Advanced technologies

2(1) (2013), 60-68

THE ROLE OF SODIUM- POLY(ACRYLATES) WITH DIFFERENT WEIGHT-AVERAGE

MOLAR MASS IN PHOSPHATE-FREE LAUNDRY DETERGENT BUILDER SYSTEMS
Vladimir S. Milojevi1*, Sneana Ili-Stojanovi2, Ljubia Nikoli2, Vesna Nikoli2,
Jakov Stamenkovi2, Dragan Stojiljkovi2
1 Henkel Srbija D.O.O., Bulevar Osloboenja 383,Belgrade, Serbia
2 The Faculty of Technology, University in Ni, Leskovac, Serbia

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.

(ORIGINAL SCIENTIFIC PAPER)

UDC 678.7 + 547.391.1 :661.185.6

Keywords: Sodium-poly(acrylate), polymer,

detergents, carbonate/zeolite builders, secondary washing performances, degree of whiteness, ash content

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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including sequestering ability, alkalinity, buffer capacity,

bleach compatibility, soil deflocculation, oral toxicity, skin
absorption, eye irritation, the effects on fish and other
aquatic animals and other environmental and economic
practicability [4].
Sodium tripolyphospate (STPP) meets the essential
requirements of a builder and therefore it was the most
widely used builder in the past. In addition to its great
capacity to remove Ca2+ and Mg2+ ions presented in hard
water and in soils, STPP facilitates the dissolution of detergents, maintains alkalinity during washing, prevents
dirt reposing on fabrics by suspending it in the wash-liquor and protects the washing machine against corrosion
and shows the efficient performance under all washing
conditions. However, phosphates are the excellent fertilizer for algae, bacteria and other flora and fauna in rivers, lakes and oceans, making them bloom at very rapid
rates, exhausting the oxygen supply both in the surface
and in the bottom layers of water bodies and fish and
plant life die. This phenomenon is called eutrophication
[5]. Though the removal of phosphates from the sewage in
treatment plants could eliminate 80-95 % of all phosphorus, the cost is considered too high to allow the immediate and general application [4]. In the mid-1980s, some
countries imposed restrictions on the use of phosphates
in household laundry detergents. Subsequently, other
water softeners such as sodium-carbonate and sodium
silicate and ethylenediaminetetraacetic acid (EDTA)
were used as a substitute for STPP. Although sodiumcarbonate and sodium silicate- built detergents show almost the same performance as the leading phosphate
formulations, their high alkalinity is harmful to our skin
and eyes. In addition, they produce deposits on fabrics
which trap dirt, provide a breeding ground for bacteria
and cause washed fabrics to become harsh, grey and to wear
out more quickly. Nowadays, zeolites, particularly zeolite A, are
used in phosphate-free detergents, necessarily together with
other builders such as ploycarboxylates, EDTA and sodium-carbonate. Zeolite A possesses a good ion exchange
capacity for the Ca2+ ion in hard waters and soils and
its performance is enhanced in concentrated detergent
formulations due to the lower total salt normality and
lower background of Na+ ions [6]. The advantages of
zeolites over other builders are that they i) offer a very
high product stability and no decomposition; (ii) are inert
under elevated temperatures, mechanical influences or alkalinity; (iii) inhibit greying and dye transfer; (iv) help in the
formulation of high performance, low cost, eco-friendly
phosphorus free detergents; (v) remove hardness from
wash water; (vi) have high liquid absorption capacities
and (vii) they are free of legislative restrictions. However, the absorption rate of zeolite A is much lower than
STPP and a small ion exchange capacity is found for the
Mg2+ ion [7,8]. The use of zeolites increases suspended
solids and may cause fouling of pipeline. It significantly
increases sludge volumes in sewage treatments plants
making the disposal of sludge more difficult. In addition,
the surfactant in the zeolite detergent is trapped inside

2(1) (2013), 60-68

the zeolite and it takes time to diffuse into wash liquor. To

compensate for the shortcomings as a detergent builder,
an alkaline compound such as soda ash or sodium silicate is added.
Polycarboxylates, such as homo- and copolymers of
acrylic acid or maleic acid, show a marked superiority to
STPP in their ability to sequester calcium ions, prevent
incrustration of fibers and re-dissolve calcium salt precipitates [4,5]. A sequestrant builder is incorporated in an
anionic detergent product formulation for a specific purpose of preventing the loss of anionic surfactant through
precipitation as its insoluble calcium salt. The free calcium ion concentration at which this surfactant loss begins
is determined by the solubility product (Ksp) of Ca (LAS)2,
or Ca (SDS)3, and averages of about 5x105 moles/liter
of hardness ion or 5 ppm as CaCO3. Poly(acrylates)
are effective calcium and magnesium ion sequestrates
and can be used to partly replace STPP in low or zerophosphate detergents. They can also be used synergistically with other low cost builders like zeolite and sodium
citrate to obtain better protection for the anionic surfactant in a total detergent formulation. Detergency is the
wash benefit arising from the soil removal, stabilization
of the soil in the wash liquor and prevention of soil redeposition. Soil is a complex mixture of particulate and
oily soiling materials such as sweat sebum, street dirt,
household soil, occupational soils and deposits of insoluble calcium/magnesium salts normally present in the
wash water. The use of these polymers leads to highly
desirable end-use effects such as improved detergency,
anti-redeposition, lime soap dispersancy, anti-encrustation, iron sequestration and anti-spotting. One of the
major reasons why polycarboxylates play an important
role in European detergents is the need to prevent encrustation of fabrics and washing appliances caused by
high water hardness. The wealth of literature deals with
mechanistic aspects of the mode of action of polycarboxylates in the washing process. Their performance correlates with their ability to disperse particles rather than
with their calcium ion-sequestering properties [1]. Based
on these findings, the prevention of carbonate encrustation was viewed as a consequence of crystal growth inhibition by polycarboxylates adsorbed onto the growing
crystal face [2]. Recently published results indicate that
this model of a linear straightforward process may be too
simplified, as different pathways are likely to be involved
simultaneously. The contribution of each individual path
to the whole process may also be dependent on the additive [10]. Under experimental conditions allowing the
extremely high local resolution, as well as time resolution
in the millisecond range, the evidence obtained showed
that polycarboxylates covered primary CaCO3 particles
extremely quickly and efficiently, giving rise to floc-like
microscopic agglomerates rather than crystals. This suggests that polycarboxylates mechanistically act both on
the primary agglomeration step to prevent the formation
of crystals and on their subsequent growth into larger
crystals. The adsorption of polyacrylates onto soil par 61

2(1) (2013), 60-68

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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

ondary washing performance.

EXPERIMENTAL
Reagents:
Sokalan PA30CL, 45 %, sodium-poly(acrylate), M w
8000g/mol (BASF, Germany)
Sokalan PA70PN, 30 %, poly(acrylic acid)/ sodiumpoly(acrylate), M w 70000g/mol (BASF, Germany)
Sokalan PA80S, 35 %, poly(acrylic acid), M w
100000g/mol, (BASF, Germany)
Sodium-Hydroxyde, 99 %, (Merck, Germany)
Persulphate-Potassium, 98 %, PP (Riedel-de-Haen,
Seelze, Germany)
Acrylic Acid, 99 %, AA (Merck, Holenbrunen, Germany)
The synthesis of basic powder detergent. Semitower, without the addition of sodium-poly(acrylate), is
manufactured in an industrial batch process method of
slurry preparation [15,16]. Slurry was sprayed at a pressure of 25bar in an industrial tower Ballestra (Ballestra,
Milan) using a two-level of Delawan nozzles, with the
hole diameter of 4,3mm with swirl chambers SDXV SWC
Swirlchamber SH Flat Back Face and dried in the hot air
temperature of 142 C in countercurrent flow regime. Basic detergent was obtained by adding thermo-unstable
components to the tower powder detergent in rotary mixer Compomix (Henkel CEE, Vienna) at a speed of 39rpm.
The synthesis of testing powder detergent. Sokalan PA70PN and Sokalan PA80S were neutralized in the
laboratory by using the 0,01mol/dm3 sodium-hydroxide
solution, until neutral reaction was reached. The final
detergent formulations used to investigate secondary
washing performances were obtained in the laboratory
by mixing of sodium-poly(acrylate) with the different
weight average molar mass (Sokalan PA30CL, Sokalan PA70PN, Sokalan PA80S or laboratory syntetized
sodium- poly(acrylate)) and basic powder detergent.
Cobuilder weight ratio in the detergent powder builder
system sodium-carbonate/zeolite/sodium-poly(acrylate)
was 9,2:2:1.
Washing test performance. With each of the samples of sodium-poly(acrylate) testing was performed
by 50 washing cycles in the washing machine Gorenje
WA512, filled with 3,5kg of white cotton laundry, composed as it is given in Table 1.
The wash cycle includes washing with the water of total hardness 9,35 dH, scouring at 95 C, rinse cycles, intermediate and final spin. Uncontaminated control cotton
fabric Krefelder Standardgewebe wfk 11A was added at
the beginning of the cycle, and after every 5 performed
cycles the sample to testing the degree of whiteness and
ash content was taken. The samples were dried in hot air
at 60 C in a closed and darkened room.

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Table 1. List of appendix clothes for washing tests per one machine load

2(1) (2013), 60-68

percentage, was calculated by the equation 1:

A=

The synthesis of poly(acrylic acid). For the synthesis

of poly(acrylic acid), water solution of AA was prepared.
PP was used as the initiator with different concentrations
compared to the mass of AA given in Table 2.
Table 2. Composition of solution for the synthesis of poly(acrylic
acid)

The polymerization was conducted for 135 min at 80 C

and after that the poly(acrylic acid) solution cooled down
to the room temperature. At the end, poly(acrylic acid) was
neutralized in the laboratory by using the 0,01 mol/dm3
sodium-hydroxide solution, until neutral reaction was
reached.
Degree of whiteness tests. To test the degree of
whiteness of the fabric samples, Datacolor 600 spectrophotometer (Datacolor) was used. The control fabric was
folded in half twice so that the ironed side of the sample was
on the side illuminated by a lamp. The fabric was exposed
to the effects of light fits CIE standard light D65 (CIE 45-15145). Refractometer measured the value R (%), light reflected from the surface of fabric in the wavelength range
360-700nm at ten different points on the fabric surface.
The value obtained at a wavelength of 470 nm was taken
as a relevant Refractometric value, R (%).
Examination of the ash content. The examination of
the ash content after combustion of the control fabric
sample was performed by using the gravimetric method. The sample with the mass of 3 g, calculated on the
weight of dry fabric (m0), was prepared. The sample of
the cotton fabric was pre-burned by free combustion in
an empty pot with the specified weight (m1), and then exposed to the final combustion in the furnace Nabertherm
LE4/11/R6 for 1h at 800 C. After the final combustion,
the mass of the pot with the ash included (m2) was measured. The content of total remains (A), expressed as a

( m 2 m1 ) * 100
m0

.......................................................(1)

Characterization of the obtained polymers and

cotton fabrics
SEM microscopy. In the preparation phase of the cotton fabric samples for SEM microscopy, a thin layer of
gold was applied on the surface by using the technique
of cathode spraying with the diffuser JEOL JFC-1100E.
SEM microscopy was performed by using the scanning
electronic microscope JEOL JSM-5300.
Determination of residual monomer by HPLC
method. Shredded polymer samples (25 mg) were immersed in methanol (25 cm3) and the residual monomer
extraction was performed during 48 h. The methanol solution was separated from the polymer by filtration, while
the concentration of poly(acrylic acid) in methanol was
determined by HPLC under the following conditions- column:
XDB ZORBAX C-18, 250 x 4,6 mm, 5 m; eluent: 80 %methanol/20 % redestilated water; flow rate: 0,65 cm3/min at
the pressure 125 bar; column temperature: 25 C, detector: DAD; UV detection: 205nm.
Determination of the molecular weight by GPC
method. The solution of polymer samples was prepared
by dilution with water to the concentration of 5 mg/cm3.
After filtration, M w distribution of poly(acrylic acid) samples was determined by GPC under the following conditions- column: ZORBAX PSM300; eluent: redestilated
water; flow rate: 1 cm3/min at the pressure 90 bar; column temperature: 30 C, detector: DAD; UV detection:
205 nm
RESULTS AND DISCUSSION
Residual monomer determination. In the samples
of poly(acrylic acid) the amounts of residual monomers
of AA were determined by HPLC method. Residual
amounts of monomers were determined in order to confirm AA conversion rate during the polymerization process. HPLC chromatogram shows a retention time of AA,
Rt = 3,051 min, and the UV spectrum shows the wavelength of the maximum absorbance max = 205 nm. For
a series of solutions of AA in acetone HPLC chromatograms were done and for each concentration the specific
surface area of the obtained peaks were determined by
using Agilent ChemStation software.

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2(1) (2013), 60-68

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.

equation 3 can be obtained by which the concentration

of the monomer from certain peak surfaces for the linear
range of monomer concentration can be calculated.
..............................................................(3)
From the concentration of the residual monomer in
the extracts, the mass of the unreacted monomer per
gram of polymer was calculated and these results are
shown in Table 2. Generally, it can be concluded that after polymer was synthesized, the concentrations of residual monomers significantly lowered reaching the values of 0.0139 to 0.0426 mg/ cm3. It is estimated that the
mass of the residual monomers would not significantly
affect the performance of polymer during the washing
tests, so no other treatment of polymer is needed. Table
4 shows the mass of residual monomers in the samples
of poly(acrylic acid) made with different quantities of the
initiator, PP.
Table 4. Mass of residual monomers in the samples of
poly(acrylic acid)

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.

For the peak surface up to 44000 mAU*s and for this

range of the concentration, the equation 2 can be applied:

A = 1156,28 + 283924,72 C .....................................(2)

where A is the peak surface, mAU*s, and C is the concentration of the monomer, mg/cm3. From Equation 2 the

Determination of the molecular weight by GPC

method. Determinations of the average mass molecular
weight of synthesized poly(acrylic acid), used for further
examinations of detergent secondary washing performance was performed by using the GPC method. The
results of examinations are shown in Table 5.

Table 5. Molecular weights of poly(acrylic acid) in the samples made with different quantities of the initiator, PP

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Figure 2 shows SEM image of the control cotton fabric

before the washing-test treatment with the tested powder
detergent. The fabric contained a high number of textile
fibers wrapped together into the more structured fabric
structures, with the approximately cylindrical shape and
very smooth surface.

2(1) (2013), 60-68

With the molecular weight increase, the damages

became more present and visible, with a much higher
level of damage. SEM image of the fabric sample tested
with the detergent containing sodium-poly(acrylate) with
the weight average molar mass of 436840 g/mol shows
primary layers of textile fibers fully damaged, interwoven
between each other all over the fabric surface as shown
in Figure 4.

Figure 2. SEM image of sodium-poly(acrylate), cotton fabric

before washing tests; magnification x 2000, bar = 10 m

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.

Figure 4. SEM image of sodium-poly(acrylate), sample 1; magnification x 2000, bar = 10 m

With further sodium-poly(acrylate) weight average

molar mass increase, up to 474920 g/mol, fiber damages
became deeper and deeper, fiber layers became more
and more interwoven, in some parts influencing complete loosing of textile pre-structure as shown in Figure 5.

Figure 5. SEM image of sodium-poly(acrylate), sample 2; magnification x 2000, bar = 10 m

Figure 3. SEM image of sodium-poly(acrylate), Sokalan
PA80S; magnification x 2000, bar = 10 m

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2(1) (2013), 60-68

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.

The highest value indicates the degree of whiteness

of the fabric sample after washing with the detergent
containing sodium-poly(acrylate) with the molecular
weight of 70000 g/mol, slightly above the value of the
pattern fabric washed with the detergent containing sodium-poly(acrylate) molecular weight of 100000 g/mol.
Detergent samples containing sodium-poly(acrylate) with
high molecular weight values, between 436840 g/mol and
523100 g/mol, showed a lower degree of whiteness values, while the lowest values were notified in the case
of the fabric washed with detergent samples containing
sodium-poly(acrylate) with the lowest molecular weight,
8000 g/mol. The values of the degree of whiteness
within a series of washing detergents containing sodium-poly(acrylate) with the same high-mass molecular
weight did not differ significantly, regardless the number
of washing cycles.
Examination of the ash content. The values of the
ash content after washing with the detergent containing
sodium-poly(acrylate) with different molecular weights
depending on the number of washing cycles are shown
in Figure 8.

Figure 6. SEM image of sodium-poly(acrylate), sample 3; magnification x 5000, bar = 5 m

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.

Figure 7. The influence of the number of washing cycles (N) on

the reflectivity of the cotton fabric (R) in case of detergents containing sodium-poly(acrylate) with different values of molecular
mass

66

Figure 8. The influence of the number of washing cycles (N)

on the ash content of the cotton fabric in the case of detergents containing sodium-polyacrilates with different values of
molecular mass

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

2(1) (2013), 60-68

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[12] Langbein, I., Biological and Physicochemical Aspects
of Polycarboxylate Behavior in the Environment, in
Detergents in the Environment, edited by M.J. Schwuger,
Marcel Dekker, New York, 1997, p. 247-261.
[13] Opgenorth, H.J., Polymeric Materials Polycarboxylates,
in The Handbook of Environmental Chemistry, edited by
O. Hutzinger, Springer-Verlag, Berlin/Heidelberg, 3 (F)
(1992) 337350.
[14] Product Information SokalanPolymeric Dispersants,
BASF, Ludwigshafen, Germany, 1992.
[15] D. Jung in: Ullmann's Encyclopedia of Industrial Chemistry,
Wiley- VCH, Weinheim 1985, p.385.
[16] K. Masters: Spray Drying Handbook, Fifth Edition,
Longman Scientific & Technical, New York 1991.
[17] ISO 2267:1986, Surface active agents- Evaluation of
certain effects of laundering- Method of preparation and
use of unsoiled cotton control cloth

67

2(1) (2013), 60-68

Advanced technologies

Izvod

ULOGA NATRIJUM- POLI(AKRILATA) RAZLIITIH SREDNJE- MASENIH

MOLEKULSKIH MASA U BILDERSKIM SISTEMIMA BEZFOSFATNIH
DETERDENATA ZA PRANJE RUBLJA
Vladimir S. Milojevi1*, Sneana Ili-Stojanovi2, Ljubia Nikoli2, Vesna Nikoli2,
Jakov Stamenkovi2, Dragan Stojiljkovi2
1 Henkel Srbija D.O.O., Beograd, Srbija
2 Univerzitet u Niu, Tehnoloki fakultet, Leskovac, Srbija

U ovom radu sinteza natrijum-poli(akrilata) izvrena je polimerizacijom akrilne

kiseline u vodenom rastvoru, uz primenu tri razliite koncentracije kalijumpersulfata kao inicijatora. Karakterisanje dobijenih proizvoda uraeno je primenom HPLC i GPC metoda u cilju definisanja rezidualnog monomera i srednje masene molekulske mase poli(akrilne kiseline) U cilju odreivanja uticaja
natrijum-poli(akrilata) kao kobildera u karbonat/zeolitnom bilderskom sistemu
na sekundarne karakteristike pranja deterdenta, ispitivane su sekundarne karakteristike pranja deterdenata sa podjednakim sadrajem natrijumpoli(akrilata) razliitih srednje masenih molekulskih masa Vrednost stepena
beline i sadraj pepela, najznaajnijih sekundarnih karakteristika pranja, u
velikoj meri zavise od efikasnosti natrijum-poli(akrilata) u njegovoj primeni
kao inhibitora rasta kristala, stabilizatora suspenzije neistoa i agensa za
spreavanje ponovnog taloenja neistoa na povrini tkanine. Smanjena aktivnost natrijum-poli(akrilata) u bilderskom sistemu deterdenta umanjuje njegovu sposobnost da sprei oteenje tekstilnih vlakana, i kao rezultat toga
prouzrokuje pogoranje sekundarnih karakteristika pranja deterdenta. Stepen beline kontrolne pamune tkanine raste sa poveanjem srednje masene
molekulske mase natrijum-poli(akrilata), Mw, sve do vrednosti od 70000 g/mol,
nakon ega sa daljim poveanjem srednje masene molekulske mase do vrednosti od 100000 g/mol ili iznad, uloga bildera poinje da opada. Sadraj pepela
opada sa poveanjem srednje masene molekulske mase natrijum-poli(akrilata)
od vrednosti 8000 do 100000 g/mol, nakon koje ponovo poinje da raste sa
porastom molekulske mase. Najvie vrednosti sadraja pepela postignute su
kod uzorka deterdenata koji su sadrali natrijum-poli(akrilat) srednje masene
molekulske mase od 474920 g/mol. Efikasnost natrijum-poli(akrilata) svih
srednje masenih molekulskih masa ne smanjuje se niti znaajno menja sa
poveanjem broja ciklusa pranja.
68

(ORIGINAL NAUNI RAD)

UDK 678.7 + 547.391.1 :661.185.6

Kljune rei: Natrijum-poliakrilat, polimer, detergent, karbonat/zeolitski bilderi, sekundarna

svojstva pranja, stepen beline, sadraj pepela