Fibre Chemistry, Vol. 38, No.

3, 2006

STRUCTURAL CHANGES IN FLAX CELLULOSE IN TREATMENT

WITH WATER—ALCOHOL SOLUTIONS OF ALKALI

M. I. Voronova, S. N. Petrova, UDC 676.16:548.75

T. N. Lebedeva, O. N. Ivanova,
and A. G. Zakharov

Incorporation of aliphatic alcohols in the NaOH—water—cellulose system creates conditions for more uniform
transport of hydrated molecules of NaOH into the bulk of a fibre. Alcohols shift the concentration interval of
the phase transition of cellulose I into cellulose II toward lower concentrations of NaOH and alter the structure
of the hydrogen bonds in the cellulose. The increased accessibility of different regions of cellulose for NaOH
is not directly due to an increase in the degree of its swelling.

During separation, modification, and chemical processing, cellulose can be exposed to multicomponent alkaline solutions
containing different inorganic and organic substances in addition to hydroxides. We previously [1] investigated the structural
changes in flax cellulose in solutions of alkalis — LiOH, NaOH, KOH. We will examine the effect of aliphatic alcohols
(ethanol, isopropanol, isobutanol) on the degree of swelling and structural changes in cellulose treated with solutions of NaOH
in the present article.
The methods of determining swelling and sorption of the alkali and water are similar to those reported in [2, 3]. The
structural changes in the cellulose after elimination of the alkali were observed based on the change in the ratios of the
optical densities of a series of bands in the IR spectra [4, 5] recorded on an Avatar 360FT-IR ESP spectrophotometer in the
4000-400 cm-1 frequency region. The samples were molded into pellets containing 1 mg of analyzed substance and 100 mg of
potassium bromide. The degree of polymerization (DP) of the cellulose was determined by the viscosity of a solution in
Cadoxen [6]. The aldehyde group content was determined by titration [7] and the lignin and α-cellulose content was determined
by the methods in [8] and [6], respectively.
We used flax cellulose separated by the alkali-peroxide method in our study. The characteristics of the cellulose are
reported below:

Content, %
α-cellulose 90.1±0.5
lignin 0.6±0.1
hemicellulose 9.0±0.5
ash 0.3±0.05
Iron content, mg/kg cellulose 16±0.5
Degree of polymerization 1000±20
Degree of crystallinity, % 65±3

We know that in mercerization in alcohol medium, alkaline cellulose is formed at a much lower concentration of NaOH
than in mercerization in water. The minimum concentration of NaOH required for formation of alkaline cellulose with a degree
of substitution of 100 is 3.5% in ethyl alcohol, 3.1% in isobutyl alcohol, and 2.8% in isoamyl alcohol (for comparison: 16-18%

Institute of Chemistry of Solutions, Russian Academy of Sciences, Ivanovo. Translated from Khimicheskie Volokna,
No. 3, pp. 23-26, May-June, 2006.

0015-0541/06/3803-0207 © 2006 Springer Science+Business Media, Inc. 207

 450 2.5
400
2.0
350

Swelling, %
300 1.5

n/nö
250
1.0
200
0.5
150

100 0.0
0 1 2 3 4 5 6 7 8 0 2 4 6 8
CNaOH, M CNaOH, M

Fig.1 Fig.2

Fig. 1. Swelling of flax cellulose in aqueous (1) and water—alcohol (2-4) solutions of NaOH.
Here and in the following figures; 2) water—ethanol; 3) water—isopropanol; 4) water—isobutanol.
Fig. 2. Sorption of alkali by cellulose in aqueous (1) and water—alcohol (2-4) solutions of
NaOH (nNaOH/nc: number of molecules of NaOH per elementary unit of the cellulose
macromolecule).

1000
900 4.0
Ñald. gr .105, mole/g

800
700 3.5
DP

600
500 3.0
400
300
2.5
0 1 2 3 4 5 6 0 1 2 3 4 5 6 7 8
CNaOH, M CNaOH, M

Fig.3 Fig.4
Fig. 3. Change in DP of cellulose n treatment in aqueous (1) and water—alcohol (2-4) solutions
of NaOH.
Fig. 4. Change in aldehyde group content in treatment in aqueous (1) and water—alcohol (2-4)
solutions of NaOH.

in water) [9]. Increased sorption of alkali metal hydroxides from water—alcohol solutions by the cellulose [9], activation of a
reaction between the cellulose and alkali, confirmed by an increase in the thermal effect, and an increase in the degree of
swelling of cotton cellulose in alkaline water—alcohol solutions [10] have been proposed as causes of this event. The deeper
modification of cellulose by sodium hydroxide observed in the presence of alcohols is considered the consequence of more
effective delivery of hydrated NaOH dipoles to the crystalline regions of cellulose [11].
The degree of swelling of flax cellulose in aqueous and water—alcohol (0.1 ppm alcohol) solutions of NaOH of varying
concentration is shown in Fig. 1. For all alcohols, except for isobutanol in the 0-2 M concentration interval, swelling is either
less in the presence of the alcohol or is almost the same as the swelling in water—alkali medium. The most important changes
in swelling of cellulose were observed for ethanol: first, the degree of swelling was much lower and second, there was no
characteristic maximum at a 2.5-3.0 M concentration of the alkali. As Fig. 2 shows, swelling of cellulose varied symbatically
to the change in sorption of the alkali in all cases.
We previously [1] hypothesized that swelling of cellulose is determined by the amount of water introduced in the first
and second hydration shells of the alkali metal ion and the position of the swelling maximum is determined by the concentration
of alkali at which rearrangement of the first hydration shell of the ion takes place due to a shortage of water molecules.
Unfortunately, there are no published data on the change in the structure of the hydration shells of the Na+ ion in water—

208
 97

96

93

α-cellulose, %
91

89

87

85
0 1 2 3 4 5 6 7 8
CNaOH, M

Fig. 5. Change in α-cellulose content in treatment

in aqueous (1) and water—alcohol (2-4) solutions
of NaOH.

CNaOH, M

CNaOH, M

Fig. 6. Ratio of optical densities D1375/D1325 (a) and D3360/D2900

(b) in treatment in aqueous (1) and water—alcohol (2-4) solutions
of NaOH.

alcohol solutions. However, we can hypothesize that the disappearance of the maximum on the cellulose swelling curve with
an increase in the concentration of NaOH in the presence of ethanol is the reflection of important rearrangement of the solvation
shell of the Na+ ion in this case.
Our data thus show that aliphatic alcohols added to water—alkali solutions do not significantly increase sorption of the
alkali and correspondingly swelling of flax cellulose. However, addition of aliphatic alcohols significantly affects the intensity
of decomposition and oxidation of this cellulose while not changing the overall direction of the processes. The DP of cellulose
(Fig. 3) and the aldehyde group content (Fig. 4) always decrease with an increase in the concentration of the alkali, while the
α-cellulose content (Fig. 5) passes through a maximum. However, in the first case, the effect of isopropanol and isobutanol
alone is clearly manifested, while in the other two cases, the effect of all three alcohols is pronounced.
Formation of the crystalline modification of cellulose II is the most characteristic structural change in cellulose as a
result of treatment with concentrated solutions of sodium hydroxide.

209
 It was previously shown in [11] that addition of alcohols in treatment of wood cellulose with a solution of NaOH
decreases the intensity of crystalline reflections due to an increase in the distances between planes (002) in the crystal lattice.
The structural changes in the cellulose after alkaline treatment are intensified with an increase in the length of the alcohol’s
hydrocarbon radical. The ratio of the optical densities of the absorption bands at 1375 and 1325 cm-1 in the IR spectra are most
sensitive to a change in the crystalline modification of cellulose [4].
As Fig. 6a shows, in treatment of flax cellulose with solutions of NaOH, the phase transition of cellulose I into cellulose
II takes place in the 2-3.75 M concentration interval. Addition of the alcohols to the NaOH—water system shifts the beginning
of the phase transition to a lower concentration of NaOH. In this case, conditions for more uniform transport of hydrated
molecules of NaOH over the entire volume of the preparation, including deep in crystalline regions, probably occur.
It was assumed in [11] that the gradual transition from the structure of cellulose I to cellulose II could result in the
appearance of intermediate metaphases. We can hypothesize that cellulose with such an intermediate structure should have
high reactivity.
The presence of a large number of hydroxyl groups almost totally contained in the hydrogen bond in the cellulose
molecule makes this type of intermolecular interaction the most important in the structure of cellulose and to a great degree
determines its properties. The band at 3000-3700 cm-1 corresponds to stretching vibrations of such hydroxyl groups in the IR
spectra of cellulose. The ratio of the optical densities DOH/D2900, where the integral optical density of the band at 2900 cm-1
is used as the internal standard, characterizes the overall strength of the hydrogen bonds in cellulose [5].
The curves in Fig. 6b show that the presence of alcohol affects the character of the change in DOH/D2900 when the
concentration of alkali increases. If the pronounced extremum with a maximum of the ratio at a ~2.0 M concentration of alkali
corresponds to the water—NaOH system, the smooth S-shaped curve in the case of isobutanol and the curve consisting of three
almost linear segments in the case of ethanol and isopropanol corresponds to water—alcohol—NaOH systems. In the presence
of these two alcohols, DOH/D2900 is almost constant up to a ~3.2 M concentration of NaOH. If we assume that the change in
DOH/D2900 reflects a change in the conformation of the cellulose macromolecules during alkaline treatment, then we can
conclude that the absence of conformational changes even with a 220-330% degree of swelling is the principal feature of
swelling of cellulose in water—ethanol and water—isopropanol solutions of NaOH (see Fig. 1).

REFERENCES

1. M. I. Voronova, S. N. Petrova, et al., Khim. Volokna, No. 6, 15-18 (2004).

2. D. N. Arkhangel’skii and T. V. Yushkova, in: Advances in Viscose Chemistry and Technology [in Russian], A. B. Pakshver
and G. G. Finger (eds.), NPO Khimvolokno, Mytishchi (1983), pp. 41-49.
3. M. I. Voronova, S. N. Petrova, et al., Zh. Prikl. Khim., 76, No. 12, 2043-2047 (2003).
4. I. Yu. Levdik, M. D. Inshakov, et al., Khim. Drevesiny, No. 3, 109-116 (1988).
5. R. G. Zhbankov, Infrared Spectroscopy of Cellulose and Its Derivatives [in Russian], Nauka i Tekhnika, Minsk (1964).
6. A. K. Dibrova and V. S. Matveev (eds.), Analytical Control of Production of Man-Made Fibres [in Russian], Khimiya,
Moscow (1986).
7. F. I. Sadov, N. M. Sokolova, et al., Laboratory Manual for the Course “Chemical Engineering of Fibre Materials”
[in Russian], GNTI, Moscow (1955).
8. A. V. Obolenskaya, Laboratory Studies in Wood and Cellulose Chemistry [in Russian], Ekologiya, Moscow (1991).
9. N. I. Klenkova, Structure and Reactivity of Cellulose [in Russian], Nauka, Leningrad (1976).
10. V. N. Galashina, S. M. Gubina, et al., Khim. Drevesiny, No. 1, 36-39 (1989).
11. I. M. Rotenberg, B. V. Vasil’ev, et al., in: Proceedings of the All-Union Scientific and Technical Conference “Physical
and Physicochemical Aspects of Activation of Cellulose” [in Russian], Riga (1981), pp. 51-55.

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