Table Of ContentSurfactants in Polymers, Coatings,
Inks and Adhesives
Applied Surfactant Series
A series at research and professional level, focusing on major surfactant areas and
issues. Volumes provide an introduction to the underlying chemistry and technol-
ogy, while at the same time highlighting important current issues.
The series is directed at surfactant researchers, and at manufacturers and users of
surfactants: in particular, surfactant chemists; analytical chemists; environmental
chemists; users of surfactant formulations in the fields of speciality chemicals,
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Editorial Board
Dr David R. Karsa (Editor-in-Chief),
Akzo Nobel Surface Chemistry, Manchester, UK.
Dr Guido Bognolo, Uniqema, Everberg, Belgium.
Dr Ian C. Callaghan,
Lever Development Center, Vlaardingen, The Netherlands.
Professor Krister Holmberg,
Department of Applied Surface Chemistry,
Chalmers University of Technology. Goteberg, Sweden.
Professor David A. Sabatini,
Institute for Applied Surfactant Research,
The University of Oklahoma, Norman, USA.
Dr Kazuo Ohbu,
Lion Corporation, Tokyo, Japan.
Surfactants in Polymers, Coatings
Inks and Adhesives
Edited by
DAVID R. KARSA
Akzo Nobel Surface Chemistry
Manchester, UK
Boca Raton London New York
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Contents
Preface xiii
List of contributors xiv
1 Surfactants and emulsion polymerisation: 1
an industrial perspective
D. V. DODGSON
1.1 Introduction 1
1.2 Commercial polymers 1
1.3 The industrial process 3
1.3.1 Batch process 3
1.3.2 Semi-batch process 4
1.3.3 Continuous processes 5
1.4 Surfactants and polymers 6
1.4.1 Particle size control 6
1.4.2 Stabilisation of particles 9
1.5 Industrial applications 12
1.5.1 General properties 12
1.5.1.1 Water resistance 12
1.5.1.2 Foam 13
1.5.1.3 Filler compatibility 15
1.5.2 Adhesives 15
1.5.2.1 General adhesives 15
1.5.2.2 Pressure-sensitive adhesives (PSAs) 16
1.5.3 Construction 17
1.5.3.1 Caulks/sealants 19
1.5.3.2 Bitumen modification 19
1.5.4 Paper coatings 19
1.5.4.1 Bonded paper 21
1.5.5 Printing applications 21
1.5.6 Paint 21
1.5.7 Dipping 22
1.5.8 Non-woven fabrics 23
VI CONTENTS
1.5.9 Textile applications 24
1.5.10 Synthetic rubber 24
1.5.11 Carpets 24
1.5.12 Thickeners 26
1.5.13 Structured particles 26
1.6 Choice of surfactant 27
1.7 Types of surfactant 27
1.7.1 Alkyl sulfates 27
1.7.2 Alkyl aryl sulfonates 28
1.7.3 Mono- and diester sulfosuccinates 28
1.7.4 Carboxylates 28
1.7.5 Non-ionic surfactants 28
1.8 Conclusion 29
References 29
The role of emulsifiers in the kinetics and 32
mechanisms of emulsion polymerization
K. TAUER
2.1 Introduction 32
2.1.1 Emulsion polymerization 32
2.1.2 Emulsifiers 34
2.2 Emulsifiers and emulsion polymerization 36
2.2.1 History 36
2.2.2 General remarks 40
2.2.3 Solubilization 41
2.2.4 Stabilization 44
2.2.5 Sustainability 61
2.2.6 Suitability and support 66
References 67
Polymerisable surfactants (surfmers) for 71
emulsion polymerisation production
A. GUYOT and A. ZICMANIS
3.1 Introduction 71
3.2 Maleic and related surfmers 72
3.2.1 Synthesis and characterisation 72
3.2.1.1 Procedure 72
3.2.1.2 Characterisation 80
3.2.2 Applications in emulsion polymerisation 81
3.2.2.1 Simple hemiesters and hemiamides 81
3.2.2.2 Hemiester derivatives 82
3.2.2.3 Bifunctional derivatives of maleic surfmers 82
CONTENTS vii
3.2.3 Commercial exploitation of maleic surfmers 83
3.3 Non-ionic block copolymers of oxiranes 84
3.3.1 Synthesis and characterisation 84
3.3.1.1 From commercial polyethylene glycol
monomethyl ether 84
3.3.1.2 From a two-step ring-opening polymerisation 84
3.3.2 Behaviour in heterophase polymerisations 86
3.3.3 Commercial exploitation 90
3.4 Conclusion 90
References 91
4 Uses of anti-foaming agents in paints and 93
surface coatings
H.-G. SCHULTE and R. HOFER
4.1 Introduction 93
4.2 Theory of foam and foam control 93
4.2.1 Physicochemical fundamentals of surfaces
with regard to foam and defoaming 95
4.2.2 Theory of foam inhibition and foam destruction 99
4.2.3 Mechanical defoaming 101
4.3 Compositions of defoamers 102
4.3.1 Mineral oil defoamers 102
4.3.2 Emulsion defoamers 103
4.3.3 Powder defoamers 103
4.3.4 Silicone-based defoamers 103
4.3.5 Block copolymer defoamers 104
4.4 Defoamers for coatings, inks and polymerisation 104
4.4.1 Defoamers in polymerisation 105
4.4.2 Defoamers in paint and ink manufacture 106
4.4.3 Defoamers in paint and ink application 107
4.4.3.1 Defoamers in water-based architectural
paints and in construction materials 107
4.4.3.2 Re-dispersible powder paints 109
4.4.3.3 High-gloss paints 109
4.4.3.4 Aqueous wood coatings 110
4.4.3.5 Industrial coatings 111
4.4.3.6 Automotive coatings 112
4.4.3.7 Radiation curing systems 113
4.4.3.8 Inks 113
4.4.3.9 Defoamers in paper coating 114
4.5 Defoamer testing and selection 114
References 117
CONTENTS
5 Applications of oligomeric surfactants 120
in polymer systems
D. THETFORD
5.1 Introduction 120
5.2 Coatings 121
5.2.1 Wetting 122
5.2.2 Dispersing 123
5.2.3 Aqueous systems 124
5.2.4 Foaming/defoaming 127
5.2.5 Developments in water-based surfactants 128
5.2.6 Non-aqueous coatings 131
5.2.7 Tinting systems 134
5.2.7.1 Aqueous-based universal tinters 135
5.2.12 Aqueous multi-compatible tinters 135
5.2.7.3 Non-aqueous multi-media tinters 136
5.2.8 Radiation-cured coatings 136
5.3 Effect surfactants 136
5.3.1 Acety lenediols 136
5.3.2 Fluoro surfactants 138
5.3.3 Silicones 139
5.4 Plastic and polymer systems 141
5.4.1 Emulsion polymerisation 141
5.4.1.1 Coatings 141
5.4.1.2 Polishes 143
5.4.1.3 Adhesives 144
5.4.2 Inverse emulsion polymerisation 144
5.4.3 Siloxanes in polymer systems 144
5.4.4 Antistatic agents 145
5.4.5 Thermoset composite systems 145
5.4.6 Plastisols 147
Acknowledgements 148
References 148
6 Applications of surfactants in paints 152
K. HOLMBERG
6.1 Introduction 152
6.2 Surfactants as dispersant for the pigment 153
6.2.1 Pigment properties 153
6.2.2 Dispersants for waterborne formulations 155
6.2.3 Dispersants for solvent-borne formulations 157
CONTENTS ix
6.3 Surfactants as emulsifiers for the binder 160
6.3.1 Binders made by emulsion polymerization 160
6.3.2 Post-emulsified binders 161
6.4 Surfactants as wetting agents 164
6.4.1 Effect of the critical surface tension 164
6.4.2 The wetting agent 167
6.5 Surfactants as antifoaming agents 169
6.6 Rheology control agents 171
6.7 Effect of surfactants in the dry film 175
References 178
Surfactant-waterborne polymer interactions 180
in coating applications
P. A. WILLIAMS
7.1 Introduction 180
7.2 Interaction in dilute solutions 184
7.2.1 General aspects 184
7.2.2 Non-ionic polymers and non-ionic surfactants 186
7.2.3 Non-ionic polymers and ionic surfactants 188
7.2.4 Oppositely charged polymers and surfactants 191
7.2.5 Hydrophobically modified polymers and
non-ionic and ionic surfactants 192
7.3 Interaction in concentrated solutions 196
7.4 Interaction at interfaces 198
7.4.1 Surfactant adsorption 198
7.4.2 Polymer adsorption 200
7.5 Competitive adsorption of polymers and
surfactants on surfaces 205
7.6 Conclusion 208
References 208
Surfactants in ink-jet inks 211
B. ZHMUD and F. TIBERG
8.1 Introduction 211
8.2 Properties of surfactants 211
8.3 Dynamic surface tension 213
8.4 Micellization 219
8.5 The theory of surfactant-induced wetting 220
8.6 Ink-jet printing 228
8.7 Ink formulations 229
