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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



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



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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Page 259

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




Page 260

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



Page 261

[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)



Page 262

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



Page 263

[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



Page 264

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


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)



Page 265

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)


Polyoxypropylene (POP):

block length, effects on CMC, 8081

hydrophobe, compared to alkyl, 81

structure of, 148


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 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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