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Int. Res. J. of Science & Engineering, 2014; Vol. 3 (1): 18-23 ISSN: 2322-0015
Special eco-friendly liquid laundry detergents for washing
machines
Deshmukh AG1, Gogte BB2 and Yenkie MKN3
1Department of Chemistry, Nutan Bharat Junior college, Nagpur, Maharashtra, India.
2 Retd.Prof. and Head, Department of Oil Technology, LIT, Nagpur University, Nagpur.
3Director, Laxminarayan Institute of technology, RTM, Nagpur University, Nagpur.
*Corresponding author Email: [email protected]
Manuscript Details ABSTRACT
Received : 26.11.2014
Revised : 11.12.2014
Revised Received :29.12.2014
Accepted : 15.01.2015
Published: 25.01.2015
ISSN: 2322-0015
Cite this article as: Deshmukh AG, Gogte BB and Yenkie
MKN. Special eco-friendly liquid
laundry detergents for washing
machines, Int. Res. J. of Sci. & Engg.,
2015; 3(1):18-23.
Copyright: © Author(s), This is an
open access article under the terms of
the Creative Commons Attribution
Non-Commercial No Derivs License,
which permits use and distribution in
any medium, provided the original
work is properly cited, the use is non-
commercial and no modifications or
adaptations are made.
The use of washing machines in India and third world countries is
increasing very fast. Special ecofriendly moderate foaming and high
efficiency liquid laundry detergents must be developed which are
moderate in cost yet effective in performance. In the present work
efficient polymeric surfactants based mainly on sorbitol, polyethylene
glycol and maleic anhydride have been synthesized. The polymeric
synthesis process has been standardized properly so that we can use it
in washing machines detergents. The physicochemical and spectral
properties of polymers suggest its selection in liquid detergent
formulations. Liquid detergents were formulated using 14to20 % of this
novel polymer along with other conventional ingredients. The prepared
compositions were compared with commercial liquid laundry
detergents. The result suggests use of this formulation on pilot plant &
commercial scale.
Keywords: HLB ratio, % detergency, saponification value, polymeric
surfactants.
INTRODUCTION
All cleaning compositions like powder, cake and liquid detergents, floor
and glass cleansers, utensil cleansers are based mainly on linear alkyl
benzene sulphonate (LABS) or alpha olefin sulphonate (AOS) which are
of petroleum origin. The total dependence of various cleansing
preparations on petroleum products is not a wise investment and we
must develop ecofriendly surfactants which can partly or totally replace
active materials of petroleum origin. We have successfully developed
polymers based on sorbitol, glycerol, malenized oil and starch for
powder and liquid detergents. In the present work the intention is to
OPEN ACCESS
RESEARCH ARTICLE
Special eco-friendly liquid laundry detergents for washing machines
Int. Res. J. of Science & Engineering, 2015; Volume 3, No. 1, January –February, 2014. 19
develop high efficiency active material which will give
moderate foaming (High foaming is totally undesirable
for washing machine) and excellent performance
characteristics.
A special polymer has been synthesized based on
sorbitol, polyethylene glycol (400) and maleic
anhydride. A slightly higher amount of maleic
anhydride has been used as this gives higher cleaning
and stain removing efficiency. The polymers were
systematically analyzed for their acid value, viscosity,
surface tension and other physicochemical properties.
The selected polymers (14-20%) were used for
preparation of moderate foaming liquid laundry
detergents for washing machine. The liquid laundry
detergents were analyzed systematically along with a
commercial product for foaming, surface tension and
soil stain removal by standard methods (Gogte and
Agrawal, 2003; Maltiellow, 1944; Gogte and Donyulwar,
2004; Taylor and Marks, 1972). The special feature of
product is freedom form sodium tripolyphosphate
which is source of pollution and use of sorbitol which
gives a soothing and non-irritating feel to the skin.
METHODS AND MATERIAL
a) Synthesis of novel polymer
The preparation of novel polymer was carried out in a
glass reactor. The reactor consists of two parts. Lower
part of the reactor is a round bottom glass vessel with
very wide mouth having capacity of about 2 liters. The
upper part of the reactor is its lid, having four necks
with standard joints. The central neck has a stirrer with
speed regulator arrangement. The second neck is used
for mounting thermometer. A condenser is fitted with
the reactor through the third neck, and the fourth neck
is used for dropping the chemicals into the reactor. An
electric heating mantle is used for heating the
reactants. A regulator controlled the speed of the
stirrer. The reaction vessel and its lids are tied together
with the help of clamps. Initially, composition
mentioned in Table-1 of sorbitol, polyethylene glycol,
maleic anhydride was added in the reactor. Con. HCl
was used as a catalyst. The temperature was raised
slowly and slowly to 1300c. The reaction was continued
for 3 hours. The consistency of the paste was
maintained by adding water. At the end of this period
the batch was terminated and prepared polymer was
collected in a glass stopper bottle with least air gap. The
final yield of the product was measured.
b) Analysis of Novel polymer
Analysis of novel polymers were carried out by
determine acid value (ASTM, standard method),
saponification value (ASTM, standard method),
viscosity (Melhen, 1986), oxirane oxygen (Melhen,
1986) value solid content (ASTM, standard method,
1963-74), pH value (Jefferyetal et al., 1989), HLB
ratio (Jellinek, 1954) and % detergency (Harries,
1954).
Table 1: Composition of special polymers based on
sorbitol and Polyethylene glycol.
Sr.
No.
Raw material Concentration
Batch-1 Batch-2
1. Sorbitol (70%) 60 35
2. Polyethylene glycol(400) 10 35
3. Maleic Anhydride 30 20
4. Citric acid - 05
5. Oxalic acid - 05
Note: Catalyst- 1% Con. HCl, 3.5% Sodium metabisulphite,
3.5% sodium bisulphate.
Table 2: Physicochemical properties of synthesized polymers.
Sr. No.
Polymer property Batch-1 Batch-2
1. Acid value of polymer 136.16 138
2. pH of 1% solution 4 4
3. % solid 85.21 81.70
4. Solubility 1.Water 2. Xylene
Soluble
Insoluble
Soluble
Insoluble 5. Hydrophilic-lipophilic
balance of polymer 13.21 14.98
6. Flow time in second at 300c by Ford cup no. 4.
185 252
7. Surface tension in dyne/cm.at300c by Ostwald’s viscometer
38 34
8. Oxiraneoxygen ( %) 1.98 2.09
9. *Foam volume in cm3 by cylinder method
450 800
*Foam volume was measured for combination of 90%
polymer and 10% linear alkyl benzene sulphonate (LABS)
neutralized.
c) Preparation of liquid detergents
Various raw materials in liquid detergent
likeneutralized acid slurry, neutralized polymeric resin
and conventional ingredients were taken in aglass
reactor (Table-3) and homogenized by running the
stirrer for about an hour, refer Table-3. The solution is
cooled in refrigerator at 100c for 48 hours. The clear
liquid solution was filtered and packed in superior
grade air tight plastic containers (Garrette,1972; Puri et
al., 1997).
Deshmukh et al., 2014
20 www.irjse.in
Table 3:Composition of moderate foaming liquid detergents for washing machines based on Polymer batch -1 (% by
weight)
S. No. Raw material Concentration(% by weight)
LF-1 LF-2 LF-3 LF-4
1. AOS 02 01 00 01
2. SLES 10 10 10 10
3. Polymer 14 16 18 20
4. Urea 02 02 02 02
5. EDTA 01 01 01 01
6. Sorbitol 05 04 04 04
7. Sodium carbonate 07 07 07 07
8. CMC 10 10 09 09
9. Salt 02 02 02 01
10. Water 53 53 53 53
Note; LF-1, LF-2, LF-3.LF-4 are liquid detergents based on Batch-1. AOS- Alpha olefin sulphonate, SLES- Sodium lauryl ether
sulphate, EDTA- ethylene diamine tetra acetic acid.
Table 4: Analysis of liquid detergents at 1%, 0.5, 0.25% concentration.
S.
No.
Liquid
detergents
Concentration
% Foam volume in (cm3)
after 0,5,10 minutes.by
cylinder method
Density(g/cm3)
by density bottle
Surface tension
(dynes/cm)at 300c
by Ostwald’s
viscometer.
1. LF-1 1%
0.5%
0.25%
850
650
400
800
550
300
650
400
200
1.042
1.042
1.035
27.76
29.26
29.81
2. LF-2 1%
0.5%
0.25%
650
340
240
550
260
200
400
200
100
1.052
1.028
1.046
30.30
31.09
35.40
3. LF-3 1%
0.5%
0.25%
450
280
250
360
210
200
300
190
170
1.019
1.045
1.031
29.35
33.11
34.15
4. LF-4 1%
0.5%
0.25%
520
250
280
480
200
210
320
160
168
1.038
1.042
1.021
31.39
35.26
35.50
5. Commercial
market
liquid
detergent
1%
0.5%
0.25%
750
600
500
700
550
400
550
400
320
0.910
0.913
0.941
37.42
37.69
38.50
Table 5: Stain removing properties of moderately foaming laundry liquid detergents based on novel
polymer-Batch-1
Sample Soil Tea Coffee Spinach Cleaning score
LB-1 2 4 3 4 13
LB-2 3 4 4 3 14
LB-3 2 3 3 4 12
CD-1 3 4 4 4 15
CD-2 3 4 4 4 15
Special eco-friendly liquid laundry detergents for washing machines
Int. Res. J. of Science & Engineering, 2015; Volume 3, No. 1, January –February, 2014. 21
RESULT AND DISCUSSION
Fig.1: IR spectra of Batch-1 polymer
11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.6541
2.6706
2.6994
2.7416
3.2787
3.3047
3.3207
3.3338
3.3493
3.4164
3.4410
3.4637
3.4989
3.5257
3.5316
3.5641
3.5898
3.6217
3.6958
3.7109
3.7948
3.8738
3.9395
3.9534
4.0174
4.0308
4.0698
4.0828
4.0984
4.1145
4.1306
4.1448
4.1742
4.2027
4.2476
4.2668
4.2937
4.4144
4.7179
6.1487
6.1860
6.2861
6.3008
6.3315
6.6054
6.6646
6.6730
6.6961
6.7232
0.94
18.98
4.20
1.16
2.00
2.23
Current Data Parameters
NAME Aug13-2014
EXPNO 351
PROCNO 1
F2 - Acquisition Parameters
Date_ 20140813
Time 21.37
INSTRUM spect
PROBHD 5 mm PABBO BB-
PULPROG zgpr
TD 32768
SOLVENT D2O
NS 16
DS 2
SWH 12019.230 Hz
FIDRES 0.366798 Hz
AQ 1.3631988 sec
RG 32
DW 41.600 usec
DE 6.00 usec
TE 296.7 K
D1 5.00000000 sec
d12 0.00002000 sec
TD0 1
======== CHANNEL f1 ========
NUC1 1H
P1 10.90 usec
PL1 -3.00 dB
PL9 50.23 dB
SFO1 400.1318806 MHz
F2 - Processing parameters
SI 16384
SF 400.1300000 MHz
WDW EM
SSB 0
LB 0.00 Hz
GB 0
PC 1.00
FBRUKER
AVANCE II 400 NMR
Spectrometer
SAIFPanjab University
Chandigarh
Fig. 2 :NMR spectra of Batch-1 polymer.
RC SAIF PU, Chandigarh
Ashwini Girish-3.sp - 8/14/2014 - F
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0
-4.0
0
5
10
15
20
25
30
35
40
45
50
55
60
65
72.5
cm-1
%T
3400,2
3086,182940,18
2042,65
1715,6
1673,14
1644,17
1408,27
1359,34
1285,15
1231,191176,22
1083,20
1046,24
951,57
891,65867,65
824,65777,60
648,46583,46
Deshmukh et al., 2014
22 www.irjse.in
WATERS, Q-TOF MICROMASS (LC-MS) SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH
m/z50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
%
0
100
ASHWINI F 21 (0.222) Cm (9:30) TOF MS ES+ 3.90e3437.1
3898
393.13416
371.12516
349.12001
327.11272
305.1448
89.0313
205.0311
133.1150
303.0;249249.1177
415.12670
481.13275
476.22294
459.21721
520.22379
503.2784
525.12099
564.21791
535.1471
569.21160
608.2952
574.2549
618.2544
652.3408
706.2193 738.2
125
Fig. 3 : Mass spectra of Batch-1 polymer.
1. Composition of special polymers is given in Table-1.
2. A higher proportion of maleic anhydride (20-30%)
has been used which may give greater cleaning
efficiency to our detergent.
3. Small proportion of citric acid and oxalic acid will
also help in cleaning and stain removing properties
of the polymer.
4. The physicochemical properties of the polymer are
reported in the Table-2.
5. The acid value of samples is significantly higher as a
higher proportion of acids 30% have been used. The
pH is also acidic and H.L.B. ratio suggests the use of
these polymers in detergent compositions.
6. The samples are highly soluble in water and have
reasonable flow and viscosity properties. Use of
citric and oxalic acid give a slightly higher viscosity.
7. The surface tension reductions capacity of polymer
and presence of oxiraneoxygen will certainly help
the detergent to have better cleaning capacity.
8. The foaming properties were evaluated for (90:10)
combination of polymer with acid slurry. The %
solids are reasonably high (80-85%).
9. The composition of liquid detergents is shown in
Table-3.
10. In progressive samples the percentage of polymer
has been increased from 14-20%.
11. A very small percentage of alpha olefin sulphonate
has been used. A constant proportion of SLES,
sodium carbonate, EDTA, salt (1-2%) and sodium
carbonate.
12. The pH of final sample has been maintained
between 8 to 9.
13. The analysis of liquid detergents including foam
stability is given in Table-4.Compared to commercial
sample there is reasonable foaming property at all
concentrations. The foam is reasonably stable for
ten minutes and compares well with commercial
sample.
14. In fact our samples have moderate foaming
properties slightly lower than commercial sample.
This reduced foam is a desired property for
commercial application.
15. Excellent surface tension reduction at all
concentrations (0.25-1%) is observed which a
desirable characteristic for better performance.
16. The molecular weight of polymer is 2917(Fig.-3)
and degree of polymerization is 16.
CONCLUSION
Special polymeric surfactants suitable for developing
moderate foaming washing machine liquid detergent
can be synthesized using mainly sorbitol and
polyethylene glycol (400). The acid component is
mainly maleic anhydride and minor proportions of
Special eco-friendly liquid laundry detergents for washing machines
Int. Res. J. of Science & Engineering, 2015; Volume 3, No. 1, January –February, 2014. 23
oxalic and citric acids have been used. The
physicochemical analysis of the polymer as given in
Table-2 suggests the use of this polymer is formulation
of moderate foaming detergents for washing machines.
Several moderate foaming detergents based on 14-20%
of polymer-B1 have been formulated by standard
techniques. The analysis of these samples alog with
commercial sample indicates excellent foaming, surface
tension reduction ans soil cleaning property. These
properties are some times better than commercial
sample. The manufacturing cost of our liquid detergent
formulations is between 55 to 60Rs. Per Kg. So it can be
marketed at Rs.100/- per Kg. Pilot scale studies on
synthesis of polymers and its utilization on industrial
scale must be promoted. Our samples are ecofriendly as
they do not utilize any acid slurry or sodium
tripolyphosphate. Spectroscopic studies indicate the
presence of ester, ether, free acid and free alcohol
groups.
REFERENCES
1. Gogte BB and Agrawal AS. Sorbitol based polymeric
surfactants for detergent powder.” J.soapsdeter,Toiletris
rev., 2003; 34:19-22
2. Maltielloww JJ. Protective and decorative coatings, 4th ed.
Inc. New York, 1944: 339-345.
3. Gogte BB, Dontulwar JR. Synthesis of Ecanjulriendly
Detergent By Using White Dextrin Sorbitol Maleic
Anhydride Asia J. chem, 2004; 16(3): 1385-1390.Taylor
CJ, Marks S. Paint technology manual part III convertible
coatings, chapman and Hall publication,
London,1972,92-94.
4. ASTM standard method, 6.01 D; (For acid value of
organic coating materials.
5. Melhen Becher VC. The analysis of fats and oils Garrard
publication, champaignllinois,1960; pp 299-308.ASTM
standard method 6.03 D: (for specific gravity of drying
oils, varnishes, resins etc.), 1960, pp 1963-74.
6. Jeffery GH, Bassett J, Mendham J, Deny DC. Text book of
quantitative chemical analysis, 3rded, Longman scientific
and Technical, John Wiley and sons, Inc New York.1989.
7. ASTM standard Method 6.02 D ;( for non-volatile content
of resins)1980: pp 1259-61.
8. Jellinek. Encyclopedia of chemical Technology, 20th ed.
John Willey and sons, New York,1982: pp 780-80.
9. Harries. Detergency Evaluation and testing, Willey
Interscience publisher, 1954, pp 92-103.
10. Garrett HE. Surface active chemicals, pregamon press,
New York, 1972.
11. Puri BR, Sharma IR. Principles of physical chemistry,
Shoban Jal Nagin Chand and Co. New Delhi, 1997.
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