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. The most common and convenient remedy used by synthetic fiber producers for the elimina tion of static is the application of antistatic agents to the fiber during manufacturing.
The purpose of this research was to study in a systematic way the effects of molecular modifications of fatty n-alkyl trialkyl ammonium salts in relation to their antistatic properties on polyacrylonitrile fibers.
The work involved using nine variations of a simple quaternary ammonium salts with one linear fatty alkyl group and three small alkyl groups.
^1 R— N~ R, X I ^ ^1 where R = C^^, C^^, C^g
R. =Me, Et, n-Pr, n-Bu
X" =C1, Br, I, MeSO^
Five of these compounds were synthesized and the other four were commer cially available compounds that were purified by recrystallization from various solvents.
Also the conductivity of these compounds in solution and the fiber- to-fiber friction, yarn-to-guide friction, and moisture regain on the Xll
fiber were investigated as to their effect on the functioning of these compounds as antistatic agents, and the effects on the parameters which resulted from the molecular modifications of them.
It has been shown that the counterion (X ) is very important in determining whether a compound functions as an antistat and that chlorides are by far the best counterions. By varying the small groups around the nitrogen (R,) from methyl to ethyl to propyl to butyl, it was shown that steric hindrance to ion-pair formation caused by the bulkier groups greatly enhances the antistatic properties of a compound. The optimum chain length for the fatty n-alkyl radical (R) appears to be about C.^, but does not seem to have much influence on static elimination.
There was no correlation between the frictional properties of a compound and the compound's ability to eliminate static electricity.
Thus the results seem to favor the mechanisms of static elimination which suggest that dissipation processes take care of the bulk of antistatic action. Also no correlation was found between moisture regain of the fiber plus finish and conductivity of the finish in solution, and anti static properties. CHAPTER I
INTRODUCTION
1.1 General
Static electrification is a nuisance at many stages in the manufac ture and use of textile materials, but during the conversion of staple fiber into yarn it can be so severe as to make the process completely impossible. In the production of spun yarn, the effects of static are evidenced through ballooning of the card web, card loading, roll lapping and excessive fly during the processing steps of carding, roving, and spinning. The most common and convenient remedy used by synthetic fiber producers for the elimination of static is the application of antistatic agents to the fiber during manufacturing. They are a part of the spin finish combination.
Until the last five to ten years, the use of spin finishes was considered almost as "black magic." Some compound was tried and if it was successful, nobody knew why; i.e., the approach was empirical.
Today, fiber producers are beginning to realize that if they know why a particular compound will function as an antistatic agent or lubri cant, they can better solve their problems and optimize their products.
The purpose of this thesis is to study in a systematic way the effects of molecular modifications of fatty n-alkyl trialkyl quaternary ammonium salts in relation to their antistatic properties. Some of these compounds
Synonyms are spin finishes, textile processing aids, producer finishes. 1 * are known to be good antistats .
The work in this thesis involved using nine variations of a
simple quaternary ammonium salt with one linear fatty alkyl group and
three small alkyl groups (see Table l).
With compounds 1-3 the effects of the fatty alkyl group can be observed, with 4-7 the effects of the groups around the nitrogen other than the fatty group can be observed, and with 2,3,8, and 9 the effects of the counteranion can be observed.
Most of the research work on antistatic agents found in the liter
ature thus far did not deal with the effects of molecular structure. Of 9-7 f» the articles, only one was a systematic study of a class of chemical
compounds, relating structure to performance. Most of the work was designed to show other things. The particular article which did explore the effect of molecular structure in a systematic way, dealt with quaternary ammonium
salts as antistatic agents used as fabric finishes on nylon fabrics. The author used resistivity measurement and compounds of C.., C ,, C. , and
C_^ trimethyl ammonium and tri-n-butyl ammonium chlorides and bromides.
The composition of these compounds was varied to determine the effect of various parameters in the generation of static. The work on this thesis dealt with similar compounds but went into the contribution of other fac tors to the mechanism. Four different counteranions, four different groups around the nitrogen as well as three different fatty chain lengths were investigated.
Acrylic staple fiber was used in the evaluation of the antistatic agents as spin finishes rather than as fabric finishes. Dynamic measurements
Superscript numbers refer to items in the Bibliography. Table 1. Compounds Used in this Thesis
Compound Abbreviation Chemical Used in this Structure Thesis
1. myristyl trimethyl C^^ Me CI ammonium chloride
2. palmityl trimethyl C,, Me CI 16 ammonium chloride
3. stearyl trimethyl C,o Me CI lo '^18"37 (^3^3=1" ammonium chloride "^ -
4. palmityl trimethyl C,^ Me Br 16 S6"33 N - (="3)3 ^^" ammonium bromide
5. palmityl triethyl C,, Et Br 16 =16"33 " - (^"5)3 '^^" ammonium bromide
6. palmityl tri n-propyl C,. Pr Br 16 ^16^33 - ^ - ^^"7)3 "^" ammonium bromide
7. palmityl tri n-butyl C,, Bu Br 16 ammonium bromide S6"33-^-^^A^3^^"
palmityl trimethyl C,. Me I 16 ammonium iodide Cl6"33-^-(C"3)3lV
9. palmityl trimethyl C,, Me MeSO, 16 4 '^16"33-"-(^"3^3"^2°4' ammonium methyl sulfate wijre made of the amount of static. This approach was used because it gave a close approximation of what happens in actual textile processing.
In addition to the work done in parallel with that cited above, the conductivity of these compounds in solution and the fiber-to-fiber friction, and yarn-to-guide friction on the fiber were investigated as to their effect on how these compounds function as antistats and the effect on the parameters which resulted from the molecular modification of these com pounds.
Zefkrome acrylic fiber was chosen as the fiber for this study because (l) cationic compounds are good antistatic agents on acrylic fibers ' * * and (2) because Zefkrome is the most critical acrylic fiber for static.
To understand how these quaternary ammonium salt antistatic agents function to eliminate static electricity, something should be known about the following topics: (l) the nature and generation of static, (2) the
measurement of static, (3) the parameters affecting the mechanism of static control, (4) the chemistry and sterochemistry of quaternary ammon ium salts, (5) cationic antistats, (6) amphipathic electrolytes in solution and (7) how the compounds reside on the surface of the fiber.
1.2 Nature and Generation of Static
In the widest sense, static electrification is defined to include all actions which produce by mechanical means operating by contact Q between solids, segregation of positive and negative charges. Static electricity may be generated merely by contact followed by separation of two surfaces. These surfaces must have a different "electrostatic propensity," if net charge is to result. This can happen even if the two 9 surfaces are of the same chemical composition.
In the past decade only a few papers have been published describing
original work on basic theories of static generation. The
theories are based on the so-called "Band Theory of Solids." This theory
utilizes quantum mechanical concepts - existence of energy bands and the
equalization of Fermi levels which are outside the scope of this work.
Some authors think that the charged particles which pass from one
surface to the other are an electron transfer as occurs in the case of
conducting metals. The particles could also be atomic ions although there
IS no proof.
Rubbing usually increased charge generation.
1.3 Measurement of Static
In evaluation of antistatic finishes two basically different 15 approaches are possible. One is based on the assumption that the
improvement of fiber conductivity by the finishes is of paramount impor tance. Hence, the most valid measurement of the efficiency of antistatic agents is believed to be the results of conductivity measurements.
The other approach and the one used in this work is based on the assumption that antistatic agents act simultaneously in several different ways so that their overall performance depends on more factors than just the improvement of conductivity. Authors defending this opinion prefer to evaluate antistatic agents by measuring static generation under condi-
tions as close to processing conditions as possible. '
Although resistivity measurements are well suited to fabrics, they do not give a true picture of what happens during textile processing.
The agents used in this thesis are intended as textile processing aids and therefore the static generation was measured at the processing machine, as described in Chapter II.
1.4 Chemistry of Quaternary Ammonium Salts
1.4.1 General '
Quaternary ammonium salts are the product of the final stage of the alkylation of an amine nitrogen (i.e. the reaction of an amine with an alkyl halide or some other alkylating agent to form an amine of the next higher class - the alkyl halide undergoes nucleophilic substitution with the basic amine serving as the nucleophilic reagent). They have the formula
R N X , where R is some alkyl group and X is a counteranion. 4' The four organic groups are covalently bonded to the nitrogen, and the positive charge of this cation is balanced by the independent existence of the anion.
The quaternary ammonium salts have all the physical properties of salts; they are crystalline solids, which dissolve in water to give con ducting solutions. Often they show no precise melting point, but decompose on heating.
The reaction of fatty nitrogen compounds to form quaternary ammonium salts which can be used as antistatic agents are quite different from the reactions of lower molecular weight amines. This is discussed in more detail in the experimental section. 19 1.4.2 Stereochemistry
Ammonia (NH ) is pyramidal with nitrogen at the apex of a pyramid and a hydrogen atom at each corner of its triangular base. In ammonia, 3 nitrogen has four sp hybrid orbitals, which are directed toward the corners of a tetrahedron. (N has only 3 unpaired electrons; each occu- 3 3 pying one of the sp orbitals. The fourth sp orbital contains a pair of electrons.) Three of these orbitals overlap s orbitals of the hydro gen atoms; the fourth contains an unshared pair of electrons.
Instead of the bond angle being 109.5° as in a regular tetrahedron, the bond angle in NH^ is 107°. The unshared pair of electrons occupies more space than any of the H atoms and tends to compress the bond angles slightly.
If the three hydrogens are replaced by alkyl groups, the structure is still pyramidal. (See Figure l).
Figure 1. Pyramidal Structure of Trialkyl Amine.
It might appear that in a molecule where N carries three different groups it cannot be superimposed on its mirror image and should have optically active forms (see Figure 2). This is not so, because in NH^
Figure 2. Different Steric Forms of Nitrogen. there is an energy barrier of only 6 Kcal/mole between the different pyramidal forms, so that even at room temperature the fraction of col lisions with sufficient energy is so large that a rapid transformation between different arrangements occurs. This is also true for derivatives of NH^. Although a molecule of the amine is not identical with its mirror image, it can be made so without breaking bonds and can therefore be superimposed. There then exists in these molecules an oscillation between two different forms. 3 In quaternary ammonium salts all four sp orbitals are used to form bonds, and the quaternary nitrogen is tetrahedral in structure as is carbon in methane (see Figure 3). If all four groups are different, this compound shows optical isomerism and optical activity. In the solid state the anion has no particular position with respect to one nitrogen atom; in solution it also leads an independent existence for the greater part of the time. There is some ion-pair formation but it is not known whether the associated ions assume a certain preferred position or not.
The compounds that are used for this work are
-n +
X
Figure 3. Stereo Structure of Quaternary Ammonium Salts. with R being C,.H^Q, C,.H^^, C,gH and R., being CH to n - C H
If R., R^, R^ are bulky, ion-pair formation is sterically hindered and
thus the counteranion remains dissociated rather than paired with the
cation. Therefore, several different N-substituents (R) were used in
this work, viz., methyl-, ethyl-, n-propyl and n-butyl.
It was thought that isopropyl or isobutyl groups could be used
also, but on investigation with molecular models this was found not to
be sterically feasible. In fact, when the 3 small N-substituted alkyl
groups were larger than methyl, the structure was almost sterically hin
dered.
1.5 Cationic Surfactants Used as Antistatic Agents ' *
Tensides cover a wide variety of structures, but can be quite
simply classified according to the nature of the ionizing group. The
charged part of the molecule brings about surface activity and classi
fies the surface active agent. The active ion of this class of anti
static agents is positively charged thus they are cationic.
These can be divided into two main groups:
1. Tetra-substituted quaternary ammonium compounds in which four
separate groups are attached to the nitrogen. These can also be referred to as the linear type.
Commercially available compounds in this class include
0 R] II +r a. R-C-N (CH^i N —R^ X I 2^1 2 h «3 10
+1^ b. R- N- R^ X I ^ ^3 where R is a fatty chain ^10^23^° ^18^37' ^1' ^2' ^"^^ ^3 ^^® methyl or
ethylol usually, X is a counteranion, and n is usually 2 to 3.
2. Other compounds - The quaternary nitrogen is part of the ring
system. These are quaternary heterocylic based compounds and represent
a special case of this grouping in which three of the N-R bonds are
shared between two carbon atoms of the ring system or between these two
carbons and a group outside the ring. These can also be referred to as
the cyclic type.
This class includes imidazolinium, pyridinium, morpholinium and quinolinium based quaternary ammonium compounds. Each of these would
contain one long fatty chain.
Organic acid salts of the alkyl amines, alkyl amides and ethoxylated amines are sometimes classified as cationic also.
_1.6 Antistatic Finishes and How They Function
An antistatic agent is defined as a chemical dressing applied to the surface of the fiber which renders said fiber free from static electrical charges. Some other important properties of antistatic agents are:
1. They do not adversely affect physical and chemical properties of the fiber.
2. They are effective at low temperature and humidity. 11
3. They do not adversely detract from the dynamic yarn-to- guide, dynamic fiber-to-fiber and static fiber-to-fiber properties of the fiber when used in combination with a lubricant.
4, They improve fiber processing performance.
There is no one chemical structure which is an ideal antistatic 23 24 2 finish for all synthetic fibers ' ' . Most of the antistatic formulations must be tailored for a particular application.
All data suggest the view that static electricity is a surface 24 2 phenomenon ' . Most authors agree that a continuous surface layer of finish is important and that if the concentration of finish is too low, 25 a continuous layer is not possible, and antistatic protection is lost
Antistatic agents help to spread the finish more evenly over the fiber because of their surface active nature
The mechanism of antistatic finishes is still a point of argument.
There are various mechanisms, however, that seem to be reasonable. These are noted: 23 21 1. Mechanisms which reduce or prevent charge generation '
a. Lubrication. It is imaginable that lubrication may
substantially reduce static.generation.
b. Modification of the dielectric properties of the fiber
surface by formation of polarized or polarizable surface
layers. 2. Mechanisms which promote faster charge dissipation after 23 21 separation '
Improvement of surface or bulk conductivity of the fiber whereby
the generated charges are eliminated or dissipated to the 12
-surroundings or to the grounded machine parts.
No one mechanism is solely responsible for the antistatic action of any one agent under any one condition? all of them contribute to a greater or lesser degree. The second type of 27 mechanism is most favored in the literature
There are many different parameters which affect these antistatic mechanisms.
1. Moisture regain is very important, both of the compound and of the fiber. But greater hygroscopicity does not necessarily mean better antistatic effect '
2. The presence of electrolytes, either intentionally added to the antistat or present as impurities, increases conductivity.
3. The presence of ionizable compounds, those that dissociate into positive or negative ions, such as the compounds used in this work.
(Quaternary ammonium salts display a high level of ionization along with a smaller but definite measure of hygroscopic properties.)
4. Surface activity helps to improve wetting, giving a more even application of finish.
5. Frictional work (both fiber-to-fiber and fiber-to-metal) and generation of static are often related to each other and in many cases 29 there is actually evidence of a significant relationship . There is 30 still no clear pattern of correlation visible from experimental findings
It does appear, though, that both fiber-to-fiber and yarn-to-guide friction must be controlled.
As can be seen from the above, when a staple fiber is being processed there is much more to the mechanism of antistatics than just 13
hygroscopicity and ionization. Therefore the reduction of electrical resistivity of the fiber surface is not the entire answer.
The mechanism of conduction of electricity along a surface on which antistat-water units are deposited is speculative. The conduction along a film of antistat containing water may be ionic in nature or it 31 may be electronic as proposed by Baxter.
In this discussion an attempt was made to provide a general understanding of how an antistatic agent functions. The scope of this thesis dictated that only a general view could be presented, as an extensive volume could be written on this topic. For those who would want to investigate this subject further, there are several good review 10 32 articles ' and at least 50 papers that might be of interest.
20 33 34 1.7 Cationic Amphipathic Electrolytes in Aqueous Solution ' '
The possession of hydrophilic and hydrophobic portions by the same molecule (amphipathic compounds) tends to make such molecules concentrate at interfaces with the hydrophilic portion in the aqueous phase. In more concentrated solutions of an amphipathic substance, it is impossible for all the solute molecules to be located in the interface. When an amphipathic substance dissolves in water there is a large "sympathetic" force between the hydrophilic portion and the surrounding water molecules.
The non-compatibility between the hydrophobic portion and the water mole cules does not involve an actual repulsive force between the two. There is not a very strong attractive force between the paraffin chains. There is, however, a very strong cohesive force between the water molecules and when a paraffin chain is introduced into this strong field of attrac tion it tends to be pushed out of solution. This is opposed by the solubilizing influence of the hydrophilic portion and thus the 14
paraffin chains form themselves into groups which can remain in solution because of the hydrophilic portion of the molecule. The large cohesive force between the water molecules is due to their dipole character and this attractive force falls off as a high power of the distance. The work required to introduce a single paraffin chain into water and accordingly to separate the water molecules by a distance of about 5A° is not much less than that required to separate them to many times this distance. The introduction of an aggregate of paraffin chain is thus accomplished with a much smaller expenditure of energy than would be required if the chains were introduced as separate single chains. The compromise between the cohesive force of the water molecules and the attraction for water of the hydrophilic portion on the amphipathic molecule is thus affected by the aggregation of the hydrophobic portions which are so grouped that the exterior of the aggregate is composed of the hydrophilic portions of the molecules.
Therefore at certain concentrations, micelles are formed. These micelles are aggregates of molecules oriented such that the exterior of the micelles consists of hydrophilic heads, the hydrophobic tails being inside. There are also a certain number of gegenions associated with the micelle. At a low concentration the solute exists mainly or wholly as single molecules. The transition to the micellar condition occurs fairly sharply above a critical concentration which is characteristic of the particular amphipathic compound '
At the critical micelle concentration, usually abbreviated as
CMC, there is a rapid change in the magnitude of practically any physical property of an aqueous solution of an amphipathic electrolyte. 15
The conductivity of the solution increases rapidly as the solution concentration goes above CMC. Equivalent conductivity 37 decreases sharply^ (See Figure 4.) The surface tension of an aqueous solution of surface active agents decreases very rapidly until CMC 38 39 is reached and then stays constant at concentrations above CMC ' 40 41 Viscosity seems to increase gradually after CMC is past ' , See
Figure 5.
The effect of increasing temperature is to make the change due to micelle formation less marked, apparently due to a general loosening 20 of the structure at higher temperature
Most authors agree that micelles are formed, but there is a disagreement as to their exact nature. Most of the data support the premise that up to CMC an amphipathic electrolyte is a strong electrolyte, almost completely dissociated and unaggregated. At CMC, aggregation of the amphipathic ions begins with the formation of relatively small micelles. These micelles grow rapidly over a very limited concentration range to a size which, for a given amphipathic electrolyte, remains approximately constant with further increases in concentration. The shape of this micelle is also questionable. Some feel that it is 20 spherical others that it is either cylindrical or disk-shaped
But most agree with the concept that in simple aqueous solution there is one type of micelle whose interior contains randomly arranged paraffin chains with the hydrophilic end of the ion constrained to remain at the surface of the micelle.
These types of compounds are more hydrophilic above CMC. The formation of aggregates presents an essentially hydrophilic exterior 16
/K 1 1 !CMc; >> -p 0) ' 1 1 oa M Du xo: Xi 1 (TJ 1 11 y^ Conductivity c I 1 \ / £ \ 1 \ /
(/> \ 1 \ / CO 0) Surface Tension
U) i /\
C
. 1 >v Equivalent Conductivity
—.'. '•—^_ H 1 1 1 -• 1 > 0.1 0.3 0.5 0.7 0.9
Sodium lauryl Sulfate Percent
Figure 4. Physical Property Curves for Amphipathic Electrolytes (Preston, Reference 37). o a @ 40OC oSo.8| -
•H o o •H >
0.6 -•
@70oc
0.4.. -"zr^
0.05 0.10 0.15 0.00 N (wt. Normality) Figure 5. Effect of Temperature and Concentration on Viscosity of a Sodium Dodecyl Sulfonate Solution (Wright, Reference 40). 18
to the water. This exterior is, therefore, much more compatible with the water than the single molecules which have a large hydrophobic surface exposed to the water.
1.8 Orientation of the Antistatic Agent on the Fiber
Most surface active agents possess a strongly polar hydrophilic end-group which imparts water solubility to the entire molecules as well as large non-polar hydrophobic group,as was discussed earlier. In application of an aqueous solution or emulsion of such an antistatic agent to a hydrophobic fiber, the non-polar hydrophobic group of the molecule is thought to be adsorbed by the fiber surface in such a manner that the polar groups form an outer layer around the fiber with the 21 42 43 molecules orienting themselves perpendicular to the fiber surface ' ' .
Most authors also mention that cationic compounds are more substan tive to the fiber than anionic compounds. This concept (former) seems to neglect the fact that the thermoplastic hydrophobic synthetic fibers have a negative surface potential. Consideration of the negatives surface potential causes some other authors to suggest that instead of a hydrophobic tail bonding to the hydrophobic fiber as mentioned earlier, the cationic compounds would thus orient themselves with the positive charge in and the hydrophobic tail away from the fiber. This orientation would then account for the higher substantivity of cationic compounds.
If the same amounts of cationic and anionic finish of like structure except for ionic group; e.g.. 19
0 ^"3 II I Cationic: C^^^^s"" C—N —(C^H^) N— CH^CH^OH NO^' ^3
0 II - + Anionic: ^17^33"" ^ " ^— (^^H^) SO^ Na CH3
are put on the fiber, the fiber ground in a Wiley mill and dispersed in
a benzene/water mixture,and the residence of the finished fiber is
observed, it is noted that the anionic finished fiber resides in the
benzene layer and that the cationic finished fiber resides in the water 44 layer. (See Figure 6.) This would indicate that the cationic finish
does in fact exist on the surface of the fiber with the ionic group out
and that anionic and cationic finishes reside differently on the surface
of the fiber. It also might be noted that the cationic compound in this
case does function as an antistatic agent but the anionic one does not.
Several different concentrations of finish were tried with the same results.
Graham found that upon increasing the amount of finish the static 45 charge observed reaches maximum and minimum values in a regular sequence.
This was explained by the first mentioned orientation of the finish for
the first layer, i.e., with the ionic group out and the hydrophobic tail
in, and the next monomolecular layer is then supposed to be again radially
adsorbed, but reversed in direction, with the hydrophilic groups being
oriented towards the hydrophilic outside of the first layer and its hydro
phobic groups pointing away from the fiber. The third layer is then
supposed to arrange itself like the first one and so forth. His explanation 20
was based on the data observed and not on an actual check of the surface
chemistry. Graham also found that the degree of surface activity of the
compound was important; if a compound had low surface activity not much
order was noticed even at low concentrations. PAN + 0.25^ o.w.f. PAN + 0.25% o.w.f. anionic cationic
jZlH
C '.. -^-o
H^O
(b)
Figure 6. Finished Fibers in a Benzene/Water Mixture,
In summary, it appears that not much, if any work has been done in
surface chemistry to determine the actual orientation of the finish on the fiber. Thus the actual orientation is unknown. But the work with the benzene and water appears to indicate that a certain orientation does exist for compounds that do function as antistats, viz., an orientation with the ionic group out from the fiber. 21
CHAPTER II
MATERIALS, EQUIPMENT AND INSTRUMENTATION
2.1 The Substrate The fiber to which the antistatic agents was applied in this work p is Zefkrome (white) acrylic fiber made by the Dow Badische Company. 2.1.1 Chemical Composition p Zefkrome is a homopolymer of acrylonitrile. The long linear backbone of the polyacrylonitrile (PAN) molecule is made up of acryloni trile (AN) units formed by addition polymerization
n CH^ = CH-CN ^ 4 CH^ - CH ^ Z 2 I n CN of the monomer AN. This backbone structure is very important in the fine structural features and helps determine the physical properties of this fiber.
2.1.2 Polymerization of PAN
Vinyl polymerization may be initiated by several means - thermal, photochemical, irradiation, organic free radicals, and redox systems. Redox seems to be the most used method in the initiation of AN polymeriza tion for fibrous end uses, although peroxide catalysts are also used. The persulfate/bisulfate couple is largely favored due to its convenience and potency. With this catalyst system at least four different end groups are possible on the polymer chain. 46 p Registered Trademark for Dow Badische Co. Producer Colored Acrylic. 22
HO3S-[cH2-CHf ^ CN V4.CH2-CH^^ CN
*0 .S -f CH^— 4 I- 2 I CHX.J n CN
HO4CH2-^H]-^ CN
47 Recent research may exclude, however, sulfate anionic sites.
All of these end groups could have some effect on how much of a static electrical charge is built up on the fiber. Although these are a very small percentage of the final polymer and are sometimes neglected, they may still have an effect. Zefkrome has a greater static problem than other acrylics. This may be due to lack of ionic groups such as exist in the ternary copolymer acrylic fibers.
2.1.3 Spinning
The preparation of synthetic fibers by the wet spinning process, which is how Zefkrome is spun, involves extruding a polymer solution through small orifices into a coagulation bath. Coagulation occurs either by chemical reaction or by an interchange of solvent and nonsolvent between the extruded filament and the coagulation medium. The coagulated filaments at this stage have a very cheesy structure from which the remaining sol vent is easily removed. To render the fibers useful for textile applica tion two processes are necessary: (l) orientation, and (2) compactness.
Orientation is achieved by stretching, usually in boiling water; compactness of structure occurs during drying when the wet gel collapses. 23
48 Figure 7 shows a sample system similar to one from which p Zefkrome might be spun. This diagram shows where the finish can be added. The finish also is added to the fiber tow just before it is cut into staple. Although it could be added most anywhere in the system, these are the most probable positions.
Synthetic fibers with the same base polymer behave differently during processing on the cotton system because of different spinning sys tems, coagulation bath components (organic solvents, aqueous inorganic salt solution), and stretch conditions used on them. All these varia tions in producing the fiber lead to different surfaces and different cross-sections (Zefkrome has a round cross-section for example). Since static electrification is essentially a surface phenomenon, it is easy to see how it would vary from fiber to fiber.
2.1.4 Miscellaneous
Glass Transition Temperature (Tq). Tg is important in proper heat setting of yarns, i.e., stabilization. 49 50 Dilatometric and shear modulus or mechanical decrement give a Tg value of ca. 1040C. for the PAN homopolymer.
Moisture Regain. Moisture regain is important in determining how an antistatic agent functions because it influences the surface conduc- 51 tivity. Chancy has tabulated the moisture regain for nine acrylic ^ R fibers. Orion 42 has a value of l,b%, Zefkrome is probably less than this, e.g., 1-1.5^. (See Results Section.)
The purification of the fiber and the application of finish will
Orion is the Registered Trademark for duPont Acrylic Fiber. Coagulation Bath
Washer
Figure 7. Wet Spinning Unit
4> 25
be discussed under Experimental Procedures. 52 The yarn used in this work was obtained from Simmons' full scale cotton system processing of 3 denier x 2 inch staple length fiber supplied by the Dow Badische Company.
2.2 Chemicals Used in Obtaining the Compounds
The following chemicals were used in this thesis either as received, after distillation, after recrystallization, or as a component in a syn thesis:
From: Foremost Food and Chemical Company El Dorado Division P. 0. Box 599 Oakland, California
Formonyte D618 Lot No. 3573 Distilled primary palmityl amine
Formonyte 1617 Lot No. 4510 Monomyristyl Trimethyl quaternary Ammonium chloride
From: General Mills Chemical Division Kankakee, Illinois
Aliquat 6 Lot No. 5D801 Trimethyl palmityl ammonium chloride
Aliquat 7 Lot No. 4D259 Trimethyl Stearyl Ammonium chloride
From: Eastman Organic Chemicals Distillation Products Industries Rochester, New York
No. 164 lodomethane mi. 141.94 White Label 26
From: Eastman Organic Chemicals (Cont.)
P238 Dimethyl Sulfate MW. 126.14 Practical
3375 1-bromohexadecane MW. 305.36 White label
609 1-bromopropane MW. 123.00 White label
51 1-bromobutane MW. 137.03 White label
114 Bromoethane (Ether free) MW. 108.97 White label
From: Pennsalt Chemicals Corp. Industrial Chemicals Division 3 Penn Center Philadelphia, Pennsylvania 19102
Tri~n-propylamine No. 1635
From: Virginia Chemicals Inc. West Norfolk, Virginia
Tri-n-butylamine Lot No. 6096-3 MW. 185.35 B.P. 205-210
Tri-n-ethylamine Lot No. 66-035 MW. 101.19
From: Fine Organics, Inc. 205 Main Street Lodi, New Jersey
Bromat Lot No. 7683 Cetyl trimethyl ammonium bromide 27
From: Baird Chemical Industries, Inc, 185 Madison Avenue New York, New York 10016
Barlene 16S Lot No. 5565 Cetyl dimethyl amine
2.3 Instruments Used
2.3.1 Yarn Finish Applicator 53 Instrument Used; Atlab Finish Applicator
Precision Machine and Development Corporation, New Castle, Delaware
(see Figures 8 and 9).
Principle of Apparatus. The yarn passes through the indentation at the top of a tube that is supplied with finish from a syringe which is operated at a constant speed. The amount of finish and the speed of the yarns are such that a uniform size bubble of solution is maintained in the indentation. Thus, the yarn is always going through a solution of finish.
(See Figures 8 and 9.)
The instrument also contains a drying can. The yarn passes from the solution to the drying can and is then collected on a spool.
2.3.2 Fiber-to-Fiber Friction
Instrument Used. The fiber-to-fiber friction tester designed by 54 the Engineering Experiment Station, Georgia Institute of Technology, was used in this work. 54 Principle of Measurement. McBride has discussed the basic design and construction of this apparatus in detail. The apparatus employs a torque principle by which single fibers are rubbed over one another and the resultant friction is recorded on an X-Y plotter. 28
Figure 8. The Application Tube of the Atlah Finish Applicator
Figure 9. Atlab Finish Applicator 29
55 Bryant also reviews the literature and discusses revisions of the instrument.
2.3.3 Yarn-to-Guide Friction 56 Instrument Used. Rothschild F-meter ; Rothschild four channel 57 recorder (see Figure 10)
Principle of Measurement. The method consists in measuring sepa rately the tensions, before and after friction by means of a pair of tension measuring heads (see Figures 11 and 12). The method offers the advantage of permitting an accurate control of the tension before fric tion; indispensable for comparing coefficients of friction.
Under the conditions that the tension before friction is carefully kept constant, the friction material is always the same, and the linear yarn speed is constant, comparable results of the coefficient of friction
for yarns having identical count and twist can be calculated.
The actual measuring conditions will be described under the Experi mental Section.
2.3.4 Static Build-up
Instruments Used. A Bergischer Rotating Electrostatic Field Strength 58 Measuring Instrument (Field Mill) mounted on the card of the Shirley 59 Miniature Spinning Plant was used to measure the field strength. The results were displayed on a Rothschild 4-channel recorder (see Figures 13 and 14.)
Several authors ' have measured static on a card-web on another moving system in cotton system textile processing in a similar manner with a similar type measuring instrument, i.e., the Field Mill principle instru ment. 30
Figure 10. Rothschild F-Meter and U-Channel Recorder.
Figure 11. Picture of Rothschild Measuring Heads as Used in This Work. Friction Surface
Constant Speed
Take-off 10 gr. Measuring Head (Initial Tension, T2)
Friction Surface
100 gr. Measuring Head (Final Tension, Ti )
Figure 12. Schematic of the Yarn Going Over the Rothschild Measuring Heads and Frictional Surf ace
oj 32
Figure 13. "Field Mill" Measuring Head Mounted on the "Shirley" Miniature Card.
Figure lU. Bergischer Rotating Electrostatic Field-Strength Measuring Instrument and Rothschild Recorder 33
Principle of Measurement. In measuring static, severe difficul ties arise when attempting to report results in well-defined, absolute units that would make them comparable to data from other investigators.
Even if the results are given in well defined units, they still may not be comparable as they may have been obtained with an instrument operating according to different principles or with comparable instruments but with certain different conditions that may influence the results.
Field strength is a good way to express static electricity data but again, however, a comparison with another author's data is possible only if the geometric conditions are well defined.
One of the main problems in making a dynamic measurement of a vary ing field strength is the effect of time. The ideal solution to overcome the effect of time is the use of a special type chopper electrode as shown in Figure 15. In this device the electrostatic field formed between the charged material and the stationary sensing electrode is chopped by a grounded rotating shield. The name "field mill" is given to this type instrument and comes from the action of chopping or "milling" the electro static "field." In one position of the shield, the electrode is exposed to the field; when the shield rotates to a position between the electrode and the charged material, the electrode is shielded from the field. By this means an alternating potential is induced on the electrode. Because this potential is changing according to the frequency of the chopper, an
AC-current flows through the resistor R and an AC-signal whose amplitude is proportional to the field strength can be taken across R and connected to the amplifier input, R only reduces the AC-signal, whereas a "static"
DC-signal would vanish very rapidly through R. As R is very small compared 34
\\\\\ Screening
Charged Material
Electrostatic
Field
Stationary Sensing Electrode
Sliding Contact
AC - Amplifier and Meter
Motor
rrm Figure 15 Inductive Measuring Principle Using a Chopper Type Electrode (Gayler Reference 32) 35
to resistances of normal insulating materials, loss due to inadequate insulation can be disregarded. Even a considerable leakage, e.g., due to a defective connection cable, would still mean only a reduction and not a long term drift of the instrument reading.
Gayler ' ' discusses the measuring of static by several dif ferent instruments and principles and the problems encountered in measur ing static. In this article he states:
...the "field mill" principle is regarded as the only really accurate and reliable system to measure static by induction if measurements have to be carried out over an extended period of time without the possibility of rezeroing the measuring system.
He also concludes that
...the above outlined features make the "field Mill" the most convenient, accurate, and trouble-free instrument available for measuring static... even when operated by unskilled personnel.
2.3.5 Miscellaneous
IR
IR 10 Infrared Spectrophotometer Beckman Instruments, Inc. NaCl plates
Fluorolube Mulling Agent Grade S-30 Hooker Chem. Corp. Niagara Falls, New York
Nujol Mulling Agent Extra heavy mineral oil Plough, Inc. Saybolt Viscosity 360/390 @ 100°?. Specific Gravity 0.880/0.900 @ 60°?.
UV/vis
Du Spectrophotometer Beckman Instruments, Inc. 36
EH
Model H2 Serial 33557 Glass Electrode pH meter Beckman Instruments, Inc.
TLC
Brinkman Instruments, Inc. Silica gel G Regular apparatus for making plates
Other
Buchi Rotavapor
Conductivity Meter
Type RC-16B2 Conductivity Bridge Beckman Instruments, Inc. Inductivity cell S-29855 E. H, Sargent and Co.
Moisture Percent Measuring Instrument
Acco Moisture Meter Model 100 Serial No. 9293 United States Testing Co., Inc. Hoboken, New Jersey 37
CHAPTER III
EXPERIMENTAL PROCEDURES
3.1 Preparation and Purification of the Compounds
3.1.1 General Remarks
Infrared spectra of the substances were taken in fluorolube and
nujol mulls. This method was found to give highly resolved spectra.
(See Table 2) The melting points were determined by gradually heating a metal block in which a capillary tube, containing the material, had been
inserted. (See Table 3) Elemental analysis was determined by
Galbraith Laboratories, Inc, Knoxville, Tennessee. Thin layer
chromatography (TLC) was done on silica gel and plates with benzene;
ethanol : water (20:11:1) and acetone; aqueous ammonia (90:10) as eluting agents. (See Table 4) The materials used in this work are mentioned in Chapter 2. All the samples were dried in a vacuum oven over PrjOp^ for several days. The recrystallization steps in this work were followed with TLC for all of the products but the palmityl triethyl, tripropyl and tributyl ammonium bromides. Instead, these were observed over progressive steps using infrared spectrophotometry. It also might be added that much difficulty was encountered in the synthesis and purification of these three compounds.
3.1.2 Synthesis
Palmityl trimethyl ammonium methyl sulfate was prepared by dropwise addition of 0.100 mole of dimethyl sulfate to 0.100 mole of palmityl dimethyl amine in 200 ml. of 9b% ethanol over approximately Table 2. Important Infrared Bands of the Compounds Used
+ Compound C-N^^'"*^""' CH N-H N-H C-N C-N NH^ Coupling Vibration Stretching Bending Vibrations (amine salts) Vibrations Vibration Vibration Vibrations
1410 ^14 ^^ CI C,, Me CI 955 908 718 1140 1410 - - 16 C^gMe Cl''^ 1410 - -
Me Br 955 905 722 712 1140 1415 - - C,,16 Br 970 930 710 1160 1410 Se" 1390 Sft p-^ Br 970 910 740 720 1160 1390 C,^ Bu Bu 970 915 730 715 1148 1410 - - 16 C,, Me I 955 905 720 710 1140 1410 - - 16 Me MeSO 960 900 730 715 1150 1410 - - C,^16
only ran 2.5 - 7.5 [x similar to C, , Me CI up to there weak bands between 1000 and 910 cm"-"- see Appendix B also has bands at 1230 (S), 1005 (s), 745 (m-w), 1058 (s) cm for MeSO counterion shows crystalline split of -CH„- vibration
CO CD Table 3. Physical Properties of the Compounds Used
Compound M.W. Recrystallized M.P. ^C % C % W % H % X from Lit. Found Calc. Found Calc. Found Calc. Found Calc. Found
2 X ^n 70s. 68-70S. C,, Me CI 291.952 1 x Acetone 180d. 178-80d. 70.00 13.10 4.81 12.1 14 ^He 2 X jZfH '70 C,, Me CI 320.006 1 x Acetone 180d. ~180d. 71.50 13.20 4.40 11.1 16 C,„ Me CI 348.060 3 x j^iH 180d.'*^ 180-185d. 72.50 13.30 4.20 10.2 io
1 X fiW ^fr^H C Me Br 364.462 2 x Acetone 237-243 244-246 62.60 11.60 3.86 21.90 22.11 (m. then d.) 1 X ^W ^^^ C,^ Et Br 406.543 1 xX AcetonAc€ e 145-55 155 65.00 11.88 3.46 19.70 16 1 X EtoAc
1 X jZiH C,, n-Pr Br 448.624 2 x EtoAc 88-89 67.00 12.10 3.13 17.84 16
1 X jZlH ^HH«- C,^ n-Bu Br 490.705 2 x EtoAc 68-70 74.5 68.50 12.60 2.86 16.30 16 2 X jZfH C., Me I 411.457 2 x Acetone 16 240 55.60 55.60 10.27 9.99 3.42 30.09 30.35 C,^ Me MeSO. 395.675 2 x Acetone 16 4 158-61 60.80 11.38 3.54
^J. Org. Chem. 12 517 (l947) ^^'^C.A. _35 35992 CO ^JACS _68 754 (l946) 40
Table 4. R Values for TLC of the Compounds Used
jZlH : EtOH : H^O Acetone : NH ETC : MeOH : H^O Compound 20 :: 11 : 1 90 : 10
C,^ Me CI 0.40 0.32 14 0.35 C,. Me CI 0.36 0.41 16 C,o Me CI 0.44 0.37
C,. Me Br 0.41 0.61 0.36 16 C^, Et Br 0.77 16 C,, Pr Br 0.93 16 C,, Bu Br 0.97 16 C,. Me I 0.85 16 0.55 C,. Me MeSO^ 0.63 16 4
Ethylene trichloride 41
30 minutes. The temperature of the mixture rose to about 75°C very quickly and after the reaction ceased it returned to room temperature gradually. The reaction mixture was allowed to stand at room temperature for six hours. The ethanol was then evaporated from the reaction mix ture in the Rotavapor and the solid residue was dissolved in boiling acetone. This solution was filtered hot and allowed to cool. Upon cooling, a solid crystallized from solution and was filtered off with a Buchner funnel using Whatman number five filter paper. The recrystal- lization process was repeated and a white crystalline substance was collected, melted at 158-61°C, had one spot in the TLC, and had no unwanted bands on infrared analysis.
Palmityl trimethyl ammonium iodide was obtained by refluxing a solution containing 0.207 moles (50 gr.) of distilled palmityl amine,
0.635 mole (90 gr.) of methyl iodide, and 0.415 moles (l6.6 gr.) of sodium hydroxide for 72 hours. The reaction mixture was cooled in an ice-water bath and the solid, yellow crystalline material which settled out was filtered off. The filtrate was dissolved in boiling benzene, filtered hot over Whatman number two filter paper using a Buchner funnel to remove any inorganic salts, allowed to cool slowly to 0°C, and filtered. This process was repeated once with benzene and then twice with acetone, A white crystalline product with a sharp melting point at
240°C, giving one spot in the TLC and containing no unwanted bands on infrared analysis was obtained. Elemental analysis showed this com pound to be 55,60^ carbon, 9,99% H and 30,35% iodine. (See Table 3)
Palmityl triethyl, tri-n-propyl and tri-n-butyl ammonium bromides were prepared by refluxing 0.0492 mole of reagent grade 1-bromohexadecane with 0.0984 mole of the appropriate distilled amine (this represents 42
ca. 100 percent excess of amine) in 500 ml. of 95 percent ethanol for from three to seven days. The halide was not soluble in the ethanol, but after
adding the amine and slight heat (25-28°C) the mixture became a crystal
clear solution. The triethyl reaction was completed after ca. one day, the tri-n-propyl required three days, and the tri-n-butyl reaction required at least four to five days.
Isolation and rectystallization of these compounds was much more difficult than their trimethyl analogs. The ethanol and lower boiling amines were extracted from the reaction mixtures by using the
Rotavapor. The residues were dissolved in boiling benzene, filtered hot over Whatman No. 5 filter paper, and allowed to cool. The triethyl
sample contained a large quantity of some benzene insoluble substance that could be filtered. The solution was cooled to 0°C without any product crystallizing out of solution; either nothing would happen or the whole mixture would freeze.
(a) By using acetone, the triethyl sample was recrystallized adequately. It was also recrystallized from ethylacetate (reagent grade, distilled, B.P. 76-77°C) to obtain a white waxy crystalline substance with a sharp melting point at 155°C. TLC showed one spot and the infrared spectra showed no unwanted bands.
(b) The tri-n-propyl sample could not be recrystallized from acetone or benzene. Instead, it was recrystallized twice from ethyl- acetate fairly readily to obtain a white waxy crystalline product with a melting point at 88-89°C. Infrared spectra showed no unwanted bands and TLC showed one spot.
(c) It was very difficult to remove the tri-n-butylamine from the reaction mixture by distillation. A large portion of it was 43
removed by using a separatory funnel and collecting the bottom layer.
Infrared analysis indicated that the top layer was tri-n-butylamine.
The compound seems to be very soluble in ethylacetate as well as the other commonly used recrystallization solvents, but some product was obtainable from the first recrystallization. Analysis showed that this was not the desired product. The second recrystallization from ethyl- acetate gave a white somewhat crystalline, waxy substance with a sharp melting point at 74.5°C. TLC showed one spot and the infrared spectra contained no unwanted bands. There was a big difference in the infrared spectra after the second recrystallization as opposed to after the first from ethylacetate.
3.1.3 Purification of Commercially Available Compounds
Palmityl trimethyl ammonium bromide, which is commercially available, was recrystallized first from benzene to remove any inorganic salts and then twice from acetone. A white crystalline substance which melted at 244-246°C and decomposed after melting was obtained. TLC show one spot and the infrared spectra showed no unwanted bands.
Elemental analysis showed this compound to be 22.11% Br.
Stearyl trimethyl ammonium chloride, a commercially available product, is marketed in a 50% aqueous isopropanol mixture as are the other two chloride compounds. It was recrystallized from benzene three times and a white waxy substance was obtained. This compound did not have any real melting point but decomposed at 180-185°C. According to 64 Reck et al quaternary ammonium salts do not possess definite melting points. They begin to soften at 70°C and decompose at 180°C.
TLC show one spot and the infrared spectra show some traces of water, 44
although not much, and no other unwanted bands.
Palmityl trimethyl ammonium chloride, was recrystallized twice
from benzene and once from acetone. A white waxy substance that decomposed at ca, 180°C was obtained. This compound was a little
harder to recrystallize than the stearyl and showed traces of water in
the infrared spectra even after five days drying in a vacuum oven over
P_0 . The water bands were not very strong as compared with the ones
seen in the literature ' . TLC showed only one spot.
Myristyl trimethyl ammonium chloride was dissolved in hot ben
zene and filtered to remove any inorganic salts, but only a waxy paste
was obtained on cooling and filtering. This product was then dissolved
in boiling acetone, filtered, cooled to below 0°C with salt water plus
ice, and the white waxy substance which settled out was filtered with a
Buchner funnel using Whatman number three filter paper. This compound
began to soften at 68-70OC and decomposed at 178-180°C. An infrared
spectrum analysis indicated that there were traces of water in this com
pound even after five days in a vacuum oven drying over ^r^O^, TLC indi
cated one spot.
Lauryl trimethyl ammonium chloride was not obtainable by any of
the above procedures and infrared spectrum analysis indicated a large
amount of water even after two weeks drying over P^Op, in a vacuum oven.
Therefore, it was decided not to use this compound. ^
3.2 Purification of the Staple Fibers
Five to ten gram samples of fiber were extracted in a Soxhlet
extraction apparatus with chloroform for at least twenty-four hours. 45
The fiber was then tested by a dying technique to ascertain if all
of the finish had been extracted (see appendix for discussion of this dye
technique). No color was observable when the fiber was dyed first with
an acid dye, then with a basic dye. Therefore, it was shown that the
extraction procedure was efficient.
3.3 Purification of Yarns
A package containing 20,000 yards of yarn was scoured with 1% o.w.f.
Igepal C0730 (nonionic detergent-ethoxylated nonyl phenol containing nine moles ethylene oxide - has a cloud point at ca, 95°C), in a package dyeing machine at 95°C for three hours. The sample was rinsed with water until
the suds were removed, then scoured with water for three hours at 95°C.
The sample was again rinsed, spun dry, and air dried.
When the sample had dried it was tested for removal of finish by
the dye technique described in the appendix and found to contain no obser vable finish.
3.4 Application of Antistatic Agent to the Fiber (staple)
Each compound as a solution was applied to the fiber to give
171.25 m moles of finish/kg fiber. To obtain these results the desired amount of finish was weighed out and diluted to 120 ml. (2.285 x 10 moles/l) with distilled water. This solution was just enough to completely satu rate the 40 gram fiber sample. The fibers were air dried in a test room at 70°F and 65% R.H. for three days to insure that they reached equilibrium kept in the test room one more day, then moved to and conditioned 24 hours or more in the 70°F, 40% R.H. room where they were tested (see Table 5).
The fiber was dyed by the finish dyeing technique (see appendix) and then checked for evenness of finish application by microphotographs. 46
Table 5. Solutions Used to Apply Finish to Staple Fiber
Concentrat ion of Solut ion
Compound moles/l g/i ?D solution Amount on 40 g of Fiber
C^^Me CI 2.285 X 10-3 0.080 0.0666 6.85 X 10"^ m
Cw Me CI 2.285 X 10-3 0.0876 0.0731 6.85 X 10"^ m ID C^gMe CI 2.285 X 10-3 0.0952 0.0793 6.85 X 10"^ m
C,. Me Br 2.285 X 10-3 0.100 0.0835 6.85 X 10"^ m 16 C.^Et Br 2.285 X 10 "^ 0.1112 0.0928 6.85 X 10"^ m -3 Br 2.285 X 0.1228 0.1023 6.85 X 10"^ m ^16 '^ 10 '^ C,. Bu Br 2.285 X 10-3 0.1344 0.112 6.85 X 10"^ m 16 -3 C,. Me I 2.285 X 0.1128 0.0939 6.85 X 10"^ m 16 10 ^ -3 C,^ Me Me SO, 2.285 X 10 ^ 0.1084 0.0905 6.85 X 10"^ m 16 4 47
These showed that the finish was an even coating on the surface of the fiber (see Figure 16).
3.5 Application of the Finishes (to Yarn)
Solutions of finish of the concentration derived from the fol lowing formula:
/. . 0.6 X A X W X RPM grams/lite J.r = p
where: g/l = concentration of the finish in grams per liter
A = % finish desired on the fiber
W = weight of yarn resulting from 1000 revolutions of drying drum = (l9.8662g)
RPM = revolutions per minute of drying drum = (l7.6)
F = feed rate of selected motor-syringe combination were applied to ca. 500 yards of 15 singles, scoured Zefkrome yarn.
A 50 cc syringe and a 10 rpm motor were used so that the feed rate was equal to 35.1 cc per hour (see Table 65 see also Figures 8 and 9).
All nine samples ran extremely well; there was a very even flow from the syringe throughout the runs,
3.6 Fiber to Fiber Friction
3.6.1 Testing Procedure
Nine samples of finished staple (171.25 m moles of finish/Kg of fiber) plus two Zefkrome samples, one with the producer finish and one with the finish extracted were submitted to Mr. J. Conrad Meaders in the
Engineering Experiment Station at Georgia Institute of Technology, for kQ
i^|: Jim "^ • ^^u:yy:', - -. v:^- L'^ ^ ' Btt ^ i.."^ H'J ^' y.' -
Si.'-aa.i^ !-Sij>ife.»."i.'..r.
Figure l6. Zefkrome White with Finish Dyed - 800 x Optical Microscope, 49
Table 6. Solutions Used to Apply Finish to Yarn
Cone, of Solution Applied Amount on Compound to the Fiber Fiber
g/l molar
-•3 C^^Me CI 1.195 4.10 X 10 ^ 6.85 X 10 ^
C,, Me CI 1.310 4.10 X 10-2 6.85 X 10-3 16 C^^Me CI 1.422 4.10 X 10-3 6.85 X 10-3
C,, Me Br 1.495 4.10 X 10-3 6.85 X 10-3 ID C,. Et Br 1.661 4.10 X 10-3 6.85 X 10-3 16 -3 S^P- Br 1.835 4.10 X 10"^ 6.85 X 10 ~^ -3 Pr 2.007 4.10 X 10-3 6.85 X 10 ^ ^6 ^^
C,. Me I 1.686 4.10 X 10-3 6.85 X 10-3 16 -3 C,. Me Me SO 1.618 4.10 X 10-3 6.85 X 16 10 ^ 50
measurement. The finish was applied by the method described in Section
3.4. The measurements were made with a normal force of ca. 20 mg., a
tension of 1164 mg. and under standard or normal conditions. The rela
tive humidity was usually 50-54^ and the temperature 71-75°F (see Figure
17).
3.6.2 Interpretation of Data After frictional data for the fibers had been obtained, the data
sheets from the XY plotter were analyzed. By using planimeter integra
tion, the area under each curve was calculated. Dividing this quantity
by the length of the base line, obtained by inscribing a line on the chart
while the fiber was at rest on the needle, gave the average deflection r o-u JT u Lh in^) (2.54 m/in)^ _, . , ^, ,. •, , of the needle. H = -^^ -^ '• "^— . This deflection was converted L cm
into the kinetic frictional force expressed in milligrams. The normal
force between the fibers was measured before and after each sequence of
tests and a numerical mean obtained. This quantity was also expressed in milligrams. A coefficient of kinetic friction was obtained by using the
following expression: Friction Force _ H (1.83) r r
u, = kinetic coefficient of friction k 1.83 in mg/cm is a conversion factor for the scale (obtained by dividing the average slope of the torque deflection curve by the lever arm used in the calibration procedure).
Np = normal force
H = average deflection
A coefficient of static friction was also obtained by determining 51
the average height of the ten. highest peaks of the trace. This was cal culated using the following expression:
^ . ^. r: H (1.83) Friction Force _ _max r r
H max = Averag3e heighr t of ten highest peaks
Another item of interest was determined from the stick-slip traces, (Table 8 in Results contains these data) the ratio of the coefficient of static friction to the coefficient of kinetic friction (jig/^ij,) .
The average deflection, H and H were also recorded and their ^ ' max relationship to static was observed.
3.7 Fiber to Guide Friction Determination 3.7.1 Testing Procedure
Yarns that were finished on the Atlab Applicator so that they con tained 171.25 m moles of finish/Kg of fiber were run through a pretension- ing device set at one (arbitrary number), over the initial tension measuring head (T„), over one-quarter inch diameter ceramic pins at an angle 560° and over the final tension measuring head (T,) at a constant speed of 50 meters/minute and 28 meters/minute. A 10 gram measuring head was used at T^ and a 100 grams head at T, (see also Figures 10, 11, 12). The values T^, T^ and the coefficient of friction (fi) were recorded on the four channel recorder, [i was calculated directly by the instrument. To obtain adequate data 100-150 yards of each sample were run (15-20 cm on recorder chart run at 3600 min/hr) through the instrument with the resulting fric tion being constantly measured and recorded. 52
3.7.2 Interpretation of Data
The results of measuring the friction in over 100 yards of each sam
ple were calculated from the data obtained from the recorder. The area
under each curve was calculated by using planimeter integrations. The
average deflection of the needle was converted to scale readings (T^ =
1-10; T. = 1-100; \i - O-l) on the chart paper which is 5.5 in. wide (see
Figure 17).
)i results from the Capstan equation, T,/T_ = e^ . (This will be
discussed in the Appendix.)
3.8 Measurements of Static Electricity on the Web in the Carding Process
3.8.1 Method
Twenty grams of the staple (9 samples: each containing 171.25 m mole
of a particular finish/Kg of fiber) were opened by hand and then carded
on a Shirley type metallic card with the gauge ratios of 20/1000 x 1 and
15/1000 X 8 in 10 minutes. The speed of its 320 mm. diameter cylinder was
600 r.p.m. The static electricity on the web was measured with the Field
Mill. The measuring•head of this instrument was fixed vertically at a point 10 cm. above the web surface (see Figure 13, Chapter II), and the
field strength was recorded over about 3-5 minutes. (This is ca, 10 cm. on the recorder chart run at 1200 mm/hr.).
The Field Mill was allowed 'to warm up for a minimum of 30 minutes before use. The first carding did not sufficiently open the sample, so
sometimes the web was not very even. Several additional passes were made through the card. The static field strengths in volts/meter (v/m) were
again measured. It was found that the second and third passes gave a 53
(U > u o § •H •P O •H ^ Cm
00 Q •H O p^ o 00 •p
r^ •H
H
•H P«4
(6w) 3oyoj 54
much more uniform sample which permitted uniform measurements. If the sample was very uneven very erratic results were obtained. Air drafts in the room sometimes affected the distance of the web from the measuring head.
3.8.2 Interpretation of Data
The results of several passes of the finish staple sample through the Shirley card were calculated from the data obtained from the recorder,
By using planimeter integrations, the area under each curve was calcu lated. Dividing this quantity by the length of the base line at zero gave the average deflection of the needle. This reading was converted to scale readings. (The chart paper is 5,5 cm. from the highest negative reading to highest positive readings - see Figure 18.) The static field strength was determined from the scale readings as follows:
Sample Calculation;
(a) if on 0.3K scale (O - 300)
H = (A)(2.54)^
H = Average deflection 2 A = area under curve in (inch)
L = length of base line in cm.
2.54 cm. = inch (conversion factor)
H = scale reading (SR) 2.5/3
SR X 10^ = Field Strength (FS)
(b) if on IK scale (O - lOOO)
H _ CD 0.275 ~ ^^ 55
o or
10 !'10 11
10 i ! i 2.75 cm i I '] ! I I ! y ] i i ! i i i 5.5 cm
-Vi-
Figure l8. Static Field Strength Chart Paper, 56
SR X 10^ = FS
Scales V/M
0.3K 0-300
IK 0-1000
3K 0-3x10^
lOK 0-10x10^
3m 0 - 3x10^
3.^^ Determination of Conductivity in Solution
Solutions were made of the same concentration as those used to
apply the finish to the staple fiber, i.e., 2,285 x 10 m (see Table 5).
A solution was placed in the sample cell and the platinumized
electrode of the conductivity meter was inserted and a reading obtained.
Special precaution was taken so that the electrode would be in the same
position for every measurement. If the electrode was touching the glass
wall of the measuring cell,different readings were obtained.
To calculate the specific conductance or conductivity (ohm cm" ), the conductivity meter reading was multiplied by the cell constant of one and by the multiplier setting on the meter. o _ 1 _ 1
The equivalent conductance ( cm equil ohm ) was calculated by
dividing the conductivity by the number of gram equivalents per liter,
3.10 Determination of Whether a Solution was Above or Below Critical Micelle Concentration (CMC)
A solution of the finish at the concentration (2.285 x 10 m) used
with 3 X 10 m Sky Blue FF dye was made and to this was added ca, 1 ml,
of 2', 7' dichlorofluorescein (0.2^ alcoholic solution). These solutions 57
were then observed for color and fluorescence under ultraviolet light.
If the solution appeared yellow and fluoresced, it was above the CMC.
Also, low foam formation indicated that it was probably below the CMC.
(For more details on this technique see Appendix E.)
3.11 Measurement of Per Cent Moisture
Forty grams of finished fiber were put in the instrument (Acco moisture
Meter) under 800 lbs. pressure and the percent moisture was read directly
off the instrument.
The values were very high because this instrument is designed for
use with cotton and a synthetic hydrophobic fiber registers differently 51 on the instrument, but by dividing the value by three a reasonable figure
, for the percent moisture of unfinished Zefkrome was obtained. Thus all
the value recorded are the adjusted values. 58
CHAPTER IV
DISCUSSION OF RESULTS
During this work several different parameters thought to be involved
in the control of static electricity were measured both on the finished
fiber and with the compounds in solution. From these measurements an
attempt was made to ascertain what effect, if any, the modifications of
molecular structure of the compounds had on the parameters, and what effect
these parameters had on the control of static electricity. All of the num
bers quoted in this section should be considered not as absolute values,
, but as internally consistent with each other.
4.1 Effect of Molecular Structure
4.1.1 Static Build-up
General Remarks on the Measurements. Some of the static readings
were very erratic, i.e., there was considerable variance (see Figure 19)
and some were very even (see Figure 20). The degree of openness of the
web greatly affected the evenness of static recorded as can be seen by
the C , Bu Br sample (Figure 20).
As the card web became more even on the second and third passes,
the results were more uniform. Also the very low readings (below 80 v/m)
seem to be effected by "noise" in the system (Figures 21 and 22).
Effect of the Fatty Chain Length. The molecular structure seems
to be very important in determining whether a compound is an antistatic
agent or not. When the fatty chain length of the alkyl trimethyl ammonium 59
3rd PASS
1 M IIIi | ||]ii ||!|li|ii 1 ^ ! j V4 i 2nd PASS i i ^'1
i i j 1 ^t^»_ L I ^0.3 KU i SCALE 1 1 h, ilf 1 M SJI M 1 !^ ill ! . 1 i 111 i I i Mil i i i i 1! 1 i 1 1 1 i1}M i M ! : 1 I Li i M ! /1 i M i 1 Ml 4a'l! 60 IBO MOO 0 20 ! i .i...l I. M M i ' ^ Ml 1 MMMill' !^ rt i iTTTi^j^:O - ! 1st PASS
Figure 19. C^ Me Br Static Figure 20. C . Bu Br Static Field Strength. Field Strength. 60
3rd PASS
2nd PASS
Figure 21. C^ Me CI Static Figure 22. Co Me CI Static Field Strength. Field Strength. 61
chloride samples increases from C.. to C., to C^_, the static charge slightly increases. All three compounds produced a very low static charge and there was very little difference noticed among them. (See
Figure 23 and Table 7). It might be noted, though, that the C.^ sample displays a very low field strength (v/m) reading that may actually be due to "noise" in the system rather than static charge. The C., and C.Q samples are essentially the same. Therefore, it seems that an optimum chain length for the n-alkyl radicals appears to be about C, ..
Effect of Small Groups Around the Nitrogen. When the three small groups around the nitrogen are varied from methyl to ethyl to n-propyl to n-butyl, a drastic difference in field strength occurs. The methyl compound has a field strength (v/m) reading of between 17 and 23,000,
This is about the range where an observer can begin to visually see indi cations of static, i.e., card web ballooning. The triethyl was around
1200 and the tri-n-propyl and tri-n-butyl were essentially equal and around
160. (See Figure 23 and Table 7). The reason for this difference may be due to the well established tendency of sterically hindered quaternary ammonium ions to remain dissociated rather than paired with the counter- ion. Weaver et al. showed that the dissociation constant in ethylene chloride of n-octadecyl tri-n-butyl ammonium iodide is approximately ten times that of the corresponding trimethyl salt. The optimum chain length for the three smaller groups around the nitrogen appears to be n-propyl because the n-propyl and n-butyl groups are about equal for the control of static build-up.
Vibrations of the machine affecting the most sensitive measuring scale in the most sensitive region, i.e., the lowest region. 62
5.0 > ^ -o
o jo-
4-1 00
Qi 0< M 4J 4.0-
•H Pt,
O •H •U CO U (0 O
3.0- 4J o a; 1-w1
2.0-
1.0
Molecular Modification (R or X )
Cl6 . Cie RNMeoCifol l ••14
C16H33MfeoBr"3 Me Et Pr Bu
CisHgsfclegX" CI Br MeSO.
Figure 23. Electrostatic Field Strength Versus Molecular Modificati ons Table 7. Static Field Strength and Moisture Regain of the Fiber plus Finish
^^^ Moisture Regain Compound R.H. jop Pass Static Field Strength (v/m) Visual^ @ 6b% R.H. R R, X % ave. high low Rating Scale/3 Relative
^nd CI 40 72 -33.4 0.00 1 3.57 2.02 ^14 ^^ -77.8 3ll -22.8 -98.0 0.00 1 C, , Me CI 40 72 pnd -72.0 -196.0 0.00 1 2.92 1.65 ID ord -76.0 -239.0 0.00 1 C.gMe CI 40 72 ond +82.1 +185.2 0.00 1 2.80 1.58 ^rd +75.9 +131.0 0.00 1 C^^Me Br 40 72 pHd -17.1>:10 2 -34.6x10;: -11.0x10 2 2.74 1.55 ^rd -23.1>;10 2 -43.6x10^ -20.2x10^ 2 Br 40 72 ond -1166 -1915 -0.00 1 2.60 1.47 ^16" 3rd -1342 -2510 -0.00 1 Br. 40 72 pnd +166.0 +170.0 +157.0 1 1.84 1.04 ^6^^ 3— +158.0 +251.0 +137.0 1 2nd Br 40 72 +161.7 +207.0 +131.0 1 1.84 1.04 <=16^" ^rd +151.0 +174.5 +142.0 1 2nd C,, Me I 40 72 -85.Ox:10 ? -54.5x10^ 3 1.77 1.00 io ^rd -87.3x10^ -io9xio:-120x10^r -79.6x10^ 3 C,^ Me MeSO^ 40 72 oils. -57.7x:10 ^ -83.6x10^ -47.3x10^ 3 2.14 1.21 16 Zefkrome 40 72 -251x10,3^ * 169x10^ 4 1.44 unfinished 1.07*
^ 40^ R.H. clogged up machine; only short measurement 1 is very good; 4 is very poor
CO 64
Effect of the Counteranion. When only the counteranion in palmityl
trimethyl ammonium salts is varied, the most drastic difference in field
strength is noticed. The static field strength varies from a low of 75
v/m for the chloride sample to a value of ca. 86,000 v/m for the iodide
sample (see Table 7 and Figure 23); the order of effectiveness of the
counteranion is:
Cl" » Br' » MeSO^" » l'
Therefore, chlorides seem to be the most effective compounds.
4.1.2 Yarn-to-Guide Friction
General Remarks on Measurements. It was noticed that by running
the samples at a lower speed, i.e., 28 m/min instead of 50 m/min, more
differences were noticed between samples as well as much less stick-slip.
This is contrary to what is usually assumed, viz., higher speed less stick-
slip. Though it might be added that all of these compounds, with the
exception of the triethyl, tripropyl and tributyl ammonium bromides,
lowered the friction considerably and that several of them had high stick-
slip. Whereas the stick-slip of the poorer stick-slip samples was
improved by lowering the speed, the stick-slip of the better samples was
not greatly altered (see Figures 24 and 25). It was thus decided to use
the data obtained at 28 m/min for the interpretation of trends in this work.
Effect of Molecular Structure. The coefficient of dynamic yarn-to- guide friction (jij. ) varies as is theoretically expected with molecular ^Y-G alterations (see Figure 26 and Table 8). As the fatty chain length increases p.„ decreases, and as the three small groups around the nitrogen increase Y-G in chain length, p.„ increases. However there is not much difference ^Y-G 65
@ 50 M/MIN.
lf!j' L^^JH.!! ! II ! ! !1 J^jift" I, 1 1 1 1 i '""' II I." - '' f " i ' i Sl 1 ' i 91 ' "T''iX^^ ! I ' 1 1 1 "hiJ-I^JM^^i i ! 1 1 [i 1 I 1 1 1 1 1 LbpFi 1 1 1 i ! 1 TSTi 1 i-|fi' 1 1 i 1 1 -t- H-' -*^.5^ ^F"' -1 • 1 ll^^5\^L - •' "^' , [i 1' "•• j 1 1^ 1 ' i j i tfrTKi i' 00 i ! 1 ^^^&P\ i 1 ^ i 1 .mml 1 i l^e-il ! 1 j i ^5M1| i 1 1 1
9Z1l ! \ t^T, Mi N 1 1 1 1 ! j \i^sr 1 i ( 1 j 1 TT* -J' *" 1.1 • 1 1 I- ilST] 3^4-^1 ..ttwfijVUj/..OSJOt._.( --• tkjl- ••[• 9n f i"**" .... j U-f^ffiT^S LU III V i ^^B-A I_L1II 11 Ijl 4-i !L i^s. i iq i i '^MJ> 10-- • r- J T^-"-'-Tptej|f i I i r*Lgarf4^ !1.L.L1J _ rl-ii^fci i . 1 1 1 1 _J-^^iW* \^' \ 1 ^tTHlliIi @ 28 M/MIN, "T —T"—r i 1 i:' 10 i •' W N 1^ 1. 1 ill! Oh .i.a^^d4^6G'4- 80 Wo 0 - ,24 --to 60 80 100 1 i 1 T 1 1 j j l| ^ 11. 1 II n^' 1 j fc Tjt ^ 1 10J-| ff KF 1 •fi , 1 n 1 n tg y ^^ ' 1
'ft 1 1 R-4- —'• "•]"' ' 0 13^ 1 i 11 1 L ^ijiii 1 1 i FINAL TENSION INITIAL TENSION COEFFICIENT OF FRICTION
Figure 2k. C-^ Me Br Yarn-to-Guide Friction. 66
@ 50 M/MIN.
oq r Me MeSO, Yarn-to-Guide Friction. Figure 25. '--i^ ^^^ iicuw^ 67
/f 0.300
X y I 0.260- @50m/min ^^
®50m/min @50m/inin J
0.220- @28in/min
@28in/inin o-
0.180
@28m/min
Molecular Modifications b (R or X") 1 , > RSMegCl Ci4 Cie Ci8
CisHgafasBr" Me Et Pr Bu
CisHgaSMegX" CI Br MeSO I
Figure 26. Coefficient of Yarn-to-Guide Friction Versus Molecular Modifications Table 8. Frictional Properties of the Fiber Containing the Different Finishes.
Compound ^ Fiber-to-Fiber Friction _ R R, X A in u^ ± S.D. LL_ ± S.D. H H M-cAi/ i K. o max o K
C^^ Me CI 6.75 0.212 ± .033 0.425 ± .049 4.71 2.35 2.02
C, Me CI 6.22 0.198 ± .018 0.433 ± .029 4.70 2.15 2.20 i6 C,„ Me CI 7.58 0.245 ± .026 0.530 ± .062 5.71 2.66 2.17 io C, Me Br 5.75 0.186 ± .016 0.372 ± .045 4.04 2.01 1.98 i6 C.^ Et Br 6.37 0.204 ± .037 0.409 ± .068 4.47 2.45 2.03 16 C,, Pr Br 6.99 0.220 ± .010 0.405 ± .031 4.46 2.49 1.81 16 Z,, Bu Br 6.75 0.213 ± .026 0.414 ± .029 4.56 2.35 1.96 16 C,, Me I 6.97 0.223 ± .029 0.441 ± .044 4.87 2.43 1.99 16 C,^ Me MeSO. 6.99 0.224 ± .032 0.469 ± .034 5.29 2.54 2.12 16 4 Zefkrome 9.03 0.291 ± .033 0.609 ± .093 7.35 3.14 2.10 unfinished
(Continued)
00 Table 8. Frictional Properties of the Fiber Containing the Different Finishes (Continued)
Yarn -to-guide Friction Compc3un d Speed M- Initial Tension Fi.na l Tension R R X m/min ave. ave. high low ave. high low
^14 Me CI 50 0.244 3.47 5.09 2.00 27.3 50.9 10.9 28 0.250 3.73 4.55 2.73 37.7 49.0 23.6 C, , Me CI 50 0.228 6.06 9.45 1.82 58.6 90.9 14.5 16 28 0.212 3.80 5.09 2.55 32.5 45.5 18.2 C^gMe CI 50 0.223 3.59 5.64 2.00 30.5 54.9 10.9 28 0.164 3.75 5.26 2.18 13.1 23.6 7.27 C, - Me Br 50 0.259 2.39 5.45 2.19 37.7 65.5 29.1 io 28 0.217 3.52 4.60 3.18 25.6 40.0 12.7 Se" Br 50 0.276 4.69 7.28 3.28 68.2 98.2 42.0 28 0.272 4.45 5.45 3.09 47.2 83.6 47.2 C,^ Pr Br 50 0.285 3.49 5.64 2.18 50.7 80.0 29.1 ID 28 0.284 4.08 5.09 3.09 55.0 67.3 40.0 C,^ Bu Br 50 0.308 4.98 7.28 2.18 73.1 98.3 60.0 16 28 0.292 4.43 6.00 3.77 64.9 80.0 43.6 C- , Me I 50 16 28 C, , Me MeSO. 50 0.219 5.61 9.45 1.46 39.9 90.9 9.09 16 28 0.195 3.13 4.55 1.82 17.6 27.3 9-1 Zefkrome 28 >0.300* 4.70* 5.82"^ 3.82'^ 70. 2^^ 90.9* 56.4* unfinished
Could not really run - kept breaking after a few sec- damages fiber so not a true reading Required much different conditions to make this sample-compound - much less water soluble than the other
\0 70
between the ethyl, propyl and butyl compounds. The counterion has little effect on p.^ (at 28 m/'min). This is to be expected as the alkyl Y-G chains are usually considered to have the most pertinency in the decrease of friction.
4.1.3 Fiber-to-Fiber Friction
Kinetic Coefficient of Friction {[L^ ). This parameter seemed to F-F vary with molecular structure in the following manner:
"^16 ~ ^14 ^ ^18
Me < Et < Bu = Pr
Br"= Cl" < l"= MeSO^"
Although insufficient data were available for a statistical analysis, it was interesting to note that trends were noticed that were reasonable. The coefficient of variation for all of the samples except one (C,, Et Br) was below 15 per cent (see Figure 27 and Table 8)
Static Coefficient of Friction (ii^ ). This parameter varied with ^F-F molecular structure in the following manner:
^4 < S6 << ^8
^Ae < Pr = Et = Bu (methyl much less than other three which are about the same)
Br'"< < Cr= l"< MeSO^'
(See Table 8 and Figure 28).
When compared to the unfinished Zefkrome control samples, ail 71
0.260 •[
0.220
0.180
Molecular Modifications (R or X~)
R-SkeaCr Ci6 Cx8 Bu CisHggNRsBr Me Et Pr I CieHagSMegX" CI Br MeS04
Figure 27. Coefficient of Kinetic Fiber-to-Fiber Friction Versus Molecular Modifications 72
I P4 en
0.500
0.460
0.420-
/ 0.380 Molecular Modifications (R or X~) « ^ RSMe3Cl Cx4 Ci6 Cie
CisHsafesBr" Me Et Pr Bu
JISHSSSM eX CI Br Me SO. I
Figure 28. Coefficient of Static Fiber-to-Fiber Friction Versus Molecular Modifications 73
of these compounds significantly lower the fiber-to-fiber friction (both
[i^ and \i^ ) with the possible exception of C. „ Me CI, and its values F-F F-F are still much lower than the unfinished control. It is also interesting to note that the effect of the fatty chain length on the fiber-to-fiber friction is in the opposite direction to its effect on yard-to-guide fric tion. The effect of the small groups around the nitrogen seems to be
similar for both fiber-to-fiber and yarn-to-guide friction. The counter- ion seems to affect fiber-to-fiber friction more than yarn-to-guide fric tion.
4,1.4 Conductivity in Aqueous Solution
The results from measuring the conductivity in aqueous solution of these compounds indicate that the fatty chain length seems to be important in determining the effectiveness of a particular solution as a conductor
(See Figure 29, Table 9).
^4 > ^ ^16 ^ ^ Ss
This is probably due to CMC and the number of dissociated anions present. If the compound has a chloride counteranion it is a much better conductor than compounds with either bromide or methyl sulfate counterions,
cr> > Br"'= MeSO^'
(see Figure 29, Table 9). The smaller groups around the nitrogen have the following effect,
Et > Me = Pr = Bu
(Figure 29, Table 9). Some of the data obtained here, though orderly. 74
A
5.0 o I—I X >^ 4-1 •H > 4J O ^3 C 4.5- O
3.5
3.0-
Molecular Modifications (R or X )
> RfelegCr Cx4 Ci6 Cx8
CieHssSRsBr" Me Et Pr Bu
CieHssSMegX" CI Br MeS04 I
Figure 29. Conductivity of the Compound in Solution Versus Molecular Modifications Table 9. Solution Properties of the Compounds
Compound Molar Cone. (5)30QC @300C Above Rg ohm/cm C ohrn"^ cm ^ cm /equil ohm R R X pH 1 cmc
-3 -4 C^^ Me CI 2.285 X 10 Yes' 1750 5.72 X 10 25.00 5.24 .-3 C,^ Me CI 2.285 X 10 Yes 2410 4.15 X 10-4 18.20 4.90 16 -3 C^„ Me CI 2.285 X 10 Yes 3430 2.92 X 10 12.77 5.40 lo -3 -4 C,, Me Br 2.285 X 10 Yes 3055 3.28 X 10 14.35 5.60 16 -3 -4 C., Et Br 2.285 X 10 Yes 2565 3.90 X 10 17.06 5.50 16 -3 -4 C^^ Pr Br 2.285 X 10 Yes 3210 3.12 X 10 13.74 16 5.25 -3 -4 C.. Bu Br 2.285 X 10' Yes 3340 2.96 X 10 12.94 5.55 16 C,, Me I 2.285 X 10" Yes 16 -3 C,^ Me MeSO 2.285 X 10 Yes 3145 3.18 X 10 14.10 3.90 16
does not fluoresce as much as others but still above cmc
-J 76
seem to indicate that specific conductance (conductivity) of a micellar colloid in aqueous solution is a property that is peculiar to a compound.
4,1.5 Moisture Regain of the Fiber plus Finish
Moisture regain seems to give a very reasonable correlation with molecular structure.
^14 > ^16 ^ ^18
Me > Et » Pr = Bu
Cf > Br" » MeSO^"> l"
In general, it is what would be expected from the ratio of hydrophobic to hydrophilic portions of the molecules. Also, it is conceivable that one counteranion should lead to a higher moisture regain than another
(see Figure 30, Table 9).
4.2 The Effect of Different Parameters on Static Build-up
It can be essentially said that conductivity in solution, per cent moisture regain, and frictional properties do not directly correlate with static elimination (see Figures 31 - 35).
As mentioned in the introduction, there are two main types of mechanisms which different authors think play the most important role in the functioning of a compound as an antistatic agent. The minority of authors strongly defends the mechanisms which reduce or prevent charge generation, whereas the majority favors the mechanisms through which dis- sipative processes provide the bulk of antistatic action.
The results of this work favor the latter mechanism as a correlation 77
3.5 •H a GO 0) pi!
4J CO •H O
OJ CM
2.5
K
1.5
Molecular Modifications (R or X )
RfeleaCl ^14 Cjs Cx8
CieHasSRgBr" ^e Et Pr Bu
CisHssfaesX" CI Br MeS04 I
Figure 30. Moisture Regain of the Fiber plus Finish Versus Molecular Modifications 5.0
4.0-
3.0-
2.0 -
U. '^-<
.180 .220 .260 .300
Figure 31. Electrostatic Field Strength Versus Kinetic Coefficient Of Yarn-to-Guide Friction
00 s > 5.0 f (JO o
60 C
CO 4.0 - cu •r-l [x<
O •H 4.) CtJ 4-t W o •u 3.0 - o cu .—I
2.0--
%-]
180 .220 .260 300
Figure 32. Electrostatic Field Strength Versus Kinetic Coefficient of Fiber-to-Fiber Friction F-F
380 .420 ,460 500 .530
Figure 33. Electrostatic Field Strength Versus Static Coefficient of Fiber-to-Fiber Friction
00 o E > 5.0- 00 o
GO c QJ U •U CO 4.0 x) I—I 0) •H
4J cd 4-1 o 3.0- 4-1 a T-i
2.0-
Per Cent Moisture Regain
L_^ 1.0 2.0 3.0 4.0
Figure 34. Electrostatic Field Strength Versus Moisture Regain of the Fiber plus Finish
00 e
>• o
Xi u &0 4.0- 0) u 4J CO X) tu •H
o •H •U nJ •u 3.0 CO o 4-) O OJ
W
2.0 -
Conductivity x 10* (cm ^ ohm"^)
3.5 4.5 5.5
Figure 35. Electrostatic Field Strength Versus Conductivity of the Compounds in Solution
00 83
between frictional properties {[i^ , p.j, , p.^ ), and static was not Y-G F-F F-F observed if just coefficients of friction were plotted versus the log of
static. It was noted that if each alteration in molecular structure, viz., length of the fatty chain, length of the smaller groups around the nitrogen and counterion, was observed separately versus the log of static
build-up, that the following trends were noticed: |i„ As the frictional values of the fatty chain and smaller ^Y-G groups around the nitrogen varied compounds increase, the
static build-up decreases (inverse relationship). There was no correlation between counterion varied compounds and static build-up.
[ij. As the frictional values of the small groups around the nitrogen varied compounds increases, the static build-up decreases (inverse relationship). There was no correla tion between fatty chain length and counterion varied compounds and static build-up. p-c As the frictional values of the fatty chain length varied ^F-F compounds increases, the static build-up increases (direct relationship). As the frictional values of the smaller groups around the nitrogen varied compounds increase, static build-up decreases (inverse relationship). There was no correlation between counterion varied compounds and static build-up.
(see Figures 36, 37, 38). Thus it appeared that in most cases there was either an inverse correlation or no correlation between frictional values and static build-up when the individual molecular modifications were observed versus static build-up. In only the static coefficient of (c) a. > 00 (a) fatty chain length o (b) groups around nitrogen 4-1 00 4.0- c (c) counterion Q) U +J CO
r-)
3.0" 4J CO
2.0- -o (b)
(a)
UK Y-G
0.180 0.220 0.260 0.300
Figure 36. Electrostatic Field Strength Versus |J. of the (a) Fatty Chain Length Varied \-i Compounds (b) Small Groups Around the Nitrogen Varied Compounds (c) Counterion • Varied Compounds
00 4> 5.0- > 9 (c) GO o J5 (a) Fatty Chain Length
CJO (b) Groups Around Nitrogen C u u (c) Counterion CO 4.0"
a •H •p
CO o u 3.0 -. •M o w
2.0 -,
US- 1
.180 .220 .260 Figure 37. Electrostatic Field Strength Versus of the (a) Fatty Chain Length Varied \-i Compounds (b) Small Groups Around the Nitrogen Varied Compounds (c) Counterion 00 Varied Compounds (c) o~ _ _ ^ ~-—o
4.0" (a) Fatty Chain Length
(b) Groups Around Nitrogen
(c) Counterion
3.0 -
2.0--
U, F-F
0.380 0.420 0.460 0.500 Figure 38. Electrostatic Field Strength Versus \1 of the (a) Fatty Chain Length Varied F-F Compounds (b) Small Groups Around the Nitrogen Varied Compounds (c) Counterion Varied Compounds
00 87
fiber-to-fiber friction of the fatty chain varied compounds versus static build-up was a direct relationship noticed.
The degree of dissociation of these compounds as measured by the conductivity in solution does not appear to be the same as the dissocia tion of ions on the fiber. This difference appears reasonable since the compounds exist in a micellar form in solution as opposed to an indetermin- ant form on the fiber. The form on the fiber is probably closer to uni- molecular than micellar. The probable steric hindered ion-pair formation as observed with the palmityl trialkyl ammonium bromide compounds seems to indicate this. There does seem to be a reasonable correlation between the effect of fatty chain length and counteranion, on conductivity in solution and the effects of these parameters on static build-up (see Figure
39), but when conductivity values for all of the compound are plotted versus the log of static no correlation is noticed.
Moisture regain of the fiber plus finish would seem to indicate the relative mobility of a charge along the surface of the fiber. If each alteration in molecular structure, viz., length of fatty chain, length of smaller chains around the nitrogen and counteranion, is observed sepa rately, a direct correlation is noticed between static elimination and the moisture regain of two of the parameters (length of fatty chain and counteranion) but the other parameter has an inverse relationship between its moisture regain and field strength (see graph 40). This would indi cate that the supposed steric hindered ion-pair formation is important in how a charge is dispersed along the surface of the fiber.
Although the second and more popular mechanism seems to be supported > (c) ^ (a) Fatty Chain Length O (b) Groups Around Nitrogen
00 (c) Counterion 4.O.- c 0) !-i c•t-nJ X) t-l 0)
•I-l o •H 3.0 -- +J CO w o u +-oI I—wI
2.0"
Conductivity XIO* (cm ^ ohm"^) _l > 3.5 4.5 5.5
Figure 39 Electrostatic Field Strength Versus the Conductivity in Solution of the (a) Fatty Chain Length Varied Compounds (b) Small Groups Around the Nitrogen Varied Compounds (c) Counterion Varied Compounds
00 00 >^ (c) > -o^ (a) Fatty Chain Length WD O (b) Groups Around Nitrogen
00 (c) Counterion 4.0-- 0) u
•H fx^
O •H -M Ct 4-1 3.0- W o 5-1 4-t O
Per Cent Moisture Regain
1.5 2.5 3.5
Figure 40. Electrostatic Field Strength Versus Per Cent Moisture Regain of Fiber plus Finish of the (a) Fatty Chain Length Varied Compounds (b) Small Groups Around the Nitrogen Varied Compounds (c) Counterion Varied Compounds 00 90
by this work, it should also be remembered that all of the mechanisms probably contribute to a greater or lesser degree to the performance of an agent. 91
CHAPTER V
CONCLUSIONS
5.1 General
The effect of molecular modifications of n-alkyl trialkyl quater nary ammonium salts in relation to their antistatic properties on poly- acrylonitrile fiber has been studied. Relationships have been shown between the presence of various counteranions, groups around the nitrogen, and fatty chain length and the effectiveness of an antistatic agent. Other parameters which were thought to be important in the mechanism of static control have also been investigated, and relationships between molecular structure and the effectiveness of the compounds have been observed. Also the relationship between these parameters and static control have been described.
5.2 Specific Conclusion
1. The counteranion of a quaternary ammonium salt is a very important factor in whether the compound functions as an antistatic agent or not.
Chlorides seem to be by far the most effective, compared to bromide, iodide and methylsulfate.
2. The three groups around the nitrogen, other than the fatty chain, are important in whether a compound will be an antistatic agent or not.
The antistatic properties of a compound improve as the groups get bulkier.
This seems to support the view that steric hindered ion-pair formation 92
occurs when the groups get bulkier. The optimum chain length for the smaller n-alkyl groups appears to be n-propyl.
3. There seems to be no general correlation between frictional properties {[i^ > V'y f ^y ) of a compound and its performance as ^F-F F-F Y-G an antistatic agent. If the frictional properties of each alteration in molecular structure are separately plotted versus the log of static field strength, an inverse relationship or no correlation is observed except in the case of the fatty chain length varied compounds fric tional properties versus static build-up. In this case a direct relation ship is noted. These data seem to support the mechanisms for static electrical control which suggest that an antistatic agent functions by dissipating static charges rather than by preventing or reducing charge generation.
4. No general correlations were found between moisture regain of the fiber plus finish and conductivity in solution and static electrical con trol. There does seem to be a reasonable correlation between the effect of fatty chain length and counterion, on conductivity in solution and the effects of these parameters on static build-up. If each alteration in molecular structure is observed separately versus moisture regain, a direct correlation is noticed between static elimination and the moisture regain of two of the parameters (length of fatty chain and counterion), but the other parameter has an inverse relationship (small groups around the nitro gen) .
5. The optimum chain length for the fatty n-alkyl radical appears to be about C^ ., but it does not seem to have much influence on static elimi nation. 93
CHAPTER VI
RECOMMENDATIONS
The antistatic agents evaluated in this thesis are linear alkyl quaternary ammonium salts. There are many commercially available cationic antistatic agents which are based on heterocyclic quaternary ammonium salts. It would be interesting for someone to study the effect of molecular modifications of, e.g., imidazolinium quaternary ammonium salts, on their antistatic properties. It would be interesting to see if the counteranion was as important as it is in this work. Also many of these compounds contain a ethylol group as well as an ethyl group such as:
Ci>' A
where R = fatty chain
X"= counteranion
These compounds may be effective antistats because of the presence of steric hindered ion-pair formation. This could be shown by using just methyl group and using a counterion other than chloride.
A comparison of conductivity in aqueous solution of amphipathic electrolytes with their conductivity in a solvent where they would exist in unimolecular form and their conductivity on the fiber would be of importance. This could lead to a better understanding of how a particu lar compound actually exists on the surface of the fiber.
Of particular interest would be a surface chemistry study of how 94
a compound that functions as an antistatic agent is actually sorbed on the surface of a thermoplastic, essentially hydrophobic synthetic fiber.
A study of the effect of surface tension and viscosity of a com
pound on its antistatic properties would help in postulating a mechanism
on how antistatic agents actually function.
A related area of study would be an investigation of the fiber-to
fiber friction of lubricants that help make up a spin finish combination.
Also observing what effects the other additives have on the antistatic
agent in a spin finish combination.
Some of the compounds used in this thesis may have commercial impor
tance or lead to compounds of commercial importance, A study of synthesis
and cost of manufacture might be of interest. APPENDICES 96
APPENDIX A
SYNTHESIS OF HIGHER MOLECULAR WEIGHT
QUATERNARY AMMONIUM SALTS
In the reaction of an alkyl halide or some other alkylating agent with an amine to form an amine of the next higher class, the alkyl halide undergoes a nucleophilic substitution with the basic amine severing as the 19 nucleophilic reagent. The ease with which amino compounds undergo alkylation is related to their bascity, which is diminished by the attach- 69 ment of radicals such as acyl that are electron poor. The order of de creasing basicity of amines is R^NH > RNH^ > NH^. Therefore the reaction becomes successively easier and harder to control
+ NH^ RCl ^ RNH^ _^ R2NH _^ R^N _^ R^N as more alkylating agent is present. This is true if R is less than 70 n-butyl. From this it would seem that reactions for forming a quaternary ammonium salt are so straight forward that all that is necessary in synthesis is to put the appropriate primary fatty amine in the same vessel with the correct alkyl halide. This does not seem to be the case for quaternary ammonium compounds with the three smaller end groups larger than ethyl.
According to the literature found there are three main ways of synthesizing higher quaternary ammonium salts of the following structures: 97
R"^ — N - R ' x"
Where R = 0^2^25" ^° SS^ST" R'= CH3- to C^Hg-
X"= halogen or MeSO^, EtSO^
Type 1 + R-NH + R' X KOH, R-NR ' X" ^ NaOH ^ or Na^CO^
71 In this reaction a solution of the fatty amine hydrochloride in methanol is in a flask and to it is added, in step wise fashion, one equivalent of halide plus one equivalent of base. When the reaction becomes neutral or acid to litmus the same quantities of base and halide are added. This is repeated until three equivalents of both halide and base have been added. Then excess of both are added so that the total mixture contains one equivalent of fatty amine, 3.8 equivalents of halide and 4.5 equivalents of base. This product is collected, after distilling off the methanol and precipitating the methhalide, washed, and recrystallized from acetone. 72 Eriksen et al suggested refluxing alcoholic solutions of primary amines with alkyl iodides. The reaction mixtures were main tained at a pH of about nine by periodic addition of ethanolic potassium hydroxide.
This procedure was tried in the synthesis of some of the com- + pounds in this work and was only successful in the case of C^ ,H_-r-N-Me^ I ID 00 3
The order of reactivity of halides is, RI > RBr > RCl. Also n-alkyl halides above methyl are not as reactive as methyl halides. It seems 98
that the products that were formed in this work when the above reaction was tried (reflux C.^H^^NH^ + RBr + KOH in 9b% ethanol for one to seven it) OO Z days) were the dialkyl quaternary ammonium halides, instead of the tetra- alkyl compounds.
Type 2 RNH > RNMe^
RNMe^ > RNMe^ X
This type of reaction involves making the tertiary amine first and then doing a simple alkylation with a small alkyl halide. The reactions of this kind found in the literature dealt with, for the most part, the forming of dimethyl compounds and not the higher analogs, e.g., diethyl or dipropyl.
The methylation is usually accomplished with formaldehyde and formic acid. ' There is mentioned the forming of smaller alkyl tertiary amines, e.g., ethyl isopropyl methyl amine. Ethyl isopropyl methyl amine is prepared from acetone, ethylamine or acetaldehyde and isopropyl- amine by hydrogenation in methanol. It is not known if the reaction of an aldehyde plus its acid analog is a general alkylation reaction, but if it is, this would be a convenient method of making the tertiary amine.
The second step of this reaction to the quaternary ammonium salts is fairly straight forward. In this thesis the n-palmityl dimethyl amine was purchased and reacted with methyl iodide and dimethyl sulfate.
The results of these reactions were very favorable as they were almost quantitative at room temperature in about 30 minutes. In fact the react ion should be done by dropwise addition of the alkylating agent to the tertiary amine in alcoholic solution. 99
74 Shelton et al suggested using a 25-75^ excess of halide when forming the quaternary ammonium salt from R-NR„ (where R is fatty alkyl and R is a small alkyl group) plus a low M.W. halide. This is probably necessary if an alkylating agent above methyl or less reactive than iodide is used. They also indicated that C^ ,NMe^MeSO ~ could be made by reacting dimethyl sulfate with palmityl dimethyl amine.
Type 3
R_N + RX > RNR^ X
This type of reaction seemed to be the most used method in the literature covered and was the only satisfactory way observed to make quaternary ammonium salts with three alkyl groups larger than methyl.
The addition of tertiary amines to higher 1-chloroparaffins to form quaternary ammonium salts can be done, if at all, in suitable 70 solvents and within relatively narrow temperature ranges
1-chlorohexadecane and lower alkyl chains haloparaffins can be reacted with trimethylamine in alcohol (but not in water, acetone or without solvent) below 110°C almost quantitatively triethyl and tri-n- butyl amine react only very slugglishly here. When the reaction with
Me N is run above 110°C the yield decreases rapidly. It is also advisable to employ the tertiary amine in excess, 74 Shelton et al indicated that the reaction of a long chain alkyl halide plus a tertiary amine (a slight to 100 percent excess of amine) gave satisfactory yields of quaternary ammonium salts by
1. letting the reaction stand several days at room temperature
2. refluxing the mixture several hours
3. heating to 80-125°C in a closed vessel. 100
They said that chlorides, bromides and iodides could be made this way.
They also suggested that by adding the appropriate silver salt to
palmityl trimethyl ammonium bromide in alcoholic solution the acetate, 73 nitrate, sulfate, etc. ammonium salt could be synthesized. Robinson
also indicated that the chloride quaternary ammonium salts could be
made by adding silver chloride to the iodide quaternary salts. 75 Bromides and chlorides were made by Adam and Pankhurst by
reacting a long chain paraffinic halide with Me^N in nitromethane.
They also indicated that the iodides could be made by double decompo
sition of the bromides or chlorides with aqueous potassium iodide.
Scott and Tartar synthesized long chain trimethyl ammonium
bromides by refluxing Me N in alcohol with the appropriate 1-bromo
paraffin for one hour or more.
Compounds similar to one used in this thesis, with iodide counter
ions instead of bromide, were made by Weaver et al in the following
manner
(10% excess)
(The reaction was run in a stoppered flask at 60°C for four - six days^ and n-C^gH^^I + Me^H —> n-C^gH^^Me^ l"
(This reaction was run in a sealed tube at 60°C for seven to 10 days.)
In the work for this thesis, in order to make the palmityl triethyl,
tri-n-propyl and tri-n-butyl ammonium bromides, it was necessary to
reflux 1-bromohexadecane plus the correct tertiary amine in 9b%
ethanol solution for from one to seven days. 101
APPENDIX B
IMFRARED SPECTROSCOPY OF FATTY
QUATERNARY AMMONIUM COMPOUNDS
The quaternary nitrogen ions do not show any characteristic infrared absorption in the normal NaCl range , Also they have no
UV/vis. absorption as do the primary, secondary and tertiary amines because they contain no unshared electrons. Infrared analysis of such compounds is restricted to the identification of the substituents, while the quaternary character of the nitrogen atom is to be inferred from other properties, such as good water solubility. Other properties are the absence of N-H stretch and bending vibrations and C-N vibrations of primary, secondary amines and amine salts and the absence of C-N vibration in tertiary amines.
Since the compounds used in this thesis are of the aliphatic type, they will be the only ones discussed.
1. Lauryl, myristyl, palmityl and Stearyl-trimethyl ammonium halides. These are fatty alkyl trimethyl ammonium halides of the general formula:
CH^
-N-CH, X
CH,
The spectra of these compounds are simple. Since there are no characteristic NR. absorptions, the bands of the aliphatic residues appear only. (See Spectra Figures 41 -45). 'TIWl ^TI^S s'B una -la Q-a ^'''O 'ejcci.osds psJt^Jcjui -gti ajngij;
'Tinw Q-TI^S SB una ^OS^lAl SW ^"^0 ^Jq-osdg paj-BJCjuj '3+1 ajn^x^
OOSC 000c OOEE OOOf
'Iinw ^Tld^S SB una I aw ^^0 'Bjq.Dsds psaBjcjui 'i+| sjnSxji
OOOJ OOSI OOOE OOSE
SOI 103
WAVELENGTH IN MICRONS 5 3 3.5 * 4.5 5 5.5 6 i.5 7 7.5 8 9 10 11 12 14 16
ESnas* ^iliirifflllllllllll III llttftfete SSPP - ^SM MBwlfB S^^fflj^fflMI 1 WrmW- B^^BMH|M itipiiifeW^ T ^ffi^^Hilifiwi Iqgi^
; iiii 1800 1600 1400 1200 1000 800 600
WAVENUMBER CM'
Figure kk. Infrared Spectra C^ Pr Br Run as Split Mull.
Figure i+5. Infrared Spectra C^ Bu Br Run as Split Mull. 104
There are characteristic absorption bands in the range of 10-11 \i
(1,000 -910 CM. ~ ), which probably result from C-N stretching vibrations coupling with one another as a result of the trimethyl ammonium structure of these compounds. Two strong bands are usually observed if these compounds are run in liquid, of pastelike form, or run as a mull. The more intensive band is about 10.3 ji (972 cm l) and the other at ca. 11 [i (910 cm ""). If the samples are crystalline products and run as KBr pellets, these absorptions split into several
sharp bands, their wavelengths and intensities depending strongly upon the degree of crystallization and the type of molecule. The crystalline
state can also be recognized by the splitting of the methylene vibration at 13.9 [i (720 cm ' ) into two sharp bands at 13.7 ^L (730 cm."') and
13.9 [i.
If the compounds have alkyl residues (C,^) and if the counter-ion is CI, they tenaciously retain considerable amounts of water even after prolonged drying in a vacuum oven over P^Oc' Strong absorptions of the water are observed at 3 [i and about 6.1 p. (3333 and 1640 cm ). The halogen ions do not have characteristic absorption bands.
2. Palmityl-trialkyl (C^Hp^^ to C H 9 -) ammonium halides.
These compounds are quite similar to those discussed in Part A except they do not have the sharp bands between 10 and 11 |i. The absorption ' bands here due to the C-N stretching vibrations coupling with one another are not as intense although small bands are still observable in this range,
3. Quaternary Ammonium Compounds with methyl sulfate counter- anions. The methyl sulfate counter-anion has characteristic absorption 105
bands at 8-3.3 p,, 9.9 \i and 13.4 [i (1250-1206, 1010 and 746 cm""*"), possibly also at 9.45 |i (1058 cm ). Otherwise, these compounds are similar to the ones discussed in Parts 1 and 2. 106
APPENDIX C
THIN LAYER CHROMATOGRAPHY (TLC) OF FATTY
QUATERNARY AMMONIUM COMPOUNDS
Very little systematic work has been done in this area.
The system used in this work is described below and that used in several other works is reviewed.
The salts were checked for purity on 20 cm X 20 cm X 250 p, layers of silica gel G. Benzene: ethanol: HO (20:11: l) and acetone- 77 14 n aqueous ammonia (90:10) were used as eluting agents. The plates were developed with 0.2% alcoholic 2', 7' dichlorofluorescein.
When viewed under U.V. light, tailing of the quaternary ammonium salts was very noticeable. R- values were calculated and are reported in the experimental section. The order of increasing anion migration was
Cl" < Br' < MeSO^" < I~ ; and the order of increasing small alkyl group was Me < Et < Pr < Bu.
There was very little difference in the migration of the C ., C and
C compounds. (See Figure 46.) io 78 Gordon stated that prior to his paper in 1965, no systematic studies of cation and anion structure dependance were available in thin layer systems of quaternary ammonium salts. He said also that TLC of salts has been carried out only w ith developers containing water and usually containing electrolytes. Quaternary ammonium salts,
R . N X , (R = n butyl to n-heptyl) were used in his study. He found that unless he treated his 4 in. x 8 in. x 250 [i layer silica gel G vy
Ci8 Cx4 Cl6 Cl6 Ci6 Ci6 Ci6 Ci6 Ci6 Cl6 Me Me Me Me Me Me Me Et Pr Bu CI CI CI MeSO^ I I Br Br Br Br
r\ Plate: Silica Gel G Indicator: 2', 7' Dichlorofluorescein under U.V. light w W Eluting agent: Acetone: Aq. NHg (90: 10)
Figure 46. Thin Layer Chromatagram of the Compounds Used 108
plates with a 2.32 g. of 85% H PO^ in 250 ml of acetone solution, tailing of the quaternary ammonium salts spots was very pronounced.
The same results were obtained in this thesis.
His eluting systems were
I CHCl^ -C^HpjOH (24:1)
II CHCl^ -C2H5OH (9:1)
III Acetone - n-methyl acetamide (200:1)
His plates were developed with iodine vapor. The order of increasing R^ values for inorganic amions is CI < N0_ < Br < SCN < I
< CIO, . The separation of anions was great, but not much difference was noticed in the separation of cations. These results are similar to those found in the work for this thesis. 79 Gasco and Gatti separated several cationic detergents with
TLC, some of which are of the same chemical composition as the compound, being used in this work e.g., cetyl trimethyl ammonium chloride. They used ascending TLC on Kieselgel G plates and separated the compounds by using the system 75:18:1.5, 75:20:2, 75:40:3, and 75:40:7, Me Cl-MeOH-H^O
The Rp values were very low and development was accomplished with the
Dragendorff-Bregoff-Delwiche reagent for quaternary ammonium bases. 77 Mangold et al have published a paper on the use of TLC with industrial aliphatic lipid quaternary ammonium salts containing, one, two, or three long chain moieties. They found that silica gel G yielded the best separations; this is consistent with what was found in the work on this thesis. For chromatograms with quaternary ammonium salts they used a polar eluting agent, acetone-aqueous ammonia
(90 vol of acetone and 10 vol. of cone (l4n) aqueous ammonia). To develop 109
the plates they sprayed them with 0.2% alcoholic 2',7' dichlorofluorescein which can be seen as yellow-green fluorescent spots under U.V. light. no
APPENDIX D
DYEING TECHNIQUE FOR OBSERVING THE FINISH 80
The substrate used in this thesis is not dyeable except under 81 special conditions.
Purification of the fiber and application of the finish to fiber was done as explained in the experimental section.
One fourth gram of finished fiber (or approximately one foot of yarn) was added to a 1% solution of C.I. Acid Blue 45 (Na ~0 S -D - SO ~Na ;
bee Figure 4?) at room temperature for approximately three to five minutes.
NaOjX
Figure 47. C.I. Acid Blue 46.
(See equation 2.) The fiber was rinsed well and placed in a 1% solution of C.I. Basic Violet 3 (D' -NMe Cl";See Figure 48) for about three to five minutes (see equation 3). The fiber was rinsed thoroughly with distilled
^KCM,)^ CI (HC)N-^
Figure 48. C.I. Basic Violet 3 (Classical Name Crystal Violet). Ill
water, squeezed to remove water and air dried. If the fiber had a cationic finish on the surface, a purplish blue color was noticed.
(l) Fiber + Cationic Finish F-A"^ X' (F) (A"^ X")
(2) F- A"^ X" + D4 SO^" Na"^ )^ F-A"*" "O^S-D-SO^" Na"^
(3) F - A"*" ' O^S - D - SO^" Na"^ + D' - N"^Me2 Cl'
F — A"^ " O^S - D~SO^" **" N - D' o o I Me^
The acid dye does not have a high enough tinctorial strength to allow it to easily be seen under these conditions but the cationic dye does. 112
APPENDIX E
DETERMINATION OF CRITICAL MICELLE CONCENTRATION
(CMC) BY USE OF DYES
82 According to Corrin and Harkins CMC for cationic quaternary ammonium salts can be determined by titrating a solution of known con centration of finish plus dye [lO to 10 molar (as received)]. They suggest using Sky Blue FF (Figure 49)
Nc^O^S 503^0.
Figure 49. C.I. Direct Blue 15.
Its color supposedly changes from a blue to a red-blue when the solution plus dye goes from above to below CMC. -5 -3 Using a 1 x 10 m concentration of dye and starting with 6.85 x 10 m concentration of cetyl trimethyl ammonium bromide (C , H_^ N me^Br ), a color change was noticed (although difficult to see) after about 75.5 ml
(at approximately 25° C) of the dye had been added. This suggested CMC -4 -3 was 8.05 x 10 m, which compared with 1 x 10 for that compound in the literature. Also less foaming was noticed below CMC.
Ultraviolet and visible spectra (230-700 mu) were run on the 113
following samples to see what change took place in the dye:
(1) Sky Blue FF 3 x 10^ m
(2) Sky Blue FF 3 x 10^ m + C H^-gN-Me^ Br' (2.74 x lO" m) Above CMC
(3) Sky Blue FF 3 x 10^ m + C^^H^gN-Me Br" (6.85 x lO"'^ m) Below CMC
Both (2) and (3) appear to cause a hyposochromic shift in the major bands of Sky Blue FF, with (3) causing the greater shift (see Figures 50, 51 and 52.)
Because the color change was so hard to determine visually, it was decided to add several drops of 2', 7' dichlorofluorescein to the solutions when titrating for a color change or when trying to determine if a certain concentration of a compound was above or below CMC. Corrin 82 and Harkins mentioned that there was a drastic difference in the fluor escence of fluorescein below the CMC as compared to above CMC.
When added to the solutions (dye plus finish) this dye made a color difference much more readily detectable. Above CMC the sample was greenish yellow, and below CMC purplish. The above CMC sample fluoresced strongly under ultraviolet light whereas the below CMC sample did not.
All of the solutions used to apply finish to the fiber in this thesis were checked by the above technique to ascertain whether they were above or below CMC. As
6OO141 0,9 1 EP ^ 0.7 • 235mu B El m ID El 4 E] El t^ Q 0.5 ^ Q - m • 320inU El m - Q B El 1 0.3 B 1 m CD /^ m El 0° El Q 0.1 m m B B QEIQ ^ (mU) El < \ \ 1 \ 1 1 1 300 400 5010 600 700 Figure 50. U.V./Vis. Spectra of Sky Blue FF (3xlO~^m) As
585m|a 0.9 I E^b 0.7 EJ
E B B B 0.5 B B 0 0 B B 0.3 B B 13 B B B Q B 0.1 Q ^ (nm) Q B i 1 J_ I X 300 400 500 600 700 Figure 51. U.V./Vls. Spectra of Sky Blue FF (3xlO"^m) plus CieHggSMegBr" (2.74xlO"^in) (This concentration of Finish Should be Above C.M.C.) I-* As
0.9 580m\l
\ 0.7
Q 237mli g ra Q Q 0.5 % B dfTti El 322in|i El ^ 1 B ~ ?13, B B 0.3 - Q t D El B B B • El B B n '^ 0.1 - B ^ (mM) Q L, . i 1 1 i 1 1 1 1 1 300 400 500 . 600 700 Figure 52. U.V./Vis. Spectra of Sky Blue FF (3xlO~^m) plus CxsHgCxsHagSMegBr; " (6.85xl0"*m) (This concentration of Finish Should be Below C.M.C.) a\ 117
APPENDIX F
YARN TO GUIDE FRICTION
The coefficient of friction (p,) was calculated by the analog com
puter in the Rothschild F-meter and recorded on the 4-channel recorder.
|i. is obtained from the classical "Capstan" equation, T = T eu e in which
T^ = initial tension
T, = final tension
e = base of natural logarithm system
|i = coefficient of friction
9 = angle sustended over friction pins which is used by many as a basis for the evaluation of yarn-to-guide fric
tional properties of the finishes. It is generally agreed that the clas
sical coefficient of friction is a function of instrument geometry and
conditions of test as well as a function of the ratio between frictional
c J T J 83-88 force and load. BIBLIOGRAPHY 119
BIBLIOGRAPHY*
1. a. Brit. Patent 1,037,452 to Courtaulds Ltd. b. U. S. Patent 3,048,539 to American Cyanamid Co. c. U. S. Patent 2,694,688 to E.I. duPont de Nemours, Co. d. Brit. Patent 965,322 to American Cyanamid Co. e. U. S. Patent 2,983,628 to American Enka Corp, f. U. S. Patent 3,000,758 to American Enka Corp. g. U. S. Patent 3,052,512 to American Cyanamid Co. h. U. S. Patent 3,082,227 to American Cyanamid Co. i. U. S. Patent 3,108,011 to Bohme Kettchemie G.M. 6 H. 2. M. Hayek, Am. Dyestuff Reptr., 43, 368 (l954).
3. G. R. Ward, Am. Dyestuff Reptr., 44, 220 (1955).
4. A. E. Henshall, J. Soc. Dyers Colourists, 76, 525 (i960).
5. R. D. Fine, Am. Dyestuff Reptr., 43, 405 (1954).
6. P. Carter, "Quaternary Ammonium Salts as Antistatic Agents," paper c/lV.6, IVth International Symposium on Surface Active Substances, Brussels, Belgium, Sept. 8-11, 1964.
7. M. Buhler, Textil-Praxis, 1^, 1142-49 and 1234-45 (1957).
8. L. B. Loeb, Science, 102, 573 (1945).
9. J. Gayler, R. E. Wiggins, and J^ B. Arthur, "Static Electricity, Gen eration, Measurement, and its Effects on Textiles," The Technology and Chemistry of Textiles, No. 5, 1965, p. 3-9, School of Textiles, North Carolina State of the University of North Carolina at Raleigh.
10. D. F. Arthur, J. Textile Inst., Trans., 46, T721 (l955).
11. P. S. H. Henry, J. Textile Inst., Proc, 48, P5 (1957).
12. F. A. Vick, Brit. J. of Appl. Phys., 4 (Supp. No. 2), SI (1953).
13. V. E. Gonsalves, Textile Res. J., 23, 711 (l953).
14. S. P. Hersh and D. J. Montgomery, Textile Res. J., 26, 903 (1956).
15. Gayler et al., the Technology and Chemistry of Textile, No. 5, 1965, p. 33. _ Abbreviations used above follow the form given in Chemical Abstracts List of Periodicals. 120
16. a. W. Wegener, and W. Tangier, Z. Ges. Textil-Ind., 60, No. 24, 1050 (1958). b. W. Wegner and W. Topf, Textil-Praxis, 1_8, 327 (l963).
17. T. Fujimoto, "Antistatic Effects of Surfactants on Synthetic Filaments and Staples," paper C/lV 2, IVth International Symposium on Surface Active Substances, Brussels, Belgium, Sept. 8-14, 1964.
18. N. V. Sidgwick, Organic Chemistry of Nitrogen, p. 27-41, Oxford at the Clarendon Press, 1937.
19. R. T. Morrison and R. N. Boyd, Organic Chemistry, p. 522-5, 553-4, Allyn and Bacon, Inc. Boston, 1959.
20. J. L. Moilliet and B. Collie, Surface Activity, p. 11-20, D. Van Nostrand Co., Inc., New York, 1951.
21. J. E. Clark, Am. Dyestuff Reptr., 56, 145 (1967).
22. Gayler et al., The Technology and Chemistry of Textiles, No. 5, 1965, p. 58.
23. Ibid, p. 59.
24. M. Schlesinger, Am. Dyestuff Reptr., 54, 37 (1965).
25. E. I. Valko and G. C. Tesoro, Mod. Textiles M., 38, 62 (l957).
26. G. J. Sprokel, Textile Res. J., 27, 501 (l957).
27. Gayler et al.. The Technology and Chemistry of Textiles, No. 5, 1965, p. 60.
28. W. Wegener and W. Rohrig, Textil-Praxis, 3^8, 551 (1963).
29. J. B. Levy, J. H. Wakelin, W. J. Kauzmann, and J. H. Dillon, Textile Res. J., 27, 897 (1958).
30. Gayler et al.. The Technology and Chemistry of Textiles, No. 5, 1965, p, 31.
31. S. Baxter, Trans. Faraday Soc, 39, 207 (l943).
32. Gayler et al., The Technology and Chemistry of Textiles, No. 5, 1965.
33. J. C. L. Resuggan, Quaternary Ammonium Compounds, p. 14-24, United Trade Press Ltd., London, 1951.
34. K. Shlnoda, T. Nakagawa, B. Tamamuski, and T. Isenura, Colloidal Surfactants, p. 1-9, Academic Press, New York and London, 1963, 121
35. C. W. Hoerr and A. W. Ralston, J. Am. Chem. Soc, 64, 2824 (1942).
36. G. G. Summer, Emulsions and Their Treatment, J. and A. Churchill Ltd., London, 1954.
37. W. C. Preston, J. Phys. and Colloid Chem., 5^, 84, (1948).
38. J. Powney and C. C. Addison, Trans. Faraday Soc, 33, 1243 (1937).
39. Shinoda, p. 11, 36.
40. K. A. Wright and H. V. Tartar, J. Am. Chem. Soc, 61., 544 (1939).
41. B. D. Flockhart, J. Colloid Sci., 8, 105 (1953).
42. Gayler et al.. The Technology and Chemistry of Textiles, No. 5, 1965, p. 61.
43. M. BiJhler, Ciba Rev., ]J^, No. 132, 25-28 (June 1959).
44. P. J. Wakelyn, unpublished data.
45. G. W. Graham, Textile Mercury and Argus, 128, 16 (1953).
46. R. F. Johnson, "Some Properties of the Triphenylmethane Cationic Dye - Polyacrylonitrile Fiber System," Dissertation Prom. Nr. 3471, Eidgennossische Technische Hochschule in Zurich.
47. S. R. Palit, Makromol. Chem., 38, 96 (i960).
48. L. Tzentis, J. Appl. Polymer Sci., 1^, 1543 (1966).
49. W. R. Krigbaum and N. Tokita, J. Polymer Sci., 32, 323 (1958).
50. F. Feichmayr and A. Wurz, J. Soc. Dyers Colourists, 77, 626 (l96l).
51. D. W. Chaney in Encyclopedia of Chemical Technology 2— Edn., Interscience, New York, 1963, Vol. 1, p. 313.
52. J. Simmons, "The Investigation of a Miniature Spinning System as a Screening Agent for Spin-Finish Components on Polyacrylonitrile Fiber," M. S. Thesis, Georgia Institute of Technology 1967.
53. Anonymous, "Operating Instructions for the Atlab Finish Applicator," Precision Machine and Development Corp., New Castle, Delaware.
54. T. E. McBride, "Development of an Instrument to Measure Friction of Textile Fibers," M. S. Thesis, Georgia Institute of Technology, 1965.
55. J. P. Bryant, "An Investigation of the Factors which Influence the Frictional Properties of the Textile Fibers," M. S. Thesis, Georgia Institute of Technology, 1966. 122
56. Anonymous, "Operation Manual F-Meter R-1082TS," Rothschild, Zurich, Switzerland.
57. Anonymous, "Operation Manual Rothschild Four Channel Recorder," Rothschild, Zurich, Switzerland,
58. Anonymous, "Operating Instructions Manual Bergischer Rotating Electrostatic Field Strength Measuring Instrument Type FM 300, NRI," Bergischer Fein-Geratebau, 56 Wuppertal - Vohwinkel, Rubensstrasse 6.
59. Anonymous, "Operation, Maintenance Details," Piatt Bros. (Sales) Ltd., Oldham, England.
60. Gayler et al, The Technology and Chemistry of Textiles, No. 5, 1965, p. 26-28.
61. Ibid p. 15-34.
62. J. Gayler and R. E. Wiggons, "Description and Application of Laboratory Apparatus for Determination of Static Charges on Yarns," ASME Papers No. 64-Tex 4.
63. J. Gayler, Textile Research J., 35, 1043 (1965).
64. R. A. Reck, H. J. Harwood, and A. W. Ralston, J. Org. Chem., 1^, 517 (1947).
65. D. Hummel, Identification and Analysis of Surface-Active Agents, Vol. 1, pp. 100-116, Interscience Publishers, A Division of John Wiley and Sons, 1962 (Translation by E. A. Walkow).
66. Ibid, Vol. 2 spectra 166-177.
67. J. C. Meaders, Personal Communication.
68. H. E. Weaver and C. A. Krans, J. Am. Chem. Soc, 70, 1707 (1948).
69. R. C. Fuson, "Reactions of Organic Compounds; A Textbook for the Advanced Student", p. 271, 276, John Wiley and Sons, Inc. 1962.
70. 0. Westphal and D. Jerchel, Ber., 73B, 1002, 1940 (Chem. Abs., 35, 35992).
71. Willstatter, Ann., 317, 204 (l90l).
72. S. P. Eriksen, L. D. Tuck, and J. F. Oneto, J. Org. Chem., 25, 849 (1960).
73. R. A. Robinson, J. Org. Chem., 1^, part 2, 1911 (l95l).
74. R. S. Shelton, M. G. Van Campen, C. H. Tilford, H, C. Lang, L,. Nisonger, F. J. Bandelin, and H. L. Rubenkoenig, J. Am. Chem. Soc, 68, 753 (1946). 123
75. N. K. Adam and K. G. A. Pankhurst, Trans. Faraday Soc, 42, 523 (1946).
76. A. B. Scott and H. V. Tartar, J. Am. Chem. Soc, 65, 692 (1943).
77. H. K. Mangold, R. Kammereck, J. Am, Oil Chemists' Soc, 39, 201 (1962).
78. J. E. Gordon, J. of Chromatog., 20, 38 (1965).
79. M. R. Gasco and G. Gatti, Riv. Ital. Sostanze Grasse, 43, (4), 1975 (1966) (Abstract from Chem. Abs., 65, 2480 (l966)).
80. Dr. J. C. David, E. I. duPont de Nemours Company, Richmond, Va. (idea from personnel conference).
81. (a) T. A. Field, Jr. and G. H. Freman, Textile Res. J. 531 (1951). (b) R. C. Houtz, Textile Res. J., 20, 786 (l950) (c) W. R. Remington and H. E. Schroeder, Textile Res. J., 27» 177 (1957).
82. M. L. Corrin and W. D. Harklns, J. Am. Chem. Soc, 62, 679 (1947).
83. H. G. Howell, K. W. Mieszkis, and D. Tabor, Friction in Textiles, Textile Institute, Textile Book Publishers, Inc., New York, pp. 47-50, 189-200, (1959).
84. J. L. Meriam, Mechanics Part I - Statics, John Wiley and Sons, Inc. New York, Chapman and Hall Ltd., London, pp. 261-2, (l95l).
85. J. P. G. Beiswanger, Textile Antistats and Lubricants, General Aniline and Film Corp., Dyestuff and Chemical Div., New York, p. 5-8, 1963.
86. G. V. Lobzhanidze, Technol. Textile Ind., U.S.S.R. (English Transl.), No. 1, pp. 66-68 (1964).
87. C. Rubenstein, J. of Textile Inst., Trans., 54, T 234 (1963).
88. H. L. Ro'der, J. of Textile Inst., Trans., 44, T 247 (1953).