NO971450L - Part hydrophobic precipitated silicic acids - Google Patents

Part hydrophobic precipitated silicic acids

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Publication number
NO971450L
NO971450L NO971450A NO971450A NO971450L NO 971450 L NO971450 L NO 971450L NO 971450 A NO971450 A NO 971450A NO 971450 A NO971450 A NO 971450A NO 971450 L NO971450 L NO 971450L
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Prior art keywords
silicic acid
precipitated silicic
partially hydrophobic
acid according
hydrophobic precipitated
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NO971450A
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Norwegian (no)
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NO971450D0 (en
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Heinz-Guenter Lux
Karl Meier
Astrid Mueller
Rolf Oelmueller
Anja Ramb
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Degussa
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Publication of NO971450D0 publication Critical patent/NO971450D0/en
Publication of NO971450L publication Critical patent/NO971450L/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—Coating
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
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    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/82—Compositional purity water content
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/90—Other properties not specified above

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (AREA)
  • Zoology (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silicon Compounds (AREA)
  • Degasification And Air Bubble Elimination (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Cosmetics (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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Description

Foreliggende oppfinnelse angår delhydrofobe kieselsyrer, en fremgangsmåte for deres fremstilling, deres anvendelse som bærer for hydrolyseømfintlige virkestoffer såvel som deres anvendelse i skummingsdempere. The present invention relates to partially hydrophobic silicic acids, a method for their production, their use as a carrier for hydrolysis-sensitive active substances as well as their use in anti-foaming agents.

Det er kjent å tilsette hydrofobe kieselsyrer i en hydrofob væske for fremstilling avIt is known to add hydrophobic silicic acids to a hydrophobic liquid for the production of

en skummingsdemper (DE-C 2829906); US-A 4377.493; DE-C 3411.759; US-A 4344.858; Kalman Koczo et al., Journal of Colloid and Interface Science 1£6.> 225-238 a defoamer (DE-C 2829906); US-A 4377,493; DE-C 3411,759; US-A 4344,858; Kalman Koczo et al., Journal of Colloid and Interface Science 1£6.> 225-238

(1994), WO 95/05880). (1994), WO 95/05880).

Kjente skummingsdempere består av en blanding av ikke-polare oljer og hydrofobe partikler. Typisk ligger faststofifnnholdet ved 1-20%. Disse blandingene er effektivere skurnmingsdempere enn oljen eller de hydrofobe partiklene alene. Skummingsdempere blir benyttet i tekstil-, papir-, farve-, lakk- og vaskemiddelindustrien. Known defoamers consist of a mixture of non-polar oils and hydrophobic particles. Typically, the solids content is 1-20%. These mixtures are more effective scour suppressors than the oil or the hydrophobic particles alone. Foam suppressors are used in the textile, paper, dye, varnish and detergent industries.

Kjente plantebeskyttelsesmidler blir i det vesentlige håndtert som sprøytepulver eller som støvkonsentrater, dispergerbare granulater eller som emulgerbare konsentrater. Known plant protection agents are essentially handled as spray powders or as dust concentrates, dispersible granules or as emulsifiable concentrates.

Kjente sprøytepulvere (WP) består av de følgende komponenter:Known spray powders (WP) consist of the following components:

Pesticid virkestoff, bærerfyllstoff, dispergerings- og fuktingsmiddel såvel som eventuelt ytterligere tilsetningsstoffer. Etter grundig forhåndsblanding av disse bestanddelene føl-ger en grovmaling som blir etterfulgt av en finmaling. Anvendelsen skjer som vandig sprøyteblanding. Pesticide active ingredient, carrier filler, dispersant and wetting agent as well as any additional additives. After thorough pre-mixing of these components, a coarse grinding follows, which is followed by a fine grinding. The application takes place as an aqueous spray mixture.

Kjente støvkonsentrater (DP) består av virkestoff og fyllstoff. Formuleringen skjer analogt med formuleringen av sprøytepulvere. Støvkonsentratet blir påført støvformig etter snitting med mineraliske fyllstoffer som kaolin, talkum eller dolomitt. Known dust concentrates (DP) consist of active substance and filler. The formulation is analogous to the formulation of spray powders. The dust concentrate is applied in dust form after cutting with mineral fillers such as kaolin, talc or dolomite.

Kjente dispergerbare granulater (WG) er faste formuleringer som består av pesticide virkestoffer, bærerfyllstoffer, dispergerings-fuktingsmidler og eventuelle ytterligere tilsetningsstoffer. Disse blandingene blir finmalt og deretter granulert etter kjente fremgangsmåter. Anvendelsen skjer som vandige sprøyteblandinger. Known dispersible granules (WG) are solid formulations consisting of pesticide active substances, carrier fillers, dispersing-wetting agents and any additional additives. These mixtures are finely ground and then granulated according to known methods. The application takes place as aqueous spray mixtures.

Kjente emulgerbare konsentrater (EC) er flytende og inneholder oppløsningsmiddel-holdige bestanddeler. For unngåelse av oppløsningsmidlene som kan belaste miljøet, har man tilstrebet å erstatte de emulgerbare konsentratene med faste formuleringer. Known emulsifiable concentrates (EC) are liquid and contain solvent-containing components. In order to avoid the solvents that can harm the environment, efforts have been made to replace the emulsifiable concentrates with solid formulations.

Det er kjent ved fremstillingen av plantebeskyttelses-, skadedyrbekjempelse- eller kvegkraftformidler å anvende hydrofile felte kieselsyrer som bærestoffer (DE-B 16.19.865). De kjente tilsatte kieselsyrene oppviser et stort oljeopptak og en høy sugeevne. It is known in the production of plant protection, pest control or cattle power agents to use hydrophilic field silicic acids as carriers (DE-B 16.19.865). The known added silicic acids exhibit a large oil uptake and a high absorbent capacity.

Ufordelaktig blir det imidlertid ved anvendelse av de kjente felte, hydrofile kieselsyrene ved fremstilling av midler som inneholder hydrolyseømfintlige virkestoffer, funnet en forringet lagringsstabilitet av virkestoffet. Dette gjelder spesielt for virkestoffer innen plantebeskyttelse, som på grunn av deres hydrolyseømfintlighet hittil kun har kunnet blitt bearbeidet som emulgerbare konsentrater. Unfavorably, however, when using the well-known, hydrophilic silicic acids in the production of agents containing hydrolysis-sensitive active substances, a reduced storage stability of the active substance is found. This applies in particular to active substances in plant protection, which, due to their sensitivity to hydrolysis, have so far only been able to be processed as emulsifiable concentrates.

De kjente hydrofobe fellingskieselsyrene som f .eks. fellingskieselsyrene ifølge DE 26.28975 C2, DE-C 27.29.244, DE-A 24.35.860, EP-A 492.124, DE-A 25.13.608 er høyhydrofobe, og har således i virkestoff-formuleringen et ufordelaktig høyt fuktings-middelbehov. The known hydrophobic precipitated silicic acids such as e.g. the precipitated silicic acids according to DE 26.28975 C2, DE-C 27.29.244, DE-A 24.35.860, EP-A 492.124, DE-A 25.13.608 are highly hydrophobic, and thus in the active ingredient formulation have a disadvantageously high wetting agent requirement.

Et mål ved foreliggende oppfinnelse er således å fremskaffe et bærestoff for spesielt hydrolyseømfintlig virkestoffer, som for eksempel plantebeskyttelses- eller formidler, såvel som virkestoffer i den kjemiske industri, som muliggjør en lengre lagringsstabilitet til virkestoffet. An aim of the present invention is thus to provide a carrier for particularly hydrolysis-sensitive active substances, such as plant protection or mediators, as well as active substances in the chemical industry, which enables a longer storage stability of the active substance.

Ved anvendelse i skummingsdempere har de kjente kieselsyrene den ulempe at kieselsyrene sedimenterer ved lengre lagringstid av skummingsdempere, spesielt ved anvendelse av lave viskøse oljer og en lav faststoffandel. Ved sedimenteringen av de kjente kieselsyrene inntrer en reduksjon av skummingsdempingsvirkningen. De sedimenterte kieselsyrene må dessuten igjen bli opprørt i en kostbar fremgangsmåte før bruk av skummingsdemperen. When used in defoamers, the known silicic acids have the disadvantage that the silicic acids sediment during longer storage times of defoamers, especially when using low-viscosity oils and a low solids content. During the sedimentation of the known silicic acids, a reduction in the foaming suppression effect occurs. The sedimented silicic acids must also be agitated again in an expensive procedure before using the defoamer.

For unngåelse av sedimenteringstilbøyeligheten må det eventuelt til de kjente kieselsyrene bli tilsatt et dispergeirngsmiddel som for eksempel en pyrogen kieselsyre til skummingsdemperblandingen (Degussa-Schriftenreihe Pigmente Nr. 42, side 11). Dette betinger en endring i skummingsdemperoppskriften, som på sin side nødvendiggjør en videre uttesting som fordyrer produktet og betyr et ytterligere fremgangsmåtetrinn for innarbeidelse av dispergeringsmiddelet. To avoid the tendency to sedimentation, a dispersing agent such as, for example, a fumed silicic acid must be added to the known silicic acids for the defoamer mixture (Degussa-Schriftenreihe Pigmente No. 42, page 11). This requires a change in the defoamer recipe, which in turn necessitates further testing which increases the product's price and means a further process step for incorporating the dispersant.

Det er f.eks. fra DE 28.29.-906 C3 kjent å fremstille en tilberedning av skummings-dempervirkestoffet hvor en høy dispersjonsstabilitet blir oppnådd ved at man i en blanding av en skummingsdemperolje og en emulgator først tilsetter den hydrofobe og så den nødvendige mengden av hydrofil kieselsyre under videre omrøring. It is e.g. from DE 28.29.-906 C3 known to produce a preparation of the defoamer active ingredient where a high dispersion stability is achieved by first adding the hydrophobic and then the required amount of hydrophilic silicic acid to a mixture of a defoamer oil and an emulsifier with further stirring.

Foreliggende oppfinnelse har dessuten den fordel at man i et fremgangsmåtetrinn rører inn kieselsyren i skummingsdemperoljen og deretter dispergerer, og at det således kan bli oppnådd en stabil skummingsdemperdispersjon uten et ytterligere fremgangsmåtetrinn. The present invention also has the advantage that in one method step the silicic acid is stirred into the defoamer oil and then dispersed, and that a stable defoamer dispersion can thus be obtained without a further method step.

Gjenstand for oppfinnelsen er en delhydrofob fellingskieselsyre, som er kjennetegnet ved en metanolfuktbarhet fra 10 til 49%. Oppfinnelsens fyllingskieselsyre kan ha et DBP-opptak (vannfri) på mer enn 250 g/100 g (DBP-tall), og eventuelt ha en midlere partikkelstørrelse på 1-12 um. The subject of the invention is a partially hydrophobic precipitated silicic acid, which is characterized by a methanol wettability of 10 to 49%. The filler silicic acid of the invention can have a DBP uptake (anhydrous) of more than 250 g/100 g (DBP number), and optionally have an average particle size of 1-12 µm.

Oppfinnelsens delhydrofobe fellingskieselsyre kan ha et karboninnhold fra 0,3 til 1,85%, fortrinnsvis fra 0,5 til 1,5% og/eller en pH-verdi fra 5,5 til 10 og/eller et tørketap på 2,6 til 10%, fortrinnsvis fra 3 til 6%. The partially hydrophobic precipitated silicic acid of the invention can have a carbon content of from 0.3 to 1.85%, preferably from 0.5 to 1.5% and/or a pH value from 5.5 to 10 and/or a drying loss of 2.6 to 10%, preferably from 3 to 6%.

Spesielt kan oppfinnelsens delhydrofobe fellingskieselsyre ha en eller flere av de følg-ende fysikalsk-kjemiske data. In particular, the partly hydrophobic precipitated silicic acid of the invention may have one or more of the following physico-chemical data.

Kieselsyren kan være en fellingskieselsyre som, etter sin fremstilling og/eller under dets fremstilling, er blitt behandlet med et hydrofobieringsmiddel for å oppnå de ovenfor beskrevne måledata. The silicic acid can be a precipitated silicic acid which, after its preparation and/or during its preparation, has been treated with a hydrophobing agent in order to obtain the measurement data described above.

Fellingskieselsyrer er kjent fra Ullmanns Enzyklopådie der technischen Chemie, 4. opplag, bind 21, sidene 458 til 473 (1988). Precipitated silicic acids are known from Ullmann's Enzyklopådie der technischen Chemie, 4th edition, volume 21, pages 458 to 473 (1988).

Fremstillingen av høyhydrofobe kieselsyrer er f.eks. kjent fra DE 44.19.234 Al, DE-C 27.29.244, DE 26.28.975 C2 og DE-OSD 21.07.082. The production of highly hydrophobic silicic acids is e.g. known from DE 44.19.234 A1, DE-C 27.29.244, DE 26.28.975 C2 and DE-OSD 21.07.082.

I DE 26.28.975 C2 og DE-C 27.29.244 dreier det seg om høyhydrofobe fellingskieselsyrer. Ved begge de andre patentskriftene hhv. utlegningsskrifene dreier det seg om høyhydrofobe og delhydrofobe, pyrogene kieselsyrer med forskjellige fysikalsk-kjemiske data som ikke er identiske med dataene til oppfinnelsens fellingskieselsyrer. Anvendelsen av høyhydrofobe pyrogene kieselsyrer for påstrøing av pesticidgranulater er beskrevet i DE 29.28.585 Al, anvendelsen av pyrogene kieselsyrer som tilsetnings-stoff i virkestoffformuleringer er forklart i EP 0.111.112 Al. DE 26.28.975 C2 and DE-C 27.29.244 deal with highly hydrophobic precipitated silicic acids. In both of the other patent documents, respectively the explanatory notes concern highly hydrophobic and partially hydrophobic, pyrogenic silicic acids with different physico-chemical data that are not identical to the data for the precipitated silicic acids of the invention. The use of highly hydrophobic fumed silicic acids for sprinkling pesticide granules is described in DE 29.28.585 Al, the use of fumed silicic acids as an additive in active substance formulations is explained in EP 0.111.112 Al.

Oppfinnelsens delhydrofobe fellingskieselsyre kan bestå av 85 til 98 vekt-% fellingskieselsyre og 15 til 2 vekt-% hydrofobieirngsmiddel (silikonolje, som kan ha et karboninnhold fra 32,4%). De kan bli fremstilt ved at man, for oppnåelse av den ønskede hyd-rofobieringsgraden blander, under anvendelse av høye skjærkrefter, med en ifølge kjente fremgangsmåter fremstilt fellingskieselsyresuspensjon ifølge forhåndsgitte forhold ved svært kort oppholdstid og lav pH-verdi, filtrerer den hydrofobieringsmiddelholdige fellingskieselsyresuspensjonen og vasker saltfritt, tørker den med hydrofobieirngsmiddel homogent blandede fellingskieselsyrefilterkaken ifølge kjente fremgangsmåter, etterbehandler termisk eller tempererer og deretter underkaster den en mekanisk- hhv. stråle-maling. The partially hydrophobic precipitated silicic acid of the invention can consist of 85 to 98% by weight of precipitated silicic acid and 15 to 2% by weight of hydrophobicizing agent (silicone oil, which may have a carbon content of 32.4%). They can be produced by mixing, in order to achieve the desired degree of hydrophobicity, using high shear forces, with a precipitated silicic acid suspension prepared according to known methods according to predetermined conditions at a very short residence time and a low pH value, filtering the hydrophobizing agent-containing precipitated silicic acid suspension and washing salt-free, dries the precipitated silicic acid filter cake homogenously mixed with hydrophobic cleaning agent according to known methods, thermally post-treats or tempers and then subjects it to a mechanical or jet paint.

Spesielt kan man grundig blande silikonolje under anvendelse av høy skjærenergi med ifølge kjente fremgangsmåter fremstilt fellingskieselsyresuspensjon, med eller uten tilsetning av faseformidlingsstoffer (f.eks. fuktningsmiddel, emulgatorer). In particular, silicone oil can be thoroughly mixed using high cutting energy with precipitated silicic acid suspension prepared according to known methods, with or without the addition of phase transfer substances (e.g. wetting agent, emulsifiers).

Som kontinuerlig skjæranordning kan man anvende en Ultra-Turrax, en Kothoff-blande-sirene eller en Rheinhiitte-blander. Deretter blir den med hydrofobieirngsmiddel homogent blandede fellingskieselsyresuspensjonen skilt fra ved hjelp av kjente filtreringsap-parater (f.eks. kammerfilterpresse, dreiefilter) og det hydrofobieringsmiddelholdige fast stoffet vasket saltfritt. Her blir hydrofobieirngsmidlet fullstendig tatt opp fra fellingskieselsyrefilterkaken. Det dannede filtratet er ikke belastet med organosilisiumforbind-elser, slik at det målte TOC-innholdet < 10 mg/l. An Ultra-Turrax, a Kothoff mixing siren or a Rheinhiitte mixer can be used as a continuous cutting device. Then, the precipitated silicic acid suspension homogeneously mixed with hydrophobicizing agent is separated using known filtration devices (e.g. chamber filter press, rotary filter) and the solid substance containing hydrophobicizing agent is washed free of salt. Here, the hydrophobic agent is completely absorbed from the precipitated silicic acid filter cake. The resulting filtrate is not loaded with organosilicon compounds, so that the measured TOC content < 10 mg/l.

Den i blandeprosessen tilførte fellingskieselsyresuspensjonen såvel som hydrofobier-ingsmidlet, er kjennetegnet ved de følgende fysikalsk-kjemiske stoffdata: Fellingskieselsyre A (stoffdataene henviser til en filtrert, vasket og tørket fellingskiesel-syreprøve, uten tilsetning av hydrofobieirngsmiddel): The precipitated silicic acid suspension added in the mixing process, as well as the hydrophobicizing agent, is characterized by the following physicochemical substance data: Precipitated silicic acid A (the substance data refers to a filtered, washed and dried precipitated silicic acid sample, without the addition of hydrophobicizing agent):

Fellingssyre A (stoffdata henviser til en filtrert, vasket og tørket fellingskieselsyre uten tilsetning av hydrofobieirngsmiddel): Precipitated acid A (substance data refers to a filtered, washed and dried precipitated silicic acid without the addition of a hydrophobic agent):

Fellingskieselsyre B (stoffdata henviser til en filtrert, vasket og tørket fellingskieselsyre uten tilsetning av hydrofobieirngsmiddel): Precipitated silicic acid B (substance data refers to a filtered, washed and dried precipitated silicic acid without the addition of a hydrophobic agent):

Som hydrofobieirngsmiddel kan man spesielt anvende silikonolje bestående av dimetyl-polyisoksaner med en viskositet på 20 til 1000 mPas, fortrinnsvis med 50 mPas. Videre kan det bli anvendt R2R'Si, hvor R=CH30-, C2H5O-, Cl-, R'=CH3-, C2H5-, HMDS (heksametyldisilazan), D4 (oktametyltetrasiloksan), D6, D8, R3Si-CnH2n+r>hvor n=l-18, R=CH30-, C2H5O-, C3H5O-, C3H7-O-, Cl-, spesielt Si 108 (trimetoksyoktyl-silan), Si 166, polymetylsiloksan, polymetylsiloksanemulsjoner, (trimetyloksyheksade-cylsilan), aminopropylsilan, vinylsilan, metakrylsilan. Silicone oil consisting of dimethyl polyisoxanes with a viscosity of 20 to 1000 mPas, preferably with 50 mPas, can especially be used as a hydrophobic agent. Furthermore, R2R'Si can be used, where R=CH30-, C2H5O-, Cl-, R'=CH3-, C2H5-, HMDS (hexamethyldisilazane), D4 (octamethyltetrasiloxane), D6, D8, R3Si-CnH2n+r> where n=l-18, R=CH30-, C2H5O-, C3H5O-, C3H7-O-, Cl-, especially Si 108 (trimethoxyoctyl silane), Si 166, polymethylsiloxane, polymethylsiloxane emulsions, (trimethyloxyhexadecyl silane), aminopropyl silane, vinyl silane, methacryl silane.

Den dannede, med hydrofobieirngsmiddel homogent tilsatte fellingskieselsyrefilterkaken, blir i det etterfølgende fremgangsmåtetrinn tørket i kjente tørkeaggregater. Som tørkeaggregat kan det for tørkingen av den hydrofobieringsmiddelholdige filterkaken bli anvendt en båndtørker eller en Spin-Flash-tørker. For oppnåelse av den ønskede hydro-fobieringsgraden blir det hydrofobieringsmiddelholdige tørrproduktet ved 300°C til 400°C, fortrinnsvis 350°C, i 30 til 60 minutter underkastet en termisk etterbehandling, hhv. temperert i en diskontinuerlig, elektrisk oppvarmet rørverksbeholder hhv. i en kontinuerlig, elektrisk oppvarmet dobbelsnekkereaktor, og deretter malt mekanisk eller ved strålemøller. The precipitated silicic acid filter cake formed, homogenously added with a hydrophobic agent, is dried in known drying units in the subsequent method step. A belt dryer or a Spin-Flash dryer can be used as a drying unit for drying the filter cake containing a hydrophobic agent. To achieve the desired degree of hydrophobization, the hydrophobizing agent-containing dry product is subjected to a thermal post-treatment at 300°C to 400°C, preferably 350°C, for 30 to 60 minutes, respectively. tempered in a discontinuous, electrically heated piping container or in a continuous, electrically heated twin-screw reactor, and then ground mechanically or by jet mills.

Overfor den ovenfor beskrevne fremstillingen prinsipielt sammenlignbar med de kjente fremgangsmåtene, kan oppfinnelsens delhydrofobe fellingskieselsyrer spesielt bli fremstilt ved den følgende fremgangsmåten ved fuktig hydrofobiering, som ikke er avledbar fra teknikkens stand: Til en massestrøm på 160 kg/time av en vandig fellingskieselsyresuspensjon med et faststoffinnhold på 85 g/l, som var fremstilt ifølge kjente fremstillingsfremgangsmåter, ble det under opprettholdelse av en pH-verdi på 3, tilsatt en massestrøm på 0,424 kg/time polymetylsiloksan over en kontinuerlig blander med høyt skjærenergiopptak, ved en temperatur i begge de blandede komponentene på 25 +/- 5°C. Oppholdstiden i blandingen fikk her ikke overskride 5 sekunder. Som føringsstørrelse for beleggings-prosessen tjener den dimensjonsløse beleggingsindeksen Bj, som beskriver forholdet av virkestoffandelene av begge de blandede massestrømmene med hverandre. For oppnåelse av de ifølge oppfinnelsen hydrofobe egenskapene til fellingskieselsyren, er en beleggingsindeks på 32 nødvendig. In contrast to the above-described production, which is in principle comparable to the known methods, the partially hydrophobic precipitated silicic acids of the invention can in particular be produced by the following method by moist hydrophobization, which is not derivable from the state of the art: To a mass flow of 160 kg/hour of an aqueous precipitated silicic acid suspension with a solids content of 85 g/l, which had been prepared according to known manufacturing methods, while maintaining a pH value of 3, a mass flow of 0.424 kg/h of polymethylsiloxane was added over a continuous mixer with high shear energy absorption, at a temperature in both the mixed components at 25 +/- 5°C. The residence time in the mixture was not allowed to exceed 5 seconds. The dimensionless coating index Bj serves as a guide value for the coating process, which describes the ratio of the active ingredient proportions of both mixed mass streams to each other. In order to achieve the hydrophobic properties of the precipitated silicic acid according to the invention, a coating index of 32 is necessary.

Den med silikonolje belagte fellingskieselsyren blir deretter uten å legge vekt på en videre etter-reaksjonstid, skilt ifølge fremgangsmåter, vasket nær elektrolyttfri, tørket ved 105°C, temperert ved 370°C i 1,0 time og til sist malt. The silicone oil-coated precipitated silicic acid is then without emphasis on a further post-reaction time, separated according to methods, washed close to electrolyte free, dried at 105°C, tempered at 370°C for 1.0 hour and finally ground.

Det har vist seg at oppfinnelsens kieselsyre kan bli fremstilt spesielt ved den lave pH-verdi og den korte oppholdstid i blanderen. It has been shown that the silicic acid of the invention can be produced especially at the low pH value and the short residence time in the mixer.

Metanolfuktbarheten. som er et mål for hydrofobisiteten. blir bestemt som følger:The methanol wettability. which is a measure of the hydrophobicity. is determined as follows:

1. Grunnlag1. Foundation

Kieselsyrer hvis overflate er modifisert med ikke-hydrolysebare, organiske grupper, blir for det meste ikke fuktet av vann. Disse hydrofobe kieselsyrene lar seg imidlertid fukte med en metanol/vann-blanding. Andelen metanol i denne blandingen - uttrykt i vekt-prosent - er et mål for hydrofobisiteten til den modifiserte kiselsyren. Desto høyere me-tanolandelen er, desto mer hydrofobt er stoffet. Silicic acids whose surface is modified with non-hydrolyzable organic groups are mostly not wetted by water. However, these hydrophobic silicic acids can be wetted with a methanol/water mixture. The proportion of methanol in this mixture - expressed in weight percent - is a measure of the hydrophobicity of the modified silicic acid. The higher the methanol content, the more hydrophobic the substance.

2. Utstvr og regenser2. Issue and regencies

En 20 ml målepipette med skalainndelingA 20 ml graduated pipette

En 250 ml skilletraktA 250 ml separatory funnel

Metanol p.a.Methanol p.a.

3. Gjennomføring3. Implementation

200 mg av den hydrofobe kieselsyren og 50 ml vann ble tilsatt i en 250 ml skilletrakt. Kiselsyren forble på overflaten. Deretter dryppet man spissen til den med metanolfylte målepipetten ned i den flytende fasen (for å unngå en direkte kontakt mellom kieselsyren og den rene metanol), og lot metanolen langsomt løpe til. Imens ble skilletrakten ristet med en sirkelformet håndbevegelse, slik at det i væsken ble dannet en virvel. Det ble tilsatt metanol inntil faststoffet var fuktet. Dette er tilfelle når a) kieselsyren ikke lenger fordeler seg over hele overflaten til den flytende (allerede metanolinneholdende) fasen og den relativt klare, filmfrie væsken blir synlig. b) kieselsyrefilmen, som danner seg på fasegrensen ved skilletraktveggen, forsvin-ner. 200 mg of the hydrophobic silicic acid and 50 ml of water were added to a 250 ml separatory funnel. The silicic acid remained on the surface. The tip of the methanol-filled measuring pipette was then dripped into the liquid phase (to avoid direct contact between the silicic acid and the pure methanol), and the methanol was allowed to run in slowly. Meanwhile, the separatory funnel was shaken with a circular hand movement, so that a vortex formed in the liquid. Methanol was added until the solid was moistened. This is the case when a) the silicic acid no longer distributes over the entire surface of the liquid (already methanol-containing) phase and the relatively clear, film-free liquid becomes visible. b) the silicic acid film, which forms on the phase boundary at the separating funnel wall, disappears.

c) fuktig kieselsyreagglomerat forblir heftet på skilletraktveggen ved risting.c) moist silicic acid agglomerate remains attached to the separating funnel wall when shaking.

4. Vurdering4. Assessment

Angivelsen av metanolfuktbarheten skjer i vekt-% metanol i metanol/vannblandingen ifølge formelen: The methanol wettability is stated in weight-% methanol in the methanol/water mixture according to the formula:

Metanol forbruket ved denne fremgangsmåten kan, for den samme person og den samme prøven, skille seg ved omkring 2 ml. Methanol consumption by this method can, for the same person and the same sample, differ by about 2 ml.

DBP-opptak rPBP-tain. som er et mål for sugeevnen til fellin gskieselsyren. blir bestemt som følger; DBP uptake rPBP tain. which is a measure of the absorbency of the felling silicic acid. is determined as follows;

1. Grunnlag1. Foundation

Bestemmelsen av dibutylftalat-tallet skjedde med Brabender-plastografen. DBP-tallet er et mål for sugeevnen hhv. opptaksevnen til et pulverformig produkt av væske. Opptaksevnen er avhengig av fuktighetsinnholdet, komingen og innveien av det undersøkte ma-terialet. The determination of the dibutyl phthalate number took place with the Brabender plastograph. The DBP number is a measure of the absorption capacity or the absorption capacity of a powdery product of liquid. The absorption capacity depends on the moisture content, the arrival and the way in of the examined material.

2. Utstyr og reagenser2. Equipment and reagents

Brabender-plastograf med skriveanordningBrabender plastograph with writing device

Multi-Dosimat E 415 (50 ml) fra firmaet MetrohmMulti-Dosimat E 415 (50 ml) from the company Metrohm

DibutylftalatDibutyl phthalate

3. Gjennomføring3. Implementation

12,5 g kieselsyre ble tilsatt elteren i Brabender-plastografen. Under stadig blandinger (omløpshastighet i elteren 125 omdr./min.) strømmet dibutylftalat til blandingen med en hastighet på 4 ml/minutt. Innblandingen krevde kun liten kraft. Mot slutten av bestemmelsen sank blandingens risleevne. Dette faktum viste seg ved en økning i kraftbehovet som bevist på en skala. Ved et skalautslag på 300, ble DBP-doseringen automatisk stan-set. 12.5 g of silicic acid was added to the kneader in the Brabender plastograph. During continuous mixing (rotation speed in the kneader 125 rpm), dibutyl phthalate flowed into the mixture at a rate of 4 ml/minute. The mixing required only a small amount of force. Towards the end of the determination, the flowability of the mixture decreased. This fact was shown by an increase in the power requirement as evidenced on a scale. At a scale reading of 300, the DBP dosing was automatically stopped.

4. Bedømmelse4. Judgment

Tettheten til DBP var 1,047 g/ml.The density of DBP was 1.047 g/ml.

DBP-opptaket ble beregnet i forhold til det vannfrie, tørkede stoffet. Ved anvendnelse av fellingskieselsyrer med høyere fuktighetsinnhold blir, når denne kieselsyren ikke var tørket for bestemmelsen av DBP-tallet, verdien korrigert ved hjelp av korreksjonstabellen. Anvendelsen av korreksjonstabellen kan, sammenlignet med bestemmelsen ved tørket kieselsyre, føre til betydelige avvik. The DBP uptake was calculated relative to the anhydrous, dried substance. When using precipitated silicic acids with a higher moisture content, when this silicic acid was not dried for the determination of the DBP number, the value is corrected using the correction table. The application of the correction table can, compared to the determination with dried silicic acid, lead to significant deviations.

Korreksjonstabell for dibutylftalatuttak - vannfritt -Correction table for dibutyl phthalate withdrawal - anhydrous -

% vann% water

(Korreksjonsverdi tilsvarende vanninnholdet addert til oppnådd verdi)(Correction value corresponding to the water content added to the obtained value)

DBP-opptak DBP recording

Oppveid 12,5 g F = 8,376 Weighed 12.5 g F = 8.376

Bestemmelse av kornstørrelse (Conlter Counter) Determination of grain size (Conlter Counter)

Anvendelse: Bestemmelsen av komstørrelsen til kieselsyrer med Coulter Counter skjedde i en vandig elektrolyttoppløsning (isoton IT). Application: The determination of the particle size of silicic acids with a Coulter Counter took place in an aqueous electrolyte solution (isotonic IT).

Gjennomførin g av bestemmelsen:Implementation of the provision:

Begerglassene (2 stk. pr. telling), magneten og pipettespissen ble blåst støvfritt med en nitrogenstrøm på 5-6 bar. Begerglass ble så satt snudd på støvfritt linsepapir, magnet og pipettespissen ble hatt i en også renblåst Petriskål. The beakers (2 per count), the magnet and the pipette tip were blown free of dust with a nitrogen flow of 5-6 bar. Beakers were then placed upside down on dust-free lens paper, a magnet and the pipette tip was kept in a Petri dish that had also been blown clean.

0,100 g av stoffet som skulle undersøkes ble oppveid på analysevekten og overført til begerglass. Magneten ble tilsatt, først fuktet med noe isotonoppløsning og deretter opp-fylt til 60 ml markeringen med isoton. Suspensjonen ble så omrørt i 1/2 minutt med magnetrøreren ved stilling 3 (skala 1-10). Til sist ble begerglasset hengt i ultralydbadet og utsatt for ultralys i nøyaktig 1 minutt. Her skal det passes på at neddykkingsdybden i det destillerte vannet i ultralydbadet nøyaktig når opp til 60 ml-markeringen på begerglasset. Etter lydbelastningen ble begerglasset igjen satt opp på magnetrøreren og under omrøring (igjen stilling 3) ble det tatt en prøve av suspensjonen med automat-pipetten. Den skal bli anvendt som den totale uttatte mengden for tellingen. Dersom noe mindre suspensjon blir benyttet, skal mindre suspensjon bli tatt opp i pipettespissen. 0.100 g of the substance to be examined was weighed on the analytical balance and transferred to a beaker. The magnet was added, first moistened with some isotone solution and then filled to the 60 ml mark with isotone. The suspension was then stirred for 1/2 minute with the magnetic stirrer at position 3 (scale 1-10). Finally, the beaker was hung in the ultrasonic bath and exposed to ultraviolet light for exactly 1 minute. Here, care must be taken that the immersion depth in the distilled water in the ultrasonic bath exactly reaches the 60 ml marking on the beaker. After the sound exposure, the beaker was placed back on the magnetic stirrer and, while stirring (again position 3), a sample of the suspension was taken with the automatic pipette. It shall be used as the total quantity withdrawn for the count. If a smaller suspension is used, a smaller suspension must be taken up in the pipette tip.

Det andre 100 ml begerglasset ble fylt med isoton II-oppløsning, stilt på begerplattform-en og kappilæren (100 um) såvel som røreren dyppet ned i. Røreren ble innstilt til en passe hastighet. The other 100 ml beaker was filled with isotone II solution, placed on the beaker platform and the capillary (100 µm) as well as the stirrer dipped in. The stirrer was set to a suitable speed.

Oppløsninger og utstyr; Solutions and equipment;

100 ml begerglass100 ml beaker

Automatisk pipette - Pipetman fra fa. GilsonAutomatic pipette - Pipetman from fa. Gilson

Kunststoff-pipettespisserPlastic pipette tips

Magnetrører og magnet (lengde 3 mm)Magnetic stirrer and magnet (length 3 mm)

Ultralydbad: Fa. Bandelin, Sonorex RK 102Ultrasound bath: Fa. Bandelin, Sonorex RK 102

AnalysevektAnalytical weight

Støvfritt linsepapirDust-free lens paper

Nitrogenflaske med tørkeanordning og dyseNitrogen bottle with drying device and nozzle

PetriskålerPetri dishes

StoppeklokkeStopwatch

KornanalysepapirGrain analysis paper

Isoton II-oppløsningIsoton II solution

Coulter Counter Model TA IICoulter Counter Model TA II

Oppfinnelsens kieselsyre kan bli anvendt for fremstilling av plantebeskyttelsesmidler med hydrolyseømfintlige virkestoffer. Det kan her bli fremstilt sprøytepulver eller vanndispergerbare granulater som kan bli hatt i vannoppløselige folieposer i kartong-innpakninger. Herved kan det oppnås fordeler ved transport, ved farestoffklassifisering, ved innspart innpakningsavfall og derved forbunde kostnadsreduksjoner. The silicic acid of the invention can be used for the production of plant protection agents with hydrolysis-sensitive active substances. Spray powders or water-dispersible granules can be produced here, which can be kept in water-soluble foil bags in cardboard packaging. In this way, benefits can be achieved during transport, through hazardous substance classification, through saved packaging waste and thereby associated cost reductions.

Oppfinnelsens kieselsyre kan spesielt bli anvendt ved anvendelse av virkestoffer fra gruppen fosforsyreester (malation, diazinon etc.). The silicic acid of the invention can especially be used when using active substances from the group of phosphoric acid esters (malathion, diazinon etc.).

Analogt lar også anvendelsesformen seg formulere med et hvilket som helst annet virkestoff. Analogously, the form of application can also be formulated with any other active ingredient.

De med oppfinnelsens kieselsyre fremstilte virkestoff-formuleringer, som for eksempel plantebeskyttelsesmiddel, har dessuten fordelen ved en lang lagrinsstabilitet til virkestoffet. The active substance formulations produced with the silicic acid of the invention, such as plant protection agents, also have the advantage of a long storage stability of the active substance.

Lagring av 50WP malation og virkestoffstabilitetStorage of 50WP malathion and active ingredient stability

Fremstilling som 50W P malation:Preparation as 50W P malation:

Først ble det med Wessalon S og fuktingsmidlet Ampholak XIO fremstilt en for-blanding i forholdet 1:1. 28 g av den delhydrofobe fellingskieselsyren såvel som Wessalon S som sammenligningsstoff ble kort fluidisert i 500 ml-Quickfit-røreappa-ratet. Deretter ble 52,1 g malation (96%) langsomt dryppet til under omrøring og senere ble 6 g av forblandingen såvel som 3,0 g av dispergeirngsmidlet Empikol LZ/P tilsatt. Deretter ble 10,9 g fyllstoff (Rollokalk) tilbandet, og blandingen ble homogenisert med Turbula-blanderen. First, a pre-mix was prepared with Wessalon S and the wetting agent Ampholak XIO in a ratio of 1:1. 28 g of the partially hydrophobic precipitated silicic acid as well as Wessalon S as a comparator was briefly fluidized in the 500 ml Quickfit stirrer. Then 52.1 g of malathion (96%) was added slowly with stirring and later 6 g of the premix as well as 3.0 g of the dispersant Empikol LZ/P were added. Then 10.9 g of filler (Rollokalk) was added, and the mixture was homogenized with the Turbula mixer.

Prøven ble lagret i 4 dager ved romtemperatur for stabilisering. Deretter ble utgangsverdiene for CIPAC-sveve-evne og malation-innholdet bestemt ifølge CIPAC. Likele-des ble etter 4 dager utgangsverdiene for malation bestemt ifølge WHO, og isomalation bestemt ifølge WHO, og prøvene ble deretter lagret ved 54°C og målt etter 7 dager, 14 dager, 28 dager såvel som 56 dager. The sample was stored for 4 days at room temperature for stabilization. Then the initial values for CIPAC floatability and the malathion content were determined according to CIPAC. Likewise, after 4 days the initial values for malathion were determined according to the WHO, and isomalation determined according to the WHO, and the samples were then stored at 54°C and measured after 7 days, 14 days, 28 days as well as 56 days.

Testing av sveve- evne ifølge CIPAC- 12/ 3/ ( Mil før hhv, etter lagring ved 54°C:Testing of floating ability according to CIPAC-12/ 3/ (Mil before or after storage at 54°C:

Ved denne metoden dreier det seg om en spektralanalytisk fremgangsmåte med UV som lyskilde. Malation reagerer/hydrolyserer med alkali i Na-00-dimetylditiofosfat, og blir omdannet med Cu/Fe-oppløsning til et gult kobberkompleks og målt ved 420 um. Fuk-tingsmiddelpåvirkningen for frigiving av malation er formodentlig stor ved denne fremgangsmåten. This method involves a spectral analytical method with UV as a light source. Malathion reacts/hydrolyzes with alkali in Na-00-dimethyldithiophosphate, and is converted with Cu/Fe solution to a yellow copper complex and measured at 420 µm. The humectant effect on the release of malathion is presumably large in this method.

Test av malation-innhol det ifølge WHO/ SIF/ 10. R5 ved hjelp av gasskromatografi før hhv, etter lagrin g ved 54°C: Fremgangsmåten bygger på skilling av en stoffblanding ved stoffspesifikk fordeling mellom stasjonær fase (kolonne) og en bæregass-strøm som fører til en forskjellig hastighets/retensjonstid. Ved denne fremgangsmåten hersker ved oppløsning av mala-tionet fra kieselsyren en ekstraksjonslikevekt mellom oppløsningsmidlet og kieselsyren, som muligens utfeller til gunst for den hydrofobe kieselsyretype. En fuktingsmiddelpåvirkning er sannsynligvis ikke tilstede. Test of malathion content according to WHO/ SIF/ 10. R5 using gas chromatography before or after storage at 54°C: The method is based on the separation of a substance mixture by substance-specific distribution between a stationary phase (column) and a carrier gas flow which leads to a different rate/retention time. In this method, upon dissolution of the malathion from the silicic acid, an extraction equilibrium prevails between the solvent and the silicic acid, which possibly precipitates in favor of the hydrophobic silicic acid type. A wetting agent influence is probably not present.

Test av isomalation- innholdet ifølge WHO/ SIF/ 10. R5 ved hjelp av HPLC før hhv, etter lagring ved 54°C: For bestemmelse av isomalation-innholdet ble 0,6 g 50WP malation veid inn og blandet i 30 minutter med 65% vandig acetonitriloppløsning. Etter sentrifugenng og filtrering ble prøven målt mot en referanseoppløsning. Ved denne fremgangsmåten er det også en ekstraksjonslikevekt mellom oppløsningsmiddel og kieselsyre, som muligens utfelles til fordel for den hydrofobe kieselsyren. En fuktingsmiddelpåvirkning er sannsynligvis knapt tilstede. Test of the isomalation content according to WHO/ SIF/ 10. R5 by means of HPLC before or after storage at 54°C: To determine the isomalation content, 0.6 g of 50WP malathion was weighed in and mixed for 30 minutes with 65% aqueous acetonitrile solution. After centrifugation and filtration, the sample was measured against a reference solution. In this method, there is also an extraction equilibrium between solvent and silicic acid, which is possibly precipitated in favor of the hydrophobic silicic acid. A wetting agent influence is probably hardly present.

Lagring av l:l- malation- konsentrat og virkestoffstabilitetStorage of l:l- malathion concentrate and active substance stability

Virkestoffoppløsningen (96%) blir bragt i et forhold på 1:1 til den delhydrofobe bæreren. Denne blandingen ble så testet med hensyn på lagringsstabilitet. De således oppnåd-de verdiene kan kun tilbakeføres til virkningen av bæreren. The active substance solution (96%) is brought in a ratio of 1:1 to the partially hydrophobic carrier. This mixture was then tested for storage stability. The values thus obtained can only be attributed to the effect of the carrier.

De i eksempeldelen anvendte testene er beskrevet som:The tests used in the example section are described as:

Formulering malation 1:1Formulation malathion 1:1

28 g malation (96%) ble i løpet av 30 minutter dryppet til 28 g bærer og deretter omrørt i 3 minutter, såvel som blandet i Turbula-blanderen i 5 minutter på midlere trinn. 28 g of malathion (96%) was dripped over 30 minutes into 28 g of carrier and then stirred for 3 minutes, as well as mixed in the Turbula mixer for 5 minutes on medium steps.

Sammenlignet med den tidligere formulerte 50WP malation (28 g hydrofob bærer + 52,1 g malationoppløsning + ytterligere formuleringsbestanddeler) ble det funnet at blandingen var betydelig tørrere. Compared to the previously formulated 50WP malathion (28 g hydrophobic carrier + 52.1 g malathion solution + additional formulation ingredients) the mixture was found to be significantly drier.

Test av malation- innholdet ifølge CEP AC 12/ 3( MD1 ble ved hjelp av UV/VIS før hhv. etter lagring ved 54°C; Test of the malathion content according to CEP AC 12/3 (MD1 was by means of UV/VIS before and after storage at 54°C;

Analogt med lagring av 50WP malation.Analogous to storage of 50WP malathion.

Testing av malation- innholdet ifølge WHO/ SrF/ lQ. RS ved hielp av GC før hhv, etter la grin g ved 54°C: Testing of the malathion content according to WHO/ SrF/ lQ. RS with the help of GC before or after storage at 54°C:

Analogt med lagring av 50WP malation. Analogous to storage of 50WP malathion.

Ved vurdering av resultatene for Fischer-sveveevnen og malationinnholdet såvel som isomalationinnholdet til 50WP malation, må det bli tatt hensyn til den mulige påvirknin-gen av f.eks. fuktingsmidler på målenøyaktigheten. When assessing the results for the Fischer suspension and the malathion content as well as the isomalation content of 50WP malathion, the possible influence of e.g. wetting agents on measurement accuracy.

Fremgangsmåtefeilene ved bestemmelse av malationinnholdet ifølge CIPAC ved hjelp av UV/VIS blir angitt med ± 5% malation. Ved en prøve ble det etter 14 dager gjennom-ført en dobbeltbestemmelse, som viste et standardavvik på 0,7%. The procedural errors in determining the malathion content according to CIPAC using UV/VIS are indicated by ± 5% malathion. In the case of one sample, a double determination was carried out after 14 days, which showed a standard deviation of 0.7%.

Malationinnholdet ifølge WHO viser et standarawik mellom 0,1 og 0,7%. Standardav-viket ved isomalationinnholdet ligger ved to dobbelbestemmelser i den samme målrek-ken ved 0 til 0,03%. According to the WHO, the malathion content shows a standard deviation between 0.1 and 0.7%. The standard deviation of the isomalation content for two double determinations in the same measurement range is 0 to 0.03%.

Resultatene av virkestoffstabiliteten er grafisk fremstilt i i figurene 1 til 5.The results of the active ingredient stability are graphically presented in figures 1 to 5.

Forsøkene viser at virkestoffstabiliteten kan bli forhøyet ved anvendelse av oppfinnelsens delhydrofobe fellingskieselsyrer, og sammenlignet med de kjente høyhydrofobe fellingskieselsyrene kan det bli innspart fuktighets- og dispergeirngsmidler f.eks. i plan-tebeskyttelsesformuleringene. The experiments show that the stability of the active ingredient can be increased by using the partially hydrophobic precipitated silicic acids of the invention, and compared to the known highly hydrophobic precipitated silicic acids, humectants and dispersants can be saved, e.g. in the plant protection formulations.

Fremstilling av skummingsdemperdispersjonenePreparation of the antifoam dispersions

For fremstilling av den 5%-ige skummingsdemperdispersjonen ble 57 g av den aktuelle oljen, f.eks. Shell Risella G 118 (nå Shell Risella G 18), viskositet 40cSt. plassert i 250 ml begerglass, deretter ble 3 g av oppfinnelsens kieselsyre hhv. Sipemat D10 tilsatt og forsiktig omrørt med hverandre. Deretter fulgte dispergeringen ved hjelp av en Ultra Turrax T50 ved 10.000 omdr./min i 5 minutter. For the production of the 5% defoamer dispersion, 57 g of the oil in question, e.g. Shell Risella G 118 (now Shell Risella G 18), viscosity 40cSt. placed in a 250 ml beaker, then 3 g of the invention's silicic acid or Sipemat D10 added and gently stirred together. This was followed by dispersion using an Ultra Turrax T50 at 10,000 rpm for 5 minutes.

Stabilitetstest av skummingsdemperdispersjoneneStability test of the antifoam dispersions

For dette ble den fortsatt varme dispersjonen fylt i 100 ml glassylindere, oppbevart på et sted uten rystelser ved romtemperatur og med regelmessige tidsavstander ble en mulig faseskilling notert (angivelse i ml klar oljefase). For this, the still warm dispersion was filled into 100 ml glass cylinders, stored in a place without shaking at room temperature and at regular time intervals a possible phase separation was noted (indicated in ml of clear oil phase).

Forsøksresultater (anvendelse i skummingsdemper) Test results (use in defoamer)

Figur 6 og 7 Figures 6 and 7

Figur 6 og 7 viser at oppfinnelsens fellingskieselsyrer innarbeidet i mineraloje og silikonolje, etter 3 måneder ikke viser noen faseskilling. Derimot foreligger med den kjente Sipernat D10 allerede etter en måned i begge de anvendte oljene, en betydelig faseskilling. Figures 6 and 7 show that the precipitated silicic acids of the invention incorporated in mineral oil and silicone oil show no phase separation after 3 months. In contrast, with the well-known Sipernat D10, a significant phase separation already exists after one month in both oils used.

Skummingsdempertest ved hjelp av latexAntifoam test using latex

I et edelstålbeger ble det innveid 160 g Latex, og etter tilsetning av 0,3 g skummingsdemper ble det dannet skum med en Hamilton-Beach-Scovill-blander i sprøytestiIling L (laveste omrøringshastighet: ca. 4000 omdr./min) i 3 minutter. Vekten av 100 ml av dette skummet ble målt ved forskjellsveining i en edelstålmålesylinder. En høy Latex-vekt (nesten 100 g) står for en god skummingsdemperevne til den aktuelle prøven. Mid-delverdiene ble funnet av minst to enkeltbestemmelser. In a stainless steel beaker, 160 g of Latex was weighed, and after adding 0.3 g of antifoam, foam was formed with a Hamilton-Beach-Scovill mixer in spray style L (lowest stirring speed: approx. 4000 rpm) for 3 minutes . The weight of 100 ml of this foam was measured by differential weighing in a stainless steel measuring cylinder. A high Latex weight (almost 100 g) stands for a good anti-foaming ability of the sample in question. The intermediate values were found by at least two individual determinations.

En Hamilton-Beach-Scovill-blander er en milkshake-blander, normalt ved bruk i hus-holdningen, hvor det kan bli innstilt tre omrøringshastigheter (L, M og H). Bryterinn-stillingen "L" betyr ca. 4000 omdr./min. Stoffet som skal bli opprørt, blir opprørt ved hjelp av en vingerører med bevegelige "vinger". A Hamilton-Beach-Scovill mixer is a milkshake mixer, normally for household use, where three stirring speeds (L, M and H) can be set. Switch position "L" means approx. 4000 rpm. The substance to be agitated is agitated using a vane agitator with movable "wings".

Forsøksresultater (anvendelse i skummingsdemper) Test results (use in defoamer)

Formel for beregning av skum innholdet i % etter g jennomføring av Latextesten: Formula for calculating the foam content in % after carrying out the Latex test:

<*1>: Forskjellsveiing etter tilsetting av de aktuelle skummingsdempeme til Latex dispersjon og påfølgende tre minutter omrøring<*2>; Forskjellsveiing etter tre minutters omrøring av Latexdispersjon uten skum-mingsdempertilsetning. <*1>: Differential weighing after adding the relevant anti-foaming agents to the Latex dispersion and subsequent three minutes of stirring<*2>; Differential weighing after three minutes of stirring the Latex dispersion without anti-foam addition.

Figur 8Figure 8

Figur 8 viser imidlertid at oppfinnelsens fellingskieselsyre i mineralolje i den gjennom-førte testen viser en marginalt mindre skummingsdempervirkning enn Sipernat D10, dette resultatet må imidlertid ikke videreføres til videre anvendelsestekniske tester, stabiliteten er imidlertid meget større enn med Sipernatat D10.1 silikonolje viser oppfinnelsens fellingskieselsyre en skummingsdempervirkning som er identisk med Sipernat D10. Figure 8 shows, however, that the invention's precipitated silicic acid in mineral oil in the conducted test shows a marginally less anti-foam effect than Sipernat D10, this result must not be carried forward to further application technical tests, however, the stability is much greater than with Sipernat D10.1 silicone oil shows the invention's precipitated silicic acid an anti-foam effect that is identical to Sipernat D10.

De gjennomførte undersøkelsene viser at ved hjelp av oppfinnelsens delhydrofobe fellingskieselsyrer, kan stabiliteten til en skummingsdemperdispersjon bli betydelig forbedret, mens skummingsdempningsvirkningen er sammenlignbar med en kjent høyhydrofob fellingskieselsyre. The investigations carried out show that with the help of the invention's partially hydrophobic precipitated silicic acids, the stability of a defoamer dispersion can be significantly improved, while the defoaming effect is comparable to a known highly hydrophobic precipitated silicic acid.

Det blir henvist til den tyske prioritetssøknaden 196.12.501.4. Dets innhold er bestand-del av denne søknad. Reference is made to the German priority application 196.12.501.4. Its content is an integral part of this application.

Claims (16)

1. Delhydrofob felleinskieselsyre, karakterisert ved en metanolfuktbarhet på 10-49%.1. Partially hydrophobic felleinsilicic acid, characterized by a methanol wettability of 10-49%. 2. Delhydrofob fellingskieselsyre ifølge krav 1, karakterisert ved at den vannfri har et DBP-opptak på mer enn 250 g/100 g (DBP-tall).2. Partially hydrophobic precipitated silicic acid according to claim 1, characterized in that it anhydrous has a DBP uptake of more than 250 g/100 g (DBP number). 3. Delhydrofob fellingskieselsyre ifølge krav 1, karakterisert v e d at den har en midlere partikkelstørrelse på 1 til 12 um.3. Partially hydrophobic precipitated silicic acid according to claim 1, characterized in that it has an average particle size of 1 to 12 µm. 4. Delhydrofob fellingskieselsyre ifølge krav 1, karakterisert v e d at den har et karboninnhold fra 0,3 til 1,85%.4. Partially hydrophobic precipitated silicic acid according to claim 1, characterized in that it has a carbon content of from 0.3 to 1.85%. 5. Delhydrofob fellingskieselsyre ifølge krav 4, karakterisert ved at den har et tørketap på 2,6 til 10%.5. Partially hydrophobic precipitated silicic acid according to claim 4, characterized in that it has a drying loss of 2.6 to 10%. 6. Delhydrofob fellingskieselsyre ifølge krav 5, karakterisert v e d at den har en pH-verdi fra 5,5 til 10.6. Partially hydrophobic precipitated silicic acid according to claim 5, characterized in that it has a pH value from 5.5 to 10. 7. Delhydrofob fellingskieselsyre ifølge krav 2, karakterisert v e d at den har et karboninnhold på 0,3 til 1,85%.7. Partially hydrophobic precipitated silicic acid according to claim 2, characterized in that it has a carbon content of 0.3 to 1.85%. 8. Delhydrofob fellingskieselsyre ifølge krav 7, karakterisert ved at den har et tørketap på fra 2,6 til 10%.8. Partially hydrophobic precipitated silicic acid according to claim 7, characterized in that it has a drying loss of from 2.6 to 10%. 9. Delhydrofob fellingskieselsyre ifølge krav 8, karakterisert v e d at den har en pH-verdi fra 5,5 til 10.9. Partially hydrophobic precipitated silicic acid according to claim 8, characterized in that it has a pH value from 5.5 to 10. 10. Delhydrofob fellingskieselsyre ifølge krav 3, karakterisert v e d at den har et karboninnhold på 0,.3 til 1,85%.10. Partially hydrophobic precipitated silicic acid according to claim 3, characterized in that it has a carbon content of 0.3 to 1.85%. 11. Delhydrofob fellingskieselsyre ifølge krav 10, karakterisert ved at den har et tørketap på fra 2,6 til 10%.11. Partially hydrophobic precipitated silicic acid according to claim 10, characterized in that it has a drying loss of from 2.6 to 10%. 12. Delhydrofob kieselsyre ifølge krav 11, karakterisert v e d at den har en pH-verdi fra 5,5 til 10.12. Partially hydrophobic silicic acid according to claim 11, characterized in that it has a pH value from 5.5 to 10. 13. Fremgangsmåte for fremstilling av den delhydrofobe fellingskieselsyren ifølge krav 1 til 12, karakterisert ved at man for oppnåelse av den ønskede hydrofobieirngsgraden, hvor anvendelsen av høye skjærkrefter blander med ifølge kjent fremgangsmåte fremstilt fellingskieselsyresuspensjon etter et på forhånd angitt forhold, med meget kort oppholdstid og lav pH-verdi, filtrerer den hydrofobieringsmiddelholdige fellingskieselsyresuspensjonen og vasker saltfritt, tørker den med hydrofobieringsmiddel homogen blandede fellingskieselsyrefilterkaken ifølge kjente fremgangsmåter, etterbehandler termisk eller tempererer og deretter underkaster den en mekanisk- hhv. strålemalin.13. Process for the production of the partially hydrophobic precipitated silicic acid according to claims 1 to 12, characterized in that in order to achieve the desired degree of hydrophobicity, where the use of high shear forces is mixed with a precipitated silicic acid suspension produced according to a known method according to a predetermined ratio, with a very short residence time and low pH value, filters the hydrophobizing agent-containing precipitated silicic acid suspension and washes salt-free, dries the hydrophobizing agent homogeneously mixed precipitated silica filter cake according to known methods, thermally post-treats or tempers and then subjects it to a mechanical or radiation maline. 14. Anvendelse av den delhydrofobe fellingskieselsyren ifølge krav 1 til 12 i virkestoff-formuleringer som bærer.14. Use of the partially hydrophobic precipitated silicic acid according to claims 1 to 12 in active ingredient formulations as a carrier. 15. Anvendelse av den delhydrofobe fellingskieselsyren ifølge krav 14, i formulering av hydrolyseømfintlige virkestoffer som bærer.15. Use of the partially hydrophobic precipitated silicic acid according to claim 14, in the formulation of hydrolysis-sensitive active substances as a carrier. 16. Anvendelse av den delhydrofobe fellingskieselsyren ifølge krav 1 til 12 i skummingsdemper.16. Use of the partially hydrophobic precipitated silicic acid according to claims 1 to 12 in antifoam.
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