In this study, the synthesis of sodium-poly(acrylate) was performed by polymerization of acrylic acid in the water solution with three different contents of potassium-persulphate as an initiator. The obtained polymers were characterized by
using HPLC and GPC analyses in order to define the purity and average molar mass of poly(acrylic acid). In order to investigate the influence of sodiumpoly(acrylate) as a part of carbonate/zeolite detergent builder system, secondary
washing characteristics of powder detergent containing equal percentage of
sodium-poly(acrylate) were examined. The degree of whiteness and the ash
content as main secondary washing performances significantly depended on
the efficiency of sodium-poly(acrylate) used as crystal inhibitor, stabilizer for
suspended soil and agent for preventing the soil redeposition at fabric surface.
The decrease of the sodium-poly(acrylate) activity within the detergent builder
system worsens its capability to prevent textile fiber damages and, as a result
influences the worsening of detergent secondary washing performances. The
degree of whiteness for cotton fabrics increased with the degree of polymerization and medium-weight molecular mass, Mw, up to the value of 70000 g/mol.
In the case of further increase of the average molar masses, up to 100000 g/
mol or higher, the builder performance began to decline. The ash content decreased with the increase of the weight average molar masses from 3000 to
100000 g/mol, after which it started to increase again with the weight average
molar mass increase. The highest value was reached in the samples of the
detergent containing sodium-poly(acrylic) with the average molar mass close
to 500000 g/mol. The effectiveness of sodium-poly(acrylate) with all examined
molar masses did not decline or change significantly with the number of washing
cycles performed.
Introduction
Detergent formulations are finely balanced. The build- the pH of the wash liquor and maintain its alkalinity and,
ing blocks of the detergent formulation (surfactants, build- overall, (v) to boost the performance of the surfactants
ers, and specific additives such as bleach, enzymes etc.) and thus help to improve soil removal [3].
must complement each other in their modes of action. AlSurfactant efficiency is greatly reduced in hard water
though the performance of detergent formulations derives but they also do not show the appropriate performance
from the system as a whole, it can be simplified as a com- even in softer water. Furthermore, large amounts of surposition of more or less independent subsystems. One of factants in detergents not only significantly increased
these subsystems is the builder. The builder is expected the biological demand in water but also imposed heavy
(i) to provide the binding capacity for calcium and magne- load on sewage works and on the environment due to
sium ions in hard water [1], (ii) to disperse sparingly solu- their eco-toxicity. To remove Ca2+ and Mg2+ ions existing
ble salts, e.g. calcium carbonate, and prevent them from in hard water and in soils, and to lower the content of
growing into larger crystals which deposit on surfaces [2], surfactants in detergent formulations, detergency build(iii) to suspend colloidal soil in the wash liquor, preventing ers are often used together with surfactants. A potential
it from redeposition and graying the fabric, (iv) to buffer
builder should satisfy a large number of requirements
* Author address: Vladimir Milojevi,
Oraaka 15, 37000 Kruevac, Serbia
E-mail: vladimir.milojevic@henkel.com
The manuscript received: May, 31, 2013.
Paper accepted: Jun, 13, 2013.
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ticles help in breaking down large (50-100 m) soil agglomerates into much smaller (10 m and below) particles. These particles then remain as stable dispersions
to be discarded in a normal rinse cycle during a standard washing operation. Sodium-poly(acrylate) is a linear,
soluble macromolecular compound, their shuttle based
on molecular chain due to electrostatic repulsion, the
polymer chain stretch, adsorption function of mission led
to an exposed on the surface, adsorbed on suspended
particles in the solution of these activity, form a bridge
between particles, thus speeding up the settlement of
suspended particles. Therefore sodium-poly(acrylates)
can be used for flocculants.
Polycarboxylates are essential components of powder detergents, not only as cobuilders. Aside from their
impact in the laundering process they play an important
role in the manufacture of detergent powders and tablets. They contribute to the adjustment of their morphology and their physical properties and they are of vital
importance as a process aid already on the first stage
of manufacturing, in the slurry preparation and spray
drying [11]. Optimizing the slurry preparation is crucial
for the efficiency of the whole spray drying step. Due its
excellent performance in reducing the viscosity, polycarboxylates allows to increase significantly the content of
solid matter in detergent slurry and to reduce the water
content, respectively. This will result in substantial energy savings in the spray drying process. Further, the
increased solid content will directly lead to the increase
of the operational plant capacity of spray drying units at
unaltered volumes of mixing vessels.
Beyond its excellent performance as a process aid,
polycarboxylates features very good cobuilder properties in the laundering process as well.
Ecological properties of detergent polycarboxylates. Acrylic acid based laundry polymers are not biodegradable according to OECD criteria. They are eliminated from wastewaters by precipitation or adsorption to
sludge. The extent of elimination increases with increasing M W [12].The polymer is also removed from standing
or slow-moving surface waters by adsorption on floating
particles or by contact with the sediment. These laundry polymers do not remobilize heavy metals from river
sediments [13] and the high affinity of polycarboxylates
for soil materials results in their immobilization in sediments or soils. This in turn explains why, compared to
dissolved substances, they are much more resistant to
attack by microorganisms and hence to biodegradation.
Besides their eco-compatibility, polycarboxylates have
also proven to be toxicologically safe. No toxic effects
were observed with the high-M W copolymer in acute and
chronic tests on various aquatic organisms. Also the toxicity to mammals is very low. It does not irritate the skin
or mucous membranes, and it does not promote skin
sensitization. Furthermore, no mutagenic effects were
observed in different test systems [14].
The paper focus on study the effects of poly(acrylate)
molecular weight, used as a cobuilder, on detergent sec 62
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Table 1. List of appendix clothes for washing tests per one machine load
( m 2 m1 ) * 100
m0
.......................................................(1)
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Table 3. The values of the peak areas at Rt = 3,05 min from the HPLC chromatograms of acrylic acid
The dependence of the peak (in units of internal software mAU*s) which is derived from AA in the function of
the concentration shows that the dependence is not linear
throughout the range of concentrations of AA monomer
up to 1 mg/cm3. As shown in Figure 1. the linearity exists
up to the concentration of 0.2 mg/cm3.
Figure 1. The residual monomer calibration curve: the dependence of the peaks surface on HPLC chromatograms depending
on the concentration of acrylic acid; detection 205 nm, retention time of peak 3,05 min.
Table 5. Molecular weights of poly(acrylic acid) in the samples made with different quantities of the initiator, PP
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The condition of textile fibers was rechecked after finishing the trials of 50 washing cycles. In the fabric tested
with the detergent containing sodium-poly(acrylate) with
the weight average molar mass of 100000 g/mol (Sokalan PA80S) the damages over the textile fibers were notable, compared to the fabric fibers before the washingtest performance. However, damages were present just
in a part of the fabric, appeared only at the fiber surface,
without some deeper fiber structure damages as shown
in Figure 3.
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The cotton fabric tested by detergent with the highest sodium-poly(acrylate) weight average molar mass,
523100 g/mol, after finishing the 50 wash-test cycles,
showed the highest level of fiber damage. Textile fibers
were smeared all over the textile structure, introducing a
complete joining of fibers in some parts. Irregular damages took place instead more or less regular ones notified with the previous, lower molecular weight samples of
sodium-poly(acrylate). Fiber fanning started not to be in
a way that one layer removal was following the complete
removal of previous ones- at the same time several layers in textile fiber started to be damaged, as shown in
Figure 6.
Degree of whiteness tests. The values of the degree of whiteness after washing with detergent containing sodium-poly(acrylate) with different molecular
weights depending on the number of washing cycles are
shown in Figure 7.
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The highest value of the ash content after combustion, which corresponds to the content of the inorganic
residue after annealing, was recorded in the case of the
control fabric treated with detergent formulation containing the highest molecular weight sodium-poly(acrylate)
(above 400000 g/mol), ahead of the control fabric treated with a detergent formulation containing low molecular weight sodium-poly(acrylate) (8000 g/mol), while the
lowest values of the ash content were notified in the case
of the fabric treated with the detergent formulation containing sodium-poly(acrylate) with the average molecular
weights (70000-100000 g/mol). In the case of all samples, after the 25th washing cycle the ash content lead
to a slight increase with the number of washing cycles.
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CONCLUSION
The results of this study showed that different molecular weight sodium-poly(acrylates) can be used as an
effective remedy for builders ability improving in sodiumcarbonate/zeolite detergent formulations and therefore
secondary washing performance of laundry detergents.
Poly(acrylates) with the higher weight average molar
mass, containing a higher number of charges have a
greater capacity to bind metal ions as well as the possibility of binding in their structure agglomerates of heavysoluble salts. As the most effective, in terms of stability
and prevention of impurity suspension redeposition on
the fabrics surface has to be sodium-poly(acrylate) with
the weight average molar mass of 70000 g/mol. In spite
of increased charges on it, high molecular weight sodiumpoly(acrylate) with the weight average molar mass higher than 100000 g/mol showed to be the least effective in
the detergent builder system. Steric obstructions prevent
molecules of sodium-poly(acrylate) to interfere with other
suspended molecules and effectively act on the surface
between the fabric fiber and suspended impurities. Due
to the increased size of molecules, long polymer chains
of sodium-poly(acrylate) with the weight average molar
mass higher than 100000 g/mol are facing serious difficulty to perform a successful transfer of metal ions from
the suspension of the impurity particles to the zeolite, responsible for its binding. A decreased level of the builder
performance caused by insufficient poly(acrylate) supporting activity leads to lower protection of textile fibers,
increased damage at the fiber surface and through the
whole structure, influencing deterioration of visual characteristics, fabric strength and material life-time. The effectiveness of all molecular weight sodium-poly(acrylate)
does not decline or change significantly with the number
of washing cycles performed.
ACKNOWLEDGEMENTS
This work was supported by the Ministry of Education, Science and Technological Development of the
Republic of Serbia under the project TR-33034
ABBREVIATIONS AND SYMBOLS
PP- Persulphate potassium
AA- Acrylic Acid
EDTA- ethylenediaminetetraacetic acid
D- Dispersity index
R- Refractometric value
STPP- Sodium tripolyphospate
Mn - Number average molar mass
Mw - Weight average molar mass
Mz - Z average molar mass
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Izvod