Modern Superabsorbent Polymer Technology: Editor: Fredric L. Buchholz; Editor: Andrew T. Graham: 9780471194118: Book: : eCampus.com

A thorough, up-to-date examination of the science and practical application of superabsorbent polymers.

Modern Superabsorbent Polymer Technology takes a comprehensive look at the structure, properties, and uses of superabsorbent polymers. Prepared by editors with over 20 years of experience in the field, it offers a unified approach to polymer science technologies and examines the key interrelationships between structure, properties, behavior, and applications.

This book draws on the best and most relevant scientific papers from academia and industry, as well as numerous patents and patent applications. The result is a compact, centralized source of information on superabsorbent polymers that no polymer or chemical engineer will want to be without.

Discusses synthetic chemistry and the effects of synthesis on the structure of superabsorbent polymers
* Describes and compares industrial practices of the major manufacturers of superabsorbent polymers
* Features analytical methods for evaluation of the properties and behavior of superabsorbent polymers
* Explores structural and property relationships of crosslinked super-absorbent polymers
* Surveys new superabsorbent polymer forms and types-including fibers, foams, and biodegradable superabsorbents
* Covers current and emerging applications in personal care products, horticulture, construction, and other areas.

Preface

(4)

Acknowledgments

(2)

Contributors

xvii

1 Absorbency and Superabsorbency

(18)

Fredric L. Buchholz

1.1 Absorbents

(4)

1.1.1. Traditional Absorbent Materials

(1)

1.1.2. Physics of Absorbent Materials

(4)

1.2. Superabsorbents

(8)

1.2.1. Physics of Superabsorbents

(3)

1.2.2. Superabsorbent Polymer Types

(5)

1.2.2.1. Polyelectrolyte Vs. Nonpolyelectrolyte Hydrogels

(1)

1.2.2.2. Covalent Vs. Ionic Vs. Physical Gels

(1)

1.2.2.3. Survey of Polymers

(3)

1.3. Composite Absorbent Structures

(5)

2 Chemistry of Superabsorbent Polyacrylates

(50)

Thomas L. Staples

David E. Henton

Fredric L. Buchholz

2.1. Preparation of Superabsorbent Polyacrylates

(4)

2.1.1. Example 1: Crosslinking Co-Polymerization of Acrylic Acid

(1)

2.1.2. Example 2: Crosslinking Co-Polymerization of Partially Neutralized Acrylic Acid

(1)

2.2. Free-Radical Polymerization of Acrylic Acid and Related Monomers

(4)

2.2.1. Monomer Properties

(1)

2.2.2. Storage and Inhibition

(4)

2.2.2.1. Polymerization Inhibitors

(1)

2.2.2.2. Dimer Formation

(3)

2.3. Experimental Techniques for Studying Polymerization

(2)

2.3.1. Standard Methods: Sampling, Dilatometry, and Thermal Measurements

(1)

2.3.2. Nuclear Magnetic Resonance Technique

(1)

2.3.3. Initiator Decomposition

(1)

2.4. Mechanisms and Kinetic Expressions for Typical Radical Polymerization

(4)

2.4.1. Initiation, Propagation, and Termination

(2)

2.4.2. Kinetic Dependence of Molecular Weight

(1)

2.4.3. Inhibition and Retardation

(1)

2.4.4. Chain Transfer

(1)

2.5. Unique Aspects of Acrylic Acid and Methacrylic Acid Polymerization

(13)

2.5.1. Effect of pH and Ionic Strength

(2)

2.5.2. Monomer Concentration Dependence of Polymerization Rate

(3)

2.5.3. Inhibition

(5)

2.5.4. Reactions Near Dryness

(3)

2.5.4.1. Continuation of Polymerization

(1)

2.5.4.2. Anhydride Formation and Decarboxylation

(2)

2.5.5. Polymerization in Nonaqueous Solvents

(1)

2.6. Crosslinked Gels by Co-Polymerization

(8)

2.6.1. Standard Co-Polymerization Kinetics

(3)

2.6.2. Co-Polymerization in Gelling Systems

(1)

2.6.3. Polymerization of Acrylic Acid Gels

(4)

2.7. Crosslinking via Curing Reactions

(5)

2.7.1. Surface Versus Bulk Crosslinking

(1)

2.7.2. Ionic Crosslinking

(2)

2.7.3. Organic Reactions With Carboxylic Acids

(2)

2.8. Computer Modeling of Gel Polymerization

(9)

3 Commercial Processes for the Manufacture of Superabsorbent Polymers

(50)

Andrew T. Graham

Larry R. Wilson

3.1. Introduction

(2)

3.2. Solution Polymerization: Unit Operations and Their Effect on Product Quality

(33)

3.2.1. Introduction to Solution Polymerization Processes

(3)

3.2.1.1. Scale-Up Considerations

(1)

3.2.1.2. Overview of Unit Operations

(2)

3.2.2. Raw Material Preparation

(3)

3.2.3. Polymerization Vessels and Systems

(7)

3.2.4. Gel Handling

(3)

3.2.4.1. Post-Reactor Chemistry

(1)

3.2.4.2. Post-Reactor Gel Preparation

(2)

3.2.5. Drying

(6)

3.2.6. Handling of the Dried Material: Particle Sizing

(2)

3.2.7. Fines Recycle

(2)

3.2.8. Addition of Post-Treatments

(7)

3.2.8.1. Advanced Products

(6)

3.2.8.2. Additives for Improved Handling

103

(1)

3.3. Suspension Polymerization

104

(15)

3.3.1. General Terminology

104

(1)

3.3.2. Suspension Polymerization of Poly(Sodium Acrylate-Co-Acrylic Acid) Gels

105

(1)

3.3.3. Suspension Aids and Agitation

106

(3)

3.3.4. Particle Shape

109

(4)

3.3.5. Commercial Status of Suspension Technologies

113

(6)

4 Analysis and Characterization of Superabsorbent Polymers

119

(48)

Sergio S. Cutie

Patrick B. Smith

Robert E. Reim

Andrew T. Graham

4.1. Introduction

119

(2)

4.2. Monomer Characterization

121

(5)

4.2.1. Acrylic Acid

121

(3)

4.2.1.1. Gas Chromatography

121

(1)

4.2.1.2. Dimer of Acrylic Acid by Liquid Chromatography and NMR Spectroscopy

121

(1)

4.2.1.3. Infrared Analysis

122

(2)

4.2.1.4. Inhibitor and Residual Crosslinker Quantitation

124

(1)

4.2.2. Crosslinker Purity

124

(2)

4.3. Characterization of the Polymerization Reaction

126

(5)

4.3.1. Reaction Kinetics by NMR

126

(1)

4.3.2. Crosslinker Incorporation

127

(1)

4.3.3. Primary Chain Molecular Weight

128

(2)

4.3.4. Extractables and Percent Neutralization

130

(1)

4.4. Analysis of Components Present in the Polymer at Low Concentrations

131

(9)

4.4.1. Acrylic Acid and Dimer of Acrylic Acid

132

(1)

4.4.2. Determination of XXX-Hydroxypropionic Acid

132

(1)

4.4.3. Analysis of Crosslinkers

132

(2)

4.4.3.1. Quantitation of Unreacted Crosslinker

132

(2)

4.4.3.2. NMR Characterization of Swelling and Network Structure

134

(1)

4.4.4. Detection of Graft Substrates--Starch and Poly(Vinyl Alcohol)

134

(2)

4.4.5. Sodium Persulfate

136

(2)

4.4.5.1. Sodium Persulfate Quantitation

136

(2)

4.4.5.2. Sodium Persulfate Decomposition

138

(1)

4.4.6. Inhibitors

138

(2)

4.4.7. Surface Tension

140

(1)

4.5. Bulk Polymer Characterization

140

(7)

4.5.1. Polymer Identification by IR and (13)C-NMR

140

(1)

4.5.2. Thermal Techniques

140

(3)

4.5.2.1. Glass Transition Temperatures

141

(1)

4.5.2.2. Heat Capacity Measurements

142

(1)

4.5.3. Moisture Analysis

143

(2)

4.5.3.1. Drying

143

(1)

4.5.3.2. Anhydride Formation and Decarboxylation

144

(1)

4.5.4. Microscopy

145

(1)

4.5.4.1. Optical Microscopy

145

(1)

4.5.4.2. Electron Microscopy

145

(1)

4.5.5. Particle Size Determination

146

(1)

4.5.6. Bulk Density and Flowability

147

(1)

4.6. Polymer Analysis and Network Structure

147

(20)

4.6.1. Swelling Capacity: Theory and Practice

147

(7)

4.6.1.1. Variables in the Swelling Analysis

149

(4)

4.6.1.2. Absorbent Capacity Method

153

(1)

4.6.2. Kinetics of Swelling

154

(3)

4.6.2.1. Swelling Kinetics Methods

154

(1)

4.6.2.2. Characteristic Swelling Time by the "Vortex Time" Method

155

(1)

4.6.2.3. Vortex Time Method

156

(1)

4.6.3. Elastic Modulus

157

(1)

4.6.4. Combining the Concepts: Swelling Under Load

158

(9)

4.6.4.1. Swelling Under an Applied Compressive Load

158

(1)

4.6.4.2. Measurement of Swelling Under a Compressive Load: Absorbency Under Load

159

(1)

4.6.4.3. Permeability of Masses of Swollen Gels

160

(7)

5 The Structure and Properties of Superabsorbent Polyacrylates

167

(56)

Fredric L. Buchholz

5.1. Network Structure and Equilibrium Swelling Properties

167

(26)

5.1.1. Basic Network Theory

167

(15)

5.1.1.1. Network Free Energies

168

(3)

5.1.1.2. Crosslink Density

171

(1)

5.1.1.3. Modulus of Elasticity

171

(5)

5.1.1.4. Swelling Capacity

176

(1)

5.1.1.5. Monomer Concentration Effects

177

(4)

5.1.1.6. Ionic Networks

181

(1)

5.1.2. Network Compressibility

182

(8)

5.1.2.1. Osmotic Pressure of Networks

183

(1)

5.1.2.2. Effect of Network Structure

184

(3)

5.1.2.3. Absorbency Under Load

187

(3)

5.1.3. The Structure of Surface Crosslinked Superabsorbents

190

(3)

5.2. Network Structure and Swelling Kinetics

193

(8)

5.2.1. Maximum Swelling and the Rate Constant of Swelling

194

(1)

5.2.2. Particle Size and Distribution

195

(2)

5.2.3. Polymer Density and Surface Area

197

(2)

5.2.4. Temperature

199

(1)

5.2.5. Ionic Strength

199

(2)

5.3. Equilibrium Swelling and Kinetic Effects of Microparticles Under Load

201

(22)

5.3.1. Swelling Equilibrium Under Pressure

201

(3)

5.3.2. Time Dependence of the Elastic Modulus

204

(2)

5.3.3. Modulus Dependence of the Diffusion Coefficient

206

(1)

5.3.4. Gel Porosity and Permeability

207

(3)

5.3.4.1. Gel Porosity

207

(2)

5.3.4.2. Gel Permeability

209

(1)

5.3.5. Dynamic Swelling Under Load

210

(13)

5.3.5.1. Porosity

211

(1)

5.3.5.2. Permeability

212

(1)

5.3.5.3. Particle Size

212

(3)

5.3.5.4. Soluble Polymer

215

(1)

5.3.5.5. Areal Polymer Distribution

215

(2)

5.3.5.6. Rate Constant of Swelling Under Load

217

(6)

6 Other Superabsorbent Polymer Forms and Types

223

(28)

David S. Allan

6.1. Introduction

223

(1)

6.2. Alternative Superabsorbent Polymer Forms

224

(12)

6.2.1. Fibers

224

(7)

6.2.1.1. Preparation

225

(3)

6.2.1.2. Properties

228

(3)

6.2.2. Films and Laminates

231

(2)

6.2.3. Foams

233

(3)

6.2.3.1. Conventional Superabsorbent Polymers in Hydrophilic Foams

233

(2)

6.2.3.2. Capillary Foams

235

(1)

6.3. Biodegradable Superabsorbents

236

(9)

6.3.1. Degradability Versus Chemical Structure

237

(1)

6.3.2. Poly(Acrylic Acid)-Based Superabsorbent Polymers

238

(1)

6.3.3. Modified Polysaccharides

239

(2)

6.3.4. Poly(Aspartic Acid)

241

(3)

6.3.5. Blends and Grafts of Poly(Acrylic Acid) With Biodegradable Substrates

244

(1)

6.4. Conclusions

245

(6)

7 Applications of Superabsorbent Polymers

251

(22)

Fredric L. Buchholz

7.1. Personal Hygiene Products

252

(6)

7.1.1. Disposable Infant Diapers

252

(5)

7.1.2. Adult Incontinence Products

257

(1)

7.1.3. Feminine Hygiene Products

258

(1)

7.2. Agricultural and Horticultural Applications

258

(2)

7.3. Controlled Release

260

(3)

7.4. Water-Absorbing Construction Materials

263

(1)

7.5. Electronics and Cabling

264

(1)

7.6. Food Packaging

265

(1)

7.7. Recreational Activities

266

(1)

7.8. Sensors

267

(1)

7.9. Aqueous Waste Management

268

(1)

7.10. Miscellaneous Applications

269

(4)

Index

273

Fredric L. Buchholz is Research Associate with The Dow Chemical Company in Midland, Michigan.

T. Graham is Research Leader at The Dow Chemical Company.


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