Research Journal of Chemical Sciences ________________________________________ ISSN 2231-606X Vol. 1(6), 42-47, Sept. (2011) Res.J.Chem.Sci. International Science Congress Association 42 Novel Polymeric Surfactants Based on Oxalic Acid and Citric Acid for Detergents Deshpande A.D. and Gogte B.B.2 Department of Applied Chemistry, Shri. Shankar Prasad Agnihotri College of Engg, Ramnagar, Wardha, INDIA Department of Applied Chemistry, Indira Gandhi Priyadarshini College of Engineering, Nagpur, INDIA Available online at: www.isca.in (Received 18th July 2011, revised 26th July 2011, accepted 22th August 2011)Abstract Polymeric surfactant based on sorbitol, maize starch, acids and anhydrides have been synthesized and used successfully in detergent compositions. In the present piece of research work a small quantity of oxalic acid and citric acid along with major quantity of maize starch and sugar solution has been used in synthesis of polymer. The overall idea is to develop a polymeric surfactant using higher quantity of maize starch and substantial quantity of sugar along with oxalic acid and citric acid. These polymers may be ecofriendly are based on vegetable products. The synthesized polymers have been analyzed for physicochemical characteristics like acid value, saponification value, HLB ratio and cleaning efficiency .Selected novel polymeric surfactants based on these observations have been used in the preparation of powder detergent and liquid detergent. The acid slurry and Alpha Olefin Sulphonate based on crude petroleum have been successfully replaced by 50-70% by these novel ecofriendly polymers. The preparation of these polymers is simple and they can be recommended for commercial use. These novel polymers are comparable to commercial active ingredients and suitable for like commercial production. The novel polymers and detergents compositions can be taken up on pilot and industrial scale as they are ecofriendly and commercially and technically comparable to conventional products. Keywords:Novel polymers, carbohydrate polymers, starch-sorbitol-sugar based polymers. IntroductionThe advent of polymers represents one of the important industrial revolutions of the 21st century. The polymers containing carbohydrates are unique as they are potentially process able and biodegradable and biocompatible polymers. Synthesis of carbohydrate polymers based on sugar, sorbitol, maize starch, acid anhydrides (phthalic and maleic) and small quantity of oxalic acid and citric acid has been attempted. The oxalic acid and citric acid have been specially used to study their effect on foam, detergency and stain removing characteristics. In this synthesis various catalysts like HCl, sodium bisulphate, sodium bisulphite have been used. The detergents made out of acid slurry cause harm aquatic flora and fauna. Acid slurry has a petroleum origin. The detergents are responsible for foaming and eutrophication. By using vegetable based polymers in detergent formulations the above mentioned problems of water pollution can minimized to greater extent. Material and MethodsPreparation of Novel Polymers: The synthesis of polymers was carried out in a glass reactor. The reactor consists of two parts. Lower part of the reactor is a round bottom vessel with very wide mouth. The upper part of the reactor is its lid, having four necks with standard joints. Motor driven stirrer was inserted in the reactor through the central neck, while another neck was used for thermometer. A Condenser was fitted with the reactor through the third neck. And the further neck was used for dropping the chemicals in to the reactor. The reactor was heated by an electric heating mantle having special arrangement for smooth control of the temperature of the reactor. A regulator controlled the speed of the stirrer. The reaction vessel and its lid were tied together with help of clamps. In our earlier experiments we have successfully prepared polymeric surfactants based on natural products of vegetable origin like maize starch, sorbitol, vegetable oils and glycerin in synthesis of polymeric surfactant along with acid anhydride like maleic and phthalic anhydride. These novel polymers have been successfully used in formulation liquid, powder and cake detergents as partial or total replacement of acid slurry of petroleum origin. Now in the present work we wish to incorporate sugar which is abundantly available throughout the world and small quantity of oxalic acid and citric acid which can step up the polymeric surfactants in reference to foaming, detergency and reduction of surface tention. Sugar on hydrolysis with water splits to glucose and fructose which are potential source of hydroxyl groups for additions of ingredients refer Neutralization of Polymers: The sample of polymer is taken in beaker and neutralized with 30% KOH solution are maintained at 60 C. with constant stirring till ph of 8.0 was achieved. Analysis of Polymers: Physicochemical analysis and Spectroscopic analysis for prepared polymers were undertaken. For physicochemical properties the standard techniques have been used to evaluate various conventional constants. Research Journal of Chemical Sciences _______________________________________________________ ISSN 2231-606X Vol. 1(6), 42-47, Sept. (2011) Res.J.Chem.Sci. International Science Congress Association 43 Preparation of Powder Detergent: The various ingredients and the composition of detergents powder are as shown in the formulations. The said ingredients in the powdered form are weighed and mixed thoroughly in a tray. Then add liquid ingredients like linear alkyl benzene sulphonate, Alpha olefin sulphonate and neutralized resin. Whole mass is then homogenized thoroughly. This mixture then added in a homogenizer pot. After mixing, the homogeneous mass thus obtained is taken out in a try and kept out in open air for drying. Preparation: A special type of Whitener is developed by addition of Titanium Dioxide (50%) and Sorbitol (50%) both these are taken in mortar and pestle, triturated for about 1 hrs. and then 1% of this mixture is added to the composition. Robin Blue paste is prepared by mixing robin blue and sorbitol in 1:1 praportion. This paste in added to the composition of powder detergents Results and Discussion Powder Detergents: In the synthesis of novel carbohydrate polymers ingredients products like sugar, starch and sorbitol have been used. Maize starch has been used in powder form while sorbitol and sugar can been used in liquid form. These compounds will provide OH groups for esterification and other reactions. Small quantity of citric acid and oxalic acid has been used. There presence in the polymers give better detergency to novel polymers. These compositions have come up after doing several polymers to develop a product with good viscosity, molecular weight and foaming property. These three are selected trials which give excellent performance properties a combination of HCl, sodium bisulphate, sodium bisulphite has been used in all formulation. The exact cooking schedule of three polymers is given in Table 2.The % yield in all the batches is of order of 90 to 94%. In various batches maleic anhydride has been used the possible chemical reaction are esterification of OH group in carbohydrate ingredients and acidic groups in maleic and phthalic anhydride. A small quantity of benzoic acid has been used as chain stopper citric acid and oxalic acid have been incorporated with a view of improving detergency. Conclusion Sorbitol, sugar and starch based surfactants can be used successfully for formulations of powder detergents. A combination of small amount of organic acids like oxalic acid, phthalic anhydride and citric acid in polymer give excellent properties for detergent formulations. Particularly use of oxalic and citric acid helps in improving detergency. Conventional activities can be replaced by these novel polymers to the extent of 50 to 90% without affecting detergency. The foam is normally adversely affected in many compositions. Sugar and starch can be used in combination with sorbitol, without affecting adversely the property of detergents. We can reduce the amount of petroleum based actives to the extent of 50-80% this is very important achievement. As we are formulating a product which is vegetable based. The use of 1% HCl as catalyst is giving positive results. The use of sodium bisulphate (1.5%) and sodium bisulphate (0.5%) give good color and homogeneity to product. The following samples have been identifies as excellent. PD1, PD3, PD4 and LD2, LD3. In formulation B1 a small quantity of benzoic acid which helps in regularization. AcknowledgementI am very thankful to Dr. B.B. Gogte and Dr.B.W. Phate because without their moral and valuable support nothing is possible. They are guiding me for writing this article. I am again thankful to Mr.Pravin Dhakite for his support. References1. Paolo zini, Polymeric Additives for high performing detergent, Technomic publication, U.S.A. (1995) 2. Bauvy A. and Leversidge P., Polymeric surfactants and their use industrial application paint India, 45-52(1985) 3. Polymeric surfactants Surfactant Science Series,(42)Marcel DekkerNew York, Marcel Dekker, Inc, New York, (1992),165-176, 203-205 (2003)4. http://www.Elesvier, “Carbohydrate polymer”. 5. Goddard, E.D., JOACS, 71(1), 1-15 (1994)6. Gogte B.B., Agarawal R.S., J. Soaps, Det. Toilet Rev.,19-2234 (2003) 7. Gogte B.B. and Sorbitol based polymeric surfactant for detergent powder, soaps detergents and toiletries, 25-28 (2003) 8. Gogte B.B., Patil P.V., J. Chem. Engg. World, (40),71-75 (2005) 9. Gogte B.B., Dontulwar J.R., Asia. J. Chem., 16(3),1385-1390 (2004) 10. Kharkate S.K,.Karadbhajne V.Y., Gogte B.B., Journal of scientific and industrial research, (64), 752-755(2005) 11. http://www.nfusugar.com 12. ASTM Standard method, (For acid value of organic coating materials), published by the American society for testing materials, Philadelphia, 1639-70 (1981) 13. BIS methods for the test for detergency for household detergent, BIS4995 (2000) Research Journal of Chemical Sciences _______________________________________________________ ISSN 2231-606X Vol. 1(6), 42-47, Sept. (2011) Res.J.Chem.Sci. International Science Congress Association 44 14. Haries,”Detergency Evolution and Testing “, Wiley-interscience Publisher, 92-103 (1954) 15. ASTM standard method for NON –volatile contains of resin solutions (1981)16 ASTM Standard methods, for viscosity by ford cup method,1200-82 (1982) 17 BIS methods for the test for detergency for household detergent, BIS4995 (2000) 18 Haries, Detergency Evolution and Testing, Wiley-interscience Publisher, 92-103 (1954)Table-1 Composition of Carbohydrate Polymers Ingredients Batch B1 Batch B2 Batch B3 Sorbitol (100%) 40.82 - 21.5 Maleic anhydride 3.92 - 3.6 Phthalic anhydride 1.56 4.1 1.4 Sugar (100%) 15.72 41.2 21.5 Maize Starch 7.85 - 26.9 Benzoic acid 0.82 - - Oxalic acid 3.92 4.1 3.6 Citric acid 3.92 - 3.6 glycerol - 32.9 - Water 21.41 17.7 17.8 % yield 90.2 92.36 94.08 All data is reported for 100% solids. Actually Sorbitol was used as 70% solids and Sugar was also used as 70% solids. HCl (1%) was used as catalyst in B1, B2 and B3 and Sodium bisulphate (1.5%) and sodium bisulphate (0.5) has been used as catalyst in all batches. Table-2 Cooking Schedule of Polymers (Temp. in °c measured after cooking period of sec.) Sr.no. Initial temp. Batch B1 Batch B2 Batch B3 1 After o min. 0 0 0 2 After 30 min. 80 80 80 3 After 60 min. 130 110 110 4 After 90 min. 130 130 130 5 After 120 min. 130 130 130 6 After 150 min. 130 130 130 7 After 180 min. 130 130 130 Table-3 Physico- Chemical Analysis of Novel Carbohydrate Polymers Sr. no. Test Batch B1 Batch B 2 BatchB3 1 %solid 91.09 91.45 96.5 2 Acid value 63 32.25 61.47 3 Viscosity(by ford cup no.4at 30c in seconds) 340 312 514 5 Solubility ( soluble in) water water Water 6 PH. value 3.92 3.25 4.83 7 Molecular weight 5179.14 4892.6 5186.4 8 Ester value 488 219.55 171.12 9 Epoxy value 14.40 28.02 13.83 Research Journal of Chemical Sciences _______________________________________________________ ISSN 2231-606X Vol. 1(6), 42-47, Sept. (2011) Res.J.Chem.Sci. International Science Congress Association 45 Table-4 Stain Removing Characteristics of Various Polymers Sr. No. Medium Batch B1 Batch B2 Batch B3 S.L.S. S.L.E.S. Acid slurry 1 Soil 91.90 93.06 92.65 81.66 85.6 85.3 2 Tea 86.48 78.37 85.32 79.25 77.94 79.51 3 Coffee 88.57 80 87.54 85.34 85.26 85.14 4 palak 92.5 80 92.51 91.57 90.87 91.47 Table-5 Powder Detergent Based on These Polymers Sr. No. Ingredients PD1 PD2 PD3 PD4 1 Our Polymer (B1) 10.52 18.86 10.30 14.81 2 Acid Slurry 1.04 - 1.02 2.40 3 A.O.S. 1.04 - 1.02 2.40 4 S.L.S. 5.26 4.71 5.15 4.81 5 Dolomite 31.57 27.30 29.91 27.92 6 Sodium carbonate 30.57 27.30 28.83 27.92 7 S.T.P.P. 4.26 4.71 5.15 4.81 8 Urea 3.15 2.73 3.08 4.81 9 Sodium Sulphate 5.26 4.61 5.10 2.79 10 E.D.T.A. 0.20 0.18 0.20 0.19 11 Whitener 4.00 6.27 7.11 5.04 12 % moisture 2.13 2.41 3.05 2.10 Total 100 100 100 100 *PD1, PD2, PD3, PD4 –All samples are based on our polymer (B1) Table-6 Analysis of Powder Detergents-at 1.0% conc. Sr.No. Powder detergent Foam volume in ( cm3)foam stability after 0,5,7,10 min. Density Surface tension Dynes/cm 1 PD1 900 0.9985 900 850 0.9985 30.93 2 PD2 950 0.9958 950 950 0.9958 36.28 3 PD3 1000 0.9985 950 950 0.9985 33.10 4 PD4 1000 0.9981 950 900 0.9981 35.58 5 CD1 1000 0.9996 1000 950 0.9996 62.11 6 CD2 1000 1.02 1000 950 1.02 62.35 Research Journal of Chemical Sciences _______________________________________________________ ISSN 2231-606X Vol. 1(6), 42-47, Sept. (2011) Res.J.Chem.Sci. International Science Congress Association 46 Table-7 Effect of Powder Detergent on %Detergency Soil Stain on polyester, tericot, and cotton cloth samples R0-Reflectance measured on clean cotton cloth = 100, Rs- soiled cotton cloth = 33 R0-Reflectance measured on clean polyester cloth = 100, Rs- soiled polyester cloth = 32 R0-Reflectance measured on clean tricot cloth = 100, Rs- soiled tricot cloth = 32 Sr. No. Powder detergent Conc.%Polyster Tericot Cotton detergency detergency detergency 1 PD1 0.1 91.17 83.82 92.53 2 0.25 94.11 86.76 92.53 3 0.5 95.58 92.64 95.52 4 1 97.05 92.64 95.58 1 PD2 0.1 94.11 80.88 92.53 2 0.25 94.11 85.29 95.52 3 0.5 97.05 89.70 95.58 4 1 98.52 94.11 97.05 1 PD3 0.1 86.76 85.29 92.64 2 0.25 91.17 86.76 95.52 3 0.5 94.11 92.64 95.52 4 1 95.58 94.11 95.58 1 PD4 0.1 82.35 80.88 85.29 2 0.25 85.29 83.82 86.76 3 0.5 86.76 85.29 88.23 4 1 88.23 86.76 89.70 1 CD1 0.1 88.23 91.17 86.76 2 0.25 91.17 94.11 89.70 3 0.5 94.11 95.58 92.53 4 1 95.58 97.05 92.64 1 CD2 0.1 91.17 85.29 82.08 2 0.25 92.64 89.70 85.07 3 0.5 95.58 94.11 89.55 4 1 97.05 98.52 92.64 Table-8 Composition of Selected Liquid Detergent Sr.No. Ingredients LD1 LD2 LD3 1 Acid Slurry 7.5 - - 2 Alpha Olefin Sulphonate 7.5 - - 3 Sodium laryl Sulphate 7.5 - 7.5 4 Sodium Laryl ether sulphate 10 10 10 5 Sodium Sulphate 5 5 5 6 Urea 3 3 3 7 Sorbitol 10 10 10 8 Water 49.5 49.5 49.5 9 Our Polymer (B1) - 22.5 15.0 10 TOTAL 100 100 100 LD1-based on original composition, LD2, LD3- based on resin B1 Research Journal of Chemical Sciences _______________________________________________________ ISSN 2231-606X Vol. 1(6), 42-47, Sept. (2011) Res.J.Chem.Sci. International Science Congress Association 47 Table-9 Analysis of liquid Detergents-at 1.0% conc. Sr.No. Liquid detergent Foam volume in ( cm3)foam stability after 0,5, 7,10 min. density Surface tension Dynes/cm 1 LD1 950 1000 1000 1000 0.8308 32.59 2 LD2 950 950 950 900 0.8325 32.64 3 LD3 1000 1000 950 950 0.8402 32.69 4 CLD1 1000 950 950 900 0.8356 32.15 5 CLD2 1000 950 950 950 0.8369 32.27 *CLD- Commercial Liquid Detergent available in the Market Table-10 Effect of Liquid Detergent on %Detergency Soil Stain on polyester, tricot, and cotton cloth samples R0-Reflectance measured on clean cotton cloth = 100, Rs- soiled cotton cloth = 33 R0-Reflectance measured on clean polyester cloth = 100, Rs- soiled polyester cloth = 32 R0-Reflectance measured on clean tricot cloth = 100, Rs- soiled tricot cloth = 32 Sr.No. Liq. detergent Conc.% Polyster Tericot Cotton detergency detergency detergency 1 LD1 0.1 86.76 83.82 91.04 2 0.25 88.23 85.29 94.02 3 0.5 89.70 86.76 94.11 4 1 91.17 88.23 94.11 1 LD2 0.1 86.76 83.82 91.04 2 0.25 91.17 80.88 91.17 3 0.5 92.64 82.35 94.02 4 1 95.58 91.17 94.11 1 LD3 0.1 85.29 82.35 94.11 2 0.25 89.70 86.76 91.04 3 0.5 91.17 91.17 91.17 4 1 94.11 94.11 94.02 1 CLD1 0.1 85.29 80.88 91.04 2 0.25 89.70 86.76 91.17 3 0.5 94.11 88.23 94.02 4 1 95.58 95.58 94.11 1 CLD2 0.1 85.29 88.23 95.58 2 0.25 88.23 92.64 83.82 3 0.5 91.17 94.11 88.23 4 1 94.11 95.58 94.11