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Technical Briefing: Sequestering Agents

Complex Problems Can

Have Sugary Solutions
By Dr Naresh M. Saraf and Dr Ashok G. Sabale, of Sarex, India
THE QUALITY of water used in the textile empty orbitals of a suitable energy level to pyrophosphate, are probably the best overall,
finishing industry plays a significant part. In accommodate these electron pairs. A ligand in that, in addition to sequestering most
addition to undesired excess consumption of that is only able to supply one electron pair is metals, they also aid in cleansing the fibres.
textile auxiliaries and dyestuffs, water referred to as a monodentate. The number of They may, however, hydrolyse at high
hardness can cause disruption to processes, monodentate ligands that are able to be temperature and lose their effectiveness.
and incrustations on the textile substrate, on grouped around the central ion determines the The aminocarboxylic acid type sequestering
the machines and pipes, resulting into co-ordination number of the relevant ion. agents, such as EDTA, NTA and DTPA
inferior final fabric quality. For a chelate to form, it is necessary to have a (Diethylene triaminepentacetic acid sodium salt)
In the textile industry, a ‘sequestering’ agent is ligand that can supply at least two pairs of are very good in that they sequester most metal
understood, in the broader sense, to mean an electrons, which are sufficiently far apart from ions and are very stable under alkaline
auxiliary chemical that forms a complex with each other in the ligand molecule to be able to conditions. But generally they are not stable to
metals such as iron, copper, nickel, zinc and form a bridge. This type of ligand is a bidentate oxidising agents and have limited solubility in
magnesium, which are present in water and or a ligand with two co-ordinate bonds. The acidic medium. These are the most-used types.
affect the textile processing in many way. majority of sequestering agents are The organophosphonic acid types, such as
The alkali builders, or sequestering agents, polydentates with 4-8 co-ordinate ethylenediaminetetra (methylene phosphonic
or chelating agents, used for this process bonds. The chelates usually contain 2 moles acid), DETMP, ATMP, HEDP, are also very
deactivate the water-hardening substances and of ligand (glycine) and one mole of metal, as effective but comparatively expensive. Also,
other harmful cations in the water by precipi- demonstrated in the following figure: complexes are not stable under high
tation, ion exchange, chelating or adsorption temperature and break down to simple
on the seed-crystal surface. These agents bind phosphates, which cannot retain metal ions in
polyvalent cations such as calcium and complex form.
magnesium in water and in fibres, thus Oxalates and hydroxycarboxylic acids
preventing the precipitation of soaps. If (citrates, Tartaric acid, Gluconic acid, Oxalic
polyvalent ions are present, insoluble soaps acid, etc) are excellent for sequestering iron
may form, settle on the fabric and produce under alkaline condition but not effective for
resist spots. Even if the process water is calcium and magnesium. In order to quickly and
softened before the liquor formulation, the effectively bring the chemicals to the textile
addition of a sequestering agent brings certain material, ie. to improve their wettability and to
clear advantages in respect of the reliability of ensure that the fibrous impurities will be
the process. Conventional Sequestering removed as far as possible, it is necessary to
As the amount of additives can vary consid- Agents: Effects and Side-Effects add surfactants with good wetting and
erably, depending on the origin of the cotton There are five major types of sequestering agent washing/emulsifying properties.
and its past history (in some cases up to 2 or 3 to choose from1: In the case of polyacrylates, though they
times the average values), it is becoming 1. Inorganic polyphosphates have no demineralising effect on metal-
increasingly difficult for those carrying out the 2. Aminocarboxylic acids containing dyestuffs and are effective
pretreatment to guarantee the uniform, 3. Organophosphonic acids dispersants, they offers low chelation values as
reproducible quality of the fabric prepared for 4. Hydroxycarboxylic acids compared to the chelation values offered by
dyeing, printing or finishing. 5. Polyacrylates amino polycarboxylates or the phosphonates.
There are a number of alternative products The potential applications for sequestering
Mechanism of Chelate on the market, which claim to be as effective agents in wet textile processes of all types are
Formation as Ethylenediamine tetraacetic acid (EDTA) or diverse. The presence of the metals during
In the case of sequestration, a polyvalent cation Nitrili triacetic acid sodium salt (NTA), but bleaching or dyeing can result in pinhole marks,
is tightly surrounded as a ‘central atom’ by other most also have their restrictions. For example, reduced brightness efficiencies, change in shade
oppositely charged ions or by neutral molecules, the inorganic polyphosphates, such as or reduced depth. Metals can also contribute to
known as ligands. Ligands must be able to sodium tripolyphosphate, sodium brightness reversion, either during the bleaching
supply at least one non-binding electron pair hexametaphosphate, sodium polyphosphate, process or while the finished material is stored.
and the central cation must have a number of sodium trimetaphosphate and sodium It has therefore been difficult to find a good

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solution that matches the performance profile diverse application of

of traditional chelating agents. sequestering agents in
Also, from an ecological point of view, the use textile wet processing,
of this group of substances must be reduced, as Chelatin SA has been tested
the phosphate load is one of the most over a wide range of pH
significant contributing factors for the eutrophi- values, ranging from 4 to 12,
cation of ground water. Therefore, the search for for its calcium-binding
a cost effective alternative to the two most capacity (See Figure 1). From
frequently used chelating agents, NTA and the experimentation, it has
EDTA, has long been an industry target. Any been observed that the
alternative has to possess a good ecological and calcium-binding power of
toxicological profile – and we can also add a Chelatin SA increases with
third requirement: that the product should the increase in pH from 4 to
largely be made from renewable sources. This 10, giving chelation values in
problem has been overcome by the the range of 49.47 to Figure 1: Calcium Binding Capacity of Chelatin SA
development of sugar acrylates. 255.16 respectively, which
slightly decreases with
Sugar Acrylates increase in pH above the pH
Sugar acrylates, or sugar acrylic polymers, are value of 10.
synthesised by polymerisation of acrylic acid in
presence of enolisable sugar under alkaline Iron Chelation Power:
condition. They have sequestering values as Iron-binding capacity is
high as amino polycarboxylates or the nothing but the iron-
phosphonates and are biodegradable. Sugar hydroxide dissolution
acrylates are characterised by good chelation capacity of the sequestering
values from the acidic to the alkaline range and agent. The binding capacity
from temperatures of 45° to 115°C. They also of Chelatin SA was tested at
exhibit no de-metallising effect on metal- room temperature at various
containing dyestuffs and are non-foaming. They pH values, ranging from 5 to
are ideally recommended in pretreatment for 12. Figure 2 shows the
desizing, scouring and bleaching and as dyebath minimum and maximum Figure 2: Iron Binding Capacity of Chelatin SA

conditioners during cellulosic dyeing. values of iron chelation,

To meet stringent ‘green’ requirements, Sarex ranging from 60 to 240 for
has developed a biodegradable, sugar-acrylate- pH 5 to 12 respectively.
base sequestering agent, Chelatin SA. It is a From the measured data it is
direct alternative to NTA and EDTA, fulfilling all clear that the capacity for
of the targets set above. dissolving a significant
amount of iron from the
Efficiency Evaluation precipitated hydroxide goes
The evaluation of the efficiency of a chelating on increasing with increase
agent may be based a the number of different in pH and is maximum at
chemical and physical measures, which are pH value 12.
generally affected by the variables such as ionic
strength, pH, method of measurement, Copper Chelation
temperature, etc. Hence, a study to evaluate Power:
the chelating agent Chelatin SA was carried out In the case of the copper
Figure 3: Copper Binding Capacity of Chelatin SA
to assess its binding capacity with respect to binding power of Chelatin
metals such as calcium, copper and iron, over SA, the same trend is observed as was observed Application Study of Chelatin SA
wide range of pH. Also, as a practical- earlier in the case of iron-binding power. Here As discussed earlier, although Chelatin SA shows
application study, disperse and reactive dyeing also, copper-binding capacity increases with very good binding power, in order to judge its
was carried out to observe the change in shade, increase in pH, which is maximum at pH 12, practical viability, a study of dyeability with
depth of dyeing and dispersion properties. showing a maximum copper-binding power of respect to disperse and reactive dyeing was
240 (See Figure 3). carried out in hard water.
Evaluation of Binding Capacity From the study of the binding power of The basic experiment was carried out to
Chelatin SA, carried out over a wide pH range, it optimise the concentration of sequestering
Calcium Chelation Power: is clear that Chelatin SA achieves very good agent to chelate the water of hardness 450ppm
Normally, calcium-chelation values are chelation power at various pH values, especially containing 5g/l soda ash (See Figure 4). From the
determined at room temperature. Due to from pH 10-12. figure it is clear that 3g/l Chelatin SA is required

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Technical Briefing: Sequestering Agents

to chelate 450ppm hard water and to make it

free from metal impurities, to avoid further
processing difficulties.
A study of the effect of Chelatin SA was
carried out in disperse dyeing by using 100ppm
iron and 6ppm copper separately in the dyebath
(See Figure 5: A and B). From the figure, it is
crystal clear that a change in shade of polyester
is observed when dyed in a bath containing
100ppm iron and 15ppm copper. No shade
change of comparable depth is observed in a
polyester dyed with 2 and 3g/l Chelatin SA
respectively. Thus, Chelatin SA proves to have
very good iron and copper binding power in
acidic medium.
Also, to prove the dispersing power of
Chelatin SA, a dyeability study with reactive
dye on cotton was carried out in the presence
of 50ppm and 70ppm of copper and iron
Figure 4: Concentration optimization of Chelatin SA separately, with and without 2g/l Chelatin SA.
After dyeing, dye remainder was collected in
test tubes and kept separately (See Figure 6).
After 10 minutes, the remainder was observed
for any settlement. Settlement was observed in
test tubes a, b, c, f, g and h, which contained
copper and iron with no Chelatin SA, indicating
poor dispersing power. The dyebath remainder
in test tubes d, e, i and j, containing copper and
iron with the sequestering agent Chelatin SA,
showed no settlement, indicating very good
dispersing power, which will not allow the
precipitate to settle on the substrate during the
dyeing process.

Conclusion
The above results shows that Chelatin SA has
very good chelation and disperse capacity
and is capable of replacing conventional
polyacrylates and even phosphonates in
textile applications. It forms stable
Figure 5: Effect of Chelatin SA in Disperse Dyeing complexes with problem metals, ‘tying-up’
their reactive sites. Also, Chelatin SA is
effective during desizing, scouring, bleaching
and dyeing. It prevents the individual ions
from reacting with the dye and reducing
efficiency. The stable chelant/metal ion
complex, or chelate, can be subsequently
washed-off during further processing.
From this it is clear that Chelatin SA can
fulfil the requirements of industry as an
alternative, ‘green’ sequestering agent. ID

Reference:
1. “Selecting Sequestering Agent – More
Than a Complex”, Dr. Naresh M. Saraf and
Mr. Deepak V. Alat, International Dyer, June
Figure 6: Dispersing Power of Chelatin SA 2004.

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