ORIGINAL PAPER

Synthesis and Characterization of Carboxymethyl Cellulosefrom Tunisian Vine Stem: Study of Water Absorptionand Retention Capacities

S. Mansouri • R. Khiari • F. Bettaieb •

A. A. El-Gendy • F. Mhenni

� Springer Science+Business Media New York 2014

Abstract The aim of this work was to study the effect of the

degree of substitution (DS) and the purity of sodium car-

boxymethyl cellulose (CMCNa) prepared from Tunisian vine

stem on the absorption and retention of water. Vine stem was

first delignified using souda-anthraquione, then bleached and

finally chemically modified, in order to synthesize different

CMCNa derivatives. The carboxymethylation reaction was

carried out in presence of NaOH (40 %) and monochloro-

acetic acid (ClCH2COOH), in n-butanol as a reaction solvent.

The obtained CMCNa derivatives were characterized using

different tools such as the DS, Fourier transforms IR tech-

niques, CP-MAS 13C-NMR, the exchange capacity as well as

the determination of modification reaction yield. The perfor-

mance of the prepared derivatives in term of absorption

capacities and retention capacities was established. The per-

formance of CMCNa derivatives was compared with that

achieved by commercial counterparts and it was concluded

that the prepared ones exerted higher efficiency.

Keywords Vine stem � Cellulose � CMCNa � Degree of

substitution (DS) � Exchange capacity � Absorption

capacity � Retention capacity

Introduction

Cellulose is the most abundant biopolymer on earth with an

estimated output of over 1011 tons per year. Most of its

biosynthesis takes place in the cellular walls of plants, but

four other sources are known, animal, bacterial, chemical

and enzymatic [1]. In the recent years, the utilization of

cellulose fibers in innovative areas of materials science has

been increased considerable attention because of three

potential advantages they posses, namely: (1) their bio-

renewable character, (2) their ubiquitous availability in a

variety of forms, and (3) their low cost [1].

Cellulosic fibers are widely used for many areas such as

in textile industries, papermaking and packaging industries,

in pharmaceutical applications, and preparation of inno-

vative materials such as ‘green’ composites. Consequently,

the utilization of cellulosic fibers is rising, and it is

becoming more and more difficult to satisfy the large

demand. That is why, in the new approach, non-wood

species and the annual plants can be viewed as alternative

sources of cellulosic fibers, especially in regions that are

poor in forest resources. Non-wood fibers could potentially

be used in applications that require materials with proper-

ties similar to these fibers. Moreover, non-wood fibers are

often obtained from agricultural wastes and can therefore

be valorized. There are many reported studies which

investigate the use of annual plants or/and agricultural

wastes as a new alternative sources to produce fibers [2–7].

These strategies were already applied in various countries

for an example: Portugal [8–10], India [11, 12], Malaysia

[13, 14], Iran [15] or Tunisia [2] and so on.

Cellulose is a polymer with an extremely high internal

cohesive energy, due to its high content of hydroxyls func-

tions. Consequently, it does not dissolve readily either in

common organic solvents, or in water. The exploitation of

S. Mansouri � R. Khiari (&) � F. Bettaieb � F. Mhenni

Research Unity of Applied Chemistry and Environment,

Department of Chemistry, Faculty of Sciences, University

of Monastir, 5019 Monastir, Tunisia

e-mail: khiari_ramzi2000@yahoo.fr

R. Khiari � F. Bettaieb

Laboratoire de Genie des Procedes Papetiers (LGP2), UMR

CNRS 5518, Grenoble INP-Pagora, 461 rue de la papeterie,

38402 Saint-Martin-d’Heres, France

A. A. El-Gendy

Cellulose and Paper Department, National Research Centre,

Dokki, Giza, Egypt

123

J Polym Environ

DOI 10.1007/s10924-014-0691-6

the OH-function of cellulose yielded one of the first semi-

synthetic polymers (cellulose acetates, nitrates, etc.).

Sodium carboxymethyl cellulose (CMCNa) is also a cellu-

lose derivative, produced by the etherification of hydroxyl

group of cellulose macromolecules by monochloroacetic

acid (MCA). CMCNa was synthesized for the first time in

1920 and it is the most used cellulose derivative. It is syn-

thesized by the alkali-catalyzed reaction of cellulose with

MCA. Two steps are required to produce CMCNa. These

steps are as follows.

The CMCNa is usually known as cellulose gum. It is

an anionic water-soluble polymeric polyelectrolyte. It was

used in many fields such as textile industries [16], paper

industries [17], agro food industries applications [16],

adhesive industries [18, 19], cosmetic and pharmaceutical

industries [20]. Several studies have reported the synthesis

of carboxymethylcellulose (CMC) using starting materials

from various vegetable plants [3, 6, 21–31]. The available

literature on CMC is mostly focused on the synthesis

aspects [yield, degree of substitution (DS), exchange

capacity (EC)…]. This work will be devoted to the

potential applications of the prepared cellulose deriva-

tives. In the same strategy, many cellulosic residues are

available in Tunisia such as the waste of vine plants

(Fig. 1).

This agricultural plant grapevine is commercially

grown. According to the Food and Agriculture Organiza-

tion report in Tunisia, grape production reached

1.31 9 108 tons in 2011. Owing to grape production, sig-

nificant quantities of vine fragments accumulate on

Fig. 1 Vine stem

ð1Þ

ð2Þ

J Polym Environ

123

Tunisian agricultural lands. This requires the cleaning of

the vineyards every autumn after grape harvesting [32].

This biomass is characterized by relatively high amounts of

extracts, lignin, and interesting amounts of holocellulose

compared to annual, non wood and wood plants [32]. In the

present study, the valorization of this biomass to produce

CMCNa, which have not been reported before, was con-

ducted as well as the investigation of the water absorbent

behavior of the prepared materials.

Experimental Section

Preparation of the Raw Material: Vine Stem

The stems were obtained from Monastir in December 2012

and dried under natural conditions (average relative

humidity: 65 %; average temperature: around 20 �C). They

were then washed in order to eliminate sand and were dried

again under the same conditions. Before pulping, the vine

stems (VS) were cut into small pieces with lengths of about

1–3 cm and crushed to 250 lm. All chemicals and solvents

used were reagent grade and used without further treatment

or purification.

Extraction and Bleaching of Cellulose from Vine Stem

The delignification procedure was carried out as mentioned

by Mansouri et al. [32]. Briefly, the preparation of extracted-

bleached cellulose is conducted in two steps. First, 10 g of

VS are impregnated in 100 mL of an aqueous soda solution

(15 % w/w) under stirring, for 2 h at 140 �C and under a

pressure of 3.6 bars. The ensuing fibers were then extensively

washed with water until neutrality, before being bleached

using 100 mL of sodium hypochlorite solution (12 % of

active chlorine) in alkaline medium pH around 12, for

15 min. Finally, the bleached fibers (BF) were extensively

washed with water until neutrality and air dried before

further use. Each delignification condition was carried out, at

least in duplicate and the difference between the various

values obtained was within an experimental error of 5 %.

Synthesis of CMCNa from VS and BF Prepared

from Agricultural Biomass

The cellulosic materials from vine stem (VS and or BF)

were used to prepare several qualities of CMCNa as

described in the Fig. 2. As reported Aguir and Mhenni [3]

and Khiari et al. [6, 33], two steps were needed to

accomplish the reactions namely: (1) the alkalization and

(2) Etherification. In alkalization pre-treatment about 5 g

of unmodified material was weighed and added to 30 mL

of 40 % aqueous sodium hydroxide followed by 30 mL of

1-butanol. Then the mixture was stirred for 24 h at 80 �C in

order to convert the hydroxyl to alcoolate groups. After

alkali treatment, etherification reaction was conducted by

adding 8.7 g and or 13.05 g of MCA to the reaction mix-

ture, heated up to 80 �C and stirred for 8 h. The slurry was

neutralized with 80 % acetic acid (vol/vol) until pH 6–8.

Then 400 mL of ethanol was added for precipitation. The

precipitated CMCNa was filtered and purified by washing

with ethanol for five times to remove undesired by pro-

ducts. Finally the CMCNa was filtered and dried at 50 �C

in an oven for 24 h.

Characterization of the Prepared Materials

In the following, several methods were established in order to

characterize the raw materials as well as the prepared sodium

of carboxymethylcellulose (CMCNa) from VS and BF.

Fourier Transform Infrared Spectroscopy and CP MAS

NMR

The infra red spectrum of extracted cellulose and car-

boxymethyl cellulose product were recorded by using

carb

oxym

ethy

lati

on

carboxymethylation

Extraction and bleaching of cellulose

washed, milled and sieved

Vine stem

V S BF

CMCNa-VS-1 CMCNa-BF-1

CMCNa-BF-2 CMCNa-VS-2

Fig. 2 Schematic

representation of the different

steps used to produce different

qualities of CMCNa from vine

stem

J Polym Environ

123

Fourier Transforms IR (FTIR) instrument with a resolution

of 16 cm-1 and scanning a wavelength range from 500 to

4,000 cm-1. KBr-based solid pellets made of a suspension

of 1 mg of the material under investigation and 100 mg of

anhydrous KBr were prepared and examined.

The CP-MAS 13C-NMR spectra were performed using

a ‘‘Avance400 BRUKER’’ with 4 mm ZrO2 rotors and The

magic angle of spinning was performed at 12 kHz spinning

rate. The CP/MAS spectra were recorded with a contact

time of 1.5 ms, a repetition delay of 5 s, a decoupling field

of 100 kHz and a 9000 proton pulse of 2.6 ls.

Determination of the Degree of Substitution and Yields

Reaction

The reaction yields and the DS were established to char-

acterize the prepared CMCNa. The reaction yield for each

obtained quality was evaluated by gravimetric method. The

measurement was repeated at least in duplicate and the

difference between the various values obtained was within

an experimental error of 5 %.

The DS was determined using a calcination-titration

method as described by Khiari et al. [6, 33]. A mass (m) of the

grafted cellulose was weighed into a ceramic crucible and then

it was mineralized in an oven at maximum temperature of

600 �C. The furnace temperature is increased from 25 to

550 �C for 20 min and 550 to 600 �C for 30 min. The sample

was held at 600 �C for 4 h. Finally, it was cooled at room

temperature. Ash containing Na2O and possibly traces of

NaCl, was dissolved in hot distilled water (80 �C). Then red

methyl indicator was added to the solution which turned to

yellow. The solution is then dosed with 0.1 mol L-1 H2SO4

(0.05 M) until a red color appeared. The reddish solution is

heated to remove the dissolved CO2 until the yellow coloration

regenerates. A second titration is performed with 0.1 mol L-1

H2SO4. DS was calculated using the following equation:

DS ¼162� 0:1�A

m

1� 80� 0:1�Am

ð3Þ

where: 162 is the molecular weight of the anhydrous glu-

cose unit and 80 the net increment in the anhydrous glucose

unit for every substituted carboxymethyl group. A: the total

volume of H2SO4 added and m the mass of CMCNa.

Conductimetric method (Gran’s Method) was also tested

and the obtained results were found in agreement with

those obtained by calcination, which was chosen because

of the availability and the expertise of our group. More-

over, calcination is more suitable to estimate the COO-

content especially when the starting sample may contain

some impurities, as it is the case of our material.

Because of the heterogeneity of the chemical composi-

tion of vine stem, it will be rough after modification to

calculate the DS of the hydroxyl functions, data that is

typically used to characterize the cellulose derivatives. So,

it is better to determine the EC. For that aim, a back

titration method was used. This technique was described in

literature for carboxymethylated Posidonia and cationized

cotton reported by Aguir et al. [4].

Study of Absorption and Retention Capacities’

of Prepared CMCNa from Vine Stem

The procedure inspired from the standard STN2:117/87 of

the German Codex [6, 34] was used for the determination of

the absorption capacity (AC) and retention capacity (RC) of

various prepared materials. A quantity of samples (W0)

were soaked in distilled water at 25 �C for 30 min after that,

it were drained for 5 min, the weight is noted W1. After that,

the drained sample was centrifuged during 16 min at

1,000 rpm. Finally it was weighed and dried at 105 �C for at

least 24 h [6] which the weight is noted W2. The AC and RC

were calculated using the following equation:

AC ¼ ðW1 �W0

W0

Þ ðg=gÞRC ¼ ðW2 �W0

W0

Þ ðg=gÞ ð4Þ

where: W0, W1 and W2 are the initial weight of the material,

the weight of the sample after soaked in water and dried for

5 min, and the material weight after centrifugation and

drying, respectively. The measurement was repeated at least

in duplicate and the difference between the various values

obtained was within an experimental error of 5 %.

Results and Discussion

Vine Stem: Characterization and Delignification

Previous to starting preparation of sodium carboxymethyl-

cellulose from VS or BF, its delignification process was

established. As expected, the analysis of chemical compo-

sition of the stem vine (VS) according the standards method

shows that the waste is characterized by relatively high

amounts of lignin (28.1 %), holocellulose (65.4 %) and

extractives, especially in ethanol-toluene mixture (11.3 %).

In contrast, the a-cellulose content is low (35 %) [32].

However they are similar to those observed for other annual

plants or agricultural crops [32, 33]. The important amounts

of polysaccharides in vine stem which justified envisaging

the valorization of such crops in cellulose derivatives field

and/or as a source of fibers for papermaking applications or

cellulose fibers-reinforced composite materials. The delig-

nification of vine stem using souda-anathraquione gave lig-

nocellulosic materials with yields ranging from 40 to 45 %.

The kappa number of the obtained pulp was about 18, which

corresponds to about 1–3 % of residual lignin in the pulp, if

one applies the common relationships between these two

J Polym Environ

123

parameters and uses the coefficient corresponding to soft-

wood. The second step of treatment was the bleaching of the

extracted lignocellulosic fibers (BF) with sodium hypo-

chlorite solution and gave yields approximately 40 %. As

expected, bleaching stage resulted in elimination of lignin

and pectin from the cellulosic materials. The kappa number

of the bleached pulps was 5, which corresponds to less than

1 % of residual lignin in the pulps.

The overall conclusion to be deduced from this part; that

despite the quite difference of composition element of vine

stem when comparing with some annual plants [6, 8, 35–

38], this biomass remains an interesting cellulosic source

and comparable with those of annual plant which justified

also their advantages for use as derivatives fibers or as new

absorbent materials.

Figure 3 shows the FTIR spectra of extracted and

bleached cellulose. The spectrum presents a typical profile of

cellulose in the zone between 1,500 and 500 cm-1. In par-

ticular, three characteristic peaks are present between 1,150

and 950 cm-1 attributed to the vibration and elongation of

the hydroxyl –O–H linkages. In addition, in the region

950–850 cm-1, the presence of the peak characteristic of

glucosidic units can be observed. The peak at 1,319 cm-1

indicates the (–O–H) bending. The band at 1,642 cm-1

corresponds to the bending mode of the absorbed water [41].

The spectrum shows also (–C–H) stretching vibration at peak

with wavenumber of 2,897 cm-1. Finally, the absorption

band at 3,347 cm-1 is due to the stretching frequency of the

(–OH) group as well as the intra- and inter-molecular

hydrogen bonds within cellulose macromolecules [39, 40].

Synthesis and Characterization of the Sodium

Carboxymethylcellulose

Effect of the Vegetal Specimen and the Initial Cellulosic

Substrate

Six absorbent materials qualities have been prepared from

vine stem waste as described in Fig. 2 which indicates the

followed steps to prepare these different qualities.

From the prepared materials VS and BF, four qualities

of CMCNa (VS-1, VS-2, CMCNA-BF-1 and CMCNA-BF-

2) were prepared. Two steps were needed to accomplish

this synthesis: The first step is activation of cellulose with

an aqueous NaOH in the slurry of an organic solvent as

shown in (5). The second step is the activation of cellulose

reacts with MCA as shown in (6). By the way, the side

reactions that occur are shown in (7) [42].

Cell� OHðcelluloseÞ

þ NaOH! Cell� ONa þ H2O ð5Þ

Cell� OHðcelluloseÞ

þ ClCH2COOH! Cell� OCH2COOH

þ NaCl ð6Þ

NaOH þ ClCH2COOH! HOCH2COOH þ NaCl ð7Þ

All the obtained derivatives were characterized by their

DS or their exchange capacities which are summarized in

Table 1.

Table 1 recapitulate the estimated DS, the exchange

capacities and the reaction yield values associated with

CMCNa derived from VS and BF prepared from vine stem.

The DS varied from 1.17 to 1.65 for CMCNa prepared

from BF and from 0.77 to 1.29, for CMCNa prepared from

vine stem, respectively. The reaction yield followed also

the same trend as it increased from 63 to 75 % and from 40

to 43 %, for BF and VS, respectively. As expected the

highest DS and reaction yield were obtained for the second

quality of CMCNa synthesis (CMCNa-VS-2 and CMCNa-

BF-2), whatever the used starting material. The difference

is due to MCA concentration. Also the important values are

justified by the reaction time [40].

The EC was established especially for the CMCNa

prepared from the raw materials which indicate more

serious the fixed quantities of ‘‘-CH2COONa’’ into VS.

The value of (EC) varied from 1.61 9 10-3 mol g-1 and

7.23 9 10-3 mol g-1. The substitution amounts are in

according with the quantities of MAC added. Table 1

recapitulates also the obtained DS from others materials

such as Posidonia oceanica and date palm rachis. From this

table, one can also draw the following concluding remarks:

• All the prepared qualities of CMCNa from vine stem

(CMCNa-VS-1 and CMCNa-BF-1) present a DS higher

than those obtained from Posidonia oceanica whereas

lower than those obtained from date palm rachis. These

differences can be explained by, as reported by Khiari

et al. [6] as well by several works, the higher porosity

of date palm rachis and consequently its better acces-

sibility towards the etherifying agent.

• The DS of CMCNa obtained from the original vine

stem, date palm rachis and Posidonia oceanica were

0.77, 0.98 and 0.67 for CMCNa-VS-1, QR1and QP1,

respectively.

100030004000 1500 50025003500 2000

Wave number (cm-1)

T (

%)

Fig. 3 FTIR spectrum of extracted-bleached cellulose from vine

stem

J Polym Environ

123

• As expected, these values are lower than those obtained

for the cellulose derivatives prepared from extracted

bleached cellulose, which were 1.17, 1.25 and 1.06 for

CMCNA-BF-1, QE1 and QC1, respectively. This can

be easily explained by the higher purity of the starting

substrate used in the synthesis, as the higher the purity

of the substrate the higher the facility of modifying it

[6]. This is not surprising since the lignin and the

hemicelluloses form between them are complex and

constitute as ‘‘glue’’ for cellulosic fibers, which per

consequence is a limiting factor in the reactivity of the

etherifying reaction. The idea here is the use of the

entire material without any fractionation, because we

are dealing with the valorization of a waste. Any

additional purification step will induce extra costs and

will make meaningless the full approach. Nevertheless,

it is worth to mention that the presence of more reactive

species such as hemicelluloses and lignin induce

overconsumption of chemicals and consequently

decreases the yield and the DS.

• The yield of CMCNa product depends on numerous

parameters. It is certainly a function of the amount of

material lost during alkalization and etherification

steps. More degradation occurred and larger amount

of low molecular weight material were released when

more drastic reaction conditions (higher temperature,

NaOH and MCA concentration) is applied [31].

Characterization of the Synthesized CMCNa

Figure 4 illustrates the spectrum of CMCNa derived from

Tunisian vine stem. It is worth to note that the presence of a

new and strong absorption band at 1,603 cm-1 is due to the

(–COO-) group ensuing from (–COO-Na?) structure. It is

evident that hydroxyl group of cellulose was replaced with

carboxyl group when carboxymethylation reaction occurs

(see Fig. 3). Methyl group (–CH2) is found at wavelength

of 1,419 cm-1. The peak at 1,314 cm-1 is attributed to

(–OH) group. As reported in literature, peaks appearing at

wavelength of 1,620 cm1 and 1,423 cm-1 represented

specific functions in CMC [31, 43–46]. The intensity of the

peak at 1,025 cm-1 for C–O–C stretching slightly

decreased due to the degradation of the cellulose simple

during the modification’s process [40].

The infrared spectra of modified vine stem (CMCNa-VS-1

and CMCNa-VS-2) is given in Fig. 4. Indeed, it indicates the

presence of a typical profile of the carboxymethyl cellulose.

Table 1 Yield reaction, DS and

exchange capacity of CMCNa

prepared from vine stem and

other cellulosic material from

annual plants

* Estimated DS

Yield (%, w/w) DS EC (10-3 mol g-1) Reference

Commercial CMC – 0.7–1.2 1.46–6.9

Raw materials

Vine stem CMCNa-VS-1 40 0.77* 1.61 (this work)

CMCNa-VS-2 43 1.29* 7.23 (this work)

Posidonia oceanica QP1 33 0.67* – [6, 18]

Date palm rachis QR1 50.7 0.98* – [6, 18]

Extracted and bleached cellulose

Vine stem CMCNa-BF-1 63 1.17 – (this work)

CMCNa-BF-2 75 1.65 – (this work)

Posidonia oceanica QC1 51.5 1.06 – [6, 18]

Date palm rachis QE1 57.0 1.25 – [6, 18]

Fig. 4 FTIR spectrum synthesized CMCNa prepared from a VS and b BF

J Polym Environ

123

The presence of bands around 3,434 cm-1 may correspond

to stretching vibrations of OH bonds of the cellulose mole-

cule. The peaks at 2,922 cm-1 indicate the presence of CH

and CH2 bonds of cellulose. Furthermore, peaks to wave-

number 1,607 cm-1 may be attributed to the stretching

vibrations of C–O bond of the carboxylate groups. The

analysis of this spectra and compairing it with that of

extracted-bleached cellulose (CMCNa-BF-1 and CMCNa-

BF-2) spectra, show the appearance of others peaks in

preapred CMCNa from the VS. This can be explained by the

presence of lignin and other lignocellulosic components

which persite after etherifying reaction.

The analyses of the CP-MAS 13C-NMR spectra were

also established for CMCNa derivatives and illustrate in

Fig. 5, taken as an example for the vine stem VS before

and after modifing it to CMCNa-VS-1. It can be deuced

that the fingerprints of cellulose units (100–60 ppm) pres-

ent in CMCNa is changed. This is due to (1) the substitu-

tion and (2) the shorter cellulose chains and consequently

the preponderance of amorphous to crystalline areas which

clearly observed by missing of crystalline region at

88.7 ppm to C4 and C6 at 64.8 ppm whereas the persis-

tence of amorphous region to C4 at 83 ppm and 62 ppm to

C6. The spectra displayed the presence of the main peaks

associated to carboxyl functions at around 178.8 ppm. In

addition, to these main signals, the CP-MAS 13C-NMR

spectra (Fig. 5a, b) revealed the presence of different sig-

nals originating from residual impurities such as lignin and

Fig. 5 13C-NMR spectrum of

a extracted cellulose and

b CMCNa from vine stem

J Polym Environ

123

hemicelluloses, but their intensity is much reduced com-

pared to that observed in the raw material. This results

account should be taken of these impurities that can lead to

overestimate the DS found particularly in the case of

CMCNa synthesized from raw materials.

Preliminary observations concerning the water solubility

of the obtained samples were carried out. Thus, all pre-

pared CMC grades are partially soluble; however, those

obtained from raw material displayed a lower solubility to

compare with those prepared from extracted and bleached

VS.

Study of the Absorption and Retention Capacities

of the Prepared CMCNa from Vine Stem

One of the important properties of lignocellulosic materials

and their derivatives is their behavior in wet conditions [47,

48]. For instance, textile cotton products are used in wiping

because of the hydrophilic character. Chemical modifica-

tion can either improve or destroy this behavior. The AC of

a material is the weight of the absorbed water (w/w) with a

time of impregnation equal to 30 min followed by a time of

draining of 5 min. Nevertheless, the RC defined by the

water quantity that remains retained after carrying out the

procedure allowing the measurement of the AC then the

centrifugation of the sample during 20 min. The absorption

and retention capacities of the prepared CMCNa were

evaluated and the results were summarized in Fig. 6 which

reports respectively the evolution of the absorption and

retention capacities function of the DS. It is worth to notice

that: (1) the alkalization and etherification of cellulose and

vine stem ameliorate the absorption and retention capaci-

ties. (2) This two studied parameters increased when DS

increased.

The AC varies between 3.05 and 5.09 g of liquid per

gram of material. While, the retention capacities values are

ranged between 6.96 and 11.02 g of liquid per gram of

material corresponding respectively to the DS of 0.77 and

1.65. The best quality of CMCNa corresponds to CMCNA-

VS-2. The performance comparison (in terms of absorption

and retention capacities) of the prepared CMCNa with the

commercial cellulosic pulp (as reported by Khiari et al. [6])

shows that the prepared derivatives from vine stem have

largely higher RC ones.

Conclusion

This work present the synthesis and the characterization of

lignocellulosic derivatives from Tunisian vine stem. Sev-

eral qualities of CMCNa were prepared and characterized

using many techniques such as the FT-IR and CP-MAS13C-NMR spectra which confirmed that the carboxymeth-

ylation reactions were established whatever the starting

material. Moreover, DS and CE were determined and show

that the effect of purity when you starting material from

lignocellulosic (VS) or extracted-bleached cellulose (FB)

from Tunisian vine stem can be affected enormously. At

the end, the different prepared materials were evaluated in

terms of absorption and retention capacities’. The perfor-

mance of CMCNa derivatives was compared with that

achieved by commercial counterparts and it was concluded

that the prepared ones shows that the prepared derivatives

from vine stem have largely higher RC then the commer-

cial cellulosic pulp.

Acknowledgments The authors gratefully express their sincere

gratitude to MARIE-CHRISTINE BROCHIER-SALON for her help

and availability. As well as to the ‘‘Comite Mixte Permanent Tuniso-

Egyptian’’ and the ‘‘PHC-UTIQUE CMCU’’ for their financial

support.

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0,00

2,00

4,00

6,00

8,00

10,00

12,00

0,77 1,17 1,29 1,65

Retention capacties Absorption capacties

Fig. 6 Evaluation of the absorption and retention capacity of

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