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Crop Protection Emulsifiable Concentrate Crop Protection

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Crop Protection Emulsifiable Concentrate Crop Protection Powered By Docstoc
					0208080_Reis_Broschuere   05.09.2002   13:49 Uhr      Seite 16




                                                                                                            Exactly your chemistry.




                                                                                                                                      Functional Chemicals Division




                                                                                                            Crop Protection
                                                                                                                             Formulations
                                                                                                            Emulsifiable
                                                                                                                  Concentrate
                                   Exactly your chemistry.
                                   Clariant GmbH, Functional Chemicals Division, Crop Protection
                                   D-65926 Frankfurt am Main, Germany
                                   Marketing: Tel.: +49 61 96 757 78 34, Fax: +49 61 96 757 89 35
                                   Research & Development: Tel.: +49 69 305 80 23 4, Fax: +49 69 31 84 35
                                   E-Mail: cropprotection@clariant.com, Internet: http://fun.clariant.com




                                                                                                                                          Product Range
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                                                             Contents
                                                             Aim of this publication                  3   Overview:                                 3
                                                                                                          Clariant’s products for ECs
                                                             Disclaimer                               3
                                                                                                          Guide formulations                        3
                                                             Explanation of terms and                 3
                                                             techniques




                                                             Aim of this publication
                                                             Dear Customer,                               your actives or whether you want only           please refer to the brochure “Emul-
                                                             Emulsifiable concentrates are still one      three emulsifiers for all your actives,         sifiers for Crop Protection Formula-
                                                             of the most important formulation            Clariant can offer both: single-compo-          tions”)
                                                             types for crop protection products           nent emulsifiers on the one hand or             guide recipes for single-component
                                                             worldwide.                                   optimized emulsifier blends suitable for        application (part A) and matched
                                                             Clariant offers a broad range of anionic     many actives-matched pairs.                     pairs (part B).
                                                             and nonionic emulsifiers to meet the                                                       If you have any questions about our
                                                             needs of our customers with their dif-       This brochure will give you                   products, please do not hesitate to
                                                             ferent active ingredients, climates,           a short introduction to the basics of       contact your local Clariant partner.
                                                             water conditions and formulation               EC development
                                                             equipment. Whether you can handle              a brief overview of our product
                                                             the individual emulsifiers for each of         groups (for detailed information




                                                             Disclaimer
                                                             The aim of this publication is to provide    This information is not intended to           sary preliminary tests, which alone can
                                                             our customers with the basic informa-        replace technical data sheets or safety       ensure that a product is suitable for a
                                                             tion necessary for choosing Clariant         data sheets, which must be consulted          given use.
                                                             products for use in the development of       for further details. It must on no account
                                                             EC formulations.                             be used as a substitute for the neces-




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                                                             Explanation of terms relating to
                                                             Emulsifiable Concentrates
                                                             Active ingredient (a.i. or AI).                                  Water hardness
                                                             Chemical in a product that is responsible for the pesticidal     A measure of the amount of calcium and magnesium ions in
                                                             effect.                                                          water. The water hardness has a major influence on the
                                                                                                                              stability of emulsions. A good guide recipe should give stable
                                                             Emulsifiable concentrate (EC)                                    emulsions in soft water (20 ppm CaCO3 ), hard water (342
                                                             A liquid, homogeneous preparation to be applied as an            ppm CaCO3 ) and very hard water (500 ppm CaCO3 ), thus
                                                             emulsion after dilution in water. Emulsifiable concentrates      making the manufacturer of the formulation independent of
                                                             are made from oily active ingredients or from low-melting,       the hardness of the water used in the specific region where
                                                             waxy, solid active ingredients which are soluble in nonpolar     the pesticide is applied.
                                                             hydrocarbon solvents.
                                                                                                                              HLB value
                                                             Solvents                                                         Hydrophilic-lipophilic balance. Defined for ethoxylated
                                                             The most important solvents for EC formulations are non-         nonionic surfactants. It is the ratio of the hydrophilic part,
                                                             polar hydrocarbon solvents such as xylene, solvent naphtha,      ethylene oxide, to the lipophilic part, alcohol. It is commonly
                                                             Solvesso1 grades and Shellsol2 grades. Major factors influ-      used to select the appropriate nonionic surfactant for a par-
                                                             encing the choice of solvent are solubility of the formulation   ticular application. For polyoxyethylene nonionic surfactants,
                                                             in it, price, toxicity and flash point.                          the HLB can be calculated as follows:


                                                             Emulsifier                                                                                   weight%EO
                                                             A surface-active agent that suspends a lipophilic phase (e.g.                 HLB =
                                                             oil) in a hydrophilic system (water) or vice versa. A suitable                                   5
                                                             emulsifier should emulsify an EC formulation spontane-
                                                             ously to form a stable emulsion. The blooming of the EC          Cream and oil
                                                             formulation is an indication of spontaneity.                     Cream and oil are undesired separations in emulsions. Cream
                                                                                                                              is an emulsion of water in oil, usually separating at the top
                                                             Co-emulsifier                                                    of the emulsion. Oil is a separation of hydrophobic compo-
                                                             A co-emulsifier is a third nonionic emulsifier component         nents that are no longer emulsified. It is often observed at
                                                             which is sometimes necessary when the hard water stability       the bottom of the emulsion when the density of the active
                                                             of the emulsion cannot be sufficiently improved by altering      ingredient is more than 1 g/cm3. Unlike oil, cream can often
                                                             the ratio of nonionic and anionic emulsifier. These co-emul-     be easily re-emulsified.
                                                             sifiers are often EO/PO block polymers.


                                                             Blooming
                                                             Qualitatively describes the excellent formation of an emul-
                                                             sion on pouring the EC concentrate carefully into a test tube
                                                             with water. It is observed as a white-blue opalescence co-
                                                             ming from very small emulsion droplets when seen against a
                                                             source of light.




                                                             Solvesso® is a registered trademark of Exxon Corp
                                                             1


                                                             Shellsol® is a registered trademark of Shell Corp
                                                             2




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        Assessment methods for emulsifiable
        concentrates
        Guide recipes are provided to give you a starting point for     To test a guide recipe, the following simple laboratory
        your own EC formulations. They are tested under specific        method is useful:
        conditions, which may vary from yours. In this brochure the
        standard methods of the CIPAC (Collaborative International      1. The EC formulation is prepared as described in the
        Pesticides Analytical Council Limited, CIPAC Handbook 1,        guide recipe.
        p. 910 et seq. ”MT 36 Emulsion Characteristics of Emulsifia-
        ble Concentrates, 1970, Great Britain) were employed.           2. 95 ml test water (usually CIPAC/ WHO standard water)
                                                                        are placed in a graduated cylinder.
        They describe in particular
          the type of water used and its preparation                    3. Whilst pouring 5 ml of the homogeneous EC formula-
          the temperature at which the stability is tested              tion into the test water, the blooming is carefully observed.
          the time schedule for observing of the emulsion stability
          the dilution of the emulsion                                  4. The cylinder is stoppered and then inverted ten times.
          the amount of cream and oil tolerated after specific times
                                                                        5. The resulting emulsion is evaluated immediately and
        The EC formulations outlined in part A (single-component        after the time that meets your requirements.
        emulsifier) were tested in 20 ppm, 342 ppm and 500 ppm
        water in 5 % dilution at 30°C. The stability of the emulsions   6. The emulsion is evaluated by observing the amount of
        was observed immediately after emulsification and again af-     separated oil and cream.
        ter 1 hour, 3, 6 and 24 hours. The form ation of cream and
        oil was noted and used as a parameter for the emulsion sta-     Should it be necessary to adjust the guide recipes to your
        bility. Acceptable values were absence of cream or oil after    needs (due to the special quality of the active ingredient,
        6 hours and 1 ml cream and traces of oil after 24 hours.        climate, type of water, etc.), the same method can be used
        These values meet the highest standards. If lower values are    but the emulsifier ratios given in the guide recipes must be
        satisfactory for your application, much lower emulsifier        varied slightly.
        amounts may be used.
                                                                        A few general principles are helpful when you have to
        The guide recipes in part B (Matched Pairs system) were         optimize a guide recipe:
        also tested in 20 ppm, 342 ppm and 500 ppm water in 5 %           anionic surfactants make emulsions more stable at higher
        dilution at 30 °C. However, emulsion stabilitry was recorded      temperatures
        up to two hours, which is sufficient for many users               nonionic surfactants are unaffected by water hardness. If
                                                                          an emulsion breaks when very hard water is used, it may
                                                                          be helpful to increase the ratio of nonionic surfactant.
                                                                          nonionic surfactants improve the stability of the emulsion
                                                                          at higher temperatures




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        Clariant products for EC formulations

          1. Anionic emulsifiers                                                                                                                        3. APE-free matched pairs


        Clariant offers a broad range of anionic emulsifiers for EC              40 % active. Other benzene sulfonate derivatives with diffe-         The matched pairs emulsifier system is a versatile, APE-free        Furthermore, the new matched pairs system from Clariant
        formulations. The most commonly used ones are the calcium                rent counterions are also available but were not used in this        system containing few components for multiple active ingre-         does not contain any alkylphenol ethoxylates (nonylphenol
        dodecylbenzene sulfonates. These may be supplied as linear               brochure (For more information on this see the brochure:             dient solutions.                                                    or isooctylphenol ethoxylates). Our matched pairs system
        or branched-chain products in isobutanol at 70 % active or               Emulsifiers in Crop Protection Formulations).                                                                                            already meets APE-free requirements, which are becoming
        in high flash point solvents (Solvesso 150, Solvesso 200) at                                                                                  Matched pairs are emulsifier blends with optimized perfor-          more and more important all over the world. Our matched
                                                                                                                                                      mance. Thus you can formulate numerous active ingredients           pairs emulsifier blends are called Emulsogen MP grades.
          Branched acid                Linear acid            Solvent               Stabilizer    Concentration    Flashpoint             EPA         with only a few of our blends. This will save storage space and
                                                                                                     [% w/w]           [ºC]       (40CFR §180.1001)   make handling of formulations much easier. Instead of seve-
                                                                                                                                                      ral emulsifiers only two to four of our blends are necessary.

          Phenyl sulfonate           Phenyl Sulfonate        Isobutanol               none             ~ 70            ~ 30               c(d)e
                                                                                                                                                        Blend                       composition                   Viscosity                   Appearance
          CA                               CAL
                                                                                                                                                                                                                  [mPa at 25º C]
          Phenyl Sulfonate                                   Solvesso                Genapol          40 + 10         ~100                c–e
          CA 100                                                200                   X 060
          Calsogen EH                 Calsogen 4814       2-Ethylhexanol              none             ~58             ~75                c(d)e         Emulsogen MP1               anionic/                      approx. 17000               brown, clear solution
                                                                                                                                                        Emulsogen MP2               nonionic blend                approx. 1240                light brown, clear solution
                                                                                                                                                        Emulsogen MP3                                             approx. 2040                brown; hazy at 20º C, clear at 30º C

          2. Nonionic emulsifiers


        Nonionic emulsifiers are various types of polyoxalkylated                both emulsion formation and stability. Among these factors
        products. A great variety of nonionic emulsifiers is neces-              are water hardness, temperature, lipophilicity of the solvent
        sary to cope with different factors having an influence on               and the active ingredient.


          Clariant name for nonionic                    Chemistry                                     Remarks
          emulsifier product group


          Arkopal grades                                nonylphenol ethoxylates                       cheap and versatile
          Sapogenat grades                              tributylphenol ethoxylates                    excellent emulsifying properties,
                                                                                                      NPE replacement
          Emulsogen TS grades                           tristyrylphenol ethoxylates                   excellent emulsifying properties,
                                                                                                      NPE replacement
          Emulsogen EL grades                           castor oil ethoxylates
          Emulsogen V 1816, V2436                       EO/PO block polymers                          very good stabilizing properties,
          3510                                                                                        special applications
          Genapol grades                                fatty alcohol ethoxylates                     NPE replacement




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        The following table gives guide recipes for some active in-                   may have to be modified slightly. This is done by a simple test
                                                                                                                                                          Propanil + Butachlor EC 27.5 % / 27.5 %; 36 % / 27.5 %
        gredients. Depending on the quality of the active ingredient,                 method (CIPAC test), which can be obtained from Clariant.
        solvent or water used in the spray tank, these guide recipes
                                                                                                                                                             Active ingredient           Xylene/cyclohexanone              Emulsogen FP                  Emulsogen EL   Phenyl sulfonate CA
                                                                                                                                                                  28.4 / 29.6                   up to 100 %                    15.0 %                       1.75 %            2.25 %
                                                                                                                                                                  37.1 / 29.6
        Emulsifiable concentrate (EC)
        formulations – guide recipes                                                                                                                      Butachlor EC 60 %


                                                                                                                                                                 Active ingredient                            Xylene                      Phenyl sulfonate CA           Emulsogen EL
          Carbosulfan EC 20 %
                                                                                                                                                                       64.5 %                              up to 100 %                           4.7 %                      5.3 %
                                                                                                                                                        *see also the matched pairs guide recipes below
                 Active ingredient                        Solvesso 150                    Phenyl sulfonate CA                Emulsogen 3510
                       22.5 %                             up to 100 %                            5.0 %                            5.0 %
                                                                                                                                                          Endulsofan EC 35 %


                                                                                                                                                             Active ingredient                    Xylene                 Phenyl sulfonate CA             Emulsogen EL    Sapogenat T 180
          Cypermethrin EC 10 %; 25 %; 35 %
                                                                                                                                                                   36.4 %                       up to 100 %                     4.4 %                       2.6 %              4.0 %
                                                                                                                                                        *see also the matched pairs guide recipes below
                 Active ingredient                            Xylene                      Phenyl sulfonate CA                 Emulsogen EL
                        10 %*                             up to 100 %                            3.8 %                            6.2 %
                        26 %                              up to 100 %                            3.8 %                            6.2 %                   BPMC EC 50 %
                        35 %                              up to 100 %                            3.8 %                            6.2 %
        *see also the matched pairs guide recipes below                                                                                                      Active ingredient                 Solvesso 100              Phenyl sulfonate CA             Emulsogen EL     Arkopal N 300
                                                                                                                                                                   52.0 %                       up to 100 %                    4.58 %                       3.37 %            2.05 %
                                                                                                                                                        *see also the matched pairs guide recipes below
          Cypermethrin EC 20 %


             Active ingredient                 Solvesso 150             Phenyl sulfonate CAL             Arkopal N 300          Emulsogen 3510            Deltamethrin EC 1.5 %; 3 %
                    20 %                        up to 100 %                       3.0 %                      1.0 %                   2.0 %
                                                                                                                                                             Active ingredient                    Xylene                 Phenyl sulfonate CA        Emulsogen EL 540     Sapogenat T 300
                                                                                                                                                                   1.52 %                       up to 100 %                     7.3 %                       5.45 %            2.25 %
                                                                                                                                                                   3.10 %                       up to 100 %                     7.3 %                       5.45 %            2.25 %
          Malathion EC 57 %; 83 %


          Active ingredient                                   Xylene                      Phenyl sulfonate CA                Emulsogen 3510
                       60.0 %                             up to 100 %                            3.75 %                           3.75 %                  Triclopyr EC 32 %
                       60.0 %                             up to 100 %                            5.0 %                            5.0 %
                       87.4 %                             up to 100 %                            4.2 %                            5.8 %                      Active ingredient                    Xylene                 Phenyl sulfonate CA             Emulsogen EL     Emulsogen 3510
                       87.4 %                             up to 100 %                            4.7 %                            7.3 %                            33.1 %                       up to 100 %                     4.5 %                       4.5 %              1.0 %
        *see also the matched pairs guide recipes below                                                                                                            33.1 %                       up to 100 %                     3.8 %                       6.2 %               –



          Propanil EC 36 %


                 Active ingredient                   Xylene/cyclohexanone                    Emulsogen FP                     Emulsogen EL
                       37.1 %                             up to 100 %                            15.0 %                             –
                       37.1 %                             up to 100 %                            15.0 %                           3.0 %


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        Emulsifiable concentrate (EC)
        formulations – guide recipes
          Prochloraz EC 25 %                                                                                                                                             Diazinon


          Active ingredient                                      Xylene                               Emulsogen IT                           Sapogenat T 180                Active ingredient                     Xylene            Phenyl sulfonate CA         Emulsogen EL 360          Genapol O 180
                        26.0 %                                up to 100 %                                 13.3 %                                    5.7 %                           60 %                       up to 100 %                   2%                       8.75 %                  17.5 %




          Prochloraz EC 25 %; 40 %*; 50 %* (evaluated at 23º C)                                                                                                          Diomethoate


                  Active ingredient                              Xylene                               Emulsogen IT                           Sapogenat T 180                Active ingredient               Solvent naphtha         Phenyl sulfonate CAL        Sapogenat T 180
                        26.0 %                                up to 100 %                                 13.3 %                                    5.7 %                           60 %                       up to 100 %                   1%                        4%
                        41.6 %                                up to 100 %                                 14.3 %                                    4.7 %
                        52.0 %                                up to 100 %                                 14.3 %                                    4.7 %
        *Prochloraz 40 %, 50 %: Occasionally up to 6 % propylene glycol monomethyl ether have to be added in order to avoid crystallisation of the active ingredient
                                                                                                                                                                         Dimethoate


                                                                                                                                                                          Active ingredient          Cyclohexanone              Xylene          Phenyl sulfonate CA   Emulsogen EL 360     Sapogenat T 180
          Quizalofop
                                                                                                                                                                                 42 %                      45 %               up to 100 %                                      6

             Active ingredient                   Solvesso 100               Phenyl sulfonate CAL                 Arkopal N 060                    Arkopal N 100
                     12 %                         up to 100 %                        8.75 %                           8.75 %                           17.5 %
                     10 %                         up to 100 %                         7.5 %                            7.5 %                            15 %             Dimethoate


                                                                                                                                                                            Active ingredient               Cyclohexanone                   Xylene            Phenyl sulfonate CAL        Genapol O 200
                                                                                                                                                                                    60 %                       up to 100 %                  20 %                      1.5 %                   3.5 %
          Mineral oil


             Active ingredient                  Genapol C 030               Phenyl sulfonate CAL
                     90 %                             9%                               1%                                                                                Parathion-methyl
                     85 %                            13.5 %                           1.5 %

                                                                                                                                                                            Active ingredient                     Xylene            Phenyl sulfonate CA          Emulsogen 3510          Emulsogen EL 360
                                                                                                                                                                                  78.5 %                       up to 100 %                  2.75 %                    2.25 %                   2%
                                                                                                                                                                                    90 %                                                    4.5 %                     5.5 %
          Mineral oil (white oil)
                                                                                                                                                                       see also the matched pairs guide recipes below

             Active ingredient                  Genapol C 030               Phenyl sulfonate CAL                 Arkopal N 040
                     96 %                            1.3 %                            1.6 %                            1.1 %                                             Parathion-ethyl
                     97 %                         up to 100 %                        8.75 %

                                                                                                                                                                            Active ingredient                     Xylene            Phenyl sulfonate CA         Emulsogen V 2436          Genapol PF 10
                                                                                                                                                                         40 % up to 100 %                         2.9 %                     2.1 %
                                                                                                                                                                                    60 %                                                    4.5 %                     3.5 %                    2%
                                                                                                                                                                       see also the matched pairs guide recipes below




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        Matched pairs (MP) guide recipes

             Active ingredient                    Emulsogen             Emulsogen    Emulsogen      Solvent
                content in %                         MP1                      MP2      MP3        up to 100 %*
                                                       %                      %         %


                  Butachlor                            3.1                    3.9                   xylene
                     60 %
           Chlorpyriphors (94 %)                       2.1                    2.9                   xylene
                     40 %
                Cypermethrin                           2.0                    3.0                   xylene
                     25 %
                 Dimethoate                                                    6                  10 % xylene/
                     42 %                                                                        cyclohexanone
            2,4-D Isooctyl ester                      1.25                    2.75                  naphtha
                     60 %                                                     4.0       2.0         xylene
                                                       2,5                    4.0                  petroleum
                 Endosulfan                                                             6.0         xylene
                     35 %
            Fenobucarb (BPMC)                                                 7.8       2.2         xylene
                     50 %
              Malathion (95 %)                        2.25                    2.75                  xylene
                     50 %                              2.0                    3.0                 Solvesso 150
               Parathion-ethyl                         2.4                    2.6                   xylene
                     50 %
              Parathion-methyl                                                 3         3          xylene
                     60 %                               2                      6                  Shellsol AB
                 Permethrin                            2.5                    3.5                   xylene
                     25 %
                  Trifluralin                          3.0                    4.0                 Solvesso 150
                     48 %
        *depends on the purity of the active ingredient used




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Description: Crop Protection Emulsifiable Concentrate Crop Protection