Sequestering Agent

Tania Akther
Lecturer
Department of Wet Process Engineering
Bangladesh University of Textiles
Introduction
Sequestering agents or chelating agents are negatively charged and are capable of forming strong ring structures (Fig. 4-3)
with the metal ions present in hard water and in pectins of cotton. The positively charged metal ions, particularly Fe3+ and
Ca2+ are readily available for reaction with any negatively charged anion such as OH- or CO3-2 and insolubilize soap in the
fibre which may disturb subsequent operation. For this sequestering agent is needed.
Sequestering agents work by a mechanism of complex formation, often in the form of chelation. A chelating agent
contains substituents suitably located to form one or more chelate rings by electron donation to the metal ion the
resulting complex remaining soluble and innocuous under the conditions of processing. The most useful donating
atoms are nitrogen, as found in amines or substituted amines, and oxygen in the form of carboxyl, phosphate or ionized
hydroxy groups. As in the formation of dye–metal chelates (such as chrome mordant and metal-complex dyes), at least
two electron-donating atoms in the sequestering agent structure must be arranged so that a stable ring can be formed
with the metal ion, the highest stability resulting from five- and six-membered rings.

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 Sequestering Agent

Classification
A great many chemicals exhibit sequestering capability but not all are of commercial value in textile processing. There
are three main types:
– Aminopolycarboxylates
– Phosphates, mainly inorganic
– Hydroxycarboxylates.
However, environmental awareness, in addition to commercial and technical exploitation, has resulted in
considerable activity in this area, leading to a greatly expanded range of products in recent years, a classification has
been adopted here is as follows:
– Aminopolycarboxylates and their analogues, e.g. hydroxyaminocarboxylates
– Phosphates and phosphonates
– Hydroxycarboxylates
– Polyacrylic acids and derivatives.

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Aminopolycarboxylates and their analogues:
These are powerful chelating agents and derivatives of iminodiacetic acid, having good environmental properties.
Important members include:
– Ethylenediaminetetra-acetic acid(EDTA)
– Diethylenetriaminepenta-acetic acid (DTPA)
– Nitrilotriacetic acid (NTA)
These products are sold as free acids or sodium salts.

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Analogues of these aminopolycarboxylic acids include the hydroxyaminocarboxylic acids. These structures are derived by
replacing one or more carboxymethyl groups of the aminopolycarboxylate by a hydroxyethyl group. Examples include:
• N-(hydroxyethyl)ethylenediaminetriacetic acid HEDTA: in which one of the carboxymethyl groups of EDTA has been
replaced by a hydroxyethyl group.

• N,N-bis(hydroxyethyl)glycine DEG: in which two of the carboxymethyl groups of NTA have been replaced by
hydroxyethyl groups.

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These aminopolycarboxylates act as sequestering agents by forming complexes in which each metal ion is chelated
into one or more five-membered rings. The nature of the complexes actually formed, however, may depend on other
factors such as the pH of the medium. EDTA–calcium complex shown in structure 10.10, in which the arrows represent
coordination bonds and the calcium ion is held by three five-membered rings. At pH values below 11 the structure
tends to be more like that shown in 10.11, which also resembles the complex formed with NTA (10.12).

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A more elaborate representation of an EDTA-metal complex (10.13), which gives some indication of the three-
dimensional aspects of the structure, shows a complex of five five membered rings. A similar representation of a
DTPA-metal complex shows a system of eight five-membered rings.

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Polyphosphates
Various polyphosphates are effective sequestering agents under appropriate conditions. The best known of these are-
Sodium hexametaphosphate, Cyclic hexamer of sodium orthophosphate, Cyclic trimer sodium trimetaphosphate, Dimeric
pyrophosphate, Trimeric tripolyphosphate and Other linear polyphosphates
All of these polyanions function by withdrawing the troublesome metal cation into an water-soluble complex by a process
of ion exchange as shown in below for sodium hexametaphosphate.

Hence these compounds are sometimes referred to as ion-exchange agents.

The disadvantage of the polyphosphates is that-
• At the temperatures (100 °C or higher) used in many textile processes they can be hydrolyzed into simpler phosphates
that cannot retain the metal atom in the sequestered form. For example, dicalcium disodium hexametaphosphate
hydrolyses on prolonged boiling to yield the insoluble calcium orthophosphate. This is one of the main reasons why
polyphosphate sequestrants are used much less extensively than the more versatile and stable aminopolycarboxylates.

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A structural compromise between these two types of compound (I,e Phosphates and phosphonates) can also
give products with sequestering properties, although they are phosphonates rather than phosphates, since
they contain C–P rather than C–O–P linkages. Examples of these aminopolyphosphonates are:
– ethylenediaminetetramethylphosphonic acid EDTMP
– diethylenetriaminepentamethylphosphonic acid DETMP
– nitrilotrimethylphosphonic acid ATMP
– hydroxyethylethylenediaminetrimethylphosphonic acid HEDTMP
– hexamethylenediaminetetramethylphosphonic acid HMDTMP

Two sequestrants of the phosphonate class unrelated to aminopolycarboxylic acids are:

1-hydroxyethane-l,1-diphosphonic acid HEDP
2-phosphonobutane-1,2,4-tricarboxylic acid PBTC
The consumption of these phosphonates in textile processing is small in relation to that of the
aminopolycarboxylates; they are mainly used in detergent formulations as sodium, potassium, ammonium or
alkanolamine salts.

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Hydroxycarboxylates
The hydroxycarboxylic acids provide a range of sequestering agents of which the best known are citric, tartaric
and gluconic acids. The toxic oxalic acid is now rarely used. However, these acids are much less important as
sequestering agents for textile processes than either the aminopolycarboxylates or the polyphosphates.
Hydroxycarboxylates are easily biodegraded but do have a high COD.

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Polyacrylic acids and their derivatives
Recent research has led to some more complex sequestering agents, particularly the polymeric carboxylic acids
referred to as polycarboxylates. Common monomers used in the production of these compounds, either as
homopolymers or as copolymers with each other, include acrylamide and various unsaturated acids. The
common and essential feature of these monomers is the carbon–carbon double bond.

Polymers which have been suggested for use as sequestering agents include:
• Poly(butadiene-1,2-dicarboxylic acid) EMA which is an ethylene–maleic acid copolymer.
• Poly(α-hydroxyacrylic acid) PHAS.
• Poly(3-hydroxymethylhexatriene-1,3,5-tricarboxylic acid)which is a copolymer of acrylic acid with
hydroxymethacrylic acid [10.37].
• Poly(3-formylhexatriene-1,3,5-tricarboxylic acid) which is a copolymer of acrylic acid with 2-formylacrylic
acid [10.38].
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These agents are generally described as ion-exchange reagents rather than complex-forming chemicals. They
tend to operate by sequestering the metal by an ion-exchange mechanism and as a result of their
polyelectrolytic character they keep the complex dispersed. Oligomers with a molecular mass of 1200–8000
(i.e. relatively low) are said to give optimum sequestering power. Polymers of high molecular mass (i.e. Mr =
106–107) are useful as flocculating agents or migration inhibitors.
A further development is the formation of so-called sugar–acrylate copolymers in which acrylic acid is
copolymerized with glucose or other saccharides. Unlike other sequestering agents these polymers are said to
be readily biodegradable, this being the main reason for their development. An unusual type of sequestering
agent is triethanolamine. This compound is cheap and exclusively useful for complexing iron(III) in strongly
alkaline solutions, e.g. up to 18% sodium hydroxide. It does in fact remain active as a complexing agent even in
more strongly alkaline solutions although solubility can be a problem.

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Formation of Complexes
Most polyvalent ions can form complexes with certain ions or molecules. This type of complex formation is called
coordination chemistry. The types of molecules or ions that form coordination complexes are called Ligands,
abbreviated "L". Metal ions are electron acceptors (Lewis Acids) and Ligands are electron pair donors (Lewis Base).
The bond that is formed is a Coordinate Covalent Bond. Formation Constant is a measure of the strength and stability
of a complex. It is a measure of the extent the complex will form or dissociate when the system has reached
equilibrium. Complex formation is an equilibrium process.

Where K = equilibrium constant and log K = formation constant (stability constant). The higher the formation
constant, the more strongly held is the metal ion in the complex. Therefore Ligand that give high log K values with a
particular metal are very effective sequestering agents. Table 9 lists some formation constants for several chelating
agents. The data shows the specificity of some agents, i.e. gluconic acid which is particularly effective for iron. Also
the data shows that EDTA is effective across the board.

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Formation Constants(Table 9)

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The Uses of Sequestering Agents
• Sized warp yarns sometimes contain metal salts or complexes (e.g. copper or zinc compounds) as fungicides
or bactericides and these can interfere with enzyme action in subsequent desizing. Phosphonates such as
ATMP, DETMP, EDTMP and PBTC are suitable for use here, sequestering the heavy metals at pH 6.8–7.0, the
effectiveness of each agent being dependent on the type of enzyme and the metal ions present. The use of
the phosphonates HEDP or PBTC helps to reduce cellulose damage to a minimum in oxidative desizing with
persulphate.
• In the kier boiling of cotton, the action of sodium hydroxide can be intensified by the use of sequestering
agents. The phosphonates EDTMP, HEDP and PBTC have been recommended. In practice, however, the
tendency is to use synergistic mixtures, such as:
– Phosphonate and gluconate
– Phosphonate and triethanolamine
– Aminopolycarboxylate and gluconate or triethanolamine.
• Under the strongly alkaline conditions of mercerizing, addition of either gluconate or triethanolamine with a
little HEDP is useful. The presence of a polycarboxylate helps to prevent precipitation on machine
component.

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• Certain transition-metal salts catalyze redox reactions, leading to uneven treatment and perhaps damage to
the substrate. Sequestering agents are therefore employed to complex these metal ions and so to inhibit
their catalytic activity. In reductive bleaching with dithionite, PBTC acts as a stabilizer at pH 5.5–6.5 and EDTA
also gives good results. For oxidative bleaching with hypochlorite or chlorite, the amine oxides of ATMP and
PBTC may be used. Aminopolycarboxylates are less suitable, whilst the amine oxide of NTA is unsuitable. In
the stabilization of peroxide with silicate, the use of a polycarboxylate, perhaps in combination with a
polyphosphonate such as DETMP (or PBTC in a lesser amount) helps amongst other things in preventing
fibre damage and incrustations on fabric or machine.
• In the pretreatment and dyeing of synthetic fibres, the aminopolyphosphonates can assist in the removal of
oligomers.
• Some dyes contain a coordinated transition metal as an essential part of their chromogenic structure and
this must be left undisturbed by any sequestrant used to complex extraneous metal ions in the system.
Hence a balance of properties is needed, phosphates and hydroxycarboxylates being useful. It is claimed that
polycarboxylates can be molecularly engineered to give the required balance of properties.
• Wool is exceptionally prone to absorb metal ions, particularly in the weathered tips of the fibres, leading to
shade differences on subsequent dyeing, especially if cheatable dyes are used. Hence sequestering agents
can be essential additions to scouring, rinsing and dyeing baths in order to remove this absorbed metal.
However, it is difficult to say which sequestrant or mixture of sequestrants gives the best results. Careful
laboratory tests need to be carried out beforehand, taking into account the chemical structure of the dyes to
be used, the type of metal ions involved, the pH value of the dyebath and the type and concentration of
electrolyte present.

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• The addition of triethanolamine with vat dyes can be beneficial in helping to prevent unnecessary loss of
reducing agent or over- oxidation. Triethanolamine together with EDTMP or HEDP can be used where the
concentration of alkali is less than 10 g/l NaOH (or 22 ml/l caustic soda liquor 38°Bé). Bronzing of sulphur
dyeing's can often be prevented using triethanolamine with polyphosphate, polyphosphonate or
polycarboxylate. Azoic combinations can be very sensitive to metal contamination. EDTA, or perhaps
combinations of polyphosphate, polyphosphonate or polycarboxylate, can help in the solubilization of
naphtholates and in the stabilization of their colloidal solutions, whilst EDTA, for example, can assist in
protecting solutions of diazonium salts from metal-induced catalytic decomposition.
• Polyphosphates, or in lower amounts the very effective polyphosphonates, are helpful in applications of
fluorescent brightening agents. Sequestering agents can be useful additions in the after washing of dyeings
and prints, for example polyphosphates, polyphosphonates or polycarboxylates such as, amongst others, a
polyacrylate of molecular mass 3000–4000 or an acrylic–maleic acid copolymer.
• In the soaping of vat or azoic dyeings, recrystallisation is accelerated and rubbing fastness improved by the
use of sequestering agents, examples being mixtures of polyphosphonates and polycarboxylates, such as
HEDP and an acrylic–maleic acid copolymer.
• The sugar–acrylate polymers are recommended for applications similar to those mentioned above for
polycarboxylate polymers and copolymers.

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THANK YOU