Dispersants for Liquid and Solid

Pesticide Formulations

Santiago Chile May 2017

Types of Liquid and Dry Formulations

Liquid Formulation Code Dry Code

Formulation
Suspension SC Water WDG or WG
Concentrate Dispersible
SuspoEmulsion SE Granule

Capsule Suspension CS Wettable WP

Powder
Emulsifiable EC
Concentrate
MicroEmulsion ME
All highlighted in Green
require Dispersants
Soluble Liquid SL

2
 What do dispersants do?

Prevent agglomeration during production, prevent settlement

during application.
Prevent settling out

Milling – particle size reduction

3
Sustainability
Forests

Saw Mill Pulp Mill

Sawdust Crude Tall Oil Black liquor

MWV Value Added Processing

ACTIVATED CARBON PINE CHEMICALS LIGNIN

Air Purification Road Construction Agrochemicals
Automotive Printing Dyes
Water Oil Field Drilling
Chemicals/Pharmaceuticals Adhesives
 WOOD COMPONENTS & THEIR APPROXIMATE PROPORTIONS
CH OH
2
H O OH CH2 OH H
H ~55% H O OH H O OH
OH H H H
OH H OH HO OH H
HO H HO H
H OH CELLULOSE H H H OH
d-glucose beta-d-mannose beta-d-xylose

H
H C OH
C
~11.5%
C HEMICELLULOSE
CH3
~30%
OCH3 CH3
OH LIGNIN
Polymer of coniferyl alcohol HO

TALL OIL ~3% beta sitosterol

~0.5%
CH3(CH2 ) CH:CH(CH2 ) COOH
7 7

TURPENTINE oleic acid

linoleic acids COOH

alpha - pinene abietic acid

5 Presentation title │ Date
Chemical Structure of Kraft Lignin

Functional Chemistry
 Polymeric
 H-Bonding acceptor
and donor sites
 Π-Bonding, aromatics
 Anti-oxidant

6
Ingevity’s Kraft Lignin Product Chemistry

Our chemicals are Polyfon

(aliphatic)
precise because they
are manufactured in Reax 825E
our specialty ethoxylation of Reax 1425E
chemical plant. phenol

Unsulfonated lignin
(reactive unit) Reax
(aromatic)

Reax & Kraftsperse

(hybrid)
Suspension Concentrates (SC)
&
Seed Treatment (FS)

8
Suspension Concentrates (SC)
 A stable suspension of solid A.I. in a fluid usually
intended for dilution with water before use.
 2 week stability of >85%
Product Diluted
Basic formula

Active
Ingredients (20-
50%)
Wetting agent
Dispersant
Water

9
Solution Concentrate (Flowable) Process

Thickener
Anti-Freeze
Water Finished
Concentrate
Product
>2-8
mm

Testing
AI • Suspension
Wetting Agent • Dispersibility
Dispersant • Attrition
Water
Dispersion Mechanisms
Dispersants function with a Dispersants function by
repulsive force generated from providing steric stabilisation.
the presence of an electrical
double layer at the solid/liquid
interface.

In SC this is the
dominant mechanism
Single most important factor influencing dispersion and
stability in SC is dispersant adsorption to the surface of the
a.i.
Order of significance
Impact of lignosulfonate properties on formulations

Degree of sulfonation

Molecular weight
 Desorption from Hydrophobic Particles
(pH 7, 80°C): Degree of Sulfonation

8
Low sulfonation 0.7
7

6
mg SLS / g Red 60

5 Low sulfonation (1.3)

4

1 Med sulfonation 1.7

0
High sulfonation 2.8
0 5 10 15 20 25 30
Time (min)

Low sulfonation lignin adsorbed most strongly due to

lower water solubility.
Select low degree of sulfonation dispersant to maximize
suspension stability.
Mz+1 Greatest Impact on Steric
Stabilization, Mw Impacts Viscosity

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Degree of Sulfonation and Molecular
Weight Impact on Suspension Stability
Polyfon H REAX 907

Good
Dispersant

Better
Dispersant

 Low Deg of  Low Deg of

Sulfonation Sulfonation
 Low Mw and  High Mw and
low Mz+1 High Mz+1
SC Formulation Suggestions
Example of a formula Formulation Tips
Ingredients (45% Active) Percentage, %  anionic wetting agents are best
Active Ingredient 45  Kraft Lignins act as a freeze
Anionic Wetting Agent 1–3 point depressant, reducing the
Dispersant 3-5 need for glycol
Freeze Protection 2–4  synergize with thickeners,
Defoamer only if needed 0.2 allowing less use than with
Thickener 0.1-0.5 small molecule dispersants
Water up to 100

Product recommendation
Degree of
Product Mw Mz+1
Sulfonation
Kraftsperse 8288 0.8 10,000 181,000 HyAct only in
HyAct® 0.8 25,000 300,000 combination with a
Reax® 907 1.2 13,400 255,000 milling aid, like
Reax® 910 1.5 10,200 205,000 Kraftsperse 25M
Kraftsperse® 25M 2.9 4,400 276,000
Selecting a low degree of sulfonation and high MZ+1.
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Milling Efficiency Improvements with two
Kraft lignosulfonates

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Surfactant Recommendations
Compatible Surfactant Types
Na Alkylnapthalenesulfonate
• Geowet HR Incompatible Surfactants
• Morewet D-425 (Condensate) Alcohol ethoxylate and propoxylate
Sodium dodecyle sulfate Low HLB non-ionics
Octylphenol ethyoxylate (with NSF)
• Tergitol NP6
• Sodium lauryl sulfate
• Supragil WP from or Solvay Patent Literature
• US 5380350 A
• Rhodacal BX-78 from Rhodia
• US 6071858 A
• Igepal CO-610
• Triton X-114 from Dow (Non-ionic,
used in combination with anionic)

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Dispersant Requirement for Stable SC’s

Typical Recommendation is in the 3-5% range, Higher if particle

size small and AI loading is high ( > 40% )

Smaller Particles sizes require higher dispersant loading as the surface

area is larger, Surface Area= 𝟒𝝅𝒓𝟐

Can observe sample after bead mill and stirring

• Thin brown layer on top, enough dispersant as the air-water interface
is also a hydrophobic surface
• Thick brown layer on top, excess dispersant
• No brown layer, exposed hydrophobic surfaces and SC will not be
stable over time

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SuspoEmulsion Formulation Suggestions

Example of a formula Product recommendation

Ingredients (45% Active) Percentage, % Degree of
Product Mw Mz+1
Active Ingredient 45 Sulfonation
Anionic Wetting Agent 1–3 Kraftsperse 8288 0.8 10,000 181,000
Dispersant 5-9 Reax® 907 1.2 13,400 255,000
Freeze Protection 2–4 Reax® 910 1.5 10,200 205,000
Defoamer only if needed 0.2 Polyfon H 0.7 4,300 43,000
Water up to 100
Select a low degree of sulfonation
Increase Dispersant
and high MZ+1.

SC + EC SE

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Capsule Suspension

Active Ingredient
Liquid or organic soluble

Thin Polymer Shell,

Usually Diisocyanate
reaction with Polyamine

Degree of Na2SO3
Product Mw
Sulfonation Salt
REAX 88B 2.9 3,100 181,000
Reax® 100M 3.4 2,000 255,000

Kraftspersere 25M 2.9 4,400 205,000

REAX 105M 3.4 2,000 43,000

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 Water Dispersible Granules
&
Wettable Powders

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Wettable Powders (WP)
 A solid pesticide formulation – micronized to powder
form and typically applied as suspended particles after
dispersion in water
Product Diluted
Basic formula

Active Ingredients
(25-80%)
Wetting agent
Dispersant

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WP Process

Finished
Dry Mix Product
>10 <10
mm mm

AI Anti-Caking agent
Wetting Agent
REAX/Polyfon
Filler Testing
• Suspension Stability
• Particle Size
• Viscosity
• pH
 Examples of WP Formulations

Component % Component %

Imidacloprid (95%) 74
Chlorothalonil (95%) 78.8
Polyfon H 7
REAX 88B 6
REAX 88B 3
Kaolin Clay 13.2
Wetting Agent 2
Kaolin Clay 14

Polyfon H increases suspension stability

25
 Wettable Powder Performance
Carbendazim 50% WP
100
Formulation %
90 95% tech 53
Dispersant 7
80 NSF wetting agent 1
Silica 3
70 Kaolin 36

60

50

40

30 Wetting time (sec)

20 Suspension (%)

10

0
Reax 210 Reax 260 Reax 280 Competitive Sulfite
Lignin

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Wettable Powder Performance
Thiophanate-Methyl 70%WP
100

90
Formulation %
95% tech 73
80
Dispersant 7
70 NSF wetting agent 1
Silica 3
60 Kaolin 16

50

40

30

20 Wetting time (sec)

10 Suspension (%)

0
Reax 210 Reax 260 Reax 280 Competitive Sulfite
Lignin

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WDG Extrusion Process

Extruder

Water 15-25%
Dry Mix
>10 <10
mm mm

AI
Wetting Agent
REAX/Polyfon Finished
Filler Testing
Product
• Suspension Stability
• Attrition (Dust)
• Disintegration
• Moisture
Formulation for Product Performance
Comparisons

WDG Extrusion

Ingredients (80%Active) Percentage, %

Chlorothalonil 84

Dispersant 12

Sodium isopropyl naphtalene sulfonate 3

Sodium sulfate 1.0

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Water Dispersible Granule

Need a Balance between Dispersability and Suspension Stability.

Generally it is more difficult to achieve

disintegration than suspension stability.

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Mixture of Dispersants in WDG’s

Dispersant Blend % Suspension***

% Low % High Dispersion ***

(# of Inversions) 2 Weeks at
Sulfonation Sulfonation Initial
54°C
(0.8) (2.9)

0 12 6 88 60
2 10 12 92 90
4 8 12 90 93
10 2 45 65 65
12 0 50 55 58
Ratio of 5:1 Higher DOS: Low DOS ***CIPAC MT.15.1 and MT.46.1
often gives best results if
need increase in % Suspension
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Kraftsperse DD8 Comparisons in Extruded
WDG Chlorothalonil

Dispersant Suspension % Inversions Suspension % Inversions

Initial Initial 5°C Aged Aged 5°C
DD8* 93 12 94 17
DD5 93 20 94 25
DW5 92 24 79 27
REAX 88B 89 18 75 14
Stepsperse 78 19 30 19
DF-500
Morewet 450 63 40 68 35

342 ppm, H2O, Aged 1 month at 54 °C

CIPAC MT.15.1 and MT.46.1

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Adsorption on AI Surface Prevents
Agglomeration under Heat

Particle Size Change in Spray Drying

6
REAX 85A
5 Borresperse NA
90% particle size (µm)

naphthalene sulfonate
4

0
70 80 90 100 110 120 130 140 150 160
Spray dryer Inlet temperature(℃)
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Product Recommendations for WDG’s

Degree of
Product Mw Mz+1
Sulfonation
REAX 88B/A 2.9 3,100 33,000
REAX 100M 3.4 2,000 18,000
Kraftsperse DD8 2.9 5,800 13,000
Kraftsperse DW5 0.8 9.700 43,000
Kraftsperse EDF-350 2.9 5,700 17,000
Kraftsperse EDF-450 3.3 3,700 11,000
Kraftsperse 25M 2.9 4,400 276,000
Polyfon T 2.0 2,900 13,000
Polyfon F 3.3 2,900 13,000
REAX 825E 2.0 3,700 105,000
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Thank you