Development of a biobased superabsorbent polymer

from recycled cellulose for diapers applications

Clément Lacoste, José-Marie Lopez-Cuesta, Anne Bergeret

To cite this version:

Clément Lacoste, José-Marie Lopez-Cuesta, Anne Bergeret. Development of a biobased superab-
sorbent polymer from recycled cellulose for diapers applications. European Polymer Journal, Elsevier,
2019, 116, pp.38-44. �10.1016/j.eurpolymj.2019.03.013�. �hal-02424970�

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Development of a biobased superabsorbent polymer from recycled cellulose
for diapers applications
⁎
Clément Lacoste , José-Marie Lopez-Cuesta, Anne Bergeret
Centre des Matériaux des Mines d’Alès(C2MA), IMT Mines Ales, Université de Montpellier, France

1. Introduction 74 µm respectively. The surface area as well as the availability of the

hydroxyl groups are determinant to achieve a high substituted struc-
Superabsorbent polymers (SAPs) are functional materials composed ture. The selection of carboxymethylation conditions (temperature,
of a crosslinked hydrophilic polymer in a loose three-dimensional net- time, concentration) are also essential to prepare high substituted CMC.
work used in many applications such as diapers, cosmetics and absor- For commercial CMC products, the most common DS value is usually
bent pads [1]. Due to their highly crosslinked structure, SAPs possess an between 0.4 and 1.4. Nowadays it exists considerable interest in finding
extraordinary capacity to absorb a large quantity of liquid, and can also cheaper and environmental-friendly alternative methods and raw ma-
retain the absorbed liquid during a long time even under compression terials to produce CMC. Some authors have reported the synthesis of
[2]. CMC from various cellulosic sources as alternative to virgin softwood
The principal superabsorbent polymer commercially used is a pulp. Heydarzadeh et al. [8] successfully synthesized CMC from alkali
crosslinked partially neutralized polyacrylic acid. The polymer is made cotton fibers with DS of 0.15–0.70 and excellent purity of 99.3% re-
from acrylic acid and sodium hydroxide (or sodium carbonate), which commended for pharmaceutical applications. Unlü [9] has studied the
are inexpensive reagents. Although the SAPs pose no direct threat to synthesis of CMC from newspaper in aqueous medium and obtained a
human life or health, the disposal of synthetic SAP waste is a source of DS of 0.3–0.7 with 84–94% CMC content. Joshi et al. [10] have pulped
various environmental pollutants [3]. and deinked office waste paper with a yield measured at 80.62 ± 2.0%
Bio-based SAPs are attractive due to their renewability and biode- to prepared CMC with a maximum DS of 1.07. Haleem et al. [5] have
gradability. Among them, carboxymethyl cellulose (CMC), a water so- produced CMC from waste cotton grinning and found a maximum
luble and biodegradable cellulose derivative (Fig. 1), could be a good DS = 0.874. Mondal et al. [11] have extracted alpha-cellulose from
precursor for the synthesis of bio-SAP [4]. Nowadays, CMC is manu- corn husk to prepare high purity CMC with yield 2.4 g/g, DS 2.41, and
factured in significant amounts and produced by the 2-step reaction of water holding capacity of 5.11 g/g. Other authors like Bidgoli et al. [12]
cellulose with alkali and monochloroacetic acid (MCA), using organic have produced CMC from cotton and viscose textiles and have obtained
solvents under heterogeneous conditions [5]. In the first step, the cel- a DS between 0.50 and 0.86.
lulose is treated with NaOH in the presence of inert solvent, which acts In the first part of this study, the production of CMC from waste
both as a swelling agent and as a diluent and thus facilitates good pe- cardboards and cellulose fibers was investigated, as precursor for the
netration of NaOH into the cellulose structure. The alkali cellulose is synthesis of a SAP.
consequently accessible and reactive toward MCA, which is added to In the recent past, the new class of hydrogels SAP has emerged
the reaction in the second step. The CMC can be neutralized and dried based on natural derivatives such as CMC having good structure sta-
immediately to give a technical grade or neutralized and washed to give bility and biocompatibilities properties [15]. However, chemically
a purified grade and used in many industrial applications (cement, crosslinked hydrogels might exhibit cytotoxicity due to the chemical
paper and coating industries, adhesives, drug delivery, tissue en- nature of the unreacted crosslinkers (i.e. aldehydes). Therefore, there is
gineering, wound dressing) [4,6,7]. a need to promote the use of non-toxic and bio-based crosslinker
The properties (viscosity, solubility, biodedradability) of CMC are through the entire process. Citric acid is a cost-effective bio-based
mainly depending on the degree of substitution (DS). The theoretical monomer that has three carboxylic and one hydroxyl group which
maximum DS that can be achieved is 3. CMC is soluble in water when provides both hydrophilicity and crosslinking sites and it is also known
DS is higher than 0.4 and the biodegradability decreased with the in- to be non-toxic [13].
crease of the DS. Yeasmean and Mondal [7] have observed the increase In this work, bio-SAPs were synthesized by crosslinking citric acid
of the DS from 0.21 to 2.41 during the carboxymethylation of corn husk with carboxymethyl cellulose, derived either from cellulose fibers as
cellulose particles when the particles size decreased from 1071 µm to reference source, or from recovered cardboard. Different particle sizes

⁎
Corresponding author.
E-mail address: [email protected] (C. Lacoste).
 Carboxymethylcellulose (CMC) Citric acid (CA) Fig. 1. Carboxylmethyl cellulose (CMC) and citric
acid chemical structures.

Table 1
Cellulose raw material, CMC, and bio-SAP samples.
Cellulose name Cellulose origin (median fiber size) CMC name Bio-SAP name Citric acid concentration (%)

ref Commercial CMC_ref SAP_ref 0 – 5 – 10 – 15 – 20

A1 Softwood (300 µm) CMC_A1 SAP_A1 10
A2 Softwood (23 µm) CMC_A2 SAP_A2 10
A3 Softwood (8 µm) CMC_A3 SAP_A3 10
RCC Waste cardboard (900 µm) CMC_RCC SAP_RCC 10

were used and their influence on the final properties of the bio-SAPs is isopropanol. Isopropanol was used as solvent to provide miscibility and
described. The synthesized CMC was characterized in terms of degree of accessibility of the etherifying reagent to the reaction center of the
substitution, FTIR and thermal properties. The water absorption capa- cellulose chains [10]. Synthesis of CMC was carried out in a two steps-
city of the bio-SAP was measured and the influence of the crosslinker reaction: (i) alkalization followed by (ii) etherification. Alkalization
concentration was also discussed. was done by drop to drop addition of 20 mL aqueous NaOH (20% w/v)
under continuous stirring over a period of 1 h at room temperature.
2. Materials and methods Finally, predissolved monochloro acetic acid (MCA) (10 g) in 10 mL
isopropanol was added to the alkali treated mass under continuous
2.1. Materials stirring. The mixture was heated at 50 °C and stirred 2 h. When reaction
period was over, the pH was neutralized with glacial acetic acid and the
Waste cardboards were kindly supplied by a local recycling facility, product was filtered and washed three times with ethanol. The re-
PAPREC, France. All other reagents (glacial acetic acid, sodium hy- maining material was dried overnight at room temperature and then 8 h
droxide, monochloroacetic acid, isopropyl alcohol, ethanol, acetone, at 60 °C in oven.
methanol, acetic acid, sodium silicate) used for cellulose extraction and
carboxymethylation were analytical grades, purchased by Merck 2.4. Synthesis of bio-based superabsorbent polymers
(Sigma-Aldrich), France.
Some commercial products (cellulose, CMC, and SAP) were used as CMC (2 g) was stirred at room temperature in 100 mL distilled water
reference and their properties were compared to the synthetized pro- until complete dissolution occurred. Then, the crosslinking agent (i.e.
ducts of the present study. For cellulose, the fibers Arbocel® (cellulose citric acid) was added in different amount (Table 1) and the CMC so-
content > 99%) were provided by J. RETTENMAIER & SÖHNE, lutions were stirred continuously for 1 h. The solutions were poured
Germany. They are industrially produced from softwood pulp which into aluminum molds and were allowed to dry at room temperature for
contain around 45–50% of cellulose extracted through a kraft process 24 h to remove water. In the sequence, the samples were cured at 80 °C
and named A1 (fiber length = 300 µm), A2 (fiber length = 23 µm) and in oven for 24 h for the cross linking reaction. After curing, the samples
A3 (fiber length = 8 µm). Carboxymethyl cellulose (DS = 1.2; mole- were cut with a Retsch® ZM200 grinder at 8000 rpm using a 1 mm grid.
cular weight = 250,000 Da) was provided by Merck, France. A com-
mercial polyacrylate SAP, named HYSORB 9400, was purchased from
BASF, Germany. 2.5. Determination of CMC yield and DS

2.2. Isolation of cellulose from waste cardboards The CMC yield was calculated according to the following equation
(Eq. (1)):
A triple knife mill (Alpine, type 20/10R0, 1500 rpm, and granulator weigthofthedriedsynthetizedCMC (g )
grid of 1 mm) was used to grind the cardboards into particles with Yield (%) = × 100
weigthofthedriedinitialcellulose (g ) (1)
average length of 0.9 ( ± 0.2) mm. Purification of cardboards was done
using alkaline peroxide treatment. A designed amount of cardboards The degree of substitution (DS) is the average number of hydroxyl
particles were dispersed in 250 mL aqueous NaOH (20 wt%) and stirred group in the cellulose structure which was substituted by carbox-
1 h. Then, addition of NaOH/H2O2/Na2SiO3 mixture was done and ymethyl groups at C2, C3 and C6 sites. It was determined by the fol-
stirred 2 h at room temperature. Hydrogen peroxide (H2O2), sodium lowing method. Prepared CMC sample (4 g) was stirred in a beaker with
silicate (NaSiO3) and alkaline (NaOH) concentrations were kept con- 100 mL acetone for 5 min. 12 mL of chloric acid (6 M) was added to this
stant at 1% w/w, 2% w/w, and 2% w/w. The pulp obtained was filtered solution and stirred for 30 min in order to obtain acid CMC (H-CMC).
and washed with distilled water and dried in a fume hood at room The H-CMC obtained was filtered under vacuum and the residue was
temperature overnight. The recovered cardboard cellulose (RCC) was washed with methanol. The residue is then stirred in acetone for 5 min,
then dried 2 h at 60 °C and weighted. filtered, and dried at 60 °C for 2 h.
Aqueous solution of H-CMC (0.5 g) mixed with 20 mL of 0.2 M
2.3. Synthesis of carboxymethyl cellulose NaOH solution and 50 mL of distilled water was titrated with 0.05 M
HCl by phenolphthalein indicator. To estimate the degree of substitu-
10 g of cellulose (RCC, A1, A2 or A3) was dispersed in 100 mL tion, following Eqs. (2) and (3) were used:
 Fig. 2. FTIR spectra of cellulose fibers (a) A1, (b) A2, (c) A3, raw cardboard (d) and recovered cardboard cellulose RCC (e).

BC − DE ms − m 0
A= Q (g /g ) =
F (2) m0 (5)

0.162 × A where ms and m0 are the swollen and dry weight of the SAP respec-
DS = tively.
1 − (0.058 × A) (3)

where A = milli-equivalents of consumed HCl per gram of specimen; 2.8. Environmental scanning electron microscopy
B = volume of NaOH added; C = molarity of NaOH; D = volume of
consumed HCl; E = molarity of HCl; F = CMC in grams; 162 Da is the SAPs particles were placed in a Peltier module in an environmental
molecular weight of the anhydrous glucose unit and 58 Da is the net scanning electron microscope (ESEM) (FEI Quanta 200). The working
increment in the anhydrous glucose unit for every substituted carbox- temperature was 5 °C and the pressure was 4.9 Torr in order to obtain a
ymethyl group. relative humidity of 90% in the working chamber. The samples were
left in the chamber for 240 min and pictures were taken every minute.
2.6. Spectral and thermal characterizations
3. Results and discussion
The thermal properties of the products were studied through dif-
ferential scanning calorimetry (DSC), thermogravimetric analysis 3.1. Characterization of cellulose recovered from cardboards (RCC)
(TGA), and Fourier Transform infrared (FTIR) analysis. Each measure-
ment was done in duplicate. In the first step, cellulose was recovered from waste cardboard by
DSC measurements were performed on a Perkin Elmer Diamond alkaline peroxide treatment. This method is used to fractionate crop
operating under a constant flow of nitrogen (30 mL min−1). Samples wastes into cellulose, hemicellulose, and lignin [9]. Hydroperoxide
were weighed (around 15 mg) into aluminum crucibles. Analysis in anion radicals and oxygen radicals are generated in the solution from
comparison to a blank crucible was performed using a temperature H2O2 and NaOH. These radicals oxidize cellulose–hemicellulose and
profile (ramp rate of 10 °C.min−1) from 0 °C to 250 °C. Thermal tran- hemicellulose–lignin bonds to solubilize cell wall components and ob-
sitions were calculated from Perkin software through tangent method. tain recovered cellulose. Recovered cellulose was 88% by weight with
Measurements of mass loss versus temperature were performed respect to the starting material.
using a Perkin Elmer thermogravimetric analyzer (TGA) module Pyris FTIR analyses were performed to characterize both cellulose fibers
1, under N2 purge (flow rate of 50 mL.min−1). Typically, 8–10 mg of (A1, A2 and A3) and recovered product (RCC) (Fig. 2). The spectrum of
sample were placed on an aluminum oxide pan, and heated from 30 °C the RCC showed typical pattern of cellulose. As a general trend common
to 600 °C at 10 °C min−1. to cellulosic samples, it can be observed the broad band in the
FTIR spectra of sample pellets in potassium bromide (10 wt%) were 3700–3000 cm−1 region assigned to νO-H vibrations and the peaks at
recorded with a Bruker Vertex 70 spectrometer in transmission mode. 2905 cm−1 related to νC-H vibrations. The spectrum of RCC shows
The spectra were recorded in the range of 4000–400 cm−1 with a re- additional absorption bands located at 1512 cm−1 and in the
solution of 2 cm−1 and 32 scans per sample. 1620–1690 cm−1 region compared to cellulose fibers. These bands
belong to aromatic ring vibrations of phenylpropane skeleton and non-
2.7. Absorption capacity of the bio-SAPs conjugated and conjugated carbonyl group respectively [6]. The pre-
sence of these additional absorbance bands reveal the presence of small
SAPs particles (200 mg) were placed in a 50 mL beaker and im- amount of lignin fragments bonded to cellulose. Complete removal of
mersed in excessive amount of distilled water or 0.9% NaCl solution for lignin was not attended in these mild conditions and could be probably
1 h. The swollen gels were separated from the water and wiped with a achieved by stronger reaction conditions (higher temperature or alka-
filter paper to remove the excess of liquid and carefully weighted. The line peroxide concentration). As residual lignin will not interfere with
absorption capacity was calculated with the following equation (5): carboxymethylation [9], any further purification was done and the
Table 2
Cellulose content, yield and degree of substitution of the CMC samples compared to literature.

Name Cellulose content of the raw material (%) Carboxymethylation yield (g/g) DS Reference

CMC_A1 45–50% 1.602 1.40 ( ± 0.01) This study

CMC_A2 45–50% 1.459 1.29 ( ± 0.01) This study
CMC_A3 45–50% 1.619 1.35 ( ± 0.40) This study
CMC_RCC 65–70% 1.120 1.41 ( ± 0.14) This study
Waste of cotton ginning > 90% 1.437 0.87 [5]
Corn husk 35–45% 1.001–2.406 0.21–2.41 [11]
Office waste papers 75–80% 1.508 1.07 [10]

recovered cellulose wad used as it is for carboxymethylation. proved that carboxymethylation reaction was performed successfully
for the samples.
3.2. Characterization of carboxymethyl cellulose (CMC)
3.2.3. Thermal stability
3.2.1. Degree of substitution and yield of the carboxymethylation The results of the TGA analysis are given in Table 3. It can be seen
The objective of the present study is to use CMC obtained from RCC that the degradation temperature of the cellulosic samples are between
as precursor for the synthesis of a SAP in water medium. The solubility 349 °C (A3) and 361 °C (RCC). The recovered cellulose from cardboards
of the synthetized product is then of major consideration. Mondal et al. (RCC) is slightly more stable than the others fibers samples. It can be
[11] have studied the solubility of CMC and found that with DS lower due to the presence of lignin fragments as seen previously. Lignin is
than 0.4, CMC is insoluble. The reaction time (2 h) and the reaction more resistant to thermal degradation than cellulose and its thermal
temperature (50 °C) was then chosen in the present study to achieve a degradation is observed on the curves in Fig. 4. The char content is also
DS higher than 0.4. higher for this sample resulting also from the lack purity and the pre-
The DS determination of the samples was performed using the ti- sence of mineral charges usually observed in cardboards (≈12%) [14].
tration method and the results are reported in Table 2. CMC_A1, CMC samples have a lower thermal stability with a decomposition
CMC_A2 and CMC_A3 have a DS of 1.40 ( ± 0.01), 1.29 ( ± 0.01), and temperature measured between 294 °C (CMC_A2) and 314 °C
1.35( ± 0.40) respectively, whereas CMC_RCC has a DS of 1.41 (CMC_RCC). One time more the higher thermal stability of CMC_RCC
( ± 0.14). No influence of the particles size on the DS was observed. could be due to lignin. The pyrolysis of hemicellulose and cellulose
The DS obtained is quite high considering the mild conditions used in occurs quickly with a weight loss from 220 to 315 °C for hemicellulose
the present study. Haleem et al. [5] have measured a maximum DS of and from 315 to 400 °C for cellulose. Lignin decomposes over a wider
0.87 for CMC derived from cotton ginning after strong cellulose ex- range of temperature (from 160 to 900 °C) and generates a high char
traction (10% of H2SO4 at 80 °C) and carboxymethylation with MCA at yield [15]. However, the quantity of char at 900 °C is huge higher than
40–60 °C for 3 h. Joshi et al. [10] have obtained a maximum DS value of those of cellulose fibers and similar char content values (∼30%) were
1.07 for a carboxymethylation at 50 °C for 3 h. It is possible to increase observed for all CMC samples. The decrease of the decomposition
the DS by increasing the reaction temperature, time, or the NaOH temperature indicates a lower thermal stability of the CMC samples
concentration [11]. compared to cellulose. But the chemical grafting of carboxyl methyl
The yield of the carboxymethylation in the present study was groups on cellulose backbone induce the formation of a stable char.
measured between 1.459 g/g (A2) and 1.619 g/g (A3) for CMC samples Many authors have reported a similar phenomenon after the chemical
synthetized from cellulose fibers. The yield for cellule fibers is higher grafting on natural polymers [16].
than for CMC derived from office waster papers [10] with similar
synthesis conditions. For CMC_RCC, the yield decrease at 1.120 g/g 3.3. Characterization of the bio-SAPs
(Table 2). As the fiber length of RCC is higher (≈0.9 mm ( ± 0.2)), the
kinetic of the carboxymethylation was modified. However, the com- 3.3.1. DSC
parison of the carboxymethylation yield with several studies from lit- SAP_ref were prepared with varying amount of crosslinker from 5%
erature supports the suitability of arbocel fibers and RCC as sustainable to 20% (Table 1) and DSC curves are presented in Fig. 5. Two glass
sources for CMC production. transition temperatures were observed by DSC. The results are given in
Table 4. The addition of citric acid from 5% to 20% slightly increases
3.2.2. FTIR analysis the Tg1 from 52.8 °C to 64.9 °C respectively. A glass transition tem-
The infrared spectra of synthetized CMC from A1, A2, A3, and RCC perature was clearly observed for SAP_ref containing 5% and 10% of CA
are shown in Fig. 3. The broad absorption ban at 3335 cm−1 belongs to located at 120.9 °C and 115.1 °C respectively indicating the crosslinking
the stretching frequency of the OH group and the band at 2890 cm−1 is reaction between carboxyl groups of CMC and citric acid. At a con-
due to C-H stretching vibration. After carboxymethylation, hydroxyl centration of CA 15%, the intensity of the second transition decreases
groups of CMC_A1 are still present in a significant amount compared to (Table 4) and reaches ΔH = 0.35 J/g.°C, and finally no transition was
the other samples. The high specific surface area of A1 fibers observed for SAP_ref with CA 20%. These DSC results indicate that for a
(length = 300 µm) can reduce the accessibility of the reactive sites. For concentration of CA of 5%, 10%, and 15%, CMC is partially crosslinked
CMC_RCC, the quantity of hydroxyl groups is clearly reduced after the with citric acid but for a concentration of 20% of CA, the network is
reaction. However, the presence of a strong absorption band at completely crosslinked. In Fig. 5(b) no transition was observed and all
1620 cm−1 confirms the presence of asymmetric elongation of carboxyl samples are completely crosslinked during the second run. This result
groups and the band at and 1425 cm−1 is attributed to carboxyl groups also indicates that the curing temperature during the synthesis of the
as salt. These bands were also found on the spectra of the other samples SAP should be selected carefully. The temperature chosen in this work
but the intensity for CMC_A1 was lower. As the carboxymethylation was 80 °C and was convenient.
took place in basic medium, CMC samples were in sodium salt form
(eCOO−Na+) rather than in acid form (eCOOH). The acid form was 3.3.2. Gel swelling
indeed not detected in the sample due to the absence of the char- Gel swelling characterizations were performed in distilled water as
acteristic bands usually observed at 1715–1730 cm−1. FTIR analyses the swelling media. Fig. 6a shows the absorption capacity (Q) of
 Fig. 3. FTIR spectra of the carboxymethyl cellulose samples (a) CMC_A1, (b) CMC_A2, (c) CMC_A3, (d) CMC_RCC.

Table 3 the formation of the gel. The polymer is swelling up to a maximum

Results of the TGA analysis for the cellulose and CMC samples. absorption corresponding to a CA concentration of 10%. But the con-
Decomposition Temperature (°C) Char900°C (%) centration of hydroxylate groups is progressively reduced with the
addition of the acid. A decrease of the swelling capacity was observed at
Cellulose samples higher crosslinker concentrations (> 10%), which evidence the for-
A1 356 °C 10.2
mation of a rigid polymer network with a slow motion. It limits the
A2 350 °C 8.8
A3 349 °C 3.2
polymer chains elongation which is a necessary condition of the volume
RCC 361 °C 17.1 change. The expansion is then limited by the crosslinking density.
Carboxymethylcellulose samples It is known that absorption capacities of SAPs depend on the pH and
CMC_A1 312 °C 29.4 the salt concentration of the solution [13,17,18]. This specificity is due
CMC_A2 294 °C 32.9
to the presence of ionic charges spaced along the polymer chains
CMC_A3 298 °C 28.9
CMC_RCC 314 °C 29.5 (carboxylate groups) that are strongly solvated in the presence of water
solution. If ionic components are present in the liquid to be absorbed,
ion exchange may occur and alter the absorbancy of the liquid How-
SAP_ref as a function of the citric acid (CA) concentration. It can be ever, saline absorption is an important characteristic of a SAP con-
observed that without crosslinker, the Q was only 2.5 g/g and at low sidering it simulates urine. The results showing the water and saline
crosslinker concentration (i.e. 5%), the absorption increased up to absorption capacities of SAP_ref as a function of the crosslinker con-
32.9 g/g showing the production of a superabsorbent hydrogel. The centration is shown in Fig. 6a. The saline absorption capacity is as
presence of hydroxylate groups, as negatively charge groups, allowed expected lower than for water, and the mean value was found to be

Fig. 4. Evolution of the weight of all cellulose and CMC samples as a function of the temperature.
 Fig. 5. DSC curves of SAP_ref containing different quantity of citric acid (a) first and (b) second run.

Table 4 Fig. 7(A) and (C), both SAP particles have not yet absorb the ambient
Results of the DSC analysis of SAP_ref with varying citric acid concentration. humidity. The edges of the polyhedron particules were cleary observed
Sample Citric acid Tg1 (°C) ΔH (Tg1) (J/ Tg2 (°C) ΔH(Tg2) (J/
as the particule is still dried. After 240 min at 90% RH, the volume
(%) g.°C) g.°C) enhancement of the particles was perceived corresponding to the pe-
netration of the water molecules into the polymer chains leading to a
SAP_ref 5 52.8 0.05 120.9 5.64 swollen hydrogel. The phenomenon was more evident on the com-
10 54.5 0.06 115.1 2.04
mercial product which has a water absorption capacity of 300 g/g. The
15 63.6 0.10 123.8 0.35
20 64.9 0.08 – – bio-SAP obtained from carboxymethyl cellulose and crosslinked with
citric acid appeared as a swelling hydrogel.

7.45 g/g. The maximum value was 9.03 g/g for CA 5%. No significant 4. Conclusion
influence of the concentration was observed. However, it can be noticed
that the saline absorbency value is only 6 time lower than the water Cellulose was successfully recovered from waste cardboards under
absorbency. Such deviation has already been observed in literature for mild oxidizing alkaline conditions with a yield of 0.88. FTIR analyses
polysaccharides derived hydrogels [17]. indicate the presence of some residual lignin fragments bonded to the
In Fig. 6b, the absorption capacity of SAP_A1, SAP_A2, SAP_A3 and recovered cellulose which slightly increase the thermal stability of the
SAP_RCC crosslinked with 10 wt% of citric acid is shown. The absor- product. However, the presence of residual lignin fragments does not
bency of the SAP_RCC was 31.5 g/g. The particles size of the raw ma- interfere with the carboxymethylation. The degree of substitution was
terial seems to influence the absorbency of the final SAP product. In- found to be around 1.4 for all samples without any influence of the
deed, the water absorption capacities of the SAP_A1, SAP_A2, and cellulose source. The carboxymethylation yield was found to be 1.12 g/
SAP_A3 were found to be 33.8 g/g, 36.0 g/g and 38.4 g/g respectively, g and with range 1.46–1.60 g/g for the cellulose recovered from card-
whereas the particle sizes of these products were 300 µm, 23 µm, and board material and from micrometrics cellulose fibers respectively,
8 µm respectively. The highest water absorbency was 45.87 g/g mea- which confirms the sustainability for industrial production. The results
sured for SAP_ref. SAP-RCC shows a good absorption capacity in com- demonstrated that bio-SAPs crosslinked with citric acid were produced.
parison with SAP_ref and confirmed the successful synthesis of a SAP SEM analysis evidenced the formation of the hydrogel. The water ab-
from waste cardboards. sorption capacity was depending on the crosslinker concentration (op-
timum at 10 wt%) with a maximum measured at 45.87 g/g. The saline
3.3.3. ESEM observation solution swelling capacity was 7.45 g/g on average without any sig-
ESEM pictures (Fig. 7) of the SAP_ref in comparison with a com- nificant influence of the crosslinker concentration. The complete pro-
mercial poyacrylate SAP (Hysorb) were taken after 240 min exposition duction of a bio-SAP was successfully developed from recovered cel-
in a Peltier chamber regulated at 90% of relative humidity (RH). In lulose and could be a promising material for many industrial

Fig. 6. Water and saline absorption capacity Q (g/g) of (a) SAP_ref as a function of the citric acid concentration and (b) water absorption capacity of all SAPs
crosslinked with 10% of citric acid.
 t = 3 min t = 240 min

A B

HYSORB 9400

200 μm 200 μm

C D
SAP_RCC

200 μm 200 μm

Fig. 7. SEM pictures of Hysob 9400 after (A) 3 min and (B) 240 min; and SAP_RCC after (C) 3 min and (D) 240 min, at 90% of relative humidity.

applications. for potential wound dressing applications, Int. J. Bio. Macromol. 108 (2018)
1218–1234.
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lulose depending on cellulose particle size, Int. J. Biol. Macromol. 80 (2015)
725–731.
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version of alkali cellulose to fine carboxymethyl cellulose at mild conditions, World
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The research leading to these results is part of the European project [9] C.H. Ünlü, Carboxymethylcellulose from recycled newspaper in aqueous medium,
POLYBIOSKIN (H2020 - grant agreement N°745839) and all the authors Carbohyd. Polym. 97 (2013) 159–164.
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acknowledge the funding support from Bio-Based Industries.
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