OPEN ACCESS Int. Res. J. of Science & Engineering, 2014; Vol. 3 (1): 18-23

ISSN: 2322-0015

RESEARCH ARTICLE

Special eco-friendly liquid laundry detergents for washing machines Deshmukh AG1, Gogte BB2 and Yenkie MKN3

1Department 2 Retd.Prof. 3Director,

of Chemistry, Nutan Bharat Junior college, Nagpur, Maharashtra, India.

and Head, Department of Oil Technology, LIT, Nagpur University, Nagpur.

Laxminarayan Institute of technology, RTM, Nagpur University, Nagpur.

*Corresponding author Email: [email protected]

Manuscript Details 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.

ABSTRACT 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 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 noncommercial and no modifications or adaptations are made.

© 2014| All right reserved

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 18

Special eco-friendly liquid laundry detergents for washing machines

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

1.

Sorbitol (70%)

2. 3. 4.

Polyethylene glycol(400) Maleic Anhydride Citric acid

5.

Oxalic acid

Concentration Batch-1 Batch-2 60 10 30

35 35 20

-

05

-

05

Note: Catalyst- 1% Con. HCl, 3.5% Sodium metabisulphite, 3.5% sodium bisulphate. Table 2: Physicochemical properties of synthesized polymers. Sr. Polymer property Batch-1 Batch-2 No. 1. Acid value of polymer 136.16 138 2.

pH of 1% solution

3.

% solid

4.

8.

Solubility 1.Water 2. Xylene Hydrophilic-lipophilic balance of polymer Flow time in second at 300c by Ford cup no. 4. Surface tension in dyne/cm.at300c by Ostwald’s viscometer Oxiraneoxygen ( %)

9.

*Foam

5. 6. 7.

4

4

85.21

81.70

Soluble Insoluble 13.21

Soluble Insoluble 14.98

185

252

38

34

1.98

2.09

cm3

volume in by 450 800 cylinder method *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).

Int. Res. J. of Science & Engineering, 2015; Volume 3, No. 1, January –February, 2014.

19

Deshmukh et al., 2014 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 %

1.

LF-1

1% 0.5% 0.25%

850 650 400

800 550 300

2.

LF-2

1% 0.5% 0.25%

650 340 240

3.

LF-3

1% 0.5% 0.25%

4.

LF-4

1% 0.5% 0.25%

5.

Commercial market liquid detergent

1% 0.5% 0.25%

Density(g/cm3) by density bottle

Surface tension (dynes/cm)at 300c by Ostwald’s viscometer.

650 400 200

1.042 1.042 1.035

27.76 29.26 29.81

550 260 200

400 200 100

1.052 1.028 1.046

30.30 31.09 35.40

450 280 250

360 210 200

300 190 170

1.019 1.045 1.031

29.35 33.11 34.15

520 250 280

480 200 210

320 160 168

1.038 1.042 1.021

31.39 35.26 35.50

750 600 500

700 550 400

550 400 320

0.910 0.913 0.941

37.42 37.69 38.50

Foam volume in (cm3) after 0,5,10 minutes.by cylinder method

Table 5: Stain removing properties of moderately foaming laundry liquid detergents based on novel polymer-Batch-1 Sample

20

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

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Special eco-friendly liquid laundry detergents for washing machines

RESULT AND DISCUSSION RC SAIF PU, Chandigarh

72.5 65 2042,65

60

867,65 891,65 824,65 777,60

55

951,57

50 45

648,46 583,46

40 35 %T 30

1359,34

25 1408,27

20

1046,24 1176,22 1231,19 1083,20

15

3086,18 2940,18

10

1644,17 1285,15 1673,14

5 1715,6

0 3400,2

-4.0 4000.0

3600

3200

2800

2400

2000

1800

1600

1400

1200

1000

800

600

400.0

c m-1

Ashwini Girish-3.sp - 8/14/2014 - F

Fig.1: IR spectra of Batch-1 polymer F 6.7232 6.6961 6.6730 6.6646 6.6054 6.3315 6.3008 6.2861 6.1860 6.1487 4.7179 4.4144 4.2937 4.2668 4.2476 4.2027 4.1742 4.1448 4.1306 4.1145 4.0984 4.0828 4.0698 4.0308 4.0174 3.9534 3.9395 3.8738 3.7948 3.7109 3.6958 3.6217 3.5898 3.5641 3.5316 3.5257 3.4989 3.4637 3.4410 3.4164 3.3493 3.3338 3.3207 3.3047 3.2787 2.7416 2.6994 2.6706 2.6541

BRUKER AVANCE II 400 NMR Spectrometer SAIF Panjab University Chandigarh Current Data Parameters NAME Aug13-2014 EXPNO 351 PROCNO 1 F2 - Acquisition Parameters Date_ 20140813 Time 21.37 INSTRUM spect PROBHD 5 mm PABBO BBPULPROG 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

11

10

9

8

7

6

5

0.94

18.98

4.20

1.16

2.00

2.23

F2 - Processing parameters SI 16384 SF 400.1300000 MHz WDW EM SSB 0 LB 0.00 Hz GB 0 PC 1.00

4

3

2

1

0

ppm

[email protected]

Fig. 2 :NMR spectra of Batch-1 polymer.

Int. Res. J. of Science & Engineering, 2015; Volume 3, No. 1, January –February, 2014.

21

Deshmukh et al., 2014 WATERS, Q-TOF MICROMASS (LC-MS)

SAIF/CIL,PANJAB UNIVERSITY,CHANDIGARH

ASHWINI F 21 (0.222) Cm (9:30)

TOF MS ES+ 3.90e3

437.1 3898

100

393.1 3416

481.1 3275

415.1 2670 371.1 2516 476.2 2294

520.2 2379 525.1 2099

%

349.1 2001

564.2 1791

459.2 1721

327.1 1272

569.2 1160 608.2 952 503.2 784

89.0 313 133.1 150

0 50

535.1 471

305.1 448

574.2 549

205.0 311 249.1 303.0;249 177

618.2 544

652.3 408 706.2 193 738.2 125

m/z 100

150

200

250

300

350

400

450

500

550

600

650

700

750

800

850

900

950

1000

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, 22

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

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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.

2.

Gogte BB and Agrawal AS. Sorbitol based polymeric surfactants for detergent powder.” J.soapsdeter,Toiletris rev., 2003; 34:19-22

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.

Maltielloww JJ. Protective and decorative coatings, 4th ed. Inc. New York, 1944: 339-345.

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