Chemistry and Technology of

Agrochemical Formulations

Edited by

D. A. Knowles
FORM-AK Formulation Consultancy Services,
Tonbridge, Kent, UK

Kluwer Academic Publishers

Dordrecht / Boston / London
Contents

Preface xiii
List of contributors xv
1 Introduction 1
D. A. KNOWLES
References 7

2 Review of major agrochemical classes and uses 8

L. G. COPPING
2.1 Introduction 8
2.2 Future needs 9
2.3 World markets, 1996 9
2.4 Sales by category, 1995 10
2.5 Sales by crop, 1995 12
2.6 Sales by region, 1995 13
2.7 Herbicides 13
2.7.1 Photosynthesis 15
2.7.2 Amino acid biosynthesis 17
2.7.3 Lipid biosynthesis 17
2.7.4 Interference with plant hormones 18
2.7.5 Cell division 19
2.7.6 Cellulose biosynthesis 19
2.7.7 Respiratory uncouplers 19
2.8 Insecticides 20
2.8.1 Organophosphorus insecticides (OPs) 21
2.8.2 Carbamate insecticides 22
2.8.3 Insecticides that interact with neurotransmitter ligand
recognition sites 22
2.8.4 Insecticides that interlBrerwith ion channels 23
2.8.5 Inhibition of oxidative phbspitorylation 24
2.8.6 Insect growth and regulation 25
2.8.7 Compounds^ wkh-'uifcertJiin .modes .of action 26
2.9 Fungicides .. 27
2.9.1 Protectant fungicides. ^ \r - ,, 27
2.9.2 Protein biosynthesis . . . • " ' 28
2.9.3 Nucleic acid metabolism 28
2.9.4 Cell division 28
2.9.5 Sterol biosynthesis 28
2.9.6 Triglyceride biosynthesis 29
2.9.7 Chitin biosynthesis 29
2.9.8 Respiration 29
2.9.9 Indirectly acting fungicides 30
2.10 Plant growth regulators 30
2.11 Biological screening: discovery and development of a new agrochemical 30
2.11.1 Chemical synthesis 31
2.11.2 Biological evaluation 35
References 38
VI CHEMISTRY AND TECHNOLOGY OF AGROCHEMICAL FORMULATIONS

3 Formulation of agrochemicals 41
D. A. KNOWLES

3.1 Introduction 41
3.2 Conventional formulations 43
3.2.1 Granules (GR) 43
3.2.2 Solution concentrates (SL) 44
3.2.3 Emulsifiable concentrates (EC) 45
3.2.4 Wettable powders (WP) 46
3.2.5 Suspension concentrates (SC) 47
3.2.6 Seed treatments (DS, WS, LS, FS) 49
3.3 New-generation formulations 50
3.3.1 General trends 50
3.3.2 Oil-in-water emulsions (EW) 51
3.3.3 Suspoemulsions (SE) 52
3.3.4 Microemulsions (ME) 53
3.3.5 Controlled-release formulations 53
3.3.6 Water-dispersible granules (WG) 55
3.3.7 Formulations using a built-in wetter 56
3.4 Surfactants for agrochemicals 57
3.4.1 General characteristics 57
3.4.2 Adsorption and surface tension 59
3.4.3 Micellization 61
3.4.4 Krafft temperature and cloud point 61
3.4.5 Wetting and contact angle 61
3.4.6 Particle and droplet stabilization 62
3.4.7 Wetting agents 63
3.4.8 Dispersion 64
3.4.9 Emulsification 65
3.4.10 Solubilization 66
3.4.11 Bioenhancement 67
3.4.12 Conventional surfactants 67
3.4.13 Recent surfactant developments 70
3.5 Other formulation additives 71
3.5.1 Carriers and diluents 71
3.5.2 Solvents 71
3.5.3 Anti-settling agents 73
3.5.4 Water-soluble polymers 74
75
3.5.5 Preservatives
3.5.6 Anti-freeze agents 78
78
3.5.7 Anti-foam agents
78
3.5.8 Anti-caking agents
79
References

Water-dispersible granules 80
G. A. BELL

4.1 Introduction 80
4.2 Manufacturing methods 83
4.3 Physical properties 87
4.3.1 Granule size and shape 88
4.3.2 Particle assemblies and structures 91
4.3.3 Quantity and type of binders 98
4.4 Design: modern methods 112
References 114
 CONTENTS Vll

Recent developments on safer formulations of agrochemicals 121

P. J. MULQUEEN
5.1 Introduction 122
5.2 Liquid formulations 125
5.2.1 Emulsifiable concentrates (EC) 125
5.2.2 Concentrated emulsions (CE) 126
5.2.3 Suspension emulsions (or suspoemulsions) 130
5.2.4 Microemulsions 131
5.2.5 Multiple emulsions 131
5.2.6 Suspension concentrates 132
5.3 Controlled-release formulations 132
5.3.1 Methods of encapsulation 134
5.3.2 Advantages of microencapsulation 142
5.3.3 Microencapsulated products 146
5.3.4 Future trends in microencapsulation 147
5.4 Water-soluble packaging 147
5.5 Dry products (water-dispersible granules) 148
5.6 Adjuvants 148
5.7 Other formulation types 149
5.7.1 Seed treatment formulations 149
5.7.2 Biotechnological improvements 149
5.8 Summary and future possibilities 152
References 154

Agrochemical formulations using natural lignin products 158

S. T. HUMPHREY
6.1 Introduction 158
6.1.1 Lignosulphonates: some basic information 158
6.1.2 Lignin modification 159
6.2 Wettable powders (WP) 160
6.2.1 Formulation 160
6.2.2 Production methods 162
6.3 Water-dispersible granules (WG) 163
6.3.1 Formulation 164
6.3.2 Production methods 166
6.4 Suspension concentrates (SC) 167
6.4.1 Formulation 167
6.4.2 Production methods 170
6.5 Oil-in-water emulsions (EW) 172
6.5.1 Formulation 172
6.5.2 Production methods 172
6.6 Controlled release 172
6.6.1 Granules 173
6.6.2 Tablets 173
6.6.3 Gels 173
6.6.4 Microencapsulation 174
6.7 Ultraviolet protection 175
6.8 Compatibility agents 176
6.9 Adjuvants 176
6.10 Complexing agents 177
6.11 Environmental and regulatory information 177
6.11.1 Personnel 177
6.11.2 Environmental 177
References 178
Vlll CHEMISTRY AND TECHNOLOGY OF AGROCHEMICAL FORMULATIONS

7 Novel surfactants and adjuvants for agrochemicals 179

S. REEKMANS
7.1 Polymeric surfactants and stability 179
7.1.1 Introduction 179
7.1.2 (De)stabilization of colloidal systems 179
7.1.3 Colloidal stabilization 180
7.1.4 Structure of polymeric surfactants for steric stabilization 183
7.1.5 Polymeric surfactants in agricultural formulations 187
7.1.6 Conclusion 195
7.2 Trends towards environmentally safer surfactants 196
7.2.1 Surfactants and the environment 196
7.2.2 Toxicity and biodegradation 197
7.2.3 Hazard labelling of surfactants 204
7.2.4 Effect of chemical structure 204
7.2.5 New-generation surfactants 209
7.2.6 Conclusion 211
7.3 Enhancing biological activity using adjuvants 212
7.3.1 Introduction 212
7.3.2 Relevance of a surfactant's properties 213
7.3.3 Built-in activators and spray-tank mixtures 220
7.3.4 Future trends in surfactants and adjuvants 221
7.3.5 Conclusion 226
Acknowledgements 226
References 226

8 Improving agrochemical performance: possible mechanisms

for adjuvancy 232
P. J. HOLLOWAY
8.1 Introduction 232
8.2 Chemical composition of adjuvants 233
8.2.1 Surfactants 233
8.2.2 Emulsifiable oils 237
8.2.3 Polymers 239
8.2.4 Polymer-forming compounds 240
8.2.5 Phospholipids 240
8.2.6 Inorganic salts 241
8.2.7 Other ingredients 241
8.3 Mechanistic approaches for investigating adjuvancy 241
8.3.1 Atomization 241
8.3.2 Retention 244
8.3.3 Predicting retention performance 246
8.3.4 Spreading and coverage 250
8.3.5 Uptake and translocation 252
8.3.6 Predicting uptake enhancement performance 253
8.4 Future; prospects 257
Acknowledgements 259
References 260

Packaging of agrochemicals 264

P. D. CURLE, C. D. EMMERSON, A. H. GREGORY,
J. HARTMANN and P. NIXON
9.1 Selection of packaging types 264
9.1.1 Selection of packaging materials for solid
formulations 264
 CONTENTS IX

9.1.2 Selection of packaging materials for liquid formulations 267

9.1.3 Plastics 267
9.1.4 Metal 269
9.1.5 Glass 269
9.1.6 Recommended tests to be carried out on the main types of
containers 269
9.1.7 Specifications 271
9.1.8 Packaging instructions 271
9.2 Closures 272
9.2.1 Prevention of leakage 272
9.2.2 Tamper evidence 273
9.2.3 Closure diameter - liquid products 274
9.2.4 Dispensing liquid products from packs designed for pouring 275
9.3 Labelling 277
9.4 Shelf life 278
9.5 Pack design with regard to easy rinsing and disposal 279
9.6 Types of secondary packaging 279
9.6.1 Unit cartons 281
9.6.2 Combination with primary pack 281
9.6.3 Methods for protection of unit loads 281
9.7 United Nations performance tests 281
9.8 Rinsing methods 283
9.9 Closed transfer systems 285
9.10 Collection of containers after use 287
9.11 Summary of key design criteria 289
9.12 Returnable packaging systems 289
9.12.1 Small-volume returnable containers 289
9.12.2 SVR design criteria 290
9.12.3 Stewardship 290
9.12.4 Closures 291
9.12.5 Labelling and marking 291
9.12.6 Handling 291
9.12.7 Disposal 291
9.13 ECPA standard SVR interface 291
9.13.1 Container interface/extractor valve 291
9.13.2 Coupler 292
9.13.3 Extractor valve and coupler combined 293
9.14 Future direction 295
Glossary of terms and definitions 295
Bibliography 299

10 Application techniques for agrochemicals 302

G. A. MATTHEWS

10.1 Hydraulic nozzles 302

10.1.1 Types of hydraulic nozzle 308
10.2 Portable sprayers 312
10.3 Tractor sprayers 315
10.3.1 Portable lines 320
10.3.2 Orchard sprayers 320
10.4 Aerial application 321
10.5 ULV and CDA ground application 324
10.6 Fogs, mists and aerosols 327
10.6.1 Mists 328
10.7 Electrostatically charged applications 329
10.8 Chemigation 330
10.9 Granule, dust and seed treatments 331
10.9.1 Seed treatment 332
X CHEMISTRY AND TECHNOLOGY OF AGROCHEMICAL FORMULATIONS

10.10 Miscellaneous 332

10.10.1 Weed wiper 332
10.10.2 Lure and kill 332
10.10.3 Tree injection 332
10.11 Standards 333
References 333

11 Regulatory requirements in the European Union 337

W. K. DE RAAT, I. A. VAN DE GEVEL,
G. F. HOUBEN and B. C. HAKKERT
11.1 Introduction 337
11.2 Some basic features of 91/414/EEC 339
11.2.1 Which plant protection products? 339
11.2.2 Authorization of active substances and plant protection products 339
11.2.3 Existing and new active substances 340
11.2.4 Harmonization of methods and procedures 341
11.2.5 Quality standard 341
11.2.6 Mutual recognition 342
11.2.7 Data protection 342
11.2.8 Exemptions from the 'standard' authorization procedures 343
11.3 Overview of authorizations 344
11.4 Data requirements 345
11.5 Dossier preparation 348
11.6 Inclusion of active substances in Annex I of 91/414/EEC 353
11.6.1 Introduction 353
11.6.2 Initial evaluation 355
11.6.3 Detailed evaluation and the preparation of the monograph 356
11.6.4 Procedure 361
11.7 Authorization of plant protection products 361
11.7.1 General requirements 361
11.7.2 The Uniform Principles 362
11.7.3 Evaluation 363
11.7.4 Authorization criteria 366
11.8 Transitional measures and the review programme 370
11.8.1 Transitional authorizations 370
11.8.2 Review programme 371
11.9 Adjuvants 374
Acknowledgements 374
Appendix 11.A An overview of European Community general legislation
associated with plant protection products 375

12 Regulatory requirements in the USA 377

J. M. WAGNER
12.1 Introduction 377
12.2 Federal pesticide laws 377
12.2.1 Federal Insecticide, Fungicide, and Rodenticide Act 378
12.2.2 Federal Food, Drug, and Cosmetic Act 379
12.2.3 Food Quality Protection Act, 1996 379
12.3 EPA Office of Pesticide Programs 383
12.3.1 Organization 384
12.3.2 Operating objectives 385
12.4 Product registration: obtaining a license to sell 386
12.4.1 Experimental Use Permit 386
12.4.2 Registration 387
12.4.3 Tolerances and exemptions from tolerances 393
 CONTENTS XI

12.5 Registration and tolerance data requirements 397

12.6 Data evaluation 397
12.6.1 EPA risk assessment process 402
12.6.2 Industry interaction with EPA: practical advice 403
12.7 Data protection and compensation 404
12.8 Reregistration and product defense 405
12.8.1 Data Call-in and industry task force groups 406
12.8.2 Special review process and cancellation of registrations 406
12.9 Product labeling 407
12.10 State registration requirements 409
12.11 Conclusions 411
Acknowledgements 412
Appendix 12.A Index of EPA study guidelines 412
Appendix 12.B Sources of registration information 412
Appendix 12.C Office of Pesticide Programs: senior E P A contacts 415
References 416

13 Waste management and disposal of agrochemicals 418

K. S. JOHNSON
13.1 Introduction 418
13.2 Site management responsibilities 418
13.3 Waste minimization 419
13.3.1 General principles and definitions 419
13.3.2 Examples of source reduction options 420
13.3.3 Example of recycling, use and reuse of waste and reclamation 421
13.4 Waste types 422
13.5 Waste handling 422
13.5.1 Operator safety 422
13.5.2 Workplace designated waste collection areas 423
13.5.3 Site waste collection 423
13.5.4 Secure waste storage 423
13.5.5 Waste preparation prior to disposal 423
13.5.6 Detoxification of containers 427
13.5.7 Toxic wastes 428
13.6 Documentation and records 428
13.6.1 Waste producer (originator) 428
13.6.2 Identification 428
13.6.3 Consignment 428
13.7 Waste disposal 428
13.7.1 Waste disposal options 429
13.7.2 Waste disposal contractors 429
13.7.3 Waste transfer stations 429
13.7.4 Transport 429
13.8 Treatment and disposal of aqueous effluents arising from formulation
and packaging of agrochemical products 430
13.8.1 Introduction 430
13.8.2 Treatment process 430
13.8.3 Plant details and layout 431
13.8.4 Final effluent quality 431
13.8.5 Effluent disposal 434
13.8.6 Sludge disposal 434
References 434

Index 435