac) of cellulose acetate in acetic acid was used. To verify that gsp ac can properly describe the degradation process, we correlated it with intrinsic viscosity in ``cuen'' solution, for cellulose regenerated from eight corresponding cellulose acetate samples and a linear relationship between these quantities was obtained (Eq. (1)). gsp ac 0X035 1X265gY 14X254 r 0X985 1

Kinetic curves for cellulose acetate degradation in dierent hydrolysis media are depicted in Fig. 2. It is observed that in systems containing toluene, the chain degradation in the rst period of reaction (about 16 h) is lower and in the last one is higher than in a toluene-free system (curves II and I, respectively). Also, in systems with 20% toluene, the molecular weight is better protected when using a higher proportion of water (curve III). For higher amount of toluene in the mixture, the chain degradation in the rst 16 h is faster, when using only 3% water (curve IV) and comparable with that observed in the toluene-free system for 8% water (curve V).

We may assume that both the substituent distribution and rate of degradation observed in the presence of toluene can be explained by taking into account the composition of the solvation shell of cellulose acetate macromolecules. Kamide et al. [8] pointed out that the contact polymer-solvent occurs especially by means of polar moieties of the solvent and O-acetyl and hydroxyl groups of macromolecules. On the other hand, toluene has a better compatibility with acetic acid than with water, so its presence in the hydrolysis bath will lead to a decrease of acetic acid and a corresponding increase of water content in the solvation shell; the irreversible pseudo-rst-order kinetics of the hydrolysis performed in some toluene-containing systems was observed [4]. Therefore, the hydrolysis is favored and the re-esterication is diminished, especially at the more reactive primary hydroxyl groups (Fig. 1ac). However, this behavior is no more valid for DS values lower than about 2.00. Also, the chain degradation by acetolysis may be signicantly reduced in the presence of toluene (Fig. 2, IIII), due to the lower acetic acid content in the vicinity of macromolecules. This eect seems to be more pronounced for acetates with higher DS values. With respect to the eect of water proportion in a mixture containing toluene, it may be noted that an increase of water percentage will lead to an increase of compatibility between catalyst and the reaction medium and, therefore, to a dilution of the catalyst in the solvation shell which explains the slower degradation rate. When using smaller amounts of water, the reverse situation is valid, but it must be also added that a small quantity of water in the solvation shell favors a decrease of the acidity function (H0 ) of the catalyst [4] and, as a consequence, the rate of degradation increases (curve IV).

References
[1] Malm CJ, Fletcher CL. US Patent 2,013,830 10 September, 1935. [2] Bogan RT, Kuo CM, Brewer RJ. KirkOthmer Encycl Chem Technol, 3rd ed., vol. 5. 1979. p. 118. [3] Geurden J. Pure Appl Chem 1967;14:507. [4] Olaru N, Olaru L, Andriescu A, Tudorachi N. Die Angew Makromol Chem 1996;241:6776. [5] Tanghe LJ, Genung LB, Mench JW. In: Whistler RL, editor. Methods in carbohydrate chemistry, vol. 3. New York: Academic Press, 1963. p. 201. [6] Goodlett VW, Dougherty JT, Patton HW. J Polym Sci (Part A-1) 1971;9:155. [7] Tanghe LJ, Genung LB, Mench JW. In: Whistler RL, editor. Methods in carbohydrate chemistry, vol. 3. New York: Academic Press, 1963. p. 198. [8] Kamide K, Okajima K, Saito M. Polym J (Tokyo) 1981; 13:115.

Fig. 2. Kinetic curves for the degradation of cellulose acetate in the hydrolysis systems IV.