water pressure produced wit water-borne coatings and pressure-sensitive adhesives produced ...

315 Pages·2016·5.12 MB·English

WWAATTEERR-BBOORRNNEE CCOOAATTIINNGGSS AANNDD
PPRREESSSSUURREE-SSEENNSSIITTIIVVEE AADDHHEESSIIVVEESS
PPPRRROOODDDUUUCCCEEEDDD WWWIIITTTHHH PPPOOOLLLYYYMMMEEERRRIIIZZZAAABBBLLLEEE
SURFACTANTS
ZZiioorrttzzaa AAgguuiirrrreeuurrrreettaa AAlloonnssoo
CChheemmiiccaall EEnnggiinneeeerriinngg GGrroouupp
UUnniivveerrssiittyy ooff tthhee BBaassqquuee Country UUPPVV//EEHHUU
Donostia-San Sebastián
(2016)
(cc)2016 ZIORTZA AGUIRREURRETA ALONSO (cc by-nc-nd 4.0)

Contents

1. Introduction 1
1.1. Introduction 1
1.2. Background of polymerizable surfactants 4
1.2.1. Reported product improvements 5
1.2.2. Optimal behavior of polymerizable surfactants 13
1.2.3. Synthesis of high solids content latexes using polymerizable
16
surfactants
1.3. Motivation and main objective of the thesis 21
1.4. Outline of the thesis 22
1.5. References 24

I
2. Characterization of polymerizable surfactants 35
2.1. Introduction 35
2.2. Experimental 41
2.2.1. Chemical structure 41
2.2.2. Surface properties 41
2.2.3. Homopolymerization 44
2.2.4. Copolymerization 45
2.3. Results and discussion 45
2.3.1. Chemical structure of Latemul®PD-104 45
2.3.2. Surface properties 48
2.3.2.1. Determination of the critical micelle concentration 48
2.3.2.2. Determination of the parking area 54
2.3.3. Homopolymerization 56
2.3.4. Copolymerization 59
2.4. Conclusions 64
2.5. References 65

II
3. Assessing the performance of polymerizable surfactants in
67
emulsion polymerization
3.1. Introduction 67
3.2. Experimental 71
3.2.1. Materials 71
3.2.2. Emulsion polymerization 72
3.2.3. Characterization 72
3.3. Results and discussion 73
3.4. Conclusions 87
3.5. References 90

III
4. Synthesis of high solids content latexes using
95
polymerizable surfactants
4.1. Introduction 95
4.2. Experimental 100
4.2.1. Materials 100
4.2.2. Emulsion polymerization 100
4.2.3. Characterization 106
4.3. Results and discussion 107
4.3.1. Synthesis of high solids content latexes using polymerizable
107
surfactants
4.3.1.1. Latexes synthesized under basic conditions 107
4.3.1.2. Latexes synthesized under acidic conditions 111
4.3.2. Polymer microstructure: gel content 123
4.4. Conclusions 128
4.5. References 131

IV
5. Water sensitivity and mechanical properties of water-borne
135
coatings produced with polymerizable surfactants
5.1. Introduction 135
5.2. Experimental 139
5.3. Results and conclusions 141
5.3.1. Colloidal stability against freeze-thaw cycles 141
5.3.2. Water sensitivity 142
5.3.2.1. Films cast from latexes synthesized under basic conditions 142
5.3.2.2. Films cast from latexes synthesized under acidic
152
conditions
5.3.3. Mechanical properties 167
5.3.3.1. Films cast from latexes synthesized under basic conditions 167
5.3.3.2. Films cast from latexes synthesized under acidic
169
conditions
5.4. Conclusions 174
5.5. References 176

V
6. Synthesis of water-borne pressure-sensitive adhesives
181
(PSAs) using polymerizable surfactants
6.1. Introduction 181
6.2. Experimental 183
6.2.1. Materials 183
6.2.2. Emulsion polymerization 183
6.2.3. Characterization 185
6.3. Results and discussion 186
6.3.1. Synthesis of high solids content latexes acrylic PSAs by emulsion
186
polymerization
6.3.1.1. Effect of the pH 188
6.3.1.2. Effect of the surfactant concentration and surfactant type 190
6.3.2. Polymer microstructure 197
6.4. Conclusions 201
6.5. References 203

VI
7. Improving the properties of water-borne pressure-sensitive
207
adhesives (PSAs) produced with polymerizable surfactants
7.1. Introduction 207
7.2. Experimental 209
7.3. Results and discussion 216
7.3.1. Assessing surfactant migration in PSAs films 216
7.3.1.1. Incorporation degree of polymerizable surfactants into
216
the polymer backbone
7.3.1.2. Surfactant migration to the air-film interface 217
7.3.1.3. Surfactant aggregation within the film 222
7.3.2. Adhesive properties of PSAs 225
7.3.2.1. Adhesive properties of latexes synthesized using the
226
conventional surfactant Dowfax®2A1
7.3.2.2. Adhesive properties of latexes synthesized using
229
polymerizable surfactants or polymerizable stabilizer
7.3.3. Water whitening resistance of PSAs 236
7.3.3.1. Effect of the pH 236
7.3.3.2. Effect of the conventional anionic surfactant
242
concentration
7.3.3.3. Improving water whitening resistance using
246
polymerizable surfactants/stabilizer
7.4. Conclusions 250
7.5. References 253
VII
8. Conclusions 257

List of publications and conference presentations 263

Laburpena eta ondorioak 265

Appendixes 271
271
Appendix I. Characterization methods and techniques
Appendix II. Film properties and characterization methods 279
Appendix III. Some aspects to consider for the successful synthesis of high solids
285
content (HSC) latexes with controlled particle size

VIII