Synthesis and application of Green Liquid detergents based on diethanolamine neutralized polymer and acid slurry.

 

Jeevan R. Dontulwar*

Dept of Chemistry, Priyadarshini Institute of Engineering and Technology, Nagpur 440019, India

*Corresponding Author E-mail: jdontulwar@yahoo.co.in

 

 

INTRODUCTION:

In the present context there is global trend towards use of liquid detergents because of their convenience, ease of dispensation and dispersion in water, owing to such characteristics liquid detergents are gaining popularity.

From manufacturing angle liquid detergents can be manufactured using relatively simple equipments. Liquid detergents are of various types

1. Heavy duty liquid detergents for regular washings

2. Light duty liquid detergents wool, silk etc.

3. Dish washing liquid detergents.

 

In the present work few green liquid detergents were formulated using diethanolamine neutralized carbohydrate polymers and acid slurry.

 

Liquid detergents formulated using diethanolamine neutralized carbohydrate polymers have shown good results in terms of performance like reduction in surface tension of water, foam volume, percent detergency.

Neutralization using diethanolamine has brought excellent appearance, feel and color to the samples of liquid detergents.

 

In the previous work1 the synthesis and characterization of biodegradable polymers from white dextrin, sorbitol and maleic anhydride was discussed. The synthesis and application of detergent from above source was also discussed2. 

 

The resin manufactured from white dextrin, sorbitol, starch, glycerol, maleic anhydride are found to be biodegradable in nature3.

The various powder detergents were formulated using white dextrin, sorbitol, maleic anhydride resin and used in cleaning of cloth successfully4 and various liquid detergents were formulated using white dextrin, sorbitol, maleic anhydride.5

 

EXPERIMENTAL:

Table-1 describes the composition of the green polymer.

 

Table1:

Synthesis of Polymer Based On White Dextrin, Sorbitol, Glycerol, Maleic Anhydride (Composition % by Weight)

Raw Material

Batch 10

White Dextrin

30.76

Sorbitol

53.86

Glycerol

nil

Maleic anhydride

15.38
Table 2:

Physico-Chemical Properties of Polymer 10

Sr. No.

Polymer Property

Observation

1

Acid value of the polymer

115

2

pH  value

2.00

3

Saponification value

156.24

4

Solid (%)

80

5

Color

White

6

Solubility of polymer

(i) in water

(ii) in Xylene

(iii) in alcohol + water

(iv) in NaOH solution

 

Soluble

In soluble

Partially soluble

Soluble

7

Hydrophilic Liphophilic Balance Ratio of polymer

12

8

Molecular Weight of the polymer

1850

 

Preparation of Liquid Detergent

Various Raw Materials in liquid detergent like Neutralized Acid Slurry neutralized polymeric resin and conventional ingredients were taken in a glass reactor and homogenized by running the stirrer for about half an hour. Refer. table2

 

The Solution is cooled in refrigerator at 10°C for 48 hrs. The clear liquid solution was filtered and packed in superior grade air tight plastic containers.           

 

Table 3

Composition Of Liquid Detergents Using Di-Ethanol Amine Neutralized Polymer 10. (By % Weight Method)

Raw Materials

D1

D2

D3

D4

D5

Diethanol Amine Neutralized Polymer (100%)

5

5

5

5

5

Diethanol Amine Neutralized Acid Slurry (100%)

5

5

5

5

5

Ethylene Di-Amine Tetra-Acetic Acid

5

3

2

1

0

Urea

5

5

5

5

5

Sodium Sulfate

5

7

8

9

10

Sodium Lauryl  Sulfate

2

2

2

2

2

Sodium Lauryl Ether Sulfate

2

2

2

2

2

Carboxy Methyl Cellulose

1

1

1

1

1

Water

70

70

70

70

70

Note: Di-Ethanol amine neutralized polymer was used as a solution (20%Solid) di-ethanol amine neutralized acid slurry was used as a solution (13%Solid)

 

Liquid detergents prepared by above methods were analyzed for physical properties like density, pH value, and viscosity etc. ref. table. 4

 

Table 4:

Properties of Liquid detergents

Sr. no.

Sample

Density in g/l

pH value

Viscosity time (seconds)

1

d1

0.990

8

38

2

d2

0.986

8

50

3

d3

0.987

8

40

4

d4

0.989

8

45

5

d5

0.992

8

60

 

Surface tension of various liquid detergents determined using stalgnometer method and the results are presented in table 5

 

Table 5:

Study of Surface Tension of Water at Various Concentration of Detergent- Polymer 10

 

Sample

Concentration

(%)

Surface Tension (Dynes/Cm)

% Reduction In Surface Tension  of Water

D1

0.1

60.78

14.61

0.25

45.45

36.14

D2

0.1

59.35

16.61

0.25

46.09

35.24

D3

0.1

58.72

17.50

0.25

39.04

45.13

D4

0.1

57.64

19.04

0.25

41.49

41.71

D5

0.1

62.96

11.54

0.25

53.34

25.06

Surf excel liquid

0.1

16.28

77.13

0.25

15.95

77.59

 

Foam Volume3 Foam volume was determined by using bubble cylinder method

 

1) Bubble Cylinder Method: Foam characteristics are measured in terms of volume and the following steps are carried out for it.

 

Take 1000 ml cylinder provided with stopper, add to it 100 ml solution of particular concentration whose foam characteristics is to be measured. Give it 30 up-down rotation within time period of 30 seconds. Keep that cylinder on table and observe the foam above liquid level and note down reading at min. The readings were measured after 5, 10, 15 min. respectively. Same procedure is carried out for the solution at different concentration like 0.1%, 0.25%, 0.5% and 1.0%

 

 

 

 

Table 6:

Study of Foam Volume At 0.1 % Concentration of Detergent

Sr. No.

Sample

Foam Vol In Cm3  (Time In Minutes)

0

05

10

15

20

1

D1

140

130

130

130

130

2

D2

160

150

150

150

150

3

D3

150

150

150

150

150

4

D4

200

180

180

180

180

5

D5

220

200

200

200

200

6

Surf excel liquid

121

119

111

111

111

 

Table 7:

Study of Foam Volume At 0.25 % Concentration of Detergent

Sr. No.

Sample

Foam Vol In Cm3  (Time In Minutes)

0

05

10

15

20

1

D1

470

200

200

200

200

2

D2

550

460

460

460

460

3

D3

310

300

300

300

300

4

D4

250

250

250

250

250

5

D5

290

280

280

280

280

6

Surf excel liquid

142

133

131

118

118

Percent detergency

Soil medium: The soil medium was prepared by mixing Carbon (28.4 %), coconut oil (35.8 %), lauric acid (17.9 %) and mineral oil (17.9 %).

 

Preparation of soil solution: This was prepared by adding2 g of above soil paste in 500 ml of carbon tetrachloride solution. Mix it well and use for further cloth sample preparation. The solution was filled in packed bottle.

 

Method of application: The cotton cloths of size 24 cm × 32 cm were prepared. Take 50 ml of soil solution in beaker. Dip this cloth sample in it for 5 min. The same cloth dried in open atmosphere for 2 h. Then this cloth was cut into test sample size of 6 cm × 8 cm and these samples were used for washing purpose. The solutions of different concentration of detergent were prepared and heated to 60 °C temperature. Soiled cloth sample was dipped in it for 5 min and given to and fro 10 hand washes. Washing was carried out in distilled water only. After rinsing these samples in fresh water are kept for drying purpose. The samples which were washed, dried and ironed were used to find out per cent detergency.

 

The %detergency was determined using lamberts and sanders formula.

Percent detergency

 

Where, Rw, Rs and Ro are reflectance measured on washed cloth, soiled cloth and clean cloth, respectively. The reflectance of the cloth samples were measured by using reflectance meter manufactured by Universal Engg. Corporation, Ambala Road, Saharanpur. This was standardized by using the magnesium oxide or tile which was provided along with the instrument. This tile having brightness of 81.3 %was adjusted using the knob provided on instrument. After adjustment was done the samples were kept on the instrument

 

And the readings were noted down and the percent detergency was calculated (Table-7).

 

Method of Application (Tea and Coffee)

The cotton cloth of size 24 x 32 cm2 were taken and make checks with the help of size 6 x 8 cm2. Then take the above staining solution in a pipette and add in a center or checks one drop and then kept the stain cloth sample in oven at 100-105°C for half an hour. Then this stained cloth is cut into test sample size and these samples were used for washing purpose.

 

Table 8:

Study of percent detergency at various concentration of detergent on soiled stained cotton cloth.

       RO=Reflectance measured on white cloth=80.1

       RS=Reflectance measured on soiled cloth=40.1

       RW=Reflectance measured on washed cloth

Sr. No.

Samples

Concentration

% Detergency

1

D1

0.1

67.25

 

0.25

76.88

2

D2

0.1

64.84

 

0.25

76.19

3

D3

0.1

61.74

 

0.25

70.69

4

D4

0.1

61.40

 

0.25

70.52

5

D5

0.1

61.06

 

0.25

67.42

6

Surf excel liquid

0.1

75.32

 

0.25

78.62

 

 

Table 9:

Study of Percent Detergency at Various Concentration of Detergent on Tea Stained Cotton Cloth.

       RO=Reflectance measured on white cloth=80.1

       RS=Reflectance measured on soiled cloth=41.5

       RW=Reflectance measured on washed cloth

Sr. No.

Samples

Concentration

% Detergency

1

D1

0.1

71.92

 

0.25

73.44

2

D2

0.1

65.01

 

0.25

66.96

3

D3

0.1

58.75

 

0.25

62.64

4

D4

0.1

58.10

 

0.25

68.69

5

D5

0.1

54.43

 

0.25

58.96

6

Surf excel liquid

0.1

76.30

 

0.25

77.25

 

Table 10:

Study of Percent Detergency at Various Concentration of Detergent on Coffee Stained Cotton Cloth

             RO=Reflectance measured on white cloth=80.1

             RS=Reflectance measured on soiled cloth=44.8

             RW=Reflectance measured on washed cloth

 

Sr. No.

Samples

Concentration

% Detergency

1

D1

0.1

89.7

 

0.25

95.55

2

D2

0.1

79.95

 

0.25

83.85

3

D3

0.1

76.05

 

0.25

82.48

4

D4

0.1

70.59

 

0.25

76.44

5

D5

0.1

68.44

 

0.25

72.93

6

Surf excel liquid

0.1

72.24

 

0.25

75.10

 

 

RESULTS AND DISCUSSION:

As evident from table-1 that a green carbohydrate polymer was synthesized using 30.76%white dextrin,53.86% sorbitol and 15.38% maleic anhydride having BOD to COD ratio 1.14 having extreme biodegradability.

 

The carbohydrate polymer having good molecular wt. and has shown HLB ratio12 suggesting its application in detergent formulation.

 

Various liquid detergents were formulated by varying percentage of various constituents to observe the possible difference in performance characteristics of liquid detergents at changed composition of active components of detergents.

 

The formulations D1 to D5 have different proportion of active components of detergency. (Refer table3). In all those formulation the complexing agent EDTA varied from five to zero percentage. EDTA is usually incorporated in premium quality detergents owing to its cost.

 

Percentage of usually incorporated cheap sodium sulfate was varied from 5 to 10.

 

As evident from table 4 that all detergents have shown pH value 8 and in alkaline medium better detergency is obtained. All samples have shown reasonably good viscosity and density.

 

Every detergents performance is evaluated on the basis of its effects on various functional parameters like effect of detergents on surface tension of water, foam volume of water and percent detergency of cloth.

 

Table 5 shows the surface tension study of various liquid detergents starting from D1 to D5 and liquid surface excel. The samples D3 and D4 have shown highest reduction in surface tension of water at 0.1 percent and 0.25 percent concentration of detergents reply.

 

And the second important parameter considered to be important is foam volume. Diethanol amine neutralization has brought a marked effect in the foam vol of water. Foam generation helps to keep removed dirt away from the cloth and avoids redeposition of dirt. It is evident from table 6 and table 7 related to study of foam volume of D1 to D5 liquid detergents at 0.1 and 0.2 percent concentration of detergents has shown that the samples have excellent foam generation capacity and foam stability.

 

In the D series, samples D4 and D5 have highest foam generation capacity and stability at 0.1 percent concentration of detergents and at 0.25 percent concentration samples D1 and D2 have shown excellent results.

 

The study of percent detergency of detergents on various clothes is depicted in tables 8, 9, 10.It is evident from these that samples D1 and D2 have shown good cleaning action on soil stained cloth. The sample D1 at 0.1 and 0.25 concentration of detergent have shown 67.25 and 76.88 percent detergency on soil stained cloth and sample D2 has shown 64.84 and 76.88 percent detergency at 0.1 and 0.2percent concentration of detergents.

 

The better cleaning actions of detergents like D1and D2 certainly because of more percentage of EDTA in these samples and performance of these samples are comparable with commercial one. And similar kinds of results are seen on tea stained and coffee stained cloths and samples D1, D2 have shown 71.92 and 65.01 percent detergency on tea stained cloth at 0.1percent concentration of detergent.

 

The samples D1, D2 have shown 73.44 and 66.96 percent detergency on tea stained cloth at 0.25percent concentration of detergent. On coffee stained cloth the same samples D1, D2 are showing excellent cleaning action and even better than commercial sample.

 

CONCLUSION:

The formulation of liquid detergents using green carbohydrate polymer is new area application. In the present study an attempt has been made to see the effect of diethanol amine neutralization on liquid detergent performance.

 

The effect of diethanol amine neutralization of green polymer and acid slurry have shown better results in terms of performance like color, feel, appearance and reduction in surface tension of water, foam volume, percent detergency.

 

REFERENCES:

1.        Synthesis and characterization of biodegradable polymers from mix carbohydrates and Maleic anhydride as a precursor. Carbohydrate Polymers, 63(2006)375-378 (Elsevier Publication).

2.        An esteric polymer synthesis and its characterization using starch, glycerol and maleic anhydride as precursor. Carbohydrate Polymers, Volume 65(2006)207-210 (Elsevier Publication).

3.        Biodegradation Studies of Selected Polymers of Carbohydrate Origin. Asian Journal of Research in Chemistry 5(2012), 197-199.

4.        Synthesis of Eco-friendly detergents by using white dextrin, Sorbitol, Maleic anhydride. Asian Journal of Chemistry, 16(2004)1385-1390.

5.        Synthesis of Green Liquid Detergents using Carbohydrate Polymers Based on White Dextrin, Sorbitol and Maleic Anhydride. Asian Journal of Chemistry Volume 23(2011)6, 2511-2514.

 

 

 

 

Received on 13.07.2012        Modified on 16.08.2012

Accepted on 18.09.2012        © AJRC All right reserved

Asian J. Research Chem. 5(9): September, 2012; Page 1186-1189