Chapter 4

Chemical Functionalization of Cellulosic Materials —

Main Reactions and Applications in the Contaminants
Removal of Aqueous Medium

Roosevelt D.S. Bezerra, Paulo R.S. Teixeira, Ana S.N.M. Teixeira, Carla Eiras,
Josy A. Osajima and Edson C. Silva Filho

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/61431

Abstract
The cellulose is the most abundant biopolymer in the world and presents a higher chemi‐
cal variability for presence of several hydroxyl groups. These hydroxyl groups allow sur‐
face modification of biomaterials, with insertion of several chemical groups which change
cellulose characteristics. This natural biopolymer and its derivatives have been used a lot
as adsorbent, from several contaminants of aqueous medium due to biocompatibility,
chemical degradability, and variability. Therefore, this chapter has the objective to review
the literature about several cellulose surfaces or cellulosic material (incorporation of car‐
boxymethyl, phosphorus, carboxyl, amines, and sulfur), presenting the main characteris‐
tics of reactions and showing its adsorption in application of aqueous medium (metals,
dyes, and drugs), locating the main interactions between biomaterial/contaminant.

Keywords: cellulose, chemical modification, interations

1. Introduction

The cellulose (Figure 1) is the most abundant polysaccharide on the earth, being the main
structural component of plants and seaweed cell walls. The cellulose is formed from the
repeated units of D-glucose, which are linked by glycosidic linkages β(1 → 4). This natural
polysaccharide has become the more used material due to its physical and structural properties
and its biocompatibility. These properties arise from multiple interactions of hydrogen, which
result in semicrystalline polymer, containing highly structured crystalline regions, and also,
in materials with high tensile strength [1].

© 2015 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
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94 Cellulose - Fundamental Aspects and Current Trends

OH
O O
H
H
OH H
H

H OH
n

Figure 1. Molecular structure of cellulose.

The cellulose is mainly obtained from four resources: forest, agriculture, industrial, animal
waste. The biomass which is obtained from all sources has three main components: cellulose,
hemicellulose, and lignin, with its percentage depending highly on the obtained source.
Therefore, the biomass has been extracted and processed in order to separate different
components and to isolate cellulose [1].
The cellulose has lot of hydroxyl groups which can bond to several functional groups through
variability of chemical modifications [2]. These chemical modifications provoke the formation
of covalent bond through interaction between the modifier agent and the interactive center of
solid surface, where insertion of organic molecules, in the surface of solid support, gives it
advantageous and additional properties that differ from the original support [3].
The cellulose derivatives modified by several chemical reactions have various application
possibilities in different fields. Among the various possibilities, one can be highlighted the
usefulness of cellulosic derivatives in contaminants removal of aqueous medium. For example,
the modified cellulose with diethylenetriamine was applied in the adsorption of Cu (II) and
Pb (II) [4]. The cellulose modification with aminoethanethiol was more efficient with adsorp‐
tion of red reactive dye RB [3] than pure cellulose. The phosphated cellulose presented higher
adsorption capacity of ranitidine drug [6] than the pure cellulose [7]. Both the phosphated
bacterial cellulose as well as the bacterial cellulose containing quaternary salt were efficient in
protein adsorption.
Therefore, this chapter’s goal is to perform a review of the literature about the main chemical
reactions on cellulosic material surfaces and its applications in contaminants removal of
aqueous medium.

2. Modifications and applications in contaminants removal

2.1. Carboxymethylation

The sodium carboxymethylcellulose (CMC) is a polyelectrolyte formed when the chloroacetic

acid, or its sodium salt, reacts with alkaline cellulose. The CMC is a copolymer of two units:
β-D-glucose and salt β-D-glucopyranose 2-O-(carboxymethyl)-monosodium, not spread
randomly around macromolecules which are linked by β-1,4-glycosidic linkages [8].
The CMC is used in a lot of industrial fields, such as in food industry as thickener or viscosity
modifier for stabilizing emulsion, in the petroleum industry as ingredient of drilling mud.
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Moreover, it is a component of a lot of products, such as detergents, toothpaste, water-based

paints, textile sizing, and several paper products. Lately, it has been applied in green synthesis
study and stabilization of silver nanoparticles [9].
The CMC synthesis is divided in two stages: (I) alkalinization and etherization (II). In stage (I),
the cellulose is dispersed in sodium hydroxide solution and ethanol. In stage (II), the sodium
chloroacetic is added to solution; the mixture is hectic at 353 K, according to Figure 2 [9,10,11].

OH ONa OCH 2COONa

O O O O O O
H H H
H NaOH H Sodium Chloroacetate H
OH H OH H OH H
H CH3CH2OH H 353 K
H
H OH H OH H OH
n n n

Figure 2. Preparation scheme of the CMC.

After the introduction of carboxymethyl group, the cellulose presents an anionic feature and
there occurs an increase in its water solubility [12]. This carboxymethylation changes com‐
pletely the electric charge of cellulose surface, turning it in ion exchanger. And the increase of
carboxymethyl groups also promotes the increase of zeta potential value on CMC on to pure
cellulose [10]. After carboxymethylation, these new characteristics acquired by celluloses are
very important in the application in contaminants removal of aqueous medium, because the
adsorption process is extremely affected by interactions which can occur between adsorbate
and adsorbent, and they can be affected by pH of the medium [5,6,7].
For example, in the removal study of the methylene blue cationic dye (MB) (Figure 3 (a)), the
pH is an important factor in the adsorption process of CMC. In acid conditions, the carboxy‐
methyl group of CMC is protonated, and there occurs an ion exchange (-CH2COONa turning
into -CH2COOH), and thus adsorption of MB is a disadvantage. In alkaline conditions, the
carboxymethyl group is totally deprotonated (-CH2COO–), furthering the MB dye adsorption.
These results indicate which adsorption mechanism of the MB in CMC is due to ion exchange
reactions, according to Figure 3 (b) [11].
The adsorption of the metal strontium (II) (Sr2+) in CMC proved efficient and independent of
pH. The ion exchange is the main reason for adsorption of ions Sr(II) in carboxymethyl groups
of the CMC. In acidic pH, i.e., pH less than 2.0, the excess ions will compete to the Sr (II) ions,
for match to –COO–, as shown in Eq.1. Thus, as the pH of the medium increase, there will be
an increase in the polymer hydrolysis, and hence it will grow the available sites for interaction
to the strontium ions (II) [13].

( 2–n ) +
éë n ( -COO ) Sr ùû + nH + « nCOOH + Sr 2+ ( n = 1,2 ) (1)

The adsorption of Sr (II) in CMC is highly influenced by ionic force from the medium. As the
concentration of KCl increases, the ionic force of the solution grows, and the ion adsorption Sr
96 Cellulose - Fundamental Aspects and Current Trends

N
-
Cl
H3C
+
N S N CH3
CH3 H3C

(a)

OCCH2OONa OCCH2OOMB
O O O O
H + H
H MB H +
OH H OH H + Na
H H

H OH H OH
n n

(b)

Figure 3. Figure
(a) Molecular
3. (a)structure
Molecularof methylene
structure blue dye. (b) Adsorption
of methylene blue dye.mechanism of the MB
(b) Adsorption in CMC isofdue to ion
mechanism
exchange.
the MB in CMC is due to ion exchange.

(II) in CMC decreases. The ionic force effect can be explained by two factors: (I) despite the
presence of KCl in adsorption system which can improve the electrostatic attraction among –
COO– groups present in the CMC and the Sr (II) ions, the K+ ions destroy the ionic bond among
–COO– groups and the Sr (II) ions, similar to H+ (Eq.2) ions, (II) the affinity growth between
KCl and water, after adding KCl, decreases the metal mobility, which provokes the decrease
in adsorption [13].

( 2–n ) +
éë n ( -COO ) Sr ùû + nK + « nCOOK + Sr 2+ ( n = 1,2 ) (2)

2.2. Phosphating

The chemical incorporation of phosphate in cellulose structure changes its properties mean‐
ingfully, since the synthetized biomaterial starts showing the characteristics of the phosphate
group. This phosphated biomaterial is used in textile industry such as flames delayer to
cellulose based. Also, it is used as a biomaterial for the disease treatment about calcium ions
transport [6].
Due to importance of the phosphated group, a lot of methods to cellulose phosphating have
been developed, either by free hydroxyl groups in positions C2, C3, or C6 or by shift from the
ester or ether group already in the cellulose. The latest groups are usually used in homogene‐
ous reaction using toxic reagents and mainly organic solvents which promote partial or total
break of cellulose fibers. The synthesis of phosphate cellulose derivatives have been performed
in several solvents [dimethylsulfoxide (DMSO)-methylamine, DMAc-LiCl, SO3-triethylamine,
formic acid, trifluoroacetic acid, N,N-dimethylformamide (DMF)-N2O2, paraformaldehyde,
DMF, molten or aqueous urea, NaOH] with various phosphorus-containing compounds
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(phosphoric acid and phosphinic acid, phosphorus oxyacids, phosphorus pentoxide, amido‐
phosphates, alkyl or aryl derivatives of phosphorous acid) [14].
The phosphoric acid (H3PO4) is the main phosphate precursor used in cellulose phosphating
reaction. The reaction using phosphoric acid, such as phosphate precursor, can be performed
by two manners (heterogeneously and homogeneously), and depending on the way followed,
the reaction will produce different phosphated products [14, 15].
The cellulose reaction with phosphoric acid in aqueous medium (heterogeneously) is
performed through adding H3PO4 (85%) in a system which has only cellulose. The system
temperature is raised to 373 K and maintained at this temperature for 30 min, as shown in
Figure 4. In this reaction, the phosphoric acid is linked to cellulose chain under the form
phosphorous acid group, by ester linkage, through reactions from cellulose hydroxyl group.
The product formed in this reaction also established a tautomeric equilibrium, due to the
presence of hydrogen atom linked directly to phosphorus, as can be viewed on Figure 4 (a
and b) [14].

OH
OR
O O
H O O
H H3PO 4 H
H
OH H
OR H
H 373 K, 30 min H
H OH -H2O
n H OR
n

R = H or H P OH or HO P OH
O O
O
HO P H
HO P OH
O
O
O O
H
O O
H H
OH H H
OH H
H
H
H OH
n H OH
n
(a)
(b)

Figure 4. Reaction scheme of cellulose phosphorylation with H3PO4 in aqueous medium, and possible tautomeric
products (a and b) of phosphated cellulose structure.

The cellulose reaction as phosphoric acid in molten urea (homogeneously) is initially per‐
formed merging urea at 413 K. Then, it adds cellulose the suspension, water, and phosphoric
acid. The reaction takes place for 30 min at 423 K, as shown in Figure 5. In this reaction, in
addition to the listed structures (Figure 4 (a and b)), the phosphoric acid can form ester
products disubstituted and trisubstituted from cellulose [14].
The cellulose phosphorylation using phosphoric acid and urea can also be performed using
DMF as solvent. Initially, in this reaction, it puts cellulose in contact with urea. After 1 hour,
98 Cellulose - Fundamental Aspects and Current Trends

H
OH
O O
O
H HO Cel H +
H H3PO 4, Ureia -H2O, NH 4
OH H P O N NH2
H
423 K, 30 min HO H H O
O
H OH
n

Cel Cel
OH
O O
O P O
or O P O or O P O or
Cel OH
Cel OH Cel O
Cel

OH H
O P O P O
Cel OH Cel OH

Figure 5. Reaction scheme of cellulose phosphorylation H3PO4 in molten urea and the possible gained products.

it adds phosphoric acid and the mixture are stirred for 4 h at 403 K. The reaction products are
monophosphated cellulose and water, as shown in Figure 6 [16,17].
O
HO P OH
OH O
O O O O
H H
H H
(NH2)2CO
OH H + H3PO 4 OH H + H2O
H DMF H
H OH H OH
n n

Figure 6. Reaction scheme of cellulose phosphorylation H3PO4 in urea using DMF as the solvent.

The cellulose phosphorylation increases the capacity of cellulose ionic exchange, because the
introduction of phosphated group in the structure promotes the growth of the active groups.
This characteristic was noticed by addition of cellulosic solvents [rice straw (37.4% of cellu‐
lose, 44.9% of hemi-cellulose, 4.9% of lignin and 13.1% of ashes) and phosphate rice straw] in
contact with a 1 mol L–1 de NaCl solution. The ionic exchange reaction occurs by substitution
of H+ of the adsorbents for Na+ which is in solution, generating HCl in solution, according to
Figure 7 [18].
O O
HO P OH NaO P ONa
O O
O O O O
H H
H H
OH H OH H
H H
+ +
H OH 2Na 2H H OH
n n

Figure 7. Ionic exchange solution from the phosphated solution.

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The ionic exchange capacity is very important in the application in adsorption of heavy metals
from aqueous medium. Surveys have showed which bacterial cellulose has no adsorption
capacity of lanthanides metals (La3+, Sm3+ e Ho3+), since phosphated bacterial cellulose presents
adsorption capacity of these metals. This adsorption process is influenced by the pH of
medium. This pH dependence in adsorption indicates the pH mechanism is cation exchange.
In addition, the bacterial phosphated cellulose has high adsorption capacity of lanthanides
ions “stiff acid”, based on the high affinity of the phosphoric acid group “stiff base” by the
principle of base acid stiff acid (HSAB) [16].

The phosphated cellulose also proved efficient in the removal of drug ranitidine (Figure 8).
Surveys have shown that after phosphating reaction, a growth of negative charge of cellulose
occurred, due to the presence of phosphate group. It made the drug ranitidine reaction higher
on modified cellulose surface than on pure cellulose surface. The ranitidine adsorption
mechanism on the phosphated cellulose surface was through electrostatic interaction, where
the negative charge of phosphate groups interacts with positive charge on the nitrogen atom
of drug. As the same way, the ΟΗ– ions can interact with the positive ions of drug, stopping
drug interaction with phosphated cellulose, as reported above [6,7].

NO2
CH3

N S CH3
H3C O NH NH

Figure 8. Molecular structure of ranitidine.

2.3. Acylation

The acylation with cyclic organic anhydrides of five members is a well-established reaction,
which at first it involves all three hydroxyl groups of the cellulose unity (acts as nucleophiles),
for getting a steady ester and reactive groups from carboxyl acids. In the practical use, these
acylation processes are used in covering, cosmetics, in the pharmaceutical and food industries,
as membranes and antibody filters, enzyme, protein, ion separation, etc. [19].

The cellulose derivatives which have free carboxyl groups are prepared by cellulose reaction
or cellulosic material with succinic, maleic, or phthalic in the solvent absence. This process
consists of heating cellulose with the amount of each anhydride up to anhydride melting
fusion. For each case, the cellulose/anhydride proportion is 1/10, the mixture is stirred for 20
min and the reaction is interrupted by addition of DMA [20]. The full scheme of reaction is
shown in Figure 9.

The three reactions shown above have covalent incorporation of carboxyl groups. This
incorporation can be confirmed by the growth of the amount of carbon in the cellulose [20,21].
The cellulose reaction with maleic anhydride presents a high incorporation level, due to
absence of solvent in this synthesis, which is well-proportioned by high temperature and by
easy availability of reagents. The maleic anhydride presents incorporation, which after
100 Cellulose - Fundamental Aspects and Current Trends

O OH

O
OH O
O O O O
H O H
O O
H H
OH H OH H
H H
H OH
326 K
n H OH
n

(a)

O O
OH COOH
O
O O O
H
O O
H H
OH H H
O OH H
H
H
H OH 404 K
n H OH
n

(b)

OH
O
O
OH
O O O
O
O O O O
H H
H H
OH H OH H
H H
H OH 392 K H OH
n n

(c)

Figure
Figure 9. Cellulose reaction9.scheme
Cellulose reaction
or cellulose scheme
material or cellulose
with anhydride material
(a) maleic, with
(b) phthalic, andanhydride
(c) succinic. (a)
maleic, (b) phthalic, and (c) succinic.
opening the ring forms two isomers of the cellulose: the cellulose maleate (cis) and cellulose
fumarate (trans). This possibility to form both isomers is due to the presence of withdrawing
groups near to unsaturation, which can affect isomerization according to the potential effect
for removing electrons, and also due to impediment caused by these groups. In addition, the
reaction α,β-unsaturation, with hydroxyl C(2), C(3), and (C6), through Michael’s addition can
produce other composts as sub products [21].

The cellulose reaction with phthalic anhydride also has a high level of anhydride incorporation
by the same reasons quoted above in the cellulose reaction with maleic anhydride. The reaction
using this aromatic anhydride can create some attractive interactions involving the aromatic
rings of the anhydride, aromatic–aromatic interactions (Ar–Ar). These interactions can be
strong enough to disturb the β-(1 → 4) bonds [22]. The cellulose reaction with succinic
 Chemical Functionalization of Cellulosic Materials — Main Reactions and Applications in... 101
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anhydride is similar to cellulose reaction with maleic anhydride, the only difference being no
formation of cis–trans isomer, due to the absence of unsaturation in succinic anhydride.

These cellulose derivatives are enough in the removal of several contaminants from the
aqueous medium. For example, the cellulose derivatives modified with maleic and phthalic
anhydride were applied in adsorption of green malachite dye (Figure 10 (a)), and were shown
to be more effective than pure cellulose. The dye adsorption was influenced by initial pH of
medium. The addition of green malachite dye, on the surface of two cellulosic derivatives,
increased as the pH increased until pH 6, where adsorption was established. This happened
because in low pH, the carboxyl groups, of modified biopolymers, can be protonated, due to
high proton concentration, decreasing the amount of adsorbed cationic dye. Also, this survey
has shown the higher amount of carboxyl groups in cellulose, higher is the adsorption of green
malachite dye [23]. The cellulose derivative modified with maleic anhydride showed effective
in adsorption of divalent metals (Co2+ and Ni2+), where the adsorption mechanism in this
system is complexation among basic centers of carboxyl groups and divalent cations, as shown
in Figure 10(b). For facilitating this complexation, and any lower minimization of pH, the
protons of carboxyl groups were substituted by sodium. Figure 10 (b) is shows a counter-ion
for neutralizing free cationic charge, where the cation can interact with a carboxyl group or
two distinct basic centers [21].

CH3 CH3
+
N N
H3C CH3

(a)

-
- NO 3 -
O O O O NO 3
2+ 2+ 2+
M M M
- - - -
O O O O NO 3

- -
O - -
O O O NO 3
2+ 2+ 2+
M M M
- O - O -
O O NO 3 NO 3

(b)

Figure 10. (a)10.

Figure Molecular structure of green
(a) Molecular malachite
structure cationic malachite
of green dye. (b) Possible structures
cationic dye.for formation of divalent cati‐
(b) Possible
on complex and modified cellulose with maleic anhydride.
structures for formation of divalent cation complex and modified cellulose with maleic
anhydride.
102 Cellulose - Fundamental Aspects and Current Trends

The cellulose derivatives modified with succinic and phthalic anhydrides proved efficient in
adsorption of metal Cu2+. In these cases, the adsorption is favored by growth of pH, where the
sorption is favored in solutions with high pH to the point of zero charge (pHpzc) for each
modified material (modified cellulose with phthalic anhydride pHpzc= 5.4 and with succinic
anhydride pHpzc= 5.7). Under acid conditions, the chemically modified biopolymers can be
protonated, due to high concentrations of H+ ions, decreasing the amount of adsorbed cation.
On the other hand, the growth of pH deprotonates carboxyl group, a condition which favors
chelating capacity, and consequently, the capacity of adsorbed Cu2+ increases [20]. The cotton
fibers and other cellulosic derivatives have an improvement about 40% in the adsorption of
blue methylene cationic dye (Figure 3(a)) after the chemical modification with succinic
anhydride. The presence of carboxyl groups in biomaterials means significant rise in the
adsorption, which can result from electrostatic interactions among these groups and dye
reactive groups [24].

2.4. Amination

The molecule incorporation which has basic centers (primarily nitrogen, oxygen, and sulfur)
in the cellulose structure raises its contaminants’ adsorption capacity [3]. Thus, the nitrogen
incorporation in cellulose or in the cellulosic materials is an important chemical modification
which allows the insertion of active sites in this biomaterial. These sites can interact in aqueous
medium with contaminants molecules, in heterogeneous system in which the interactive
processes are defined by solid/liquid interface [25].

An example of incorporation of basic centers in cellulose structure is the reaction with

ethylene-1,2-diamine. The first stage of reaction consists in allogeneic derivative synthesis. In
the halogenation, chlorine addition is preferable, since it is the most effective allogeneic, whose
preferential sequence is: chlorine > bromine, iodine > fluorine [25]. The first step of reaction
series consists in the cellulose chlorination, a favored process by nucleophilic attack from
thionyl chloride on hydroxyl group in the biopolymer backbone, resulting in chlorine atom
pending in polymer structure. This replaced atom is more reactive than the original hydroxyl
group, where a total substitution of hydroxyl in C6 by chlorine can happen. It happens due to
hydroxyl group which is in C6 being more reactive than other hydroxyl groups, following
order C6>> C3≈C2, as shown in Figure 11 [26,27].

OH
Cl
O O
H O O
H DMF H
H
OH H + SOCl 2 OH H + SO 2 + HCl
H 353 K
H
H OH
n H OH
n

Figure 11. Reaction of cellulose chlorination.

The second step of reaction consists in chlorinated cellulose reaction to react with ethylene-1,2-
diamine under reflux for 3 h in the absence of solvent, according to Figure 12 [28]. When the
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ethylene-1,2-diamine reacts with chlorinated cellulose and replaced chlorine, the inter- and
intramolecular reactions present in biomaterial which are very much responsible for its
organization and crystalline arrangement become amorphous. In addition, the molecule
incorporation of ethylene-1,2-diamine provides the growth of the amount of carbon in the
structure, the increasing C7 and C8 [29].

H2N

NH
Cl
O O O O
H H
H H2NCH2CH2NH2 H
OH H OH H
+ HCl
H H

H OH H OH
n n

Figure 12. Reaction of chlorinated cellulose with ethylene-1,2-diamine.

Another important reaction of amination is organic molecule incorporation of 2- aminome‐

thylpyridine. As the latest example, initially cellulose is chlorinated and, then it reacts with
2-aminomethylpyridine under reflux for 4 h [25], according to Figure 13. The amount of
incorporated nitrogen in cellulose by this reaction is low, when compared to similar
patterns. This fact can be explained by steric impediment which is caused by molecule
hydrophobicity [30].

NH
Cl
CH2
O O O O
H N H
H H
OH H + 4h OH H + HCl
H H
H OH H OH
n NH2 n

Figure 13. Reaction of chlorinated cellulose with organic 2-aminomethylpyridine.

These cellulosic derivatives containing basic centers (in this case nitrogen) are extremely
used in the contaminants removal of the aqueous medium. For example, the modified
cellulose 2-aminomethylpyridine is proved to be effective in divalent cations removal (Cu2+,
Co2+, Ni2+, and Zn2+). In this case, the adsorption mechanism is based on the complexation
process of a cation in two basic centers, which indicates that cellulose chain acts as a
104 Cellulose - Fundamental Aspects and Current Trends

bidentate chelating agent. The scheme of metal complexation is shown in Figure 14 (a),
where the available nitrogen centers are coordinated to divalent cations, with charge being
counterbalanced for counter-ions. The modified cellulose with ethylene-1,2-diamine also
proved to be efficient in divalent cations removal quoted above. In this case, the adsorp‐
tion order was: Co2+ > Cu2+ > Zn2+ > Ni2+. Its adsorption mechanism is similar to that quoted
above, where there is transfer of cations from solutions to available basic centers in
ethylene-1,2-diamine anchored in the cellulose, by cations complexation through available
amine groups, as shown in Figure 14 (b) [28].

-
O3 N N
2+
M
-
O3 N
NH

CH2
O O
H
H
OH H
H

H OH
n

(a)

H
H 2+ H
H N 2+
H N
M N H
M

HN NH
NH

O O O O
H O O H
H H
H H
OH H OH H
OH H
H H
H
H OH H OH
n H OH
n
n

(b)

Figure
Figure14. (a)
14.Proposed scheme of
(a) Proposed complexation
scheme for divalent cations
of complexation with a modified
for divalent cationscellulose
with with 2-aminomethylpyr‐
a modified
idine. (b) Proposed scheme of complexation for divalent cations with the modified cellulose with ethylene-1,2-diamine.
cellulose with 2-aminomethylpyridine. (b) Proposed scheme of complexation for
Another amination
divalent cations with example is the
the modified introduction
cellulose of ethylene-1,2-diamine in the cellulose
with ethylene-1,2-diamine.
structure through a rusty cellulosic intermediate. The first stage consists in nanocrystalline
cellulose synthesis (NCC) through hydrolysis with sulfuric acid. In the second stage, the carbon
C2 and C3 of the cellulose is oxidised with sodium periodate (NaIO4), in the absence of light
at 313 K, forming nanocrystalline dialdehyde from cellulose. After this, ethylene-1,2-diamine
is added, the mixture is continuously stirred for 6 h at 303 K. Finally, with imine intermediate
reduction through addition of NaBH4 at room temperature, as shown in Figure 15 [31], the
zeta potential of the final product of this reaction is formed, which is highly influenced by pH.
In lower pH, the zeta potential was positive due to amine protonation (NCC–NH3+). By the pH
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growth, the zeta potential decreases and it becomes negative in alkaline region, resulting in
amine group deprotonation (NCC–NH2) and dissociation of sulfate groups on surface [31].

OH OX
OX
H
O O
H
O O H O
O
H H NaIO4 n
OH H + H2SO 4 OH H
absence of light, 313 K
H H H
H OH H OH O O
n n

2 H2NCH2CH2NH2 303 K
X = H or SO 3

OX OX
H O H O
O O
n n
NaBH4
H H

H2NH2CH2CHN NHCH2CH2NH2 H2NH2CH2CN NCH2CH2NH2

Figure 15. Oxidation with sodium periodate and reaction of nanocrystalline cellulose amination.

These cellulosic derivatives containing basic centers were efficient in dye removal. For
example, the modified cellulose with ethylene-1,2-diamine, having as intermediate an
oxidized cellulose derivative, was efficient in adsorption of the red anionic acid dyes GP, congo
red 4 BS, and pale yellow reactive K-4G (Figure 16). The pH affected adsorption of the three
dyes on the structure of modified cellulosic biomaterial with ethylene-1,2-diamine. The
isoelectric point (pHpzc) of this material is about 8, which indicates its surface at pH < 8 is
positively charged, whereas at pH > 8 is negatively charged. Hence, in acid conditions the
interaction occurs between the protonated amine group of the cellulosic material and the active
anionic site of dye, which favors the adsorption. Whereas in alkaline regions, the surface charge
of biomaterial becomes negative, and, consequently, it narrows interaction with dye anionic
active site, due to electrostatic repulsion [31].

2.5. Sulfonation

The cellulose functionalization with sulfur incorporation is more used in contaminants

removal of the aqueous medium. Several reactions are studied and their products are applied
in contaminants adsorption. Among reactions that have been studied is the cellulose oxidation
forming a dialdehyde, reacting with sodium bisulfite and creating a sulfonated cellulosic
material [32]. In this reaction, initially the cellulosic material oxidation occurs with sodium
periodate (NaIO4), as shown in Figure 15. Then, the cellulosic material 2,3-dialdehyde formed
is dispersed in water and it is treated with sodium bisulfite (NaHSO3), creating a sulfonated
cellulosic material, according to Figure 17. Afterward, sulfonation and oxidation of the surface
morphology of cellulosic material are modified. In this case, the cellulose nanospheres are
106 Cellulose - Fundamental Aspects and Current Trends

CH3

N N

- +
SO3 Na

(a)

O O
N S - +
N O Na
NH2
O N H2N
S N
- +
O O Na

(b)

N NH
NH
N N O
O
S - +
S Cl O Na
Na O
+ - N O
O
N

HO CH3
N N

Cl

Cl
O S O
- +
O Na

(c)

Figure
Figure 16. Chemical
16. Chemical structure
structure of the redof thedyes
acid redGR
acid
(a), dyes
congoGR (a),(b),
red 4BS congo redyellow
and pale 4BS (b), andK-4G
reactive pale(c).
yellow reactive K-4G (c).
gradually deformed, losing their spherical forms with oxidation/sulfonation growth. Howev‐
er, these changes in the nanosphere molds were stretched after sulfonation, with formation of
rods aggregates. In addition, the presence of sulfonic group has provided an increasing value
of water retention in the cellulosic material structure [32].

OH
OH H O
O O
H O n
n
Sulfonation H
H
NaHSO3 HO OH
- -
O O O3 S SO3

Figure 17. Sulfonation of cellulosic material.

 Chemical Functionalization of Cellulosic Materials — Main Reactions and Applications in... 107
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The sulfonated cellulosic derivative (obtained from wheat straw) modified similar to the latest
reaction proved efficient in heavy metal lead removal (Pb2+). The sulfonic group introduction
in the cellulosic biomaterial structure provokes the growth of electron density of the bioma‐
terial, increasing its affinity for metal ions. In lower levels of pH, the sulfonic groups are
protonated, which results in bad ions adsorption Pb2+. Since the increase in pH provides
adsorption growth, because sulfonic groups are deprotonated, and consequently in its ionic
form, the soft acids form higher covalent complex than ionic with binders containing sulfur.
Thus, in the beginning of adsorption, ions can bond with two binders to form complexes, soon,
in lower concentration, the ions (all Pb2+) can interact with two linkage locals, having a higher
adsorption. Another possible mechanism is ionic exchange with adjacent carboxyl group, but
as happens with other materials, there is possibility both mechanisms can participate together
during the adsorption, since there are several different active groups on adsorbent surface [33].
Another example of sulfur molecule incorporation is chemical modification of cellulosic
biomaterials, derivative from mesocarp and epicarp from babaçu coconut, with ethylenesul‐
fide. In this reaction, the cellulosic biomaterials are put in contact with ethylenesulfide, for 3
h at 323 K, as shown in Figure 18 (a). The amount of incorporated sulfur in these materials was
lower than the amount of incorporated sulfur in chitosan, which occurs due to amino reactive
center free of chitosan, being higher than hydroxyl groups of carbon 6, of these cellulosic
biomaterials [34,35]. Another methodology used to incorporate ethylenesulfide in cellulose
chain is by reaction with available amine group, which is from the reaction ethylene-1,2-
diamine (Figure 12). Since this amine group has been introduced by reaction with chlorine
cellulose (Figure 11) for increasing the cellulose surface reactivity, in this reaction, after
amination and chlorination, the cellulose containing amine groups are placed in contact with
ethylenesulfide for 4 h at 328 K, according to Figure 18 (b) [19].
The cellulosic biomaterials derivative from mesocarp and epicarp from babaçu coconut proved
efficient in adsorption of copper divalent cation (Cu2+). This adsorption process was influenced
by pH, where the increase in pH promoted the increasing ions adsorption, with maximum
adsorption at pH 6 for two biomaterials. This occurs because the surface of bio-adsorbents
changes its polarization with the value of pH of solution and with pH(pzc) of solid. The pH(pzc)
is the parameter that indicates the pH value in which a solid exhibit electrically neutral surface
so the number of positive charges equals the number of negative charges. The pH(pzc) of two
modified cellulosic biomaterials is 5.6, then in pH lower of this value the biomaterial surface
is positively charged, which disfavors the adsorption of cation ions Cu2+. Whereas in pH values
above pH(pzc), the biomaterials surface is negatively charged, and consequently fostering cation
adsorption occurs [34].
The modified cellulose with ethylenesulfide, according to Figure 18 (b), also proved to be
efficient in removal of several divalent cations (Pb2+, Cd2+, Ni2+, Co2+, Cu2+, and Zn2+). This
modified biomaterial presents higher capacity in extracting cations from aqueous solution,
due to presence of nitrogen and sulfur acids, which are highly reactive adsorption sites which
can coordinate with metal cations. The cations adsorption order was: Pb2+ > Cd2+ > Ni2+ > Co2+
> Cu2+ > Zn2+. The copper is less preferred by modified cellulose than nickel and cobalt, because
they have favorable complexation equilibrium constants [29].
Another reaction of sulfur incorporation in cellulose structure is its reaction with aminoetha‐
nethiol, using the cellulose chlorination with intermediate reaction. At first, chlorine cellulose
108 Cellulose - Fundamental Aspects and Current Trends

OH OCH 2CH2SH
O O O O
H H
H
323 K, 3 h H
OH H + OH H
H S H

H OH H OH
n n

(a)

HS

H2N HN

NH NH

O O 328 K, 4 h O O
H H
H H
OH H + S
OH H
H H
H OH H OH
n n

(b)

Figure
Figure 18. (a) 18. biomaterials
Cellulosic (a) Cellulosic biomaterials
reaction reaction (b)
with ethylenesulfide. with ethylenesulfide.
Cellulose (b) Cellulose
reaction, containing amine groups
with ethylenesulfide.
reaction, containing amine groups with ethylenesulfide.

is made, as shown in Figure 11. Then, the chlorine cellulose is placed in contact with aminoe‐
thanethiol at 363 K, after the triethylamine is used for removing excess of HCl, according to
Figure 19. The molecule introduction of aminoethanethiol in the cellulose structure provokes
changes in inter- and intramolecular interactions in biomaterial; these interactions are respon‐
sible by bigger part of biomaterial organization, by biomaterial crystalline arrangement, and,
consequently, if some disturbance occurs due to molecule introduction in biomaterial, it
becomes amorphous, such as with molecule introduction of aminoethanethiol [3].
HS

NH

S
Cl
O O O O
H H
H H
triethylamine
OH H + 2 H2N
SH 363 K, 4 h
OH H
H
+ HCl
H

H OH H OH
n n

Figure 19. Reaction of incorporation of aminoethanethiol group in the chlorinated cellulose structure.
 Chemical Functionalization of Cellulosic Materials — Main Reactions and Applications in... 109
http://dx.doi.org/10.5772/61431

Cl N NH
SO3Na

N N

NH SO2CH 2CH 2OSO3Na

N N

NaO3S SO3Na

(a)

H
NH +
Cl N - HN
SO3 + +
SH SH Cel
N N

-
NH SO2CH 2CH 2OSO3
N N

- -
O3 S SO3

+
NH2
+ +
SH SH Cel

(b)

Cl N NH NH
SO3H S
S Cel
H H
N N
N
NH SO2CH 2CH 2 S S Cel
N N

SO3H SO3H
NH
S S Cel
N
HS H
H S Cel

(c)

Figure 20. Molecular structure of reactive red anionic dye RB (a) and scheme of
Figure 20. Molecular structure of reactive red anionic dye RB (a) and scheme of modified cellulose interaction with
anionic dye inmodified
acid medium (b) and
cellulose basic medium
interaction with (c).
anionic dye in acid medium (b) and basic medium
(c).
This modified biomaterial with aminoethanethiol group proved efficient in removal of reactive
red anionic dye (Figure 20 (a)). In this survey, it is noted that the adsorption of dye is maximal
at pH 8 and 9, which indicate two predominant mechanisms in adsorption: one in acid medium
and other in basic medium. In acid medium, the adsorption is favored by electron interaction.
The pH(pzc) of modified material is nearest to 6, then, below this pH, the biomaterial surface is
110 Cellulose - Fundamental Aspects and Current Trends

positively charged, due to protonation of nitrogen and sulfur acids. These biomaterial positive
sites interact with negative ions in the dye favoring the adsorption (Figure 20 (b)). Since in
basic medium there will be no protonation on biomaterial surface, adsorption is favored by
hydrogen interaction and/or covalent interactions. The first stage of the mechanism involves
the group transformation of β-sulfatoethylsulfonic of dye SO2CH2CH2OSO3Na, in a vinylsul‐
fonic group, -SO2CH=CH2. In alkaline conditions, the group divides forming sulfate waste.
Then, the vinylsulfonic group interacts with the modified cellulose surface through a covalent
bond. In addition, it can have formation of hydrogen bond between sulfur/nitrogen atoms of
modified cellulose and the hydrogen sulfonic dye group (Figure 20 (c)) [3].

3. Conclusion

The chemical modification (incorporation of carboxymethyl, phosphorus, carboxyl, amines,

and sulfur) of cellulosic materials is very important for the application in the removal of
contaminants from aqueous medium. After the chemical modification, cellulosic materials
exhibit new chemical properties that are more advantageous than the starting materials. These
new chemical properties allow an increase in interaction between the modified cellulosic
materials and the contaminants (metals, dyes, and drugs) during adsorption processes in
aqueous medium and these interactions are strongly influenced by solution pH. Therefore, the
cellulosic materials modified with various chemical groups are promising for application in
removing contaminants from aqueous medium of the environment.

Acknowledgements

The authors thank the Council for Scientific and Technological Development (CNPq), Foun‐
dation for Supporting Research of Piauí (FAPEPI), and Coordination Support in Higher
Education (CAPES) for financial support. To the Federal University of Piauí (UFPI) and Federal
Institute of Piauí (IFPI), to provide work research conditions.

Author details

Roosevelt D.S. Bezerra1*, Paulo R.S. Teixeira1, Ana S.N.M. Teixeira1, Carla Eiras2,
Josy A. Osajima2 and Edson C. Silva Filho2

*Address all correspondence to: [email protected]

1 Federal Institute of Education, Science and Technology of Piaui _ Campus Teresina Central,
Teresina, Brazil

2 Federal University of Piaui _ LIMAV, Teresina, Brazil

 Chemical Functionalization of Cellulosic Materials — Main Reactions and Applications in... 111
http://dx.doi.org/10.5772/61431

References

[1] Isik M, Sardon H, Mecerreyes D. Ionic liquids and cellulose: dissolution, chemical
modification and preparation of new cellulosic materials. Int J Mol Sci 2014; 15(7):
11922 – 49. doi: 10.3390/ijms150711922

[2] Tian Y, Wu M, Liu R, Wang D, Liu X, Liu W, Ma L, Li T, Huang Y. Modified native

cellulose fibers: a novel efficient adsorbent for both fluoride and arsenic. J Hazard
Mater 2011; 185(1): 93 – 100. doi: 10.1016/j.jhazmat.2010.09.001.

[3] Silva L S, Lima L C B, Silva F C, Matos J M E, Santos M R M C, Júnior L S S, Sousa K

S, da Silva Filho E C. Dye anionic sorption in aqueous solution onto a cellulose sur‐
face chemically modified with aminoethanethiol. Chem Eng J 2013; 218: 89 – 98. doi:
10.1016/j.cej.2012.11.118.

[4] Lin Q, Zheng Y, Wang G, Shi X, Zhang T, Yu J, Sun J. Protein adsorption behaviors of
carboxymethylated bacterial cellulose membranes. Int J Biol Macromol 2015; 73: 264 –
9. doi: 10.1016/j.ijbiomac.2014.11.011

[5] Silva L S, Lima L C B, Ferreira F J L, Silva M S, Osajima J A, Bezerra R D S, da Silva

Filho E C. Sorption of the anionic reactive red RB dye in cellulose: assessment of ki‐
netic, thermodynamic, and equilibrium data. Open Chem 2015; 13: 801 – 12. doi:
10.1515/chem-2015-0079.

[6] Bezerra R D S, Silva M M F, Morais A I S, Osajima J A, Santos M R M C, Airoldi C, da

Silva Filho E C. Phosphated cellulose as an efficient biomaterial for aqueous drug ra‐
nitidine removal. Materials 2014; 7(12): 7907 – 24. doi: 10.3390/ma7127907

[7] Bezerra R D S, Silva M M F, Morais A I S, Osajima J A, Santos M R M C, Airoldi C, da

Silva Filho E C. Natural cellulose for ranitidine drug removal from solutions. J Envi‐
ron Chem Eng 2014; 2: 605 – 11. doi: 10.1016/j.jece.2013.10.016.

[8] Yasar F, Togrul H, Arslan N. Flow properties of cellulose and carboxymethyl cellu‐
lose from orange peel. J Food Eng 2007; 81: 187 – 99. doi: 10.1016/j.jfoodeng.
2006.10.022.

[9] Zhang G, Zhang L, Deng H, Sun P. Preparation and characterization of sodium car‐
boxymethyl cellulose from cotton stalk using microwave heating. J Chem Technol Bi‐
otechnol 2011; 86: 584 – 9. doi: 10.1002/jctb.2556.

[10] Lin Q, Zheng Y, Wang G, Shi X, Zhang T,Yu J, Sun j. Protein adsorption behaviors of
carboxymethylated bacterial cellulose membranes. Int Biol Macromol 2015; 73: 264 –
9. doi:10.1016/j.ijbiomac.2014.11.011.

[11] Yan H, Zhang W, Kan X, Dong L, Jiang Z, Li H, Yang H, Cheng R. Sorption of meth‐
ylene blue by carboxymethyl cellulose and reuse process in a secondary sorption.
Colloids Surf A 2011; 380: 143 – 51. doi:10.1016/j.colsurfa.2011.02.045.
112 Cellulose - Fundamental Aspects and Current Trends

[12] Kargl R, Mohan T, Bracic M, Kulterer M, Doliska A, Stana-kleinschek K, Ribitsch V.

Adsorption of carboxymethyl cellulose on polymer surface: evidence of a specific in‐
teraction with cellulose. Langmuir 2012; 28: 11440 – 7. doi: 10.1021/la302110a.

[13] Wang M, Xu L, Peng J, Zhai M, Li J, Wei G. Adsorption and desorption of Sr (II) ions
in the gels based on polysaccharide derivates. J Hazard Mater 2009; 171: 820 – 6. doi:
10.1016/j.jhazmat.2009.06.071.

[14] Kokol V, Bozic M, Vogrincic R, Mathew AP. Characterisation and properties of ho‐
mo- and heterogeneously phosphorylated nanocellulose. Carbohydr Polym 2015;
125: 301 – 13. doi: 10.1016/j.carbpol.2015.02.056.

[15] Suflet D M, Chitanu G C, Popa V I. Phosphorylation of polysaccharides: new results

on synthesis and characterisation of phosphosrylated cellulose. React Funct Polym
2006; 66: 1240 – 9. doi: 10.1016/j.reactfunctpolym.2006.03.006.

[16] Oshima T, Kondo K, Ohto K, Inoue K, Baba Y. Preparation of phosphorylated bacte‐

rial cellulose as an adsorbent for metal ions. Reac Funct Polym 2008; 68: 376 – 83. doi:
10.1016/j.reactfunctpolym.2007.07.046.

[17] Oshima T, Taguchi S, Ohe K, Baba Y. Phosphorylated bacterial cellulose for adsorp‐
tion of proteins. Carbohydr Polym 2011; 83: 953 – 8. doi:10.1016/j.carbpol.2010.09.005.

[18] Rungrodnimitchai S. Modification of rice straw for heavy metal ion adsorbents by
microwave heating. Macromol Symp 2014; 295: 100 – 6. doi: 10.1002/masy.200900146.

[19] de Melo J C P, da Silva Filho E C, Santana S A A, Airoldi C. Synthesized cellulose/

succinic anhydride as an ion exchanger. Calorimetry of divalent cations in aqueous
suspension. Thermochim Acta 2011; 523: 29 – 34. doi: doi:10.1016/j.tca.2011.06.007.

[20] Vieira A P, Santana S A A, Bezerra C W B, Silva H A S, de Melo J C P, da Silva Filho

E C. Airoldi C. Copper sorption from aqueous solutions and sugar cane spirits by
chemically modified babaçu coconut (Orbignya speciosa) mesocarp. Chem Eng J 2010;
161: 99 – 105. doi: 10.1016/j.cej.2010.04.036.

[21] de Melo J C P, da Silva Filho E C, Santana S A A, Airoldi C. Maleic anhydride incor‐

porated onto cellulose and thermodynamics of cation-exchange process at the solid/
liquid interface. Colloids Surf A 2009; 346: 138 – 45. doi: 10.1016/j.colsurfa.
2009.06.006.

[22] de Melo J C P, da Silva Filho E C, Santana S A A, Airoldi C. Exploring the favorable

ion-exchange ability of phthalytated cellulose biopolymer using thermodynamic da‐
ta. Carbohyd Res 2010; 345: 1914 – 21. doi: 10.1016/j.carres.2010.06.012.

[23] Zhou Y, Min Y, Qiao H, Huang Q, Wang E, Ma T. Improved removal of malachite

green from aqueous solution using chemically modified cellulose by anhydride. Int
Biol Macromol 2015; 74: 271 – 7. doi: 10.1016/j.ijbiomac.2014.12.020.
 Chemical Functionalization of Cellulosic Materials — Main Reactions and Applications in... 113
http://dx.doi.org/10.5772/61431

[24] Kassale A, Barouni K, Bazzaoui M, Martins J I, Albourine A. Methylene Blue adsorp‐

tion by cotton grafted with succinic anhydride. Prot Met Phys Chem 2015; 51: 382 – 9.
doi: 10.1134/S2070205115030120.

[25] da Silva Filho E C, Júnior L S S, Silva M M F, Fonseca M G, Santana S A A, Airoldi C.

Surface cellulose modification with 2-aminomethypyridine for copper, cobalt, nickel
and zinc removal from aqueous solution. Mat Res 2013; 16: 79 – 87. doi: 10.1590/
S1516-14392012005000147.

[26] da Silva Filho E C, de Melo J C P, da Fonseca M G, Airoldi C. Cation removal using

cellulose chemically modified by a Schiff base procedure applying green principles. J
Colloid Interface Sci 2009; 340: 8 – 15. doi: 10.1016/j.jcis.2009.08.012.

[27] da Silva Filho E C, Santana S A A, de Melo J C P, Oliveira F J V E, Airoldi C. X-ray

diffraction and thermogravimetry data of cellulose, chlorodeoxycellulose and amino‐
deoxycellulose. J Therm Anal Calorim 2010; 100: 315 – 321.doi: 10.1007/
s10973-009-0270-6.

[28] da Silva Filho E C, de Melo J C P, Airoldi C. Preparation of ethylenediamine-anch‐

ored cellulose and determination of thermochemical data for interaction between cat‐
ions and basic centers at the solid/liquid interface. Carbophydr Res 2006; 341: 2842 –
50. doi: 10.1016/j.carres.2006.09.004.

[29] da Silva Filho E C, Lima L C B, Silva F C, Sousa K S, Fonseca M G, Santana S A A.

Immobilization of ethylene sulfide in aminated cellulose for removal the divalent cat‐
ions. Carbohydr Polym 2013; 92: 1203 – 10. doi: 10.1016/j.carbpol.2012.10.031.

[30] da Silva Filho E C, Júnior L S S, Santos M R M C, Fonseca M G, Sousa K S, Santana S

A A, Airoldi C. Thermochemistry of interaction between cellulose modified with 2-
aminomethylpyridine and divalent cations. J Therm Anal Calorim 2013; 114: 423 – 9.
doi: 10.1007/s10973-012-2917-y.

[31] Jin L, Li W, Xu Q, Sun Qiucun. Amino-functionalized nanocrystalline cellulose as an

adsorbent for anionic dyes. Cellulose 2015; doi: 10.1007/s10570-015-0649-4.

[32] Zhang J, Jiang N, Dang Z, Elder T.J, Ragauskas A.J. Oxidation and sulfonation of cel‐
lulosics. Cellulose 2008; 15: 489 – 496. doi: 10.1007/s10570-007-9193-1.

[33] Suopajarvi T, Liimatainen, Karjalainen M, Upola H, Niinimaki J. Lead adsorption

with sulfonated whet pulp nanocelluloses. J Wat Process Eng 2015; 5: 136 – 42. doi:
10.1016/j.jwpe.2014.06.003.

[34] Santana S A A, Vieira A P, da Silva Filho E C, de Melo J C P, Airoldi C. Immobiliza‐

tion of ethylenesulfide on babassu coconut epicarp and mesocarp for divalent cation
sorption. J Hazard Mater 2010; 174: 714 – 9. doi: :10.1016/j.jhazmat.2009.09.109.

[35] Sousa K S, da Silva Filho E C, Airoldi C. Ethylenesulfide as a useful agent for incor‐
poration into the biopolymer chitosan in a solvent-free reaction for use in cation re‐
moval. Carbohydr Res 2009; 344: 1716 – 23. doi: 10.1016/j.carres.2009.05.028.