Adjuvants and Additives

Table of Contents

• 1.1 Historical background
• 1.2 Scope of report
• 1.3 Formulation additives and adjuvants
• 1.4 Delivery systems for pesticide formulations

• 2.1 Introduction
• 2.2 Formulation Objectives, Guidelines and International Codes
• 2.3 Conventional Formulations (Old Technology)
  • 2.3.1 Dusts (DP)
  • 2.3.2 Wettable Powders (WP)
  • 2.3.3 Granules (GR)
  • 2.3.4 Solution Concentrates (SL)
  • 2.3.5 Emulsifiable Concentrates (EC)
• 2.4 Safer Formulations (New Technology)
  • 2.4.1 Suspension Concentrates (SC)
  • 2.4.2 Oil-in-water Emulsions (EW)
  • 2.4.3 Capsule Suspensions (CS)
  • 2.4.4 Water Dispersible/Soluble Granules (WG/SG)

• 3.1 Introduction
• 3.2 Types of surfactants
  • 3.2.1 Anionic Surfactants
    • 3.2.1.1 Alkylbenzene sulphonates
    • 3.2.1.2 Alkyl naphthalene sulphonates
    • 3.2.1.3 Alcohol sulphates
    • 3.2.1.4 Ether sulphates
    • 3.2.1.5 Alkyl sulfosuccinates
    • 3.2.1.6 Sulphonated naphthalene /formaldehyde condensates
    • 3.2.1.7 Lignosulphonates
    • 3.2.1.8 Polycarboxylates
    • 3.2.1.9 Olefin sulphonates
    • 3.2.1.10 Phosphate ethoxylates
    • 3.2.1.11 Tristyrylphenol phosphates and sulphates
    • 3.2.1.12 Taurates
  • 3.2.2 Nonionic surfactants
    • 3.2.2.1 Alkylphenol ethoxylates (APE)
    • 3.2.2.2 Tristyrylphenol (TSP) ethoxylates
    • 3.2.2.3 Alcohol ethoxylates
    • 3.2.2.4 Aliphatic acid ethoxylates (PEG esters)
    • 3.2.2.5 Sorbitan esters and ethoxylates
    • 3.2.2.6 Castor oil ethoxylates
    • 3.2.2.7 Amine ethoxylates
    • 3.2.2.8 Polymeric surfactants
      • .....Block copolymers
      • .....“Comb” / graft copolymers
    • 3.2.2.9 lkylpolyglycosides (APG)
    • 3.2.2.10 Organosilicones
    • 3.2.2.11 Cetylenic diols
  • 3.2.3 Cationic Surfactants
    • 3.2.3.1 Quaternary ammonium compounds
    • 3.2.3.2 Amine salts
    • 3.2.3.3 Amine oxides
    • 3.2.3.4 Amine ethoxylates with low EO content
  • 3.2.4 Amphoteric surfactants
• 3.3 Properties of surfactants
  • 3.3.1 Adsorption and lowering of surface and interfacial tension
  • 3.3.2 Micelle formation
  • 3.3.3 Liquid crystal formation
  • 3.3.4 Cloud point of nonionic surfactants
  • 3.3.5 Krafft Point
• 3.4 Surfactant products and suppliers

• 4.1 Carriers and fillers
• 4.2 Solvents
• 4.3 Antisettling agents
  • 4.3.1 Montmorillonite (Bentonite) Clay Minerals
  • 4.3.2 Fumed silica
  • 4.3.3 Polysaccharides
• 4.4 Antifreeze agents
• 4.5 Antifoam and defoamer
• 4.6 Polymers
• 4.7 Preservatives
• 4.8 Sequestrants

• 5.1 Adjuvants for bioenhancement
• 5.2 Adjuvants to improve application properties (utility adjuvants)
• 5.3 Adjuvant Terminology
  • 5.3.1 Activator
  • 5.3.2 Wetting and spreading
  • 5.3.3 Sticker
  • 5.3.4 Extenders
  • 5.3.5 Humectant
  • 5.3.6 Compatibility agent
  • 5.3.7 Antidrift agents
  • 5.3.8 Antifoam/defoaming agents
  • 5.3.9 Buffering agents
  • 5.3.10 Inverting agents
  • 5.3.11 Sequestering agents
  • 5.3.12 Inorganic salts
• 5.4 Oil-based adjuvants
  • 5.4.1 Crop oils
  • 5.4.2 Crop oil concentrates (COC)
  • 5.4.3 Properties of mineral oils used as adjuvants
  • 5.4.4 Vegetable oils used as adjuvants
• 5.5 Overview of adjuvants used in tank mixes: information provided by Allen Underwood of Helena Chemical Company, Memphis, TN, US. Allen Underwood is an Executive Committee Member of the ISAA

• 6.1 Introduction
• 6.2 Atomisation
• 6.3 Transport to target
• 6.4 Droplet impaction
• 6.5 Wetting and Spreading
• 6.6 Drying of droplets and deposit effects
• 6.7 Uptake and translocation
  • 6.7.1 Contribution from Terry Grayson (retired), formerly with Shell Agrochemicals, Sittingbourne, UK
  • 6.7.2 Contribution from Allen Underwood, Helena Chemical Company, Memphis, TN, US and Executive Committee Member of the ISAA
  • 6.7.3 Contribution from David Stock of Syngenta, Jealott' s Hill, UK and Executive Committee Member of the ISAA
  • 6.7.4 Contribution from Hans de Ruiter, SURfaPLUS, the Netherlands and Executive Committee Member of the ISAA
  • 6.7.5 Contribution from Per Kudsk, Danish Institute of Agricultural Sciences, Denmark
• 6.8 Biological effect
• 6.9 Spray tank problems

• 7.1 Safer formulation developments
• 7.2 Safer Additive and Adjuvant Developments
• 7.3 Biopesticides
  • 7.3.1 Introduction
  • 7.3.2 New biopesticides
  • 7.3.3 Formulations and adjuvants
• 7.4 International Society for Agrochemical Adjuvants (ISAA)
  • 7.4.1 Objectives ISAA
  • 7.4.2 Organisation and membership
  • 7.4.3 ISAA 2004 - Adjuvant use expands in new areas
    • 7.4.3.1 New products
    • 7.4.3.2 Spray drift
    • 7.4.3.3 Herbicides
    • 7.4.3.4 Insecticides/fungicides
• 7.5 Expert Views on Future Developments in Formulation and Adjuvant Technology
  • 7.5.1 Contribution from Alan Knowles, FORM-AK Ltd, Formulation Consultancy Services, UK
  • 7.5.2 Contribution from David Stock, Syngenta UK, and Exectutive Committee Member of the ISAA
  • 7.5.3 Contribution from Hans de Ruiter, SURfaPLUS Netherlands, and Executive Committee Member of the ISAA
  • 7.5.4 Contribution from Allen Underwood, Helena Chemical Company, US and Executive Committee Member of the ISAA

• 8.1 Introduction
• 8.2 Regulation of pesticide products in the European Union
  • 8.2.1 Plant Protection Products Directive in EU
  • 8.2.2 EU pesticide review programme
  • 8.2.3 Regulation procedures for additives and tank mix adjuvants in EU countries
    • 8.2.3.1 Belgium
    • 8.2.3.2 Denmark
    • 8.2.3.3 France
    • 8.2.3.4 Germany
    • 8.2.3.5 The Netherlands
    • 8.2.3.6 Spain
    • 8.2.3.7 Sweden
    • 8.2.3.8 UK
    • 8.2.3.9 ECPA queries plans for new Directive 91/414 Annexes
    • 8.2.3.10 Phase-out of nonylphenol ethoxylate surfactants
    • 8.2.3.11 Report on registration and use of tank mix adjuvants in nine EU countries
  • 8.2.4 REACH Regulations
• 8.3 Regulation of pesticide products in US and Canada
  • 8.3.1 Background
  • 8.3.2 Categorisation of inerts
  • 8.3.3 FQPA
  • 8.3.4 Regulatory situation in individual states
    • 8.3.4.1 California
    • 8.3.4.2 Washington State
    • 8.3.4.3 Other states
  • 8.3.5 Adjuvant standards and certification
  • 8.3.6 Canada
• 8.4 Regulation of pesticide products in other countries
  • 8.4.1 Australia
  • 8.4.2 Latin America
    • 8.4.2.1 ANDEAN countries
    • 8.4.2.2 Argentina
    • 8.4.2.3 Brazil
    • 8.4.2.4 Chile
    • 8.4.2.5 Mexico
  • 8.4.3 Asia
    • 8.4.3.1 China
• 8.5 Moves towards harmonisation of regulation
  • 8.5.1 Agrochemical data supply network mooted
  • 8.5.2 Asia
  • 8.5.3 Middle East

• 9.1 Introduction
• 9.2 Global market for agrochemicals
• 9.3 Global markets for adjuvants and additives
  • 9.3.1 Global market
  • 9.3.2 US market
    • 9.3.2.1 Trends in US adjuvant markets
  • 9.3.3 Europe
  • 9.3.4 South Africa
  • 9.3.5 Market value of surfactants used in adjuvants

• Table 2.1 The main formulation types and their characteristics
• Table 2.2 Dust concentrate
• Table 2.3 Dust formulation
• Table 2.4 A typical formulation for a wettable powder is shown below:
• Table 2.5 Classification of carriers
• Table 2.6 A typical granule formulation is shown below:
• Table 2.7 A typical solution concentrate formulation is shown below:
• Table 2.8 A typical emulsifiable concentrate formulation is shown below:
• Table 2.9 A typical SC formulation is shown below:
• Table 2.10 Different polymer wall materials
• Table 2.11 A typical composition of a CS formulation made by interfacial polymerisation is as follows:.
• Table 2.12 A typical water-dispersible granule formulation is shown below:
• Table 2.13 Comparison of Granulation Processes
• Table 3.1 Examples of the use of surfactants as additives (co-formulants) for particular formulation types are shown below:
• Table 3.2 Examples of some commercially available CaDBS are shown below:
• Table 3.3 An example of this type of product is:
• Table 3.4 An example of this type of product is:
• Table 3.5 An example of this type of product is:
• Table 3.6 Examples of ether sulphate suppliers / range products are shown:
• Table 3.7 Examples of alkyl sulfosuccinate suppliers are shown:
• Table 3.8 Examples of suppliers / range products are shown:
• Table 3.9 Examples of suppliers and range products are shown:
• Table 3.10 Examples of range products are shown below
• Table 3.11 Examples of Suppliers / range products are shown:
• Table 3.12 Examples of Suppliers / range products are shown:
• Table 3.13 Examples of Suppliers / range products are shown:
• Table 3.14 Examples of products and suppliers are as shown:
• Table 3.15 Examples of Suppliers / range products are shown:
• Table 3.16 Examples of suppliers and range product TSP ethoxylates
• Table 3.17 Physical Properties of Linear Alcohol Ethoxylates
• Table 3.18 Examples of suppliers and range products are shown:
• Table 3.19 Examples of range products and suppliers are as shown:
• Table 3.20 Examples of suppliers / range products are shown:
• Table 3.21 Suppliers and trade names include the following:
• Table 3.22 Examples of suppliers and range products are shown:
• Table 3.23 Examples of suppliers and range products are shown:
• Table 3.24 Examples of Suppliers / range products are shown:
• Table 3.25 An example of this type of product is:
• Table 3.26 An example of this type of product is:
• Table 3.27 An example of a “comb” surfactant is:
• Table 3.28 An example of this type is:
• Table 3.29 An example of this type is
• Table 3.30 An example of this type of product is:
• Table 3.32 Surface tensions for water/air interface (mN/m)
• Table 3.33 Critical Micelle Concentrations of some common surfactants
• Table 3.34 Cloud Points of Some Nonionic Surfactants
• Table 3.35 Examples of surfactant suppliers and product ranges (trade names) available
• Table 4.1 Some fillers used in WP and WG formulations
• Table 4.2 Some carriers used in granule formulations
• Table 4.3 Absorptive capacities of some granular carriers
• Table 4.4 Number of particles per gram for attapulgite at various mesh sizes
• Table 4.5 Properties of some commonly used solvents for EC formulations
• Table 4.6 Phytotoxicity ratings for some solvents
• Table 4.7 Naphthalene content of some aromatic solvents
• Table 4.8 Vegetable oil methyl ester solvents
• Table 4.9 Examples of polar solvents used in liquid agrochemical formulations
• Table 4.10 Antisettling agents used in aqueous colloidal formulations
• Table 4.11 Antifreeze solutions in water
• Table 4.12 Examples of some antifoaming and defoaming agents
• Table 5.1 Examples of extenders are as follows:
• Table 5.2 Defoaming agents
• Table 5.3 Examples of micronutrients in chelate form include the following:
• Table 5.4 Physical properties of mineral oils of significance in adjuvants
• Table 5.5 Composition of some vegetable oils used in adjuvants
• Table 6.1 Contact angles for water droplets on field plants
• Table 6.2 Effect of Surfactants on Dried Deposit Areas
• Table 6.3 Solubilisation Ratios of Some Surfactants with a Triazole Fungicide
• Table 6.5 Effect of Surfactant on Uptake of a Triazole Fungicide
• Table 7.1 Formulations Listed in Pesticide Manuals 10th, 12th and 13th Editions
• Table 8.1 Active ingredients supported or lost in EU review (May 2006)
• Table 8.2 Data requirements by category for registration of adjuvants in EU countries
• Table 9.1 Global agrochemical market by region, in selected years (US$ millions)
• Table 9.2 Global agrochemical market by pesticide type, in selected years (in US$ dollars)
• Table 9.3 World rankings of the big six agrochemical companies, 2005
• Table 9.4 Growth of US adjuvant market from 1992 to 2005 in US$ millions
• Table 9.5 Surfactants used in agrochemical adjuvants by region, US$ millions
• Table 10.1 Major UK suppliers of spray adjuvants for bio-enhancement in 2006
• Table 10.2 The 3 major UK suppliers of bio-enhancing adjuvants in 2006
• Table 10.3 UK adjuvant categories
• Table 10.4 Cognis AgroSolutions - Formulation surfactant additives
• Table 10.5 Croda' s main range products relevant to agrochemicals are shown below
• Table 10.6 Details of range product adjuvants are shown below
• Table 10.7 De Sangosse auxiliary spray products
• Table 10.8 Helena Adjuvant Products by Type
• Table 10.9 Product range for the agrochemical industry
• Table 10.10 Adjuvants for bio-enhancement
• Table 10.11 Utility adjuvants
• Table 10.12 Adjuvant product range for bio-enhancement of active ingredients include the following:
• Table 10.13 Anionic Surfactants
• Table 10.14 Nonionic surfactants
• Table 10.15 Antifoam agents
• Table 10.16 Synthetic polymers
• Table 10.17 Performance concentrates and blends (North America)
• Table 10.18 Natural biopolymers
• Table 10.19 Other speciality products
• Table 10.20 Stepan Core Technologies
• Table 10.21 Stepan Products: Functionality and Chemistry

• Figure 2.1 Microcapsules prepared by Interfacial Polymerisation
• Figure 3.1 Structure of dodecylbenzene sulphonates
• Figure 3.2 Structure of alkylnaphthalene sulphonates
• Figure 3.3 Structure of alcohol sulphates
• Figure 3.4 Structure of ether sulphates
• Figure 3.5 Alkyl sulfosuccinates
• Figure 3.6 Sulphonated naphthalene / formaldehyde condensate
• Figure 3.7 Structure of lignosulphonates
• Figure 3.8 Sulphonation of lignin
• Figure 3.9 Polycarboxylate surfactants
• Figure 3.10 Olefin sulphonates
• Figure 3.11 Phosphated ethoxylates
• Figure 3.12 Phosphated and sulphated tristyrylphenol ethoxylate
• Figure 3.13 Taurates
• Figure 3.14 Alkylphenol ethoxylates
• Figure 3.15 Structure of tristyrylphenol ethoxylates
• Figure 3.16 Alcohol ethoxylates
• Figure 3.17 PEG mono- and di-esters
• Figure 3.18 Structure of sorbitan esters
• Figure 3.19 Structure of sorbitan ester ethoxylates (mono or triester)
• Figure 3.20 Castor oil ethoxylates
• Figure 3.21 Amine ethoxylates
• Figure 3.22 ABA block copolymers
• Figure 3.23 BAB block copolymer
• Figure 3.24 BAB block copolymer (PHS/PEG/PHS)
• Figure 3.25 BA block copolymers
• Figure 3.26 Styrene / maleic anhydride copolymer
• Figure 3.27 “Comb” or graft copolymer
• Figure 3.28 Alkylpolyglucosides (APG)
• Figure 3.29 Organosilicones
• Figure 3.30 Acetylenic diols
• Figure 3.31 General structure of a quaternary ammonium surfactant
• Figure 3.32 Some examples of quaternary ammonium surfactants
• Figure 3.33 Laurylamine acetate
• Figure 3.34 Lauryl dimethyl amine oxide
• Figure 3.35 Amine ethoxylate (2EO)
• Figure 3.36 Solubilisation of active ingredient within surfactant micelle
• Figure 3.37 Liquid crystalline phases
• Figure 3.38 Krafft Point of ionic surfactants
• Figure 4.1 Charged plates of montmorillonite clay particles
• Figure 4.2 Gelling properties of Montmorillonite (Bentonite) mineral clays
• Figure 4.3 Fumed silica as antisettling (gelling) agent
• Figure 4.4 Xanthan gum as antisettling (gelling) agent
• Figure 4.5 Isocyanates used in capsule suspensions
• Figure 5.1 Wetting and spreading of spray droplets on leaf surfaces
• Figure 5.2 Formation of rainfast spray deposit on leaf surface
• Figure 5.3 Composition of mineral oils
• Figure 6.1 Atomisation from a spray nozzle
• Figure 6.2 Deposition of droplets at target site
• Figure 6.3 Effect of Surfactants on Contact Angles on Plants
• Figure 7.1 Typical alkylphenol and aliphatic alcohol ethoxylates
• Figure 7.2 Typical Alkylpolyglucoside Adjuvant