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Brochure Additives For Pesticide Formulationsl
Brochure Additives For Pesticide Formulationsl
Brochure Additives For Pesticide Formulationsl
Pesticide Formulations
About Us
Evonik Industries is the creative industrial
group from Germany which operates in
three business areas: Chemicals, Energy
and Real Estate. Evonik is a global leader
in specialty chemicals, an expert in power
generation from hard coal and renewable
energies, and one of the largest private
residential real estate companies in Germany. Our strengths are creativity, specialization, continuous self-renewal, and
reliability. Evonik is active in over 100
countries around the world.
When our flagship product BREAK-THRU S 240 was introduced in 1992, our focus was on tankmix adjuvants. Since then, we have started to include different surfactant classes into pesticide
our portfolio. Drawing upon our in-house pool of surfactants and the in-depth knowledge of
interfacial processes and technologies, we have expanded our product portfolio to include
additional organomodified siloxanes and other specialty surfactants. BREAK-THRU is a registered trademark of Evonik Industries AG.
Wetting Agents
Trisiloxanes
pH stable polysiloxanes
Enhance deposition of pesticides by lowering surface
tension of spray water and improving spread
Antifoams
Suppress or eliminate foam during manufacturing,
packaging and tank-mixing
Dispersing Agents
Improve the dispersion and suspension of solid particles
Emulsifiers
Effectively emulsify oils in water
Rheology Modifiers
Stabilize active ingredients in liquid formulations
and adjust to the viscosity
Oil Enhancers
Many pesticides exhibit limited water solubility, so mineral and vegetable oils often serve as the
carriers to deliver these actives to plants or pests. When incorporated into oil-containing formulations such as ECs, EWs or ODs, the BREAK-THRU OE series of organomodified polysiloxanes lowers the bulk surface tension of the oils which leads to improved spreading and distribution of the oil droplets onto and into the target. With the improved performance of these
oil-based pesticide formulations, it is possible to increase pesticide performance and reduce the
amount of spray oil, thereby reducing cost, phytotoxicity risk and environmental concerns. As
oil types and compositions vary globally, the BREAK-THRU OE oil spreaders are designed for
a broad spectrum of formulation types. All three BREAK-THRU OE products are approved for
use under 40 CFR 180.910 and generate only little or no foam.
25 wt% of the oil phase. On a hydrophobic surface, this product at 5 wt% enhances methylated seed oil to improve spreading five fold. Since BREAK-THRU
OE 441 is also soluble in water it can be
used in SC, SL, EW and SE formulations.
Accelerated studies at pH 49 refute the
concerns of hydrolytic instability for this
robust product.
fruits confirm that it leads to improved foliar coverage and efficacy with fungicides
and insecticides. Addition of only 0.5 wt%
to a mineral oil or paraffinic oil results in
spreading up to a five fold increase after
thirty minutes.
Benefits of Oil Enhancers:
Improve pesticide performance
Approved under 40 CFR 180.910
Benign toxicity & ecotox
Soluble in most common solvents
Low use rates
BREAK-THRU OE 440
BREAK-THRU OE 441
BREAK-THRU OE 444
Water
Insoluble
Soluble
Insoluble
Soluble
Soluble
Soluble
Soluble
Dispersible
Dispersible
Mineral Oil
Insoluble
Soluble
Soluble
Paraffinic Oil
Insoluble
Insoluble
Soluble
Solvesso 150*
Soluble
Soluble
Soluble
Soluble
Soluble
Wetting Agents
Trisiloxane based Wetting Agents
While all wetting agents have the ability
to decrease surface tension, silicone wetting agents stand out in their ability to do
so at concentrations between 0.02 to 0.15
wt%. Some of them also cause super
spreading of the spray solutions whereas
others designed solely to reduce surface
tension behave as penetrants. For highperformance applications, our organomodified siloxanes are perfectly suited to
meet varying requirements.
Owing to their ultra low static surface
tensions, trisiloxane surfactants can provide superior spray coverage and are
unique among surfactants in their ability
Ortiva
0.75 l/ha
Ortiva
0.5 l/ha
250 l/ha
Ortiva
0.5 l/ha
Ortiva
0.5 l/ha
90
85
80
b*
75
70
65
without additional
surfactant
+ 200 ml/ha
BREAK-THRU S240
10 min
24 h
90
80
70
60
50
40
30
20
10
b*
a
* All values with the same letter are statistically not different at P = 0.05
pH 4
pH 9
pH 11
1 wt% solution
(0 h)
38
38
37
38
1 wt% solution
(7d at 54 C)
40
39
38
41
Static
surface
tension
@ 0.1 %
in water
Foam
tendency
EPA FIFRA
status
Product
Chemical description
Stable within
pH range
BREAK-THRU OE 441
Organomodified
Polysiloxane
49
40
Low
40 CFR
180.910
BREAK-THRU S 200
Organomodified
Trisiloxane
58
22
High
40 CFR
180.910
BREAK-THRU S 233
Organomodified
Trisiloxane
58
23
High
40 CFR
180.910
BREAK-THRU S 240
Organomodified
Trisiloxane
58
22
High
40 CFR
180.910
BREAK-THRU S 243
Organomodified
Polysiloxane
49
47
High
40 CFR
180.910
BREAK-THRU S 279
Organomodified
Trisiloxane
58
21
High
40 CFR
180.910
Antifoams
In agrochemical formulations, different surface active chemistries are used as wetting agents,
emulsifiers, dispersants, compatibilizers and even as solvents. Many of them tend to concentrate
at interfaces often generating and stabilizing foam. Foaming can occur during manufacturing
and packaging, but can also occur during field application where it is especially burdensome
to end users.
While silicone oils are excellent defoamers, they are notoriously immiscible in
water-based systems. To overcome this
obstacle, Evonik has a line of defoamer/
antifoam products with the BREAK-THRU AF designation. These silicone products are modified with other organic
groups and are tailor-made to overcome
incompatibility, while maintaining the
efficiency and low dose rates typical of
silicone oils.
Initial
Foam
Height
(ml)
Foam
Height
after 90
sec. (ml)
Control
60
50
0.0165 %
48
0.05 %
25
0.15 %
13
Trisiloxane
* Alkylpolyglycoside = APG
10
APG*
Laurylethersulfate
APG control
without
antifoam
Concentration/Form
Viscosity
(mPas)
EPA FIFRA
status
Special properties
OMS*
100/EC**
600
40 CFR
180.910
BREAK-THRU AF-9902
OMS
100/Compound
500
1000
40 CFR
180.910
Antifoam for in-can formulations; not self-emulsifying; suitable for oil based formulations
BREAK-THRU AF-9903
OMS
100/EC
500
1500
40 CFR
180.910
BREAK-THRU AF-9906
Silicone
oil
100/Compound
200
600
40 CFR
180.910
Antifoam concentrate without emulsifier for nonaqueous or solvent based systems (e. g. ODs)
BREAK-THRU AF-9908
Silicone
oil/OMS
40/Emulsion
300
Not listed
Product
Chemical
base
BREAK-THRU AF-5503
11
Dispersing Agents
Dispersing agents are surfactants which enhance the incorporation of solids into liquids and are
used in suspension concentrates and more recently in oil dispersions. Dispersing agents interact
with the surface of the particles and prevent the formation of agglomerates.
Product
Chemical description
Concentration
Formulation
suitability
EPA FIFRA
status
BREAK-THRU DA 646
Modified polyether
100 %
EC, SC
not listed
BREAK-THRU DA 652
100 %
OD
not listed
BREAK-THRU DA 655
Polyether phosphate,
electrostatical stabilisation
100 %
OD
not listed
BREAK-THRU DA 675
40 %
SC
not listed
BREAK-THRU DA 752 W
50 %
SC
not listed
BREAK-THRU EM TD 6
POE (6)
isotridecyl ether
OD
pending
EPA
approval
12
100 %
Emulsifiers
Our product range includes primary and secondary emulsifiers that are based on renewable
resources like ethoxylated or non-ethoxylated glycerol fatty acid esters, sorbitan esters, various
fatty acid polyglycol esters and lauryl polyglycol ethers. However, our focus is on the more
environmentally friendly glycerol fatty acid esters.
BREAK-THRU emulsifiers (BREAK-THRU
EM series) are non-ionic, hydrophilic and
lipophilic organic surfactants used in the
preparation of both oil-in-water and water-in-oil emulsions. By balancing the hydrophilic and lipophilic parts the properties of a surfactant can be adjusted to the
needs of different applications. Therefore
BREAK-THRU emulsifiers can also be
used as dispersants, solubilizers and wetting agents.
To emulsify a specific oil, emulsifiers with
precisely adjusted HLB values are needed.
The required HLB value can be adjusted
by selected blending. Our regional
technical service group will assist you in
finding the right formulation. Rely on our
long-standing experience and know-how
and save valuable time.
BREAK-THRU EM V 20 is one of our
vegetable-based nonionic emulsifiers
with excellent ecological, toxicological
and dermatological behavior. This surfactant also reduces the surface tension of
oils (e.g. sunflower or rapeseed oil) without any foam. With an HLB-value of 8,4
it creates emulsion spontaneity in ECs
and EWs. During screening of various
emulsifiers with a pyrethroid EC formulation it demonstrated superior performance (see publication Poffenberger et.
al ISAA 2007). In herbicide field trials
this product showed higher biological efficacy than methylated rapeseed oil, even
at lower dose rate. No phytoxicity was
exhibited in wheat and maize field trials.
BREAK-THRU EM,
for excellent emulsification
Chemical base
HLB
Recommended oil
BREAK-THRU EM V 20
POE-(20)-Glyceryl
Oleoricinolate
8.4
40 CFR 180.910
BREAK-THRU EM 0 7
PEG-(7)-Oleate
10
40 CFR 180.910
BREAK-THRU EM TD 6
POE-(6)-Isotridecyl
Ether
11,4
Pending
EPA approval
* In order to obtain the whole emulsifier portfolio brochure, please contact our regional technical groups
13
Formulation Activities
We at Evonik decided to develop prototype formulations to provide guidance to the user with
respect to product selection. For us the aim is to give you the ability to differentiate your formulation in the market place by offering superior agrochemical products. Various examples of
ongoing activities with different liquid formulation types are described on the next pages.
wt%
25.1
Dispersing agent
1.6
0.3
BREAK-THRU S 240
08.0
2.5
1.8
Water
to 100
14
120,0
120,0
108,0
108,0
96,0
96,0
84,0
84,0
72,0
72,0
60,0
60,0
48,0
48,0
36,0
36,0
Transmission [%]
Transmission [%]
a) with TSP
24,0
12,0
0,0
95
96
97
98
99
24,0
12,0
0,0
100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115
95
Position [mm]
96
97
98
99
100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115
Position [mm]
31
mg S/l
500
mg S/l
2000
mg S/l
168 a*
147 b
1d
0d
145 b
30 c
0d
Commercial formulation WG 80 %
164 ab
38 c
20 cd
Treatment
Untreated
*All mean values with the same letter are statistically not different at P=0.05
15
16
Component
wt%
Active
4.5
Oil component
61.5
20
5.0
5.0
Thickener
4.0
Emulsification behavior
of the Evonik formulation
(left) compared to a commercial standard (right)
Results
Our efforts resulted in a sulfonylurea formulation with 40 g/l load, which is easy
to handle due to its low viscosity (28
mPas). The chemical stability of the formulation was analyzed by HPLC (modified CIPAC method 709). The physical
stability was analyzed according to the
CIPAC accelerated storage test at 54C
judging the sedimentation behavior.
The biological efficacy of the Evonik formulation was evaluated in the glass house
as well as in the field and showed better
results than a commercial standard. In
10 g ai/ha
Commercial standard
60
74
Evonik formulation 1
81
90
Evonik formulation 2
62
100
17
18
wt%
Clodinafop active
8.2
Safener
2.1
Mineral Oil
64.7
BREAK-THRU EM blend
20.0
BREAK-THRU OE product
5.0
Formulation Properties
Evonik
Formulation
Commercial
Standard
Formulation stability
(24 h at -18 C)
Liquid,
clear
Turbid,
gel
Formulation stability
(14 d at 54 C)
Stable,
clear
Stable,
clear
Emulsion stability
(24 h at 4 C)
Homogeneous,
stable
Homogeneous,
stable
Emulsion stability
(CIPAC 342 ppm)
Homogeneous,
stable
Homogeneous,
stable
15 DAT
28 DAT
Evonik Formulation
72
77
Commercial Standard
65
75
the use of high shear or high energy demand and required specialized mixing
equipment. The very small particle size
distributions (see chart on right hand
side) which are derived, are specifically
useful for non-crop applications e.g. for
wood protection where a small particle
size is required for good penetration.
Guideline recipes (such as the one described for permethrin) for various actives
are available from Evonik. The surfactants
necessary to create such a microemulsion
are offered by Evonik as a package.
Benefits of Evoniks microemulsion
technology at a glance:
Simple manufacturing at room
temperature
Obtained microemulsions and their
dilutions have an unlimited shelf life
Small droplet size creates superior
biological performance
Phase separation is reversible;
microemulsions are freeze-thaw stable
0,8
EC
0,6
ME
0,4
0,2
0
1
10
Hydrodynamic radius [nm]
100
1.000
10.000
wt%
Paraffinic oil
4131
Water
510
33
Permethrin
21
Wetting agent
05
left: Microemulsion,
middle: Microemulsion diluted to 0.5 wt % active,
right: Nanoemulsion (diluted microemulsion 1:1000 with water)
19
Rheology Modifiers
In SC and OD formulations there is a general need to protect dispersed, insoluble active ingredient particles against sedimentation. This can be achieved by adjusting suitable viscoelastic
properties. In addition, their viscosity has to be low enough to make sure packages can easily be
emptied without residue.
The use of AEROSIL fumed silica supports these functionalities as a rheology
modifier and anti-settling additive. As an
efficient stabilizer AEROSIL products
prevent the agglomeration of active ingredients helping to ensure that they are
evenly distributed and show a long-term
stability.
The performance of AEROSIL fumed
silica in liquid formulations is based on
two mechanisms. First, the silica envelops
the active ingredient and prevents reagglomeration. Second, AEROSIL fumed
silica creates a three dimensional network
giving viscoelastic properties to the liquid
formulation and thus avoiding the sedimentation of solid particles. The proper
choice of AEROSIL fumed silica combines an excellent anti-settling effect with
a low shear viscosity.
Suspension Concentrates
To demonstrate the influence of some of
the above mentioned parameters the figure shows how the yield point of a waterbased AEROSIL 200 suspension depends
on the pre-adjusted pH-value and the surfactant concentration (sorbitan mono-oleate). At a given surfactant concentration
the yield point increases with lower pHvalues. At a given pH-value, there is an
optimum surfactant concentration leading
to the maximum yield point.
Oil Dispersions, OD Formulations
Mineral and natural oils containing active
ingredients are easy to stabilize using hydrophilic or hydrophobic AEROSIL products. The figure shows the strong shear
thinning effect of different AEROSIL 200
concentrations in soybean oil. AEROSIL
fumed silica establishes a yield point and
prevents settling of active ingredients.
4,0
3,5
3,0
2,5
2,0
1,5
1,0
0,5
4
6
pH-value
20
3,54
33,5
2,53
22,5
1,52
11,5
0,51
00,5
2
3
Tenside Concentration [mmol/l]
AEROSIL R972
1000
2000
AEROSIL R974
3000
4000
5000
6000
AEROSIL 200
10
100
1000
21
22
Granules (GR)
Hydrophobic silica on the surface of granulates or dusts enables the formulator to
increase stability in humid environments
or to delay (slow release) the diffusion
of the active ingredient. Hydrophilic
SIPERNAT 2200 is an ideal carrier for
liquid or low melting actives to be converted to granules. Such carried actives
are easy to be applied directly to the soil,
will not create dust and reduce direct skin
contact which facilitates their handling.
SIPERNAT 2200 is able to absorb 190 ml
liquid / 100 g silica still providing a dry
and free flowing formulation.
Use Description
AEROSIL 380
180.950
AEROSIL COK 84
180.910 + 180.950
180.960
AEROSIL OX 50
AEROSIL 200
AEROSIL 300
AEROSIL R 202
AEROSILR 812 S
AEROSIL R 972
AEROSIL R 974
Use Description
180.950
180.950
SIPERNAT 50
180.950
SIPERNAT 2200
180.950
SIPERNAT D 17
180.960
SIPERNAT 22 (1)
SIPERNAT 50(1)
SIPERNAT 22 S
SIPERNAT 50 S
SIPERNAT 320
SIPERNAT 350
SIPERNAT 22 S
SIPERNAT 50 S
SIPERNAT 350
SIPERNAT 22
(1)
23
www.evonik.com/break-thru
Asia | Pacific
The Americas
Evonik Industries AG
Goldschmidtstrae 100
45127 Essen
Germany
Evonik Degussa
Specialty Chemicals Co, Ltd.
55, Chundong Road
Xinzhuang Industry Park
Shanghai, 201108
PR China
01/2013