INTRODUCTION:

There is global need to minimize the use of petroleum products in various applications out of which detergent industry also needs the incorporation of renewable, ecofriendly locally available components. The novel ecofriendly polymers can be used as polymeric surfactants which has positive effect on the performance features of detergents viz:

1. Calcium magnesium sequisterization

2. Clay soil disperency and soil removal

3.Calcium carbonate inhibition

4. Prevention of soil redeposition

5.Helps to reduce water pollution

In the present research work experimental conditions have been worked worked out for getting a novel ecofriendly resin based on starch , glycerol and maleic anhydride. T he procedure has been standardized to get resin of desired molecular weight , HLB ration. The proportion of STPP ,EDTA has been maintained to constant level of 1.785%. The SLS and SLES to 4.46 to 0.446%

EXPERIMENTAL:

First Step: - Glycerol, Starch and Maleic Anhydride and little water mixed thoroughly and converted into a homogenous paste by using electrically controlled Homogenizer. The paste should have flow and Mobility. The paste was introduced into the reactor.

Second Step: - The Mass was slowly heated to 80°C in about 15 minutes. The reaction was controlled between +2°C by an accurate heating control.

Third Step: - The sample was observed periodically and its consistency was kept free flowing by adding calculated amount of water after every 15 minutes. The samples were checked periodically for Acid value, viscosity and the batch was terminated after 3 to 3½ hr. after getting desired characteristics

The six powder detergent formulation prepared as detailed in table no. 4.The 50% to 60%LABS has been replaced by novel polymer. The % of EDTA has been maintained to constant level 1.74%.

A very small proportion of SLS SLES and CMC has been used to have better foaming properties. The table 6and7 of surface tension and foam volume describes the effect of detergent concentration on surface tension and foam volume of water. Our samples are on par or sometimes even better than commercial products which were tested simultaneously. The percent detergency was determined using standard soiling techniques on cotton cloth.In this Experiment reflectance of cloth is measured by using digital reflectance meter.

RESULTS AND DISCUSSION:

The novel ecofriendly polymers having favorable molecular wt., acid value, HLB has been synthesised using starch glycerol and maleic anhydride. The biodegradation value of polymer was found to be ie BOD to COD ratio was found be 0.6075. The reaction conditions have been standardized and the reaction is simple but needs constant observation to avoid charring. Hydrochloric acid was used as catalyst to accelerate the rate of esterification The novel ecofriendly polymer is found to be biodegradable. The novel ecofriendly polymer has been used as 50% to 60% replacement of LABS in the formulation of detergent powders. These powder detergents have been analyzed for surface tension , foam volume and percent detergency value as described in table no.6 to 11.

The various compositions of green material are good to excellent in comparison to commercial samples of petroleum origin in which conventionally upto 45% to 50% of LABS ,35 to 40% of STPP is used.

Table 1: Synthesis of Polymer based on Starch, Glycerol and maleic anhydride

Raw Material	Batch 13 (%)
Starch	30.76
Sorbitol	nil
Glycerol	53.84
Maleic Anhydride	15.38
Phthalic Anhydride	nil
Conc. HCl	1.53
Water	92.30

Table 2: Cooking Schedule of Polymer 13

Time in Hrs. Min	Temperature (^OC)	Remarks
00.00	Room Temperature	600 g water added and batch started
00.30	48
01.00	75
01.30	95
02.00	100
02.10	101	300 g water added
02.30	103
02.40	105	300 g water added
02.50	106	Thickening of batch started
03.00	108	200 g water added
03.10	108	Batch turned viscous
03.15	116	Batch terminated

Table 3: Physico-Chemical Properties of Polymer 13

Sr. No.	Polymer Property	Observation
1	Acid value of the polymer	59.8
2	pH value	2.00
3	Saponification value	146
4	Solid (%)	74
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 of polymer	12.39
8	Molecular Weight. of the polymer	1875

Table 5: Physicochemical Properties of Powder Detergents (Polymer 13)

Sr. No.	SAMPLE	pH VALUE	MOISTURE CONTENT
1	O₁	7.55	11 %
2	O₂	7.58	12 %
3	O₃	7.63	13 %
4	O₄	7.72	11 %
5	O₅	7.79	13 %
6	O₆	7.56	11 %

Table 6: Study of Surface Tension of Water at Various Concentration of Detergent

Sample	Concentration	S.T. in dyne/cm	%Reduction in S.T. of water
O₁	0.1	34.13	52.05
	0.25	27.42	61.47
	0.5	25.32	64.42
	1	19.38	72.77
O₂	0.1	35.01	50.81
	0.25	28.21	60.36
	0.5	21.15	70.28
	1	20.28	71.50
O₃	0.1	47.21	33.67
	0.25	37.73	46.99
	0.5	31.38	55.91
	1	26.81	62.33
O₄	0.1	35.78	49.73
	0.25	32.43	54.43
	0.5	32.40	54.48
	1	25.59	64.0
O₅	0.1	40.25	43.45
	0.25	36.79	48.31
	0.5	33.20	53.35
	1	30.15	57.64
O₆	0.1	38.17	46.37
	0.25	34.37	51.71
	0.5	25.57	64.07
	1	23.66	66.76
SURF EXCEL	0.1	46.42	35.61
	0.25	42.66	40.83
	0.5	32.95	54.29
	1	22.85	67.89

Table 7: Study of Foam Volume At 0.1% Concentration of Detergent

Sr. No.	Sample	Foam Volume in cm³
		Time in minutes
		0	5	10	15	20
1	O₁	420	400	400	400	400
2	O₂	340	340	340	340	340
3	O₃	210	200	200	200	200
4	O₄	400	400	400	400	400
5	O₅	390	390	390	390	390
6	O₆	330	320	320	320	320
7	Surf excel	80	80	70	70	70

Table 8: Study of Foam Volume At 0.25% Concentration of Detergent

Sr. No.	Sample	Foam Volume in cm³
		Time in minutes
		0	5	10	15	20
1	O₁	620	620	620	620	620
2	O₂	390	390	390	390	390
3	O₃	280	280	280	280	280
4	O₄	500	500	500	500	500
5	O₅	410	410	410	410	410
6	O₅	460	460	460	460	460
7	Surf excel	150	150	140	140	140

Table 9 : Study of% Detergency on Soil Stained Cotton Cloth at Different Concentration of Detergents

R_o=Reflectance Measured On Clean Cotton Cloth=80.1

R_s=Reflectance Measured On Soiled Cotton Cloth=22

R_w=Reflectance Measured On Washed Cotton Cloth

Sr. No.	Sample	Concentration	% Detergency
1	O₁	0.1	74.99
		0.25	78.01
2	O₂	0.1	72.58
		0.25	75.33
3	O₃	0.1	60.71
		0.25	78.26
4	O₄	0.1	57.79
		0.25	86.34
5	O₅	0.1	68.28
		0.25	71.38
6	O₆	0.1	61.40
		0.25	65.87
7	Surf excel	0.1	54.18
		0.25	72.75

Table 10 : Study of % Detergency on Tea Stained Cotton Cloth at Different Concentration of Detergents

R_o=Reflectance Measured On Clean Cotton Cloth=80.1

R_s=Reflectance Measured On Tea cotton Cloth=33

R_w=Reflectance Measured On Washed Cotton Cloth

Sr. No.	Sample	Concentration	% Detergency
1	O₁	0.1	72.98
		0.25	74.92
2	O₂	0.1	69.59
		0.25	73.79
3	O₃	0.1	68.31
		0.25	71.82
4	O₄	0.1	67.68
		0.25	69.76
5	O₅	0.1	71.88
		0.25	73.77
6	O₆	0.1	72.54
		0.25	74.51
7	Surf excel	0.1	69.23
		0.25	74.43

Table11: Study of % Detergency on Coffee Stained Cotton Cloth at Different Concentration of Detergents

R_O=Reflectance Measured On Clean Cotton Cloth=80.1

R_s=Reflectance Measured On Coffee Cotton Cloth=29

R_w=Reflectance Measured On Washed Cotton Cloth.

Sr. No.	Sample	Concentration	% Detergency
1	O₁	0.1	81.47
		0.25	82.21
2	O₂	0.1	79.42
		0.25	81.74
3	O₃	0.1	72.01
		0.25	72.52
4	O₄	0.1	68.75
		0.25	70.12
5	O₅	0.1	81.21
		0.25	81.80
6	O₆	0.1	68.23
		0.25	70.16
7	Surf excel	0.1	76.49
		0.25	80.26

The following inferences can be drawn by above experimentation

1. An ecofriendly polymers based on vegetable renewable resources can be prepared by using starch glycerol and maleic anhydride by appropriation of contents of reaction.

2. The technical characteristics of detergents viz surface tension, foam volume, percent detergency can be positively achieved by replacing 50 to 70 % of LABS with novel ecofriendly glycerol polymer. The polymeric surfactant based on this novel polymer shows better performance even at smallest concentration of 0.1gm of detergnt/100 gm of water.

3. The samples formulated by using starch, glycerol, maleic anhydride based polymers namely O₁ to O₆ have shown excellent performance in reducing the surface tension of water at 0.1gm/100 gm of water.

The sample O₆ has shown 52.05% reduction in surface tension of water at 0.1gm of detergent / 100gm of water to 0.25gm of detergent/100 gm of water. The sample O₆ has shown 52.05% reduction in surface tension of water at 0.1gm of detergent /100gm of water. Where as commercial sample has shown 35.61% reduction in surface tension of water at 0.1 gm of detergent /100gm of water.

4. The sample from O₁ to O₆ has shown appreciable increase in the foam volume at each addition of 0.1gm of detergent /100gm of water with excellent foam stability.

All samples have shown excellent performance in the foam volume expt. As evident from table no. 7, 8 . The foam vol.of samples from O₁to O₆ is far better than commercial samples. The same performance was seen at 0.25% of detergent /100gm of water.

5. The % detergency study was conducted on soiled cotton cloth, tea stained cotton cloth, coffee stained cotton cloth.

It is evident from table 9 which shows the percent detergency data of different ecofriendly detergents like O₁toO₆ that sample O1 shows 74.99% detergency on soiled cotton cloth. More or less samples have shown best performance as compared to commercial one. The table 9 clearly depicts the truth. Similar findings are observed on tea stained, coffee stained cotton cloth As seen from table 10 and table 11.The sample O₁ has shown 72.98 % detergency on tea stained cotton cloth and 81.47% detergency on coffee stained cotton cloth. All these parameters like surface tension, foam volume, %detergency values for ecofriendly powder detergents like O₁ to O₆ were found to be excellent and comparable to commercial samples. The aim of formulating an ecofriendly polymeric surfactants and detergents was found to be successful without compromising on the performance criterion.

6. The commercialization of said experimentation is the need of the hour

REFERENCES:

1. Zini, Paolo Polymeric Additives High Performance Detergence (Technomic Publishing Company INC Lancaster BASEL,1995 p 15,42)

2. Gogte B.B., Agrawal R. S., Pandharipande S. L., Detergent Formulation by ANN (Chemical Engineering World Vol 38, No. 5, p 78,8, 2003)

3. Gogte B.B., Agrawal R. S., Pandharipande S. L., Badhe Y.P. Starch Sorbitol based co-polymer , A substitute for LABS (Soaps,Detergent and Toiletries review p 24,28, April 2003)

ABBREVIATIONS:

LABS: Linear Alkyl Benzene Sulfonate

HLB: Hydrophilic Liphophilic Balance

SLS: Sodium Lauryl Sulphate

SLES: Sodium Lauryl Ether Sulphate

CMC: Carboxy Methyl Cellulose

BOD: Biological Oxygen Demand

COD: Chemical Oxygen Demand

Received on 25.06.2013 Modified on 03.07.2013

Asian J. Research Chem. 6(7): July 2013; Page 690-693

Raw Materials	O₁	O₂	O₃	O₄	O₅	O₆
Polymer (100%)	8.92	8.92	8.92	8.92	8.92	8.92
Acid Slurry (100%)	8.92	8.92	8.92	8.92	8.92	8.92
sodium bicarbonate	00	00	00	00	00	53.57
Sodium Carbonate	53.57	58.03	60.71	61.60	62.5	00
Ethylene Diamine.Tetraacetic.Acid.	1.785	1.785	1.785	1.785	1.785	1.785
Sodium tripolyphosphate	1.785	1.785	1.785	1.785	1.785	1.785
Sodium Lauryl Sulphate	8.92	4.46	4.46	4.46	4.46	4.46
Sodium Lauryl Ether Sulphate.	0.446	4.46	4.46	4.46	4.46	4.46
Carboxy Methyl Cellulose	0.446	0.446	0.446	0.446	0.446	0.446
water	12	12	12	12	12	12

Table 1: Synthesis of Polymer based on Starch, Glycerol and maleic anhydride

Table 2: Cooking Schedule of Polymer 13

Polymer Property

REFERENCES: