Quaternary Ammonium Salts As Antistatic Agents On
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QUATERNARY AMMONIUM SALTS AS ANTISTATIC AGENTS ON POLYACRYLONITRILE FIBERS A THESIS Presented to The Faculty of the Graduate Division by Phillip Jeffrey Wakelyn In Partial Fulfillment of the Requirements for the Degree Master of Science in the A. French Textile School Georgia Institute of Technology June 1967 In presenting the dissertation as a partial fulfillment of • the requirements for an advanced degree from the Georgia Institute of Technology, I agree that the Library of the Institute shall make it available for inspection and circulation in accordance with its regulations governing materials of this type. I agree that permission to copy from, or to publish from, this dissertation may be granted by the professor under whose direction it was written, or, in his absence, by the Dean of the Graduate Division when such copying or publication is solely for scholarly purposes and does not involve potential financial gain. It is under stood that any copying from, or publication of, this dis sertation which involves potential financial gain will not be allowed without written permission. J-V -r- b QUATERNARY AMIWDNIUM SALTS AS ANTISTATIC AGENTS ON POLYACRYLONITRILE FIBERS Approved T" Date Approved by Chairman: ^ ^50 ' 6 / 11 ACKNOWLEDGMENTS The author is grateful to the Stribling Foundation for the financial aid which it has extended over the past year and one half, and to Dr. James L. Taylor for his support and assistance in securing this fellowship. The author wishes to express his appreciation to Mr. R. B. Belser and Mr. J. C. Meaders for their assistance on the fiber-to-fiber fric- tional work, to Dow Badische Company for furnishing the fiber and to James Simmons for furnishing the yarn and for consultation on textile processing. Special thanks are extended to the author's advisor. Dr. Ulrich Meyer, for his enthusiastic support and timely suggestions during this work. Thanks also goes to Mr. Frank Clark for graciously giving of his time for service on the reading committee. Appreciation also goes to Mr. W. Boteler for his service on the reading committee. Finally, the author wishes to acknowledge the effort exerted by Dr. Taylor and Dr. Johnson over the past years to acquire the laboratory facilities used in this research. Ill TABLE OF CONTENTS Page ACKNOWLEDGMENTS ii LIST OF TABLES vi LIST OF ILLUSTRATIONS vii SUMMARY xi CHAPTER I. INTRODUCTION 1 1.1 General 1.2 Nature and Generation of Static 1.3 Measurement of Static 1.4 Chemistry of Quaternary Ammonium Salts 1.4.1 General 1.4.2 Stereochemistry 1.5 Cationic Surfactants Used as Antistatic Agents 1.6 Antistatic Finishes And How They Function 1.7 Cationic Amphipathic Electrolytes in Aqueous Solution 1.8 Orientation Of The Antistatic Agent on The Fiber II. MATERIALS, EQUIPMENT AND INSTRUMENTATION 21 2.1 The Substrate 2.1.1 Chemical Composition 2.1.2 Polymerization of PAN 2.1.3 Spinning 2.1.4 Miscellaneous 2.2 Chemicals Used in Obtaining the Compounds 2.3 Instruments Used 2.3.1 Yarn Finish Applicator 2.3.2 Fiber-to-Fiber Friction 2.3.3 Yarn-to-Guide Friction 2.3.4 Static Build-up 2.3.5 Miscellaneous III. EXPERIMENTAL PROCEDURES 37 3.1 Preparation and Purification of the Compounds 3.1.1 General Remarks 3.1.2 Synthesis 3.1.3 Purification of Commercially Available Compounds iv TABLE OF CONTENTS (Cont.) Page 3.2 Purification of the Staple Fibers 3.3 Purification of Yarns 3.4 Application of Antistatic Agent to the fiber (staple) 3.5 Application of the Finishes (to Yarn) 3.6 Fiber-to-Fiber Friction 3.6.1 Testing Procedure 3.6.2 Interpretation of Data 3.7 Fiber to Guide Friction Determination 3.7.1 Testing Procedure 3.7.2 Interpretation of Data 3.8 Measurements of Static Electricity on the Web in the Carding Process 3.8.1 Method 3.8.2 Interpretation of Data 3.9 Determination of Conductivity in Solution 3.10 Determination of Whether a Solution was Above or Below Critical Micelle Concentration (CMC) 3.11 Measurement of Per Cent Moisture IV. DISCUSSION OF RESULTS 58 4.1 Effect of Molecular Structure 4.1.1 Static Build-up 4.1.2 Yarn-to-Guide Friction 4.1.3 Fiber-to-Fiber Friction 4.1.4 Conductivity in Aqueous Solution 4.1.5 Moisture Regain of the Fiber Plus Finish 4.2 Effect of the Different Parameters on Static Build-up V. CONCLUSIONS 91 5.1 General 5.2 Specific IV. RECOMMENDATIONS 93 APPENDICES 95 A. SYNTHESIS OF HIGHER MOLECULAR WEIGHT QUATERNARY AMMONIUM SALTS 96 B. INFRARED SPECTROSCOPY OF FATTY QUATERNARY AMMONIUM COMPOUNDS 101 C. THIN LAYER CHROMATOGRAPHY (TLC) OF FATTY QUATERNARY AMMONIUM COMPOUNDS 106 D. DYEING TECHNIQUE FOR OBSERVING THE FINISH 110 TABLE OF CONTENTS (Cont) Page E. DETERMINATION OF CRITICAL MICELLE CONCENTRATION (CMC) BY USE OF DYES 112 F. YARN-TO-GUIDE FRICTION 117 BIBLIOGRAPHY 118 VI LIST OF TABLES Table Page 1. Compounds Used in This Thesis 3 2. Important Infrared Bands of the Compounds Used 38 3. Physical Properties of the Compounds Used 39 4. R- Values for TLC of the Compounds Used 40 5. Solutions Used to Apply Finish to Staple Fiber 46 6. Solutions Used to Apply Finish to Yarn 49 7. Static Field Strength and Moisture Regain of the Fiber Plus Finish 63 8. Frictional Properties of the Fiber Containing the Different Finishes 68 9. Solution Properties of the Compounds 75 Vll LIST OF ILLUSTRATIONS Figure Page 1. Pyramidal Structure of Trialkyl Amine 7 2. Different Steric Forms of Nitrogen 7 3. Stereo Structure of Quaternary Ammonium Salts 8 4. Physical Property Curves for Amphipathic Electrolytes. 16 5. Effect of Temperature and Concentration on Viscosity of Sodium Dodecyl Sulfonate Solution 17 6. Finished Fibers in a Benzene/Water Mixture 20 7. Wet Spinning Unit. 24 8. The Application Tube of the Atlab Finish Applicator. ... 28 9. Atlab Finish Applicator. 28 10. Rothschild F-Meter and 4-Channel Recorder 30 11. Picture of Rothschild Measuring Heads as Used in This Work 30 12. Schematic of the Yarn Going Over the Rothschild Measuring Heads and Frictional Surface 31 13. "Field Mill" Measuring Head Mounted on the "Shirley" Miniature Card 32 14. Bergischer Rotating Electrostatic Field-Strength Measuring Instrument and Rothschild Recorder 32 15. Inductive Measuring Principle Using a Chopper Type Electrode 34 p 16. Zefkrome White with Finish Dyed —800 x Optical Microscope 48 17. A Typical Fiber to Fiber Friction Curve 53 Vlll LIST OF ILLUSTRATIONS (Continued) Figure Page 18. Static Field Strength Chart Paper 55 19. C Me Br Static Field Strength 59 20. C,, Bu Br Static Field Strength 59 16 21. C , Me CI Static Field Strength 60 22. C Me CI Static Field Strength 60 23. Electrostatic Field Strength Versus Molecular Modifications 62 24. C,, Me Br Yarn-to-Guide Friction 65 16 25. C , Me MeSO Yarn-to-Guide Friction 66 26. Coefficient of Yarn-to-Guide Friction Versus Molecular Modifications 67 27. Coefficient of Kinetic Fiber-to-Fiber Friction • Versus Molecular Modifications 71 28. Coefficient of Static Fiber-to-Fiber Friction Versus Molecular Modifications 72 29. Conductivity in Solution Versus Molecular Modifications 74 30. Moisture Region of the Fiber Plus Finish Versus Molecular Modifications 77 31. Electrostatic Field Strength Versus Kinetic Coefficient of Yarn-to-Guide Friction 78 32. Electrostatic Field Strength Versus Kinetic Coefficient of Fiber-to-Fiber Friction 79 33. Electrostatic Field Strength Versus Static Coefficient of Fiber-to-Fiber Friction 80 34. Electrostatic Field Strength Versus Moisture Regain of the Fiber Plus Finish 81 35. Electrostatic Field Strength Versus Conductivity of the Compounds in Solution 82 ix LIST OF ILLUSTRATIONS (Continued) Figure Page 36. Electrostatic Field Strength Versus \J,^ of the Y-G a) fatty chain length varied compounds b) small groups around the nitrogen varied compounds c) counterion varied compounds 84 37. Electrostatic Field Strength Versus \i^ of the F-F a) fatty chain length varied compounds b) small groups around the nitrogen varied compounds c) counterion varied compounds 85 38. Electrostatic Field Strength Versus \i^ of the F-F a) fatty chain length varied compounds b) small groups around the nitrogen varied compounds c) counterion varied compounds 86 39. Electrostatic Field Strength Versus the Conductivity in Solution of the a) fatty chain length varied compounds b) small group around the nitrogen varied compounds c) counterion varied compounds 88 40. Electrostatic Field Strength Versus Percent Moisture Regain of the Fiber plus Finish of the a) fatty chain length varied compounds b) small groups around the nitrogen varied compounds c) counterion varied compounds . 89 41. Infrared Spectra C Me I Run as Split Mull 102 42. Infrared Spectra C Me MeSO. Run as Split Mull 102 43. Infrared Spectra C^ , Et Br Run as Split Mull 102 44. Infrared Spectra C Pr Br Run as Split Mull 103 45. Infrared Spectra C, , Bu Br Run as Split Mull 103 46. Thin Layer Chromatogram of the Compounds Used 107 47. C.I. Acid Blue 45 110 LIST OF ILLUSTRATIONS (Continued) Figure Page 48. C.I. Basic Violet 3 110 49. C.I. Direct 15 112 50. U.V./Vis. Spectra of Sky Blue FF (3 x lO"^ m) 114 51. U.V./Vis. Spectra of Sky Blue FF (3 x lO"^ m) plus C3^^H2^Ni(CH2)3 Br" (2.74 x lO"^ m) (This concentration should be above CMC.) 115 52. U.V./Vis. Spectra of Sky Blue FF (3 x lO"^ m) plus Cj^^H2-^Ni(CH2)3 Br" (6.85 x 10""^ m) (This concentration should be below CMC.) 116 XI SUMMARY One of the big problems in textile processing and other handling operations of synthetic fibers is static electricity.