nonionic surfactants
TRANSCRIPT
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Nonionic Surfactants
Start of Citation[PU]Marcel Dekker, Inc.[/PU][DP]1996[/DP]End of Citation
Nonionic_Surfactants/0824797000/files/cover-1.html
SURFACTANT SCIENCE SERIES
CONSULTING EDITORS
MARTIN J. SCHICKConsultant
New York, New York
FREDERICK M. FOWKES(19151990)
1. Nonionic Surfactants, edited by Martin J. Schick (see also Volumes 19, 23, and 60)
2. Solvent Properties of Surfactant Solutions, edited by Kozo Shinoda (see Volume 55)
3. Surfactant Biodegradation, R. D. Swisher (see Volume 18)
4. Cationic Surfactants, edited by Eric Jungermann (see also Volumes 34, 37, and 53)
5. Detergency: Theory and Test Methods (in three parts), edited by W. G. Cutler and R. C. Davis (see also Volume 20)
6. Emulsions and Emulsion Technology (in three parts), edited by Kenneth J. Lissant
7. Anionic Surfactants (in two parts), edited by Warner M. Linfield (see Volume 56)
8. Anionic Surfactants: Chemical Analysis, edited by John Cross (out of print)
9. Stabilization of Colloidal Dispersions by Polymer Adsorption, Tatsuo Sato and Richard Ruch (out of print)
10. Anionic Surfactants: Biochemistry, Toxicology, Dermatology, edited by Christian Gloxhuber (see Volume 43)
11. Anionic Surfactants: Physical Chemistry of Surfactant Action, edited by E. H. Lucassen-Reynders (out of print)
12. Amphoteric Surfactants, edited by B. R. Bluestein and Clifford L. Hilton (see Volume 59)
13. Demulsification: Industrial Applications, Kenneth J. Lissant (out of print)
14. Surfactants in Textile Processing, Arved Datyner
15. Electrical Phenomena at Interfaces: Fundamentals, Measurements, and Applications, edited by Ayao Kitahara and Akira Watanabe
16. Surfactants in Cosmetics, edited by Martin M. Rieger (out of print)
17. Interfacial Phenomena: Equilibrium and Dynamic Effects, Clarence A. Miller and P. Neogi
18. Surfactant Biodegradation: Second Edition, Revised and Expanded, R. D. Swisher
19. Nonionic Surfactants: Chemical Analysis, edited by John Cross
20. Detergency: Theory and Technology, edited by W. Gale Cutler and Erik Kissa
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21. Interfacial Phenomena in Apolar Media, edited by Hans-Friedrich Eicke and Geoffrey D. Parfitt
22. Surfactant Solutions: New Methods of Investigation, edited by Raoul Zana
23. Nonionic Surfactants: Physical Chemistry, edited by Martin J. Schick
24. Microemulsion Systems, edited by Henri L. Rosano and Marc Clausse
25. Biosurfactants and Biotechnology, edited by Naim Kosaric, W. L. Cairns, and Neil C. C. Gray
26. Surfactants in Emerging Technologies, edited by Milton J. Rosen
27. Reagents in Mineral Technology, edited by P. Somasundaran and Brij M. Moudgil
28. Surfactants in Chemical/Process Engineering, edited by Darsh T. Wasan, Martin E. Ginn, and Dinesh O. Shah
29. Thin Liquid Films, edited by I. B. Ivanov
30. Microemulsions and Related Systems: Formulation, Solvency, and Physical Properties, edited by Maurice Bourrel and Robert S. Schechter
31. Crystallization and Polymorphism of Fats and Fatty Acids, edited by Nissim Garti and Kiyotaka Sato
32. Interfacial Phenomena in Coal Technology, edited by Gregory D. Botsaris and Yuli M. Glazman
33. Surfactant-Based Separation Processes, edited by John F. Scamehom and Jeffrey H. Harwell
34. Cationic Surfactants: Organic Chemistry, edited by James M. Richmond
35. Alkylene Oxides and Their Polymers, F. E. Bailey, Jr., and Joseph V. Koleske
36. Interfacial Phenomena in Petroleum Recovery, edited by Norman R. Morrow
37. Cationic Surfactants: Physical Chemistry, edited by Donn N. Rubingh and Paul M. Holland
38. Kinetics and Catalysis in Microheterogeneous Systems, edited by M. Grtzel and K. Kalyanasundaram
39. Interfacial Phenomena in Biological Systems, edited by Max Bender
40. Analysis of Surfactants, Thomas M. Schmitt
41. Light Scattering by Liquid Surfaces and Complementary Techniques, edited by Dominique Langevin
42. Polymeric Surfactants, Irja Piirma
43. Anionic Surfactants: Biochemistry, Toxicology, Dermatology. Second Edition, Revised and Expanded, edited by Christian Gloxhuber and Klaus Knstler
44. Organized Solutions: Surfactants in Science and Technology, edited by Stig E. Friberg and Bjrn Lindman
45. Defoaming: Theory and Industrial Applications, edited by P. R. Garrett
46. Mixed Surfactant Systems, edited by Keizo Ogino and Masahiko Abe
47. Coagulation and Flocculation: Theory and Applications, edited by Bohuslav Dobias*
48. Biosurfactants: Production Properties Applications, edited by Naim Kosaric
49. Wettability, edited by John C. Berg
50. Fluorinated Surfactants: Synthesis Properties Applications, Erik Kissa
51. Surface and Colloid Chemistry in Advanced Ceramics Processing, edited by Robert J. Pugh and Lennart Bergstrm
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52. Technological Applications of Dispersions, edited by Robert B. McKay
53. Cationic Surfactants: Analytical and Biological Evaluation, edited by John Cross and Edward J. Singer
54. Surfactants in Agrochemicals, Tharwat F. Tadros
55. Solubilization in Surfactant Aggregates, edited by Sherril D. Christian and John F. Scamehorn
56. Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache
57. Foams: Theory, Measurements, and Applications, edited by Robert K. Prud'homme and Saad A. Khan
58. The Preparation of Dispersions in Liquids, H. N. Stein
59. Amphoteric Surfactants: Second Edition, edited by Eric G. Lomax
60. Nonionic Surfactants: Polyoxyalkylene Block Copolymers, edited by Vaughn M. Nace
61. Emulsions and Emulsion Stability, edited by Johan Sjblom
ADDITIONAL VOLUMES IN PREPARATION
Applied Surface Thermodynamics, edited by A. W. Neumann and Jan K. Spelt
Vesicles, edited by Morton Rosoff
Liquid Detergents, edited by Kuo-Yann Lai
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title:Nonionic Surfactants: Polyoxyalkylene Block CopolymersSurfactant Science Series ; V. 60author:Nace, Vaughn Markpublisher:isbn10 | asin:0824797000print isbn13:9780824797003ebook isbn13:9780585354910language:subjectpublication date:lcc:ddc:subject:
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Index
A
Acclimation, bacterial, 244
Adsorption, in soil, 245
Aggregation (see Association)
Agricultural applications, 195
Alcohol ethoxylates (see Polarity index of alcohol ethoxylates)
Alcohols, as initiators, 79
Aldehydes, analysis with DNPH derivatives, 56
Aldol condensation, 22
Alkoxide ion:
fraction of, 5
nature of, 5
reactivity of, 56
Alkylene oxide polymerization (see Polymerization of alkylene oxides)
Alkylene oxides, 2
Allyl alcohol, as isomerization product of PO, 1920 (see also Analysis of unsaturates)
Amines, as initiators (see Initiator types, amines)
Analysis of unsaturates, 5253
Antifoam agents (see Foam control agents)
Antioxidants, analysis of, 5658
Applications of POA block copolymers, 186202
Aquatic toxicity (see Toxicity, aquatic)
Area per molecule at the interface, 102103
effect of number of EO units, 109
effect of POP block length, 109
effect of temperature, 109
of POP/POE versus POB/POE block copolymers, 177178
Association:
behavior of PO/EO block copolymers, dilute region, 75111
number, for Pluronic polyols, 8993
Average EO block size, 16
Average molecular weight:
by hydroxyl number, 49
by size exclusion chromatography, 4950
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B
Bacterial abhesives, 190
Bacterial acclimation (see Acclimation, bacterial)
Base catalyst (see Catalyst, basic)
Bioaccumulation, 246
Biodegradation, of POA block copolymers, 249255
analytical methods, 249250
chemical mechanism, 254255
test protocols, 250251
Block copolymers:
preparation of, 3
solution characterization methods, 7273
Block length:
(see also Block structure)
of polyoxyethylene, 16
effects on CMC, 81
effects on melting point, 16
of polyoxypropylene:
effects on CMC, 8081
Block structure, relation to oxide addition, 911
Block transition zone, effects of digest time, 2122
Blood substitutes, 227
Burn wound dressings, 191
Butylene oxide (BO) (see Alkylene oxides)
C
C20 (see pC20)
Capping efficiency, 16
with EO, 1516
Carbonyl content:
aldehydes, 56
analysis by vibrational spectroscopy, 56
in block copolymers, 56
Carboxylic acids (see Initiator types, carboxylic acids)
Catalyst:
basic, 2
choice of, 1112
coordination, 2
Lewis acid, 2
metal porphyrin, 2
Cement (see Petroleum applications, cement)
Chain propagation, 5
Chain transfer, acidbase, 5
Cleaners (see Detergent applications)
Cloud point, effects of salts, 93
CMC (see Critical micellization concentration)
CMC/C20, 104105, 110, 177178
CMT (see Critical micelle temperature)
Coal applications (see Petroleum applications, coal dewatering)
Color, unwanted, 22
Copolymers, random, 3 (see also Block copolymers)
Corrosion, prevention of, 201
Cosmetics (see personal care applications)
Critical micelle temperature (CMT), 7582
Critical micellization concentration, 7582
determination by dye solubilization, 110, (see also Dye solubilization technique)
effects of impurities, 110
effects of supplier on, 7677
effects of temperature on, 76
of E-P-E block copolymers, 7880
surface tension at, 103105
Crotyl alcohol, as rearrangement product of BO, 1920
Crude oil demulsification (see Petroleum applications, demulsification)
Crystallization:
of EPE, PEP, and PE block copolymers, 150152
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[Crystallization]
of POA block copolymers by DSC, 153154
of POA block copolymers, modification of, 153
of polyoxyethylene homopolymers, 148150
Crystals, liquid (see Liquid crystals)
D
Defoamers (see Foam control agents)
Dentifrice, 199
Detergent applications, 198199
Digestion, of oxide, 2122
Diols, 911
Dispersity (see Polydispersity)
Distribution, environmental, 246247
Draize test, 220
Draves test (see Wetting)
Drug delivery, 186188
Drug release, controlled, 188190
Dye solubilization technique, 74
E
Effectiveness (see Critical micellization concentration, surface tension at)
Efficiency (see, pC20)
Emulsion polymerization (see Polymerization, emulsion)
Emulsions:
medical, 191192
of perfluoro-surfactants, 192
of super-heavy oils, 194
End group (see Hydroxyl end group)
Enthalpy (see Micellization, enthalpy of)
Entropy (see Micellization, entropy of)
Environmental activity, of POA block copolymers, 244255
Enzyme stabilization, 193
Equivalent weight (see Hydroxyl equivalent weight)
Ethylene oxide (EO) (see alkylene oxides)
Ethylene oxide/propylene oxide ratio:
by acetyl chloride treatment, 52
by hydrobromic acid treatment, 52
by vibrational spectroscopy, 39, 51
Ethyloxirane (see Alkylene oxides)
Extraneous initiation, 4, 12
effects of counterion, 1920
effects on structure, 2021
sources of, 1620
F
Finishing (see Neutralization)
Flory's assumptions, 1416
Fluorescence probes, 74
Foam control agents, 201
Foaming properties:
of Pluronic and Tetronic block copolymers, 171, 173
of POB/POE block copolymers, 172173
Foams, polyurethane, 194195
Fourier transform infrared spectroscopy (FTIR) (see Vibrational spectroscopy)
Free energy (see Micellization, free energy of)
G
Gas chromatography:
(see also Inverse gas chromatography)
of chemical cleavage products, 52
of pyrolysis products, 52
Gel formation:
effects of additives on, 131133
of POB/POE block copolymers, 133135
of POP/POE block copolymers, 126133
thermoreversible, 126128, 188
Gel permeation chromatography (see Size exclusion chromatography)
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Gels:
applications of, 186188
for burn wound dressings, 191
Genotoxicity, 223224
Gibbs adsorption equation, 102
H
HIV inhibition, 192
HLB (see Hydrophile-lipophile balance) 157
Hoffman elimination, 7, 8
Hydration of POP block, effects of micelle formation, 77, 80
Hydrophile-lipophile balance (HLB), 157
calculation of, 157, 214
experimental determination of, 157
limitation of, 157, 159
Hydroxyl end group, 1516
(see also Hydroxyl number, by vibrational spectroscopy)
controlling number of, 2324
conversion to ester, 24
conversion to ether, 24
conversion to tosylate, 24
conversion to urethane, 24
modification of, 2225
primary, 3
primary-to-secondary ratio, 36
secondary, 3
Hydroxyl equivalent weight, 9
measurement of, 17
target, 13
Hydroxyl number, by vibrational spectroscopy, 39, 42
I
Infrared spectroscopy (IR) (see Vibrational spectroscopy)
Initiation, extraneous (see Extraneous initiation)
Initiator:
functionality, 911
hydrophobicity, 9
impurities as, 1618
selection of, 911
size, 9
types:
amines, 78
carboxylic acids, 8
noncatalyzed, 7
phenolics, 8, 1114
Interfacial tension (see Surface activity)
Interferometers, in Raman detectors, 39
Inverse gas chromatography, 157158
Iodophors, 198
Isomerization:
(see also, Extraneous initiation)
effects of base, 1920
effects of temperature, 19
of PO and BO, 1920
L
Latex, stabilization of, 196
Light scattering:
for obtaining association number, 89, 92
techniques, 7175
Liquid chromatography, 33, 5556, 58
Liquid crystals, 112118
M
Mammalian toxicity (see Toxicity, mammalian)
Mass spectrometry, 4349
by chemical ionization, 43
by electron ionization, 43
by electrospray ionization, 4548
of fragments from POP/POE copolymers, 4445
by ion cyclotron resonance, 46, 48, 49
by matrix-assisted laser desorption ionization, 45, 4849
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[Mass spectrometry]
of pluronic polyols, by chemical ionization, 4345
of pluronic polyols, by electrospray ionization, 4648
by pyrolysis, 43
with size exclusion chromatography, 46
by time of flight, 48
Maximum surface pressure (see Critical micellization concentration, surface tension at)
Medical applications of POA block copolymers, 186193
Melting behavior (see Crystallization)
Mercuric acetate, analysis of unsaturation, 53
Metabolic fate, mammalian, 223
Metal, cleaning of, 200201
Methyloxirane (see Alkylene oxides)
Micelle formation (see Micellization)
Micelles:
association number, 89
EP compared to EPE copolymers, 102
formation, with POB/POE block copolymers, 133135
hydrodynamic radius, 89
interaction, as function of temperature, 117, 119
parameters, methods of analysis, 7475
shape of, in dilute solution, 93
shape transition, 9395
structure, 8993
Micellization:
of block copolymers, theoretical calculations, 135136
effects of chain architecture, 98102
effects of composition inhomogeneity, 9598
enthalpy of, 8287
enthalpy of, by DSC, 8788
entropy of, 83, 8687
EPE compared to EBE copolymers, 177178
free energy of, 86, 177178
PEP (reverse) block copolymers, 99102
thermodynamics of, 8289
Modification:
of copolymers, 2225
of polyether backbone, 25
Molecular structure, by NMR, 3438
Molecular weight:
(see also Average molecular weight)
distribution, 45
by fieldflow fractionation, 51
limitations of, 4
number average, calculating, 11
Monols, 911
Mouthwash, 200
Mutagenicity, 223224
N
Neutralization, 89
with acid, 9
over, 9, 22
under, 9, 22
Nonfouling surfaces, 190
Nonyl phenol ethoxylates (see Polarity index, of nonyl phenol ethoxylates)
Nuclear Magnetic resonance (NMR):
carbon, 3638
determination of percent EO, 36
EO/PO distribution, 36, 5152
Fourier transform, 36
of Pluronic Polyols, 3637
proton, 3536
sample purity, 35
O
Octanol/water partition coefficient, 245
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Oil wells (see Petroleum applications)
Oncologic observations, 221223, 227228
Oral care (see Dentifrice)
Oxidation, during polymerization, 22
Oxirane
(see also Alkylene oxides)
ring opening, 34
Oxiranes, polymerization of (see Polymerization of alkylene oxides)
Oxygen carriers, fluorocarbon-based, 192, 227
P
Palatability, of POA block copolymers, 214
Paper:
(see also Pulp)
coating of, 196197
deinking of, 197
sizing agents, 197
Partition coefficient (log Kow) (see Octanol/water partition coefficient)
pC20, 103, 177178
Peroxides, analysis of, 55
Personal care applications, 199200
Petroleum applications, 193194
cement, 194
coal dewatering, 193
demulsification, 193
oil recovery, enhanced, 194
Phase behavior, 75
effects of block architecture, 122126
measured by small angle neutron scattering (SANS), 118122
of POP/POE block copolymers, 112126
in nonaqueous media, 126
in relation to cloud point, 117
of reverse and normal POP/POE block copolymers, 99100
Phase diagrams:
(see also Phase behavior)
of Pluronic/water systems, 128131
of reverse POP/POE block copolymers, 124125
Photography applications, 197
Physical properties, of polyoxyalkylene block copolymers, 147163
Plastics applications, 194195
Pluronic polyols:
description of, 187
nomenclature of, 152
research activity on, 70
Poisson distribution, 6
deviations from, 14
Polarity index, 157161
of alcohol ethoxylates, 158160
effects of hydroxyl end groups on, 159161
of nonyl phenol ethoxylates, 158160
of POA block copolymers, 156161
relation to calculated HLB, 159160
Poloxamers, description of, 187
Polydispersity:
effects on surfactancy, 16
narrow, 45
typical, 4
Polyethers, 2
as chemical intermediates, 23
Polyethylene glycol (see Polyoxyethylene)
Polymer characterization, 1213
Polymerization:
of alkylene oxides, 34
calculations, 1112
emulsion, 195196
of ethylene oxide in storage, 18
planning, 1112
rate (see Reaction rate)
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Polyoxybutylene (POB)
hydrophobicity of, 156
polarity of, 158160
structure of, 148
viscosity of, 154155
Polyoxyethylene (POE)
analysis of, in block copolymers, 58
crystallization (see Crystallization of polyoxyethylene homopolymers)
viscosity of, 154155
Polyoxypropylene (POP):
block length, effects on CMC, 8081
hydrophobe, compared to alkyl, 81
structure of, 148
viscosity of, 154155
Potassium hydroxide, 8
Properties, of POB/POE versus POP/POE block copolymers, 173178
Propylene oxide (PO) (see Alkylene oxides)
Pulp, synthetic, wetting of, 202
Q
Qualitative analysis, 34
R
Raman spectroscopy, of Pluronic Polyols, 3942
Reaction rate:
effects of alcohol acidity, 1315
effects of sterics, 1415
Rearrangement (see Isomerization)
Residual monomers/volatiles, analysis of, 5355
by headspace GC, 54
by solid-phase extraction, 54
Ross-Miles foam test, 171
Rust inhibition (see Corrosion, prevention of)
S
Safety, in alkylene oxide polymerizations, 67
Salt:
effects on gel formation, 132
residual, 9
Shampoo, 200
Shock, hemorrhagic, 192
Size exclusion chromatography (SEC), 4950
aggregation effects, 50
calibration, 50
detector types, 50
Sodium hydroxide, 8
Soil adsorption (see Adsorption, in soil)
Sol-gel transition, 120121
Solubilization, 110111
of hydrocarbons, 111
of polycyclic aromatic hydrocarbons, 202
Stability:
in acid-base media, 161162
in oxidizing media, 162
thermal, 162163
Stereoregularity, 2
Steric effects (see Reaction rate, effects of sterics)
Surface activity:
of POP/POE block copolymers, 102110
of POP/POE versus POB/POE block copolymers, 175178
table of values for POP/POE block copolymers, 104105
Surface excess concentration, 102105
Surface tension (see Surface activity)
Synthesis, nonideal, 1322
T
Thermal stability (see Stability, thermal)
Thickeners, 201202
Thrombosis, control of, 192
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