Application Note

002

Calcium Binding of Polyitaconic Acid (PIA)

Introduction
Detergent and anti-scaling applications generally require strong calcium-binding components
in their formulations. This application note shows the superior performance of polyitaconic acid (PIA)
in this capacity and demonstrates how these measurements are made.
Detergents, which generally contain a surfactant and builder, have traditionally employed
phosphates and silicates to sequester calcium. The ability to bind calcium plays an important role in that
it prevents redeposition on cleaned surfaces. In laundry soil is often bound to fabric surfaces by calcium
ion bridging. Furthermore, sequestering calcium enhances the performance of the surfactant, which might
otherwise react with the calcium present.
The classical method to test builder performance is the anti-precipitation test. We show here
how PIA compares with other calcium-binding polymers, such as polyacrylic acid (PAA) acid and
polyaspartic acid (PAsp). Furthermore, we show here how to measure the binding constant (pKe) of
PIA to compare with other known chelating agents.

Method
1) The anti-precipitation test is based on the change in turbidity with time of a polymer-carbonate
system. A stirred turbidimeter vial was filled with a 1% solution of polymer (or other builder) and
sodium carbonate (1:1) at the indicated pH. A syringe pump was used to introduce a 10% calcium
chloride solution at a rate of 0.5 ml/h.
2) The calcium selective electrode was calibrated with standards. A known amount of polymer was
titrated with calcium chloride (10%) in a stirred vial. Tests were performed at pH 9.7, 50 C.

Results and Discussion

Anti-precipitation Test
Because the turbidity is directly related to the concentration of the calcium carbonate which has
precipitated, the polymer binding capacity can be determined. The anti-precipitation test results (Figure
1) show that PIA is superior to other calcium-binding polymers, such as polyacrylic acid (PAA) acid and
1

polyaspartic acid (PAsp). The influence of then number-average molecular weight (Mn) on calcium
binding was also explored (Figure 2). For PIA with a Mn = 4000, the binding capacity is 0.61
(CaCl2/polymer g/g). In other words, one gram of PIA can bind 0.61 grams of calcium.

Figure 1. Comparison of calcium binding performance Figure 2. Influence of Mn on calcium binding

Binding Constant Determination

An ion selective electrode is used to determine the quantity of free calcium. [ ] is the
concentration of calcium bound (known from the quantity of calcium free and the quantity of calcium
bound by the polymer), is the concentration of free
calcium directly given by the electrode and
is the concentration of polymer not bound with calcium
(known with the quantity of polymer introduced at the
beginning and the quantity of calcium bound). The quantity
pKe can be determined as a function of repeat unit (Figure
3).
[ ]
=

Polyitaconic (PIA) and polyacrylic acid (PAA) both have

Figure 3. Calcium binding constant
calcium binding properties. The PAA-Zeolite binary builder
system is commonly used instead of sodium triphosphate in todays phosphate-free granular laundry
detergents. The PAA functions as a shuttle for divalent cations between the dirty surface and the zeolite
ion exchanger. Our results show PIA has a higher binding constant than PAA and could thus serve more
effectively in this capacity.

Because of its formula polyacrylic acid (PAA) can bind one atom of calcium every two repeat unit
of acrylic acid while polyitaconic (PIA) is able to catch one calcium per repeat unit (Figure 4), so in
theory, polyitaconic acid is twice as
efficient as polyacrylic acid. Moreover,
because of the space configuration, the
calcium bound by polyitaconic acid
doesnt restrict the carbon atoms of the
PIA backbone as it does with PAA,
which leads to a better stability of the
PIA-calcium complex.

Conclusions

Figure 4. PIA and PAA structural comparison

The results with polyitaconic acid (PIA) show that it has a much higher calcium binding capacity than for
both polyaspartic acid (PA) and polyacrylic acid (PAA). Furthermore, its affinity for calcium (Table 1)
surpasses that of EDTA, commonly found as an interfering competitor ligand in waste streams.2 The
superior performance of PIA suggests economical utility in detergent and anti-scaling applications.
Overall, this means less PIA can be used to do the job and translates as a direct savings to customers.
Table 1. Strength of common chelating agents

Binding constants of common chelating agents1 (with calcium @ pH = 9)

Polyitaconic acid (PIA)
Ethylenediaminetetracetic acid (EDTA)
Sodium triphosphate (STPP-Na5)
Trisodium carboxymethyleneoxysuccinate (CMOS)
Nitrilotriacetic acid (NTA)
Polyacrylic acid (PAA)
Citric acid
Maleic acid oligomer (MAO)

pKe
7.1
7.0
7.0
6.8
6.1
5.3
4.1
3.7

Acknowledgements
Experiments performed by Marion Havil. Application note by Jennifer Durant.

References
1. JAOCS (March 1983) vol 60, (3) p619
2. Zander, N. (March 2009) ARL-CR-0623 Chelating Polymers and Environmental Remediation.

Release Date

10/2009