Water soluble polymers 2002 amjad

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Water Soluble Polymers Solution Properties and Applications Edited by Zahid Amjad The B.F Goodrich Company Brecksville, Ohio Kluwer Academic Publishers New York / Boston / Dordrecht / London / Moscow eBook ISBN: Print ISBN: 0-306-46915-4 0-306-45931-0 ©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's eBookstore at: http://www.kluweronline.com http://www.ebooks.kluweronline.com To my wife, Rukhsana, for her patience and encouragement PREFACE This volume contains a series of papers originally presented at the symposium on Water Soluble Polymers: Solution Properties and Applications, sponsored by the Division of Colloids and Surface Chemistry of the American Chemical Society The symposium took place in Las Vegas City, Nevada on to 11th September, 1997 at the 214th American Chemical Society National Meeting Recognized experts in their respective fields were invited to speak There was a strong attendance from academia, government, and industrial research centers The purpose of the symposium was to present and discuss recent developments in the solution properties of water soluble polymers and their applications in aqueous systems Water soluble polymers find applications in a number of fields of which the following may be worth mentioning: cosmetics, detergent, oral care, industrial water treatment, geothermal, wastewater treatment, water purification and reuse, pulp and paper production, sugar refining, and many more Moreover, water soluble polymers play vital role in the oil industry, especially in enhanced oil recovery Water soluble polymers are also used in agriculture and controlled release pharmaceutical applications Therefore, a fundamental knowledge of solution properties of these polymers is essential for most industrial scientists An understanding of the basic phenomena involved in the application of these polymers, such as adsorption and interaction with different substrates (i.e., tooth enamel, hair, reverse osmosis membrane, heat exchanger surfaces, etc.) is of vital importance in developing high performance formulations for achieving optimum efficiency of the system A serious problem encountered in many industrial processes is the build-up of undesirable deposits on the walls of water handling equipment These deposits, especially on heat transfer surfaces in cooling, boiler, geothermal, and distillation systems, lead to overheating, loss of system efficiency, unscheduled shutdown time, and ultimately heat exchanger failure These deposits can be categorized into the following four groups: a) mineral scales (i.e., CaCO3, CaSO4•2H2O, CaSO4, CaF2, Ca3(PO4)2, etc.), b) suspended solids (i.e., mud or silt), c) corrosion products (i.e., Fe2O3, Fe3O4, ZnO, etc.), and d) microbiological mass In reverse osmosis systems, deposition of unwanted materials may result in poor water quality and premature membrane failure The development of deposits on heat exchanger and membrane surfaces continues to be a limiting factor in the efficient operation of the systems Thus, effective operation of industrial water systems continues to depend on the control of deposits in these systems In the past few years, polymers have been successfully used by the water treatment industry for numerous functions including scale inhibition, metal ion stabilization, crystal vii viii Preface modification, and dispersancy Polymers used in water treatment formulations are usually anionic and have molecular weight ranging from 500 to 20,000 daltons In wastewater treatment, high molecular weight polymer are used as flocculating and coagulating agents In cosmetics and hair care applications, the industrial chemist depends on the use of water soluble polymers to develop an aesthetically pleasing, functional, and stable product Polymers also offer unique opportunities in the controlled release of active from the formulated product In detergents use of polymers as builders is prevalent This volume provides an introduction to the use of water soluble polymers in many fields ranging from oral care, cosmetics, detergent, pharmaceutical, to industrial water treatment A wide range of expertise has been brought together to this book in such a diverse applications The first four chapters address the solution properties of polymers The next five chapters examine the growth and inhibition of hydroxyapatite, an important component of teeth, bones, and urinary stones In the next chapters use of polymers in industrial water and wastewater treatment applications is presented The final two chapters deal with the use of polymers in hair care and detergent applications I hope this book will prove to be a valuable addition to the library of the academic researchers and, even more so, for the technology-focused industrial scientist involved with polymers who are interested in expanding their applications into new fields Zahid Amjad Cleveland, Ohio ACKNOWLEDGMENTS I am grateful to all the contributors for their cooperation and hard work in preparing their respective chapters and to all those who made the symposium possible and this volume available Financial support of the national and international scientists is gratefully acknowledged Special thanks are extended to the American Chemical Society Division of Colloid and Surface Chemistry, ACS Corporation Associates, Avlon Industries, ColgatePalmolive Company, and The B.F Goodrich Company Their generous assistance contributed substantially to the success of the symposium I am thankful to Drs Michael M Reddy and Petros G Koutsoukos for serving as the various session chairmen, and to John Zibrida for his efforts in the selection of industrial speakers I want to give special thanks to Jeff Pugh for his efficient and organized handling of the considerable correspondence associated with both the symposium and the book I would like to thank the management of The B.F Goodrich, in particular Dr Victoria F Haynes, for encouragement and support in organizing this symposium and the editing of this volume Thanks are also extended to the editorial staff of Plenum Publishing Corporation, and especially to Susan Safren, for assistance during all stages of production of this book Finally, I would to thank my wife for contending with me during the several weekends I was finalizing the manuscript ix ABOUT THE EDITOR Zahid Amjad is a Research Fellow in the Advanced Technology Group of The B F Goodrich Company A native of Pakistan, he received his M.Sc in Chemistry from Panjab University and a Ph.D from Glasgow University, Scotland Dr Amjad was a Lecturer at the Institute of Chemistry of Panjab University, and was Assistant Research Professor at the State University of New York at Buffalo After spending years with Calgon Corporation, he joined The B.F Goodrich Company where he has served since 1982 Dr Amjad’s current major interests include biological and industrial applications of water soluble and water swellable polymers, interaction of polymers at solid-liquid interface, membranebased separation processes, and controlled-release of pharmaceuticals Dr Amjad has presented invited lectures at various national and international meetings, contributed to several books, and published numerous papers on the properties and behavior of water soluble and water swellable polymers, as well as on crystal growth and inhibition kinetics, control and removal of foulants from water purification apparatus—particularly membrane-based processes, and controlled release of actives He is holder of 28 patents and has edited three books He has been inducted into National Hall of Corporate Inventors, is the recipient of the 1997 EDI Innovation Award, and is a member of several professional organizations He is also on the Adjunct Faculty in Pharmaceutical Sciences at the School of Pharmacy, Northeast Louisiana University, Monroe, Louisiana 251 253 Index Terms AA: see Acrylic acid AA/AHPSE/PEGAE calcium phosphate scale inhibition and as clay dispersant agent Acrylamide, wastewater treatments and Acrylic acid characteristics of interfacial adsorption kinetics poly: see Poly(acrylic acids) 2-(Acryloyloxy)ethyltrimethylammonium chloride, wastewater treatments and Activation free energy Additives, crystallization kinetics and Adsorption activation energy and alumina powder diffusion control of electrostatic resistance to hydroxyapatite and hydroxyapatite crystal growth and hydroxypropylcellulose, on HAP kinetics of polyacrylic acid polymer: see Polymer adsorption of polyvinyl pyrrolidone on alumina of SDS on HAP of SPVPA to hydroxyapatite beads water-soluble macromolecules AIBN: see Azobisisobutyronitrile Alkaline hair relaxers Alumina, polyacrylic acid adsorption on Alumina powder adsorption Aluminum separation AMD-co-AETAC polymers characterization of flocculation experiments preparation of wastewater treatments and Amorphous silica Amphoteric acrylamide copolymers application to detergents preparation of Amphoterics Anhydrite scales, formation on heat exchanger surfaces Anionic polymers, examples of Antiscalants, silica Arrhenius expression Azobisisobutyronitrile Links 151 159 193 5 20 193 55 51 15 24 15 19 66 71 105 11 25 26 108 97 59 231 25 24 42 194 195 195 195 194 175 245 246 232 183 232 176 17 91 This page has been reformatted by Knovel to provide easier navigation 254 Index Terms Bacteria, attachment to saliva-coated beads Benzene hexacarboxylic acid, hydroxyapatite crystal growth and Boltzmann’s constant Borate–carbazole reaction, uronic acid and Boric acid, poly(vinyl alcohol) solubility and 1-Bromonaphthalene, surface tension of Brownian diffusion coefficient Calcite crystal growth Calcium carbonate formation in natural water inhibition by maleic acid copolymers Calcium carbonate crystal growth kinetic inhibition of organic inhibitors of relative inhibition of Calcium phosphate inhibitors, efficacy of Calcium phosphate nucleation on FEP on PMMA radiofrequency glow discharge and on silicone rubber Calcium phosphate scale, novel inhibitor of Calcium sulfate dihydrate scale, formation on heat exchanger surfaces Calculus, dental: see Dental calculus Capillary suction time Cationic polymers hair care and performance on sludge Cations, crystallization in presence of Chlorides, recycled water and Chondroitin sulphate, hydroxyapatite adsorption and Chromatography, high performance size exclusion Citric acid, hydroxyapatite crystal growth inhibition and Clay dispersant, AA/AHPSE/PEGAE as Colloidal particles, isolatiodseparation of Concentrated particulate suspensions Conformation: see Polymer concentration Constant composition Contact angle Cooling tower agricultural waste in biologically treated wastewater in boiler blowdown in boiler condensate in Links 95 77 18 64 34 58 124 136 132 117 119 131 131 122 150 59 59 59 59 149 183 200 233 202 58 221 71 196 84 159 193 23 56 57 214 215 216 216 This page has been reformatted by Knovel to provide easier navigation 255 Index Terms Cooling tower (cont.) low TDS water municipal wastewater in reuse of blowdown scale formation in scrubber blowdown in seawater and side-stream softening wet dry Cooling water treatment calcium phosphate scale optimization in recycled waters Copolymers of acrylic acid characterization of HMPAAs and maleic acid of pyreneacrylamide Corrosion control in recycled water control of Corrosion inhibitors molybdate/phosphonate molybdate/zinc orthophosphate zinc Cosmetics industry, water-soluble polymers in Crosslink density, in HMPAAs Crystal growth calcite hydroxyapatite: see Hydroxyapatite crystallization impurities and organophosphonate inhibition of polyelectrolytes and in pure solution pyrophosphate inhibition of of SPVPA Crystalline structure, of poly(vinyl alcohol) gels Crystallinity optimal freezing times and of poly(vinyl alcohol) Crystallization cations and of gypsum hydroxyapatite: see Hydroxyapatite crystallization of hydroxyapatite in presence of additives/impurities PVA gels and thermodynamics of Links 216 214 212 118 214 215 210 210 149 207 195 120 207 149 218 218 218 219 219 231 20 136 52 78 120 52 78 92 35 37 36 58 183 65 54 32 52 This page has been reformatted by Knovel to provide easier navigation 236 A N Syed et al Table Detangling shampoo with Polyquatemium- 10 Ingredients Percentage Deionized water Methylparaben Imidazolidinyl urea Disodium EDTA Polyquatemium- 10 Sodium lauryl sulfate Disodium cocoamphodipropionate Trideceth-7 carboxylic acid Lauramide DEA Glycol stearate Fragrance 75.00 0.20 0.30 0.20 1.50 3.50 8.00 7.00 3.00 1.00 0.30 Figure Cationic polyamine Hair relaxers change one-third of the disulfide bonds to lanthionine bonds using 2.0 to 2.4 percent sodium hydroxide in oil-in-water emulsion.19 The chemical changes that take place in the hair lead to a decrease in tensile strength by approximately 50% in the wet state.20 Hair damage during relaxing is not restricted to disulfide bond breakage alone The alkaline hair relaxer leads to an increase in hair swelling intensified by concurrent Figure Hydrogenated starch hydrolysate Water-Soluble Polymers in Hair Care 231 Figure Cross section of hair fiber breakdown of disulfide bonds.21 Rinsing with water produces additional swelling due to osmotic forces, because there is a lower salt concentration outside the fibers at this stage of a chemical process.22 It has been the objective of our study to utilize water-soluble polymers to prevent or repair damage in relaxed hair by increasing the tensile strength and reducing swelling during relaxing EXPERIMENTAL AND RESULTS 4.1 Increasing the Strength of Relaxed Hair with a Cationic Polymer The tensile strength loss of hair fibers treated with a hair straightening formula containing a cationic polyamine, such as the polyamine shown in Figure 7, versus a control A N Syed et al 238 Figure 10 Cuticles of the hair Figure 11 Cortex of the hair Water-Soluble Polymers in Hair Care 239 relaxer without polymer was tested Twelve inch long, dark brown European hair was obtained from DeMeo Brothers, New York The hair fibers were washed with a 10% solution of ammonium lauryl sulfate, rinsed thoroughly, and allowed to dry overnight Fibers of close diameter (71–80 microns) were selected for this study Each fiber was cut in half and crimped into 30 mm sections using a Dia-Stron Crimp Press The hair section closest to the root was designated as the control, and the section downstream was used for the experimental relaxer The tensile strength of the untreated hair fibers under wet conditions was measured utilizing a Dia-Stron Miniature Tensile Tester, Dia-Stron, Ltd., U.K The strength was determined by the amount of work required to extend the fibers 20% of their original length at a rate of 10.0 mm/min The hair fibers were then allowed to restore overnight in water The following day, the fibers were dried at 65% relative humidity and 21°C prior to treating with relaxers The control group was treated with hair relaxer without polymer, and the experimental group was treated with relaxer containing a cationic polyamine Both sets were processed identically for 18 minutes, followed by rinsing, and then shampooing with a mild, acidic shampoo The following day, the tensile strength of treated fibers was determined same as above using Dia-Stron MTT The F20 index loss was then calculated Table shows that hair treated with Control Relaxer without Polymers exhibited an F20 index loss of 50.94%, whereas, hair treated with Relaxer containing cationic Polyamine exhibited an F20 index loss of 45.11 %.-a statistically significant difference Table shows a prototype formulation of a hair relaxer containing cationic strengthening ingredients 4.2 Minimizing Swelling during Hair Relaxing In addition to strengthening the hair while relaxing by forming a complex in the hair, we have discovered that water-soluble polymers, especially non-ionic polymers such as starch hydrolysates, reduce the swelling of the hair during relaxing During the process of relaxing, the hair swells up to 50% or more of its original diameter Upon rinsing with water, the hair suddenly swells another 20 to 30% because of a sudden surge of osmotic pressure inside the hair fibers Much of the damage from swelling occurs during rinsing because the swelling is very rapid The hair fibers develop radial and longitudinal cracks when swelling is not controlled Figure 12 shows radial cracks and Figure 13 shows longitudinal cracks in hair fibers caused by swelling in an alkaline solution The swelling studies were performed using a LaserMike laser micrometer which measures the major and minor axis of the fiber simultaneously LaserMike laser micrometer was purchased from LaserMike in Dayton, Ohio European hair, available from DeMeo Brothers, with a uniform diameter of 71–80 microns was selected for this study The original diameter of dry hair was measured under controlled conditions of 65% relative humidity and 21°C Fibers were then immersed in relaxer for 18 minutes After 18 minutes, excess relaxer was gently removed and the diameter again measured The diameter measurements were continued through the rinsing phase Figure 14 shows a graph comparing hair fiber swelling in relaxer without polymer versus with non-ionic polymer starch hydrolysate Hair fibers treated with the control relaxer exhibited swelling of 45.21% at 18 minutes in relaxer, and peaked at 80.82% when rinsed with water Hair fibers using cream relaxer with polymer swelled to 19.78% before rinsing, and 38.46% upon rinsing Therefore, hair fibers treated with relaxer containing non-ionic polymer exhibit significantly less swelling compared to relaxers without polymers An example of a relaxer with deswelling ingredients is shown in Table 240 A N Syed et al Table Effect of cationic polymers in hair relaxer Control fibers treated with relaxer without polymer Hair fiber # Initial work* I 1.15 1.39 1.50 1.47 1.47 1.37 1.27 10 1.40 11 0.94 12 1.18 13 1.09 14 I 43 15 1.17 16 1.30 17 0.92 18 0.99 19 1.29 20 1.22 22 1.17 23 1.41 25 1.12 Average Standard deviation Coeff of variance *Work done is in millijoules Work* after F20 loss % 0.54 0.69 0.71 0.66 0.79 0.61 0.60 0.77 0.43 0.46 0.52 0.69 0.61 0.73 0.41 0.50 0.68 0.63 0.61 0.73 0.54 53.04 50.58 52.40 54.97 46.12 55.69 53.15 45.00 53.99 60.93 52.39 51.47 47.61 43.62 55.05 49.50 47.52 48.20 48.29 48.58 51.61 50.94 4.10 8.05 Experimental fibers treated with relaxer containing polyamine Hair fiber # Initial work* 10 11 12 13 14 15 16 17 18 19 20 22 23 25 Work* after F20 loss % 1.04 1.64 1.44 1.19 1.43 1.29 1.27 1.25 0.82 1.11 1.01 1.37 1.07 1.16 0.96 0.99 1.21 1.24 1.10 1.09 1.05 0.51 0.95 0.82 0.67 0.84 0.64 0.71 0.76 0.43 0.56 0.59 0.77 0.68 0.65 0.45 0.62 0.66 0.69 0.62 0.51 0.52 50.67 42.07 43.13 43.87 41.12 50.70 44.41 39.44 47.43 49.37 41.68 44.01 36.92 44.31 52.51 38.00 45.54 44.52 43.91 52.94 50.76 45.1 4.64 10.28 When used in combinations, relaxers containing combinations of deswelling and strengthening polymers leave the hair visibly and measurably healthier Table shows tensile strength results of hair treated with relaxer containing polymers versus a control relaxer without polymer Figure 15 shows a scanning electron micrograph of a hair fiber treated with relaxer containing strengthening and deswelling polymers (reproduced with permission from Avlon Industries) The cuticles lay flat, and there are no visible cracks in the structure Table Hair relaxer formulation containing cationic strengthening polymers Ingredient Petrolatum and/or mineral oil Fatty alcohols and/or emulsifying wax Emulsifiers Simethicone Lanolin Deionized water Propylene glycol Cationic polyamine (50%) Sodium hydroxide Percentage 30.0 to 35.0 6.0 to 10.0 2.5 to 4.0 0.1 0.5 46.4 to 56.9 5.0 2.0 2.2 Water-Soluble Polymers in Hair Care 241 Figure 12 Radial cracks in hair fiber (Reproduced with permission from Avlon Industries All rights reserved.) Figure 13 Longitudinal cracks in hair fiber (Reproduced with permission from Avlon Industries All rights reserved.) 242 A N Syed et al Figure 14 Hair swelling by relaxer with nonionic polymer CONCLUSIONS A series of cationic polyamines and starch hydrolysates, when used at certain levels separately and in combinations, control the swelling and enhance the strength of relaxed hair The theory is that during the relaxing process, hair is swollen to a maximum degree and the cuticle layers are widely open at this stage The cationic polyamines are able to penetrate into the cortex Upon rinsing the hair with water, as the hair deswells, the cationic polyamines are trapped in the cortex of the hair, as well as ionically bonded to the negative sites on the surface of the hair Since cationic polyamines are very elastic, they improve the elasticity and tensile strength of the relaxed hair fibers While cationic polyamines are penetrating inside the hair, the polymeric starch hydrolysates present in high concentration around and outside the hair fiber are able to reduce the osmotic pressure inside the hair, thereby reducing the swelling of hair fibers significantly This reduction in swelling helps to prevent longitudinal and radial cracks in the hair fibers The combination of deswelling and strengthening polymers results in healthier relaxed hair Table Relaxer formulation with polymeric deswelling agent Ingredient Petrolatum and/or mineral oil Fatty alcohols and/or emulsifying wax Emulsifiers Simethicone Lanolin Deionized water Propylene glycol Hydrogenated starch hydrolysate Sodium hydroxide Percentage 30.0 to 35.0 6.0 to 10.0 2.5 to 4.0 0.1 0.5 46.4 to 56.9 5.0 2.0 2.2 Water-Soluble Polymers in Hair Care 243 Table Tensile strength of hair treated with relaxers containing polymers Experimental no-base relaxer with polyamine and starch hydrolysate Control no-base relaxer without polymers Hair Initial work* 1.24 1.16 1.33 0.87 1.10 0.80 12 1.27 15 1.36 16 1.33 20 08 21 0.98 22 1.03 23 1.29 25 1.07 Average Standard deviation Coeff of variance Work* after %F20 loss 0.65 0.61 0.70 0.37 0.60 0.41 0.73 0.68 0.64 0.54 0.57 0.46 0.58 0.44 47.82 47.59 47.22 58.05 45.82 48.25 42.91 49.85 51.58 50.37 41.78 55.34 55.43 59.07 50.08 5.29 10.57 Hair 12 15 16 20 21 22 23 25 Initial work* Work* after %F20 loss 1.24 1.18 1.24 0.77 0.99 0.81 1.23 1.40 1.39 1.13 0.97 0.98 1.16 0.93 0.66 0.68 0.69 0.41 0.61 0.49 0.83 0.81 0.80 0.68 0.55 0.64 0.69 0.47 46.45 42.80 44.19 46.36 38.38 39.83 32.85 42.43 42.45 40.00 43.45 34.55 40.52 49.84 41.72 4.56 10.93 *Work done is in millijoules Figure 15 Hair fiber treated with relaxer containing deswelling and stregthening polymers 244 A N Syed et al REFERENCES Zviak C The Science of Hair Care Marcel Dekker, Inc., New York, 1986 Syed AN “Composition for Decreasing Combing Damage to Hair and Method”, U.S Patent Application 08/267,829 1993 Syed AN “Hair Strengthening Composition”, U.S Patent 5,639,449 1997 Carbopol Product Information Sheet, B.F Goodrich, Brecksville OH Syed AN Hair and Hair Care D H Johnson (Ed), Marcel Dekker, Inc., New York, 1997 Resyn 28–1310 Product Information Sheet, National Starch and Chemical Corporation, Specialty Polymers, Bridgewater NJ Amphomer® Product Information Sheet, National Starch and Chemical Corporation, Specialty Polymers, Bridgewater NJ National Starch and Chemical Corporation Formulary, National Starch and Chemical Corporation, Specialty Polymers, Bridgewater NJ Zviak C The Science of Hair Care Marcel Dekker, Inc., New York, 1986 10 Syed AN and Khalil EN, “Low Irritant Conditioning Shampoo Composition”, U.S Patent 4,205,063 1980 11 Syed AN and Khalil EN, Stable Hair Relaxer, U.S Patent 4,390,033 1983 12 UCARE Polymer Product Information Sheet, Amerchorp Corporation, Edison NJ 13 Syed AN, “Composition for Decreasing Combing Damage to Hair and Method”, U S Patent Application No 08/267/829 1994 14 Gerstein T, U.S Patent 3,990,991 1976 15 Syed AN and Ahmad K, Hair Strengthening Composition and Method, U.S Patent 5,639,449 1997 16 Syed AN and Ahmad K, “Composition and Process for Decreasing Hair Fiber Swelling” US Patent 5,348,737 1994 17 Robbins CR, Chemical and Physical Behavior of Human Hair, 3rd Edition Springer Verlag, New York, 1994 18 Swift JA, “A Course on Advanced Structure and Chemistry of Hair”, Society of Cosmetic Chemists Continuing Education Program, Elizabeth NJ, 1996 19 Epps J and Wolfram LJ, Letter to the Editor Journal of the Society of Cosmetic Chemists, 1983;34:213214 20 Syed AN, “Ethnic Hair Care: History, Trends and Formulation” Cosmetics & Toiletries, 1993; 108:99–107 21 Wolfram LJ, Hair Research: Status and Future Aspects, C E Orfanos, W Montagna, and G Stuttgen (Eds), Springer-Verlag, New York, 1981, 22 Robbins CR, Chemical and Physical Behavior of Human Hair, 3rd Edition Springer Verlag, New York, 1994 19 APPLICATION OF ULTRA-HIGH MOLECULAR WEIGHT AMPHOTERIC ACRYLAMIDE COPOLYMERS TO DETERGENTS Yoshiyuki Hayashi,1 Danian Lu,1 and Nobuo Kobayashi2 Faculty of Engineering and Design Kyoto Institute of Technology Matsugasaki, Kyoto 606 Japan 2Espo Co Ltd., 1-280-2 Takeishi Hanamigawa-ku, Chiba 262 Japan 1 ABSTRACT Ultra-high molecular weight (5–17 × 106 daltons) amphoteric copolymers prepared from acrylamide, acrylic acid, N-(dialkylaminomethy1)- and/or N-(trialkylammoniomethy1)acrylamide are shown to be excellent finishing agents for natural fibers and superior to the finishing agents prepared from natural resources such as hyaluronate and xanthan gum The detergents containing the copolymer, inorganic builders and a small amount of penetrating agent showed detergency comparable to commercial detergents INTRODUCTION The envelopes of bacteria are extremely complex The innermost layer of the envelope is always a phospholipid bilayer into which many functionally distinct proteins are inserted Surrounding this “cytoplasmic facing membrane” is a rigid shell of covalently linked peptidoglycan.1 From the glycans, a variety of carbohydrates are isolated and used for finishing agents of fibers, such as hyaluronic acid, xanthan gum and chitosan Ultra-high molecular weight amphoteric copolymers have been reported to be excellent deodorant components.2 Other polymers which have been used as components in deodorants include natural anionic polymers such as hyaluronic acid and xantham gum In the last few years, a large variety of hydrophilic polymers have been evaluated as builders for detergent formulations but only a few (notably carboxymethyl cellulose, CMC, polyacrylic acid, PAA, and acrylic acid/maleic acid based copolymers) are used commercially Water Soluble Polymers, edited by Amjad Plenum Press, New York, 1998 245 246 Y Hayashi et al Table Properties of the polymer solution Copolymer A B C Nonvolatile PH 0.47 9.7 0.50 8.9 1.00 6.7 Ultra-high molecular weight amphoteric acrylamide copolymers are excellent finishing agents for fabrics Thus, these polymers can be added to softening ingredients for laundering In this study, we have examined the detergency of formulations containing ultra-high molecular weight amphoteric polymers EXPERIMENTAL 3.1 Preparation of the Polymers Acrylamide and acrylic acid were free-radically copolymerized in water and the solution was neutralized with an aqueous solution of sodium hydroxide The Mannich reaction of a copolymer was carried out in an aqueous solution with formaldehyde and dimethylamine, affording N-(dimethylaminomethyl) cationic radical Three different polymer solutions (A,B,C: the ratio of acrylamide: acrylic acid: dimethylaminomethylacrylamide, 80: 15:5, 80: 10: 10 and 90: 10:0, respectively) were prepared and properties of the solution are shown in Table Although the exact molecular weight or molecular weight distribution of the polymer was not available, the estimated molecular weight (calculated from viscosity data) was more than ten million daltons 3.2 Deodorant Textiles Treated with an Aqueous Solution of Copolymer B Contamination of the textiles with cigarrete smell was carried out in an artificial smoking device Cat urine / ethanol solution was sprayed on the textile in a sealed bottle Table Antismelling effect of several polymers to tobacco smell on absorbed wool serge suiting (0.0 % owf as solid) Polymer Untreated fabrics absorbed tobacco smell High molecular weight polyvinyl alcohol (M.W.: 123,000) Sodium salt of polyacrylic acid Nonionic polyacrylamide (M.W.: 17,000,000) Crude amphoteric polyacrylamide Anionic polyacrylamide (M.W.: 6,000,000) Cationic polyacrylamide (M.W.: 3,000,000) Anionic polyacrylamide (M.W.: 17,000,000) Sodium hyaluronate (M.W.: 3,000,000) Xanthan gum Amphoteric polyacrylamide B Fabrics scoured Oscillator count difference 18 31 22 17 16 16 12 12 10 247 Ultra-High Molecular Weight Amphoteric Acrylarnide Copolymers After the contaminated texiles were dried in a fresh air for four hours, the textile was placed in a sealed bottle, where the concentration of the volatile organic compounds was estimated using a biomimetic sensor The results are shown in Tables to 3.3 MnO2 Dispersion Dispersion of MnO2 (0.04g) in a 0.05% builder aqueous solution (100 mL) was shaken vigorously for minutes After letting stand for 1hour, the concentration of MnO2 in the upper aqueous layer was analyzed The results are shown in Table 3.4 Detergency Swatches were soaked with an artificial soil aqueous suspension consisting of channel carbon black (5g), tomato ketchup (30g), mayonnaise (30g) in a Aerosol OT (5g) and dried The soiled swatches were washed in a home laundry machine RESULTS AND DISCUSSION Consumer concerns about the use of synthetic compounds prompted us to develop new finishing agents from natural resources We found that well-designed synthetic polymers can exhibit excellent properties as deodorant and coagulant, comparable or superior to that of natural polymers.2 The deodorancy efficiency shown by amphoteric acrylamide copolymers was found to be highly dependant on the molecular weight An average molecular weight of less than 100,000 daltons resulted in minimal deodorizing effect Those having a viscosity of at least 3,000 centipoises (corresponding to greater than 106 daltons) showed an excellent deodorizing effect The number-average molecular weight was determined by measuring the viscosity of the 1% aqueous solution of the polymer with a Brookfield viscometer using a No.2 rotor, at 20°C Viscosities of at least 1,000 centipoise roughly correspond to number average molecular weight of at least 1,000,000 dalton Although high molecular weight polymers show excellant deodorizing power, optimal performance can be achieved by combining the polymers with other ingredients such as low molecular weight organic acids, hypochlorite, carbonates, surfactants, etc Deodorant swatches have been examined on the basis of: a) rate of absorption of malodorous compounds, b) weight of absorbed malodors, c) rate of release of the absorbed malodors, d) weight of malodors released after leaving the malodorous environment by a definite time, and e) rate and/or weight of deposition of malodors Immobilized vesicle bilayers deposited on quartz crystal oscillator adsorbed malodors and adsorbability is comparable to that of biological organs The adsorbability of the artificial bilayer is highly dependent on humidity of the environment Under strictly defined conditions, the oscilla- Table Deodorant effects on silk fabrics (Tirimen) Untreated fabrics Polymer B* Tobacco smell emitted Cat urine smell emitted Sexually excited male cat smell emitted 29 16 25 248 Y Hayashi et al Table Deodorant effects on the exhaust gas from a city sewage plant (ppm by volume) At 20 °C Untreated malodorous gas Spraying fresh water Spraying the polymer soli At 28 °C Untreated malorodrous gas Spraying fresh water Spraying of the polymer sol-n NH3 (CH3)3N CH3SH H2S Panel 17 0 19 0 12.0 7.8 0.5 11 6.2 0.2 9800 5800 1740 65 18 74 21 15 15 13 tor showed to be an excellent counter for determination of the very dilute concentration of malodors Recently, the Japan Chemical Fiber Association (JCFA) issued tentative procedure for the estimation of deodorancy using malodors (such as ammonia, hydrogen sulfide and acetic acid) According to the the JCFA protocol, our polymer based deodorant formulations did not show positive results After exposing the fabrics to a malodorous atmosphere, the apparels should not release malodors when removed to fresh air for hours The results are shown in Tables to The data in Tables and show the oscillator count differences between the smellabsorbed fabrics and control fabrics We found that the oscillator count difference data was in fair agreement with those of the JEPA recognized triangle method of odor determination Spraying a dilute solution of the amphoteric polyacrylamide containing a small amount of surfactants and inorganic salts showed superior deodorant effects (Table 4) Spraying the dilute polymer solution into a suspension of soot from combustion of styrene flocculated the soot These results suggest that the amphoteric polymer trapped malodors and kept them in the film of the polymer Toxicity tests of the polymers showed none of mutagenic activity, dermal irritation, and germinative and growth influence The polymers were easily decomposed by bacteria in a aqueous solution, while silk and cotton fabrics treated with the polymer above 0.3% owf completely suppressed growth of bacteria Antistatic property of PET (tropical) fabrics treated with the polymer B is shown in Table 5, and the polymer C is clearly shown to be good antistatic agent for polyester As mentioned above, a small amounts of the polymers gave favorable effects on the treated fabrics We examined the effects of the polymer in the presence of detergents It is well known that washing efficiencies of detergents containing builders correlate with Ca2+ sequestering capacities and dispersing power for MnO2 The overall suspending power of surfactants and builders is a function of the concentration and generally shows at least one optimum and varies with the presence of other ions.4–6 The suspending power for MnO2 of the polymer A and C is shown in Table e Table Antistatic property of PET Control Polymer C (0.02% owf) Polymer C (0.2% owf) JIS L 1094 A method (half-value period, s) JIS L 1094 B method (frictional voltage, v) 38 24 –326 –230 –111 249 Ultra-High Molecular Weight Amphoteric Acrylamide Copolymers Table The suspending power of MnO2 (ppm) Conc of builder(ppm) Builder No builder Polymer A Polymer C Sodium acrylate Sodium tripolyphosphate 200 150 100 50 25 10 18 24 20 38 22 33 27 32 11 13 24 30 15 23 13 21 Table A new detergent recipe Chemicals weight (g) Ingredient Sodium Metasilicate Coplymer C 0.3% aq Soh Sodium Sulfate (+ polymer C 0.15g) Sodium Percarbonate Zeolite Megafack F 179* Sodium Oxalate EDTA 579 50 250 100 10 *A fluorocarbon penetrating agent (Dic Co.) The dispersancy of polymer C is slightly better than that obtained with polymer A but the suspension of the either polymer is considerably better than the conventional builder.4 The polymers may act as a flocculant at high concentrations (500 ppm) but the optimum concentration for deodorancy is several orders of magnitude lower and, at these concentrations, the suspending power is superior to conventional builders Additionally, the Ca2+ sequestering capacity of the polymer was found to be very low but the calcium suspension was stable compared to conventinal sequestering agents We examined several recipes of detergents containing the polymers and inorganic builders A starting recipe (Table 7) without conventional anionic surfactants showed good detergency compared to that of commercial laundry detergents (Table 8) Incorporation of enzymes and fatty soaps in the detergent also improved the detergency The prevention of soil redeposition is a critical factor for a good detergent.7 The redeposition may be prevented by the stabilization of solid soil particle in aqueous phase or by changing the hyrophilic of the soiled surface The ultra-high molecular weight polymer Table Detergency of the new recipe detergent Laundry temp (°C) 20 60 80 *Attack (Kao Co.) Recovery of whiteness (%) New detergent Commercial* 45 62 82 52 60 68 250 Y Hayashi et al was a good suspension-stabilizer and soil-releasing agent on fabrics Thus, both properties improve the overall performance of the detergent When an aqueous solution of the polymer was mixed with anhyrous sodium sulfate powder, it was absorbed into the powder Thus it is possible to formulate a powdered detergent containing the polymer (Table 7) REFERENCES J.D Watson et al (ed.), “Molecular Biology of The Gene”,The Benjamin,1987;1: 104 USP4,909,986 (Mar 20, 1990) lwasaki Y, “Olfactory Malodor Determination Method”, J Pollution Control Society, 1978; 13:246 Yoshio Abe et al., YUKAGAKU, 1981;30:757 T Fujimoto (ed)., Introduction to Polymer Chemicals (in Japanese), Sanyou Chemical Ind., Kyoto, 1992:765 Schwartz AM, and Perry JW, Surface Active Agents, Interscience, 1949 Schwartz AM et al., Surface Active Agents and Detergents, Interscience, 1958 ... discuss recent developments in the solution properties of water soluble polymers and their applications in aqueous systems Water soluble polymers find applications in a number of fields of which... care, industrial water treatment, geothermal, wastewater treatment, water purification and reuse, pulp and paper production, sugar refining, and many more Moreover, water soluble polymers play vital... has served since 1982 Dr Amjad s current major interests include biological and industrial applications of water soluble and water swellable polymers, interaction of polymers at solid-liquid
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