1) Application of Benzoxazine-Based Dimers, Oligomers, and Polymers

as Chelating Agents

Polybenzoxazines are a relatively new type of thermoset polymer that has primarily been used for
the development of composite materials. However, there is an existing interest in expanding the
applications for this family of polymers. One way of achieving this goal is by taking advantage of
the molecular structure, where the presence of oxygen and nitrogen atoms with lone electron pairs
allows the formation of coordination complexes and chelates between the benzoxazine oligomers
and polymers with metal ions. This article is focused on studying the relationship between the
spatial conformation of the polybenzoxazine and the capacity to form coordination complexes
from a fundamental point of view as well as practical applications of this concept. Thus, it can be
seen that use of polybenzoxazines for the removal of heavy metals from water and the use of
benzoxazine dimers for the synthesis of CeO2 nanoparticles are examples of very different
applications based on the same working principle.

2) Removal of Toxic Metal Ions from Water Using Chelating Terpolymer Resin as
a Function of Different Concentration Time and pH

Terpolymer resin 4-ASAUF was synthesized by the condensation of 4-aminosalicylic acid (4-
ASA) and urea (U) with formaldehyde (F) in the presence of 2 N hydrochloric acid. The structure
of the resin was characterized by various spectral techniques like infrared (FTIR) and nuclear
magnetic resonance (1H and 13C-NMR) spectroscopy. The empirical formula and empirical weight
of the resin were determined by elemental analysis. The physiochemical properties of terpolymer
resin were determined. The morphological feature of the 4-ASAUF terpolymer resin was studied
by scanning electron microscopy (SEM). The chelating ion-exchange property of this copolymer
was studied for eight metal ions, namely, Fe3+, Cu2+, Ni2+, Co2+, Hg2+, Zn2+, Cd2+, and Pb2+ ions
by using batch equilibrium method. The chelating ion-exchange study was carried out over a wide
pH range at different time intervals using different electrolyte of various ionic strengths.

3) Development and application of polymeric materials for heavy metal

ions recovery from industrial and mining wastewaters

Cross-linking is a process of chemically joining two or more molecules by covalent bonds. Cross
linking reagents contain two or more reactive ends that are capable of attaching to specific
functional groups (primary amines, sulfhydryls, etc.). The most common cross linkers which
contain at least two functional groups are dihaloalkanes such as 1,2-dichloroethane, 1,2-
dichloropropane, 1,3-dichloropropane,and 1,4- dichlorobutane, and glycidyl halides such as
epichlorohydrin, polyepoxides (Steuerle et al., 2000). In this research branched polyethylenimine
was cross-linked to achieve the water-insoluble form, which gives the advantages of being used in
situ and possibility of regeneration and re-use making it a more feasible and cost-effective
adsorbent.
The surface characteristics of the polymers are of substantial importance because many critical
interactions between the polymer and its environment occur at the surface. So the surface
composition plays a significant role in the performance of the polymers (Kumagai et al., 2007).
Polymer surface modification improves the properties of the polymers hence the specific desired
properties can rarely be achieved with one homogenous material since their surface properties are
often less than optimal for desired application. The modification of polymers by coating
(laminating) one material onto another, or by functionalization (introducing different functional
groups) gives new materials whose properties combine the desired properties of each component.
The change in the surface characteristic could be achievable without changing the bulk properties
of 41 the polymer such as the mechanical strength. This gives the advantages of manipulating the
macroscopic properties and surface characteristic to maintain favoured surface properties of the
polymer to suit the given application (Kumagai et al., 2007; Moloney, 2008; Rivas et al., 2009). A
growing demand for more selective chelating polymers is evident in many applications. This can
be achieved by functionalization. Functionalized polymers are used for many different applications
including organic syntheses, metal ion separation, pollution control, polymer drug grafts,
wastewater treatment, and uptake of trace metal ions. The modification of the polymers by
functionalization is a preferred process of enhancing metal selectivity since polymer surface
grafting offers versatile means for providing existing polymers with new functionalities (Reddy
and Reddy, 2003). In this research branched polyethylenimine (Figure 4.1) was used as one of the
most common co-ordination polymers. It is an aliphatic polyamine chelating polymer (Zhu et al.,
2006) available in a broad range of molecular weights. It is available in two different structures:
linear form and branched form.
Polyethylenimine (PEI) is well known for its metal chelating potential owing to the presence of amino
groups. It has been widely used for the retention of metal ions, but as a water soluble polymer which requires
additional techniques for effective removal such as membrane support or ultrfiltration making it difficult to
work with. It has also been used mainly for the removal of single or a few metal ions (Cojocaru et al., 2009;
Ghoul et al., 2003; Gohdes et al., 2001; Leroy et al., 2003; Masotti et al., 2010; Molinari et al., 2006;
Molinari et al., 2005; Molinari et al., 2004; Ortagi et al., 2008; Taylor et al., 2003). In this study PEI surface
has been modified by introducing different functional groups for selective removal, depending on the
difference in the affinity of donor atoms. The functionalization of polyethylenimine produced different
derivatives of polyethylenimine that have same polymer chain and only differ in their functional groups
and accordingly in their chelating properties including affinity and selectivity. So, overall purposes of this
phase were to obtain the optimum removal efficiency of the synthesized polymers by combining the
waterinsoluble properties of cross-linked polyethylenimine together with the good chelating properties of
polyethylenimine and the high selectivity of its functionalized derivatives.

4) . Adsorption on modified biopolymers and hydrogels

Biopolymers are industrially attractive because they are, capable of lowering transition metal ion
concentrations to sub-part

regenerated and their selectivity properties were better than crosslinked chitosan without crown
ether. The sorption mechanism of polysaccharide-based-materials is different from those of other
conventional adsorbents. These mechanisms are complicated because they implicate the presence
of different interactions. Metal complexation by chitosan may thus involve two different
mechanisms (chelation versus ion exchange) depending on the pH since this parameter may affect
the protonation of the macromolecule (Crini, 2005). Chitosan is characterized by its high
percentage of nitrogen, present in the form of amine groups that are responsible for metal ion
binding through chelation mechanisms. Amine sites are the main reactive groups for metal ions
though hydroxyl groups, especially in the C-3 position, and they may contribute to adsorption.
However, chitosan is also a cationic polymer and its pKa ranges from 6.2 to 7. Thereby, in acidic
solutions it is protonated and possesses electrostatic properties. Thus, it is also possible to sorb
metal ions through anion exchange mechanisms. Sorbent materials containing immobilized
thiacrown ethers were prepared by immobilizing the ligands into sol–gel matrix (Saad et al., 2006).
The competitive sorption characteristics of a mixture of Zn(II), Cd(II), Co(II), Mn(II), Cu(II),
Ni(II), and Ag(I) were studied. The results revealed that the thiacrown ethers exhibit highest
selectivity toward Ag(I). Hydrogels, which are crosslinked hydrophilic polymers, are capable of
expanding their volumes due to their high swelling in water. Accordingly they are widely used in
the purification of wastewater. Various hydrogels were synthesized and their adsorption behavior
for heavy metals was investigated. Kesenci et al. (2002) prepared poly(ethyleneglycol
dimethacrylate-coacrylamide) hydrogel beads with the following metals in the order Pb(II) >
Cd(II) > Hg(II); Essawy and Ibrahim (2004) prepared poly(vinylpyrrolidone-co-methylacrylate)
hydrogel with Cu(II) > Ni(II) > Cd(II); while Barakat and Sahiner (2008) prepared poly(3-
acrylamidopropyl)trimethyl ammonium chloride hydrogels for As(V) removal. The removal is
basically governed by the water diffusion into the hydrogel, carrying the heavy metals inside
especially in the absence of strongly binding sites. Maximum binding capacity increases with pH
increase to >6. Fig. 5 shows the schematic representation of polymerization/crosslinking reaction
that results in three-dimensional network formation of cationic hydrogel

5) Removal of heavy metals from wastewater using agricultural and

industrial wastes as adsorbents
Adsorption processes are being widely used by various researchers for the removal of heavy
metals from waste streams and activated carbon has been frequently used as an adsorbent. Despite
its extensive use in water and wastewater treatment industries, activated carbon remains an
expensive material. In recent years, the need for safe and economical methods for the elimination
of heavy metals from contaminated waters has necessitated research interest toward the production
of low cost alternatives to commercially available activated carbon. Therefore, there is an urgent
need that all possible sources of agro-based inexpensive adsorbents should be explored and their
feasibility for the removal of heavy metals should be studied in detail. The objective of this
research is to study the utilization possibilities of less expensive adsorbents for the elimination of
heavy metals from wastewater. Agricultural and industrial waste by-products such as rice husk
and fly ash have be used for the elimination of heavy metals from wastewater for the treatment of
the EL-AHLIA Company wastewater for electroplating industries as an actual case study. Results
showed that low cost adsorbents can be fruitfully used for the removal of heavy metals with a
concentration range of 20–60 mg/l also, using real wastewater showed that rice husk was effective
in the simultaneous removal of Fe, Pb and Ni, where fly ash was effective in the removal of Cd
and Cu.
5) Adsorption of heavy metal ions and azo dyes by crosslinked nanochelating resins
based on poly(methylmethacrylate-co-maleic anhydride)

Chelating resins are suitable materials for the removal of heavy metals in water treatments. A
copolymer, Poly(MMA-co-MA), was synthesized by radical polymerization of maleic anhydride
(MA) and methyl methacrylate (MMA), characterized and transformed into multifunctional
nanochelating resin beads (80–150 nm) via hydrolysis, grafting and crosslink reactions. The resin
beads were characterized by swelling studies, field emission scanning electron microscopy
(FESEM) and Fourier transform infrared spectroscopy (FTIR). The main purpose of this work was
to determine the adsorption capacity of the prepared resins (swelling ratio ~55%) towards metal
ions such as Hg2+, Cd2+, Cu2+ from water at three different pH values (3, 6 and 9). Variations in
pH and types of metal ions have not significantly affected the chelation capacity of these resins.
The maximum chelation capacity of one of the prepared resin beads (Co-g-AP3) for Hg2+ was 63,
85.8 and 71.14 mg/g at pH 3, 6 and 9, respectively. Approximately 96% of the metal ions could
be desorbed from the resin. Adsorption capacity of these resins towards three commercial synthetic
azo dyes was also investigated. The maximum adsorption of dye AY42 was 91% for the resin Co-
g-AP3 at room temperature. This insures the applicability of the synthesized resins for industrial
applications.
7) Ethylenediamine-N,N'-disuccinic acid (EDDS) as chelating agent.
8) crosslinking reaction between the melamine formaldehyde resin and the –OH
functionality of the epoxide resin.(Bookmark 5)
9) Poly(thionylphosphazenes): a new class of inorganic polymers with skeletal phosphorus,
nitrogen, and sulfur(VI) atoms.
10) Natural diatomite as an effective adsorbent for heavy metals in water and waste water
treatment
Adsorption of heavy metal ions and azo dyes by crosslinked nanochelating resins based on
poly(methylmethacrylate-co-maleic anhydride)

2.1. Materials
Benzoyl peroxide (BPO), ethylenediamine (ED), diethylenetriamine (DETA), triethylenetetramine
(TETA), (MMA), (MA), 2-aminopyridine (AP), triethylamine (TEA) and solvents were purchased from
Fluka Co. (Germany). Copper chloride (CuCl2!2H2O), mercury chloride (HgCl2), cadmium chloride
(CdCl2), and dyes such as acid yellow 42 (AY42), acid red 151 (AR151) and mordant blue 9 (MB9) were
purchased from Aldrich-Sigma Co. (Germany). All the chemicals and reagents were analytical grade and
used as received without further purification. pH adjustments were performed with HCl and NaOH
solutions.
Removal of Toxic Metal Ions from Water Using Chelating Terpolymer Resin as a Function
of Different Concentration Time and pH (Bookmark 1)

2.1. Starting Materials

4-Aminosalicylic acid is of analytical grade purity which is purchased from Acros
Chemicals, Belgium. Urea, formaldehyde (37%), metal nitrates, indicators, and disodium
salt of ethylenediaminetetraacetic acid (EDTA) were purchased from S. D. Fine Chemicals,
India. All the used solvents like N, N-dimethylformamide, dimethyl sulfoxide,
tetrahydrofuran, acetone, and diethyl ether were procured from Merck, India. Double
distilled water was used for all the experiments.

Synthesis and Characterization of Polyphosphazenes Modified with Hydroxyethyl

Methacrylate and Lactic Acid (Bookmark last)
Synthesis of Resorcinol-Based Phosphazene-Containing Epoxy Oligomers (structure given)

Synthesis of Unsaturated Polyester Resin (UPR-1)

Unsaturated polyester resin (figure-1) was prepared in the present work using technique reported
by T Sunemi Hidenari [89]. A mixture of 1.25 mol Propylene glycol (PG), 0.5 mol Phthalic
anhydride (PA), 0.2% p- Toluene sulfonic acid (PTSA) and Xylene as solvent was charged in a
three-neck reaction kettle equipped with stirrer, thermometer, nitrogen-gas introducing tube,
separator and water condenser. The mixture was mechanically stirred and heated at 1200C under
nitrogen gas stream. When reaction mass becomes clear, it was allowed to cool to 800C and then
0.5 mol Maleic anhydride (MA) was added and continues heating at 150-2000C until an acid
number of 20 was reached. During esterification reaction, water formed as by product and was
continuously removed from the reaction mass as it inhibits the rate of reaction. The Xylene was
completely distilled out and reaction product was allowed to cool. When the temperature reached
to 1600C, 20 mg of hydroquinone was added as inhibitor and when resin temperature dropped
below the boiling point of reactive diluent (i.e. Styrene), the polyester resin were mixed with
styrene by 35 weight percent of resin [90]. The polymer obtained was characterized Gel
Permeation chromatography (GPC) and IR spectroscopy.
Synthesis of SBA-15

2.1. Materials
Coal gangue was donated by Lu’an Group (Shanxi, China) and used after being grinded to
particles about 200 μm in size. Hydrochloric acid (HCl, 36%), sodium carbonate (Na2CO3,
98%), sodium silicate (Na2Si3O7, with 25 wt.% SiO2 and 14 wt.% NaOH), and acetic acid
(HAc) were purchased from SCR. The triblock copolymer EO20PO70EO20 (P123) was from
Aldrich.
2.2. The Preparation of Sodium Silicate from Coal Gangue
Raw coal gangue was ground to powder with a mesh size of less than 1000 μm using a
mechanism grinder. The powder was calcined at 750°C for 2 h and then leached with 36%
HCl at 40°C until no weight loss being observed. By this way, most aluminum oxide, ferric
oxide, and other impurities were removed, which could be used to produce polyaluminum
chloride employed as waste water purifier. The remained mixture was collected as silica
slag. After that, soluble sodium silicate was prepared with the silica slag by a new
developed low-temperature comelting method. Silica slag was mixed with Na2CO3 at a
3 : 2 weight ratio and grinded for 1 h using a ball mill (about 5–10 μm). The mixture was
calcined at a heating rate of 5°C/min up to 850°C for 3 h in a muffle furnace. Afterwards,
the liquid melt was quenched in boiled water to get small fragments and transferred into a
high-pressure reactor filled with water and heated up to 150°C for 5 h. The obtained liquid
mixture was filtered and then the as-prepared sodium silicate solution was obtained. The
contents of the coal gangue, the silica slag, and the as-prepared sodium silicate are listed
in Table 1. It can be seen that there is over 95% SiO2 in the as-prepared sodium silicate.
The mesoporous silica was prepared using a slightly modified hydrothermal route [10].
P123 2 g was dissolved in 48 mL of 2 M HCl, in which 3.1 g HAc was added and stirred
for 4 h to obtain solution A. 25 mL of the as-prepared sodium silicate solution was stirred
for 10 min at room temperature as solution B. At 40°C, solution B was added into solution
A dropwise under vigorous stirring. The mixture was stirred for 10 min at 40°C and then
was kept motionless at room temperature for 12 h. The sediment was filtrated and washed
with deionized water several times until Na+ could not be detected in the washing liquor.
Then, 20 g of deionized water was added in the washed sediment. The pH of the obtained
mixture was adjusted to 1.7 with 2 M HCl before being transferred into a hydrothermal
reaction kettle. After the hydrothermal reaction at 100°C or 200°C for 24 h, the collected
samples were filtered, washed, dried in air, and then sintered at 650°C for 5 h to get as-
prepared SBA-15 (S-slag). For comparison, pure SBA-15 samples were prepared using
commercially available (pure) sodium silicate as a silica source at 100°C and 200°C, which
were denoted as S-100 and S-200.