EP2234495A1 - Silicon dioxide dispersion - Google Patents
Silicon dioxide dispersionInfo
- Publication number
- EP2234495A1 EP2234495A1 EP08871664A EP08871664A EP2234495A1 EP 2234495 A1 EP2234495 A1 EP 2234495A1 EP 08871664 A EP08871664 A EP 08871664A EP 08871664 A EP08871664 A EP 08871664A EP 2234495 A1 EP2234495 A1 EP 2234495A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispersion
- spray
- silicon dioxide
- aerosil
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007921 spray Substances 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000002917 insecticide Substances 0.000 claims abstract description 4
- 230000000895 acaricidal effect Effects 0.000 claims abstract 2
- 239000000642 acaricide Substances 0.000 claims abstract 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 24
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 24
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 11
- 239000001273 butane Substances 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 23
- -1 for example Substances 0.000 description 20
- 229910002012 Aerosil® Inorganic materials 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 11
- 241000238876 Acari Species 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910020175 SiOH Inorganic materials 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000001282 organosilanes Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000004429 Calibre Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 229940073561 hexamethyldisiloxane Drugs 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Classifications
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
Definitions
- the invention relates to a silicon dioxide dispersion, to a process for the preparation thereof and to the use thereof.
- Pulverulent hydrophobic silica is used to combat sucking insects, the application taking place by means of dusting (DE 38 35 592) .
- aqueous dispersions likewise described in DE 38 35 592, which consist of a hydrophobic silica and water, do not exhibit satisfactory stability.
- US 5 830 512 describes a dispersion in which satisfactory stability is achieved by addition of hydrophilic substances, such as, for example, silicas. However, the active hydrophobic component is through this diluted by a hydrophilic substance. Furthermore, only a very low stability of the dispersion, from hours to a few days, is achieved.
- hydrophilic substances such as, for example, silicas.
- DE 10 2004 021 532 describes a dispersion which, in addition to water, comprises 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active substance .
- This dispersion can be used as insecticide against mites and other insects.
- pump spray bottles are not suitable because the necessary spraying pressure of more than 3 bar usually cannot be achieved. Accordingly, a good spray mist cannot be achieved and accordingly also a uniform covering of the cage area to be sprayed/treated cannot be achieved.
- This dispersion consists of an aqueous dispersion of a few percent of hydrophilic silica.
- This dispersion has the disadvantage that it takes too long to dry. Furthermore, it has an excessively high viscosity and also excessively poor spray formation.
- the spray can has to be lacquered on the inside .
- the object was accordingly to prepare a dispersion with an insecticidal action which can be satisfactorily sprayed on small surfaces and also can quickly develop its action.
- hydrophobic pyrogenically prepared silicon dioxide of: Aerosil® R805, Aerosil® R974, Aerosil® R202, Aerosil® R812, Aerosil® R812S and Aerosil® R8200.
- Aerosil® R812S Use may in particular be made of Aerosil® R812S.
- alcohol methanol, ethanol, propanol, isopropanol, 1-butanol, 2-methyl-l-propanol, 2-butanol and 2-methyl-2-propanol .
- Use may in particular be made of low-boiling-point alcohols, such as, for example, ethanol.
- HMDS hexamethyldisilazane
- HMDS results, by this additional silanization, in a virtually perfect surface modification, through which a considerably lower viscosity is achieved. If appropriate, any excess HMDS can be converted by alcoholysis to give trimethylethoxysilane, trimethylsilanol or hexamethyldi- siloxane, and NH 3 .
- Use may furthermore be made, as additive which promotes the dispersion, of other silanes which are likewise in a position to react with Si-OH groups still present on the Aerosil surface.
- any silane is suitable which exhibits a satisfactory hydrophobic group but which in this connection does not introduce, through the silanization, any accessible additional silanol group.
- This can be achieved by having present only one group in the silane molecule capable of reacting with the SiOH group of the surface, thus an ROH or X group.
- the hydrophobic "residue" of the silane molecule can have such a strong sterically shielding effect that an unreacted SiOH group of the silane molecule is not accessible.
- the silane used should exhibit a high reaction rate. A satisfactory reaction rate may possibly be achieved by an increase in temperature.
- silanes can be used as additional silanes: a) organosilanes of the (RO) 3 Si(C n H 2n+I ) and (RO) 3 Si(C n H 2n -I) type
- R alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl
- R' alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl
- X Cl, Br
- R' alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl
- R' alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl
- R' methyl, aryl (for example -C 6 H 5 , substituted phenyl radicals) -C 4 F 9 , OCF 2 -CHF-CF 3 , -C 6 F 13 , -0-CF 2 -CHF 2
- R' methyl, aryl (for example -C 6 H 5 , substituted phenyl radicals) -C 4 F 9 , -OCF 2 -CHF-CF 3 , -C 6 F 13 , -0-CF 2 -CHF 2
- R' methyl, aryl (for example -C 6 H 5 , substituted phenyl radicals)
- R' methyl, aryl (e.g. -C 6 H 5 , substituted phenyl radicals)
- R' methyl, aryl (e.g. -C 6 H 5 , substituted phenyl radicals)
- cyclic polysiloxanes of the D3, D4 and D5 type D3, D4 and D5 being understood as meaning cyclic polysiloxanes with 3, 4 or 5 units of the -O-Si (CH 3 ) 2 - type.
- octamethylcyclotetrasiloxane D4
- Hydrophobic pyrogenically prepared silicon dioxides can be very well dispersed in alcohols since these are wetted with alcohols.
- Rheology-modifying additives can be added for satisfactory adhesion of the Aerosil to the surfaces/cage areas to be covered and in order to prevent the sprayed-on dispersion from flowing off.
- Such additives can be alcohol-soluble modified celluloses.
- Hydroxypropylcellulose can in particular be used for this since it is satisfactorily soluble in alcohols.
- the hydroxypropylcellulose can exhibit a molecular weight of less than 1 000 000.
- the hydroxypropylcellulose can exhibit a molecular weight of 5000 to 500 000, in particular 80 000 ⁇ 20 000.
- the amounts of the rheology-modifying agent used also affects the activity of the dispersion.
- This amount used can be limited by the product of the average molecular weight of the hydroxypropylcellulose and the concentration in % by weight. It can be less than 250 000.
- HPC with an excessively high molecular weight of more than 1 000 000 results in a high structural viscosity which not only leads to a poor ability to be sprayed but also contributes to a reduction in the mortality.
- the dispersion according to the invention can be composed of hydrophobic pyrogenically prepared silicon dioxide, alcohol and an additive which promotes the dispersion. If appropriate, the preferred dispersion can additionally comprise a rheology-modifying additive.
- the dispersion according to the invention can be used as insecticide, in particular for combating mites.
- An additional advantage of the alcoholic dispersion according to the invention is caused by the fact that the alcohol does not have a corrosive effect on the metals used in spray cans. Internal lacquering of the cans can accordingly be dispensed with.
- This spray can additionally comprise a propellent.
- Use may be made, as propellent, of propane, butane or a mixture of propane and butane with a proportion of propellent gas of 10 to 80%.
- Nitrogen or nitrous oxide can be used as propellent gas.
- the pressure necessary for the spraying can be produced by a pump system.
- the viscosity of the dispersions produced was determined using a rotational rheometer from Physica Model 300 and the measuring cup CC 27 at 25°C.
- HMDS hexamethyldisilazane
- Aerosil® R812S hexamethyldisilazane
- HPC hydroxypropyl cellulose with a molar mass M of approximately 80 000 from Sigma-Aldrich
- the mixture is subsequently diluted with an additional 327 g of ethanol to an Aerosil® R812S content of 15%. Finally, the mixture is dispersed at 1000 rpm for 15 minutes, resulting in the dissolution of the hydroxypropyl cellulose.
- This dispersion is bottled in spray bottles and placed under pressure with a propane/butane mixture. Good spray formation can be produced. This means that a uniform coating of a surface is possible.
- HMDS hexamethyldisilazane
- Aerosil® R812S hexamethyldisilazane
- HPC hydroxypropyl cellulose with a molar mass M of approximately 370 000 from Sigma-Aldrich
- the mixture is subsequently diluted with an additional 329.7 g of ethanol to an Aerosil® R812S content of 15%.
- the mixture is dispersed at 1000 rpm for 15 minutes, resulting in the dissolution of the hydroxypropyl cellulose.
- Aerosil® R812S hexamethyldisilazane
- 200 g of Aerosil® R812S are then incorporated with stirring using a high-speed laboratory stirrer (jacketed dispersion containers, Dispermat® dissolver from VMA-Getzmann GmbH, toothed disc with a diameter of 70 mm) and subsequently dispersed at 2200 rpm for 15 minutes.
- 1.66 g of HPC hydroxypropyl cellulose with a molar mass M of approximately 1 000 000 from Sigma-Aldrich
- the mixture is subsequently diluted with an additional 332 g of ethanol to an Aerosil® R812S content of 15%.
- the mixture is dispersed at 1000 rpm for 15 minutes, resulting in the dissolution of the hydroxypropyl cellulose.
- This dispersion is now bottled in spray bottles and placed under pressure with a propane/butane mixture. Good spray formation can be produced. This means that a uniform coating of a surface is possible.
- This spray was used for the spraying of cage areas occupied by mites.
- HMDS hexamethyldisilazane
- Dispermat® dissolver from VMA-Getzmann GmbH, toothed disc with a diameter of 70 mm) and subsequently dispersed at 2200 rpm for 15 minutes. 6.66 g of HPC (hydroxypropyl cellulose with a molar mass M of approximately 1 000 000 from Sigma-Aldrich) are now added. The mixture is subsequently diluted with an additional 327 g of ethanol to an Aerosil® R812S content of 15%. Finally, the mixture is dispersed at 1000 rpm for 15 minutes and the HPC is dissolved.
- HPC hydroxypropyl cellulose with a molar mass M of approximately 1 000 000 from Sigma-Aldrich
- This dispersion is now bottled in spray bottles and placed under pressure with a propane/butane mixture. Due to the high viscosity, good spray formation cannot be achieved. This means that a uniform coating of a surface is not possible .
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Silicon Compounds (AREA)
Abstract
Dispersion comprising hydrophobic pyrogenically prepared silicon dioxide, alcohol and at least one additive which promotes the dispersion. The dispersion can be canned in spray cans and used as acaricide and insecticide.
Description
Silicon dioxide dispersion
The invention relates to a silicon dioxide dispersion, to a process for the preparation thereof and to the use thereof.
Pulverulent hydrophobic silica is used to combat sucking insects, the application taking place by means of dusting (DE 38 35 592) .
Disadvantageously, dust development is such that this method of insect control finds little acceptance.
The aqueous dispersions likewise described in DE 38 35 592, which consist of a hydrophobic silica and water, do not exhibit satisfactory stability.
US 5 830 512 describes a dispersion in which satisfactory stability is achieved by addition of hydrophilic substances, such as, for example, silicas. However, the active hydrophobic component is through this diluted by a hydrophilic substance. Furthermore, only a very low stability of the dispersion, from hours to a few days, is achieved.
EP 1 250 048 describes stabilizing the dispersion of hydrophobic silicon dioxide through gelling additives, such as, for example, xanthan gum, sodium alginates or neutralized carboxyvinyl polymers, mixtures of these additives also being possible.
These gelling additives bring about, by interaction with the hydrophobic SiO2 particles and the incorporated air, a marked structural viscosity which is exhibited when applying by spraying. Thus, during the spraying process, the viscosity of the dispersion is relatively low at the shear forces acting on it. After the dispersion drops impact the surface to be coated, the visocity again increases strongly, in order to avoid dripping/running off from in particular vertical surfaces.
According to EP 1 250 048, in addition to the hydrophobic Siθ2 particles to be dispersed, large amounts of air are incorporated. With the known dispersion processes, this cannot be avoided without the use of wetting surfactants and antifoaming agents. Thus, in Example 1, a density of only 0.6 g/ml is specified, which means that approximately 40% of the volume consists of air.
In order to achieve a satisfactory activity, a minimum weight has to be applied to the surfaces to be sprayed. If, per spraying operation, only approximately 60% of the volume of the spraying appliances can be used, this represents a significant reduction in the effectiveness.
Disadvantageously, the transportation, packaging and waste disposal costs of the required packaging are higher by this proportion.
In addition, during storage, an approximately 40% larger storage space has to be taken into account.
Furthermore, with an air-comprising dispersion, it is not possible to achieve a homogeneous bubble-free coverage of surfaces to be treated.
DE 10 2004 021 532 describes a dispersion which, in addition to water, comprises 0.5 to 20% by weight of hydrophobic silica, 0.01 to 10% by weight of a gelling or viscosity-increasing additive, 0.1 to 1% by weight of a preservative and 0 to 1% by weight of a surface-active substance .
This dispersion can be used as insecticide against mites and other insects.
It is successfully used in spacious animal houses and on large surfaces, it being possible to use appropriately large-calibre sprayers (such as garden sprayers) for the spraying.
When used in the field of pets, where the area to be treated is rather small, large-calibre sprayers, such as, for example, garden sprayers, cannot be used.
In addition, pump spray bottles are not suitable because the necessary spraying pressure of more than 3 bar usually cannot be achieved. Accordingly, a good spray mist cannot be achieved and accordingly also a uniform covering of the cage area to be sprayed/treated cannot be achieved.
It is known to spray a pet cage area with a dispersion sold under the name "Decimite Aerosol".
This dispersion consists of an aqueous dispersion of a few percent of hydrophilic silica. This dispersion has the disadvantage that it takes too long to dry. Furthermore, it has an excessively high viscosity and also excessively poor spray formation.
Furthermore, because of the water content of the dispersion, the spray can has to be lacquered on the inside .
The object was accordingly to prepare a dispersion with an insecticidal action which can be satisfactorily sprayed on small surfaces and also can quickly develop its action.
A subject-matter of the invention is a dispersion comprising hydrophobic pyrogenically prepared silicon dioxide, alcohol and at least one additive which promotes the dispersing.
Use may be made, as hydrophobic pyrogenically prepared silicon dioxide, of: Aerosil® R805, Aerosil® R974, Aerosil® R202, Aerosil® R812, Aerosil® R812S and Aerosil® R8200.
Use may in particular be made of Aerosil® R812S.
The physicochemical characteristics of these pyrogenically prepared silicon dioxides are listed in Table 1.
Table 1
1} following DIN 66131
2) following DIN ISO 787/11, JIS K 5101/18 (not sieved)
3) following DIN ISO 787/2, ASTM D 280, JIS K 5101/21
4) following DIN 55921, ASTM D 1208, JIS K 5101/23
5) following DIN ISO 787/9, ASTM D 1208, JIS K 5101/24
7) based on the substance dried at 1050C for 2 hours
8) based on the substance ignited at 10000C for 2 hours 10) in water : methanol = 1:1
11J HCl content is constituent of the loss on ignition 12) V product is supplied in bags of 15 kg net
The following can be used as alcohol: methanol, ethanol, propanol, isopropanol, 1-butanol, 2-methyl-l-propanol, 2-butanol and 2-methyl-2-propanol .
Use may in particular be made of low-boiling-point alcohols, such as, for example, ethanol.
In order to make possible good dispersing, it is, however, necessary to add an additive which promotes the dispersion, which additive covers remaining areas or new areas, not surface-modified, produced by the dispersing. The addition of hexamethyldisilazane (HMDS) has proven to be very advantageous for this.
The HMDS results, by this additional silanization, in a virtually perfect surface modification, through which a considerably lower viscosity is achieved. If appropriate, any excess HMDS can be converted by alcoholysis to give trimethylethoxysilane, trimethylsilanol or hexamethyldi- siloxane, and NH3.
Use may furthermore be made, as additive which promotes the dispersion, of other silanes which are likewise in a position to react with Si-OH groups still present on the Aerosil surface.
In principle, any silane is suitable which exhibits a satisfactory hydrophobic group but which in this connection does not introduce, through the silanization, any accessible additional silanol group. This can be achieved by having present only one group in the silane molecule capable of reacting with the SiOH group of the surface, thus an ROH or X group. Alternatively, the hydrophobic
"residue" of the silane molecule can have such a strong sterically shielding effect that an unreacted SiOH group of the silane molecule is not accessible.
Furthermore, the silane used should exhibit a high reaction rate. A satisfactory reaction rate may possibly be achieved by an increase in temperature.
Silazanes, and here in particular hexamethyldisilazane, have, due to the basic nature of the silazane group, a high affinity for SiOH surface groups. Only in the subsequent step is the trimethylsilyl group transferred. Trimethyl- silyl groups not reacted with SiOH surface groups are themselves inactivated by dimerization .
The following silanes can be used as additional silanes: a) organosilanes of the (RO)3Si(CnH2n+I) and (RO)3Si(CnH2n-I) type
R = alkyl, such as, for example, methyl, ethyl, n- propyl, isopropyl or butyl, n = 1 - 20 b) organosilanes of the R' x (RO) ySi (CnH2n+1) and R'x (RO) ySi (CnH2n-I) type
R = alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl
R' = alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl R' = cycloalkyl n = 1 - 20 x+y = 3 x = 1,2 y = 1,2 c) haloorganosilanes of the X3Si (CnH2n+1) and X3Si (CnH2n-I) type
X = Cl, Br n = 1 - 20 d) haloorganosilanes of the X2 (R' ) Si (CnH2n+1) and X2 (R') Si (CnH2n-I) type X = Cl, Br
R' = alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl
R'= cycloalkyl n = 1 - 20 e) haloorganosilanes of the X (R' ) 2Si (CnH2n+1) and
X(R1J2Si(CnH2n-I) type X = Cl, Br
R' = alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl or butyl R' = cycloalkyl n = 1-20 f) organosilanes of the (RO) 3Si (CH2) m-R' type R = alkyl, such as methyl, ethyl or propyl m = 0, 1-20 R' = methyl, aryl (for example -C6H5, substituted phenyl radicals) -C4F9, OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-CH=CH2,
g) organosilanes of the (R" ) x (RO) ySi (CH2) m-R' type
R" = alkyl x+y = 3 = cycloalkyl x = 1,2 y = 1,2 m = 0, 1 to 20 R' = methyl, aryl (for example -C6H5, substituted phenyl radicals) -C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-CH=CH2,
h) haloorganosilanes of the X3Si (CH2) m-R' type
X = Cl, Br m = 0,1 - 20
R' = methyl, aryl (for example -C6H5, substituted phenyl radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2
-CH=CH2,
i) haloorganosilanes of the (R) X2Si (CH2) m-R' type X = Cl, Br
R = alkyl, such as methyl, ethyl or propyl m = 0,1 - 20 R' = methyl, aryl (e.g. -C6H5, substituted phenyl radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -Q-CF2-CHF2
-CH=CH2
j) haloorganosilanes of the (R)2X Si(CH2)m-R' type
X = Cl, Br R = alkyl m = 0,1 - 20
R' = methyl, aryl (e.g. -C6H5, substituted phenyl radicals)
-C4F9, -OCF2-CHF-CF3, -C6F13, -0-CF2-CHF2 -CH=CH2,
k) silazanes of the R1R2Si-N-SiR2R' type
H R = alkyl, aryl R' = alkyl, aryl
1) cyclic polysiloxanes of the D3, D4 and D5 type, D3, D4 and D5 being understood as meaning cyclic polysiloxanes with 3, 4 or 5 units of the -O-Si (CH3) 2- type. E.g. octamethylcyclotetrasiloxane = D4
(m) polysiloxanes or silicone oils of the type
Y-O- -20
Si (CH3) 20H, Si (CH3) 2 (OCH3) Si (CH3) 2 (CnH2n+1) n=l-20
R alkyl , such as CnH2n+1, in which n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, H
R' = alkyl , such as CnH2n+1, in which n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, H,
R" = alkyl , such as CnH2n+1, in which n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, H
R'" = alkyl , such as CnH2n+1, in which n = 1 to 20, aryl, such as phenyl and substituted phenyl radicals, H
Hydrophobic pyrogenically prepared silicon dioxides can be very well dispersed in alcohols since these are wetted with alcohols.
Furthermore, rapid drying of the sprayed surfaces/cage areas is achieved by the use of in particular highly volatile alcohols, such as ethanol or isopropanol. The lethal action also starts more quickly through this.
Rheology-modifying additives can be added for satisfactory adhesion of the Aerosil to the surfaces/cage areas to be covered and in order to prevent the sprayed-on dispersion from flowing off. Such additives can be alcohol-soluble
modified celluloses.
Hydroxypropylcellulose (HPC) can in particular be used for this since it is satisfactorily soluble in alcohols.
The hydroxypropylcellulose can exhibit a molecular weight of less than 1 000 000.
In a preferred embodiment of the invention, the hydroxypropylcellulose can exhibit a molecular weight of 5000 to 500 000, in particular 80 000 ± 20 000.
It can be seen from the examples that the amounts of the rheology-modifying agent used also affects the activity of the dispersion. This amount used can be limited by the product of the average molecular weight of the hydroxypropylcellulose and the concentration in % by weight. It can be less than 250 000.
HPC with an excessively high molecular weight of more than 1 000 000 results in a high structural viscosity which not only leads to a poor ability to be sprayed but also contributes to a reduction in the mortality.
With the dispersion according to the invention, it is possible, by the use of alcohol, to dispense with an addition of additives for the preservation of the hydroxypropylcellulose employed.
In a particularly preferred embodiment of the invention, the dispersion according to the invention can be composed of hydrophobic pyrogenically prepared silicon dioxide, alcohol and an additive which promotes the dispersion. If appropriate, the preferred dispersion can additionally comprise a rheology-modifying additive.
The dispersion according to the invention can be used as insecticide, in particular for combating mites.
The dispersions according to the invention can be
satisfactorily sprayed with propellent gas sprays.
An additional advantage of the alcoholic dispersion according to the invention is caused by the fact that the alcohol does not have a corrosive effect on the metals used in spray cans. Internal lacquering of the cans can accordingly be dispensed with.
An additional subject-matter of the invention is a spray can which comprises the dispersion according to the invention .
This spray can can additionally comprise a propellent.
Use may be made, as propellent, of propane, butane or a mixture of propane and butane with a proportion of propellent gas of 10 to 80%.
Nitrogen or nitrous oxide can be used as propellent gas.
The pressure necessary for the spraying can be produced by a pump system.
Examples
Determination of the viscosity of the dispersions
The viscosity of the dispersions produced was determined using a rotational rheometer from Physica Model 300 and the measuring cup CC 27 at 25°C.
Determination of the activity (mortality) against adult mites
In order to determine the action (mortality) on completely saturated adult mites, in each case approximately 100 mites are deposited on a dried active substance coating (wet film thickness 200 μm) on galvanized sheet steel in a plastic petri dish which, after closing with a fine web/gauze, is stored in a climate-controlled chamber (23°C and variable
relative air humidity) . After, for example, 24 h, the living, injured or dead mites are counted under a stereomicroscope . The test is carried out at 50% and 100% relative air humidity. In order to achieve a uniform layer thickness on using the spray, a sufficient amount is sprayed into a glass and the dispersion is applied with a doctor blade (wet film thickness 200 μm) .
Example 1
798 g of ethanol are introduced and 2 g of HMDS (hexamethyldisilazane) are added. 200 g of Aerosil® R812S are then incorporated with stirring using a high-speed laboratory stirrer (jacketed dispersion containers, Dispermat® dissolver from VMA-Getzmann GmbH, toothed disc with a diameter of 70 mm) and subsequently dispersed at 2200 rpm for 15 minutes. 6.66 g of HPC (hydroxypropyl cellulose with a molar mass M of approximately 80 000 from Sigma-Aldrich) are subsequently added. The mixture is subsequently diluted with an additional 327 g of ethanol to an Aerosil® R812S content of 15%. Finally, the mixture is dispersed at 1000 rpm for 15 minutes, resulting in the dissolution of the hydroxypropyl cellulose.
This corresponds to a concentration of use with the HPC of 0.5% by weight. With a molecular weight of 80 000, this results in a product % x M of 40 000.
This dispersion exhibits the viscosity curve represented in Figure 1.
This dispersion is bottled in spray bottles and placed under pressure with a propane/butane mixture. Good spray formation can be produced. This means that a uniform coating of a surface is possible.
This spray can now be used for the spraying of cage areas occupied by mites.
The Aerosil® R812S used is a pyrogenically prepared silicon dioxide with the physicochemical characteristics given in Table 1.
Result:
After 24 h and 50% relative humidity, a mortality of 100% is achieved. This is an excellent activity.
Example 2
798 g of ethanol are introduced and 2 g of HMDS (hexamethyldisilazane) are added. 200 g of Aerosil® R812S are then incorporated with stirring using a high-speed laboratory stirrer (jacketed dispersion containers, Dispermat® dissolver from VMA-Getzmann GmbH, toothed disc with a diameter of 70 mm) and subsequently dispersed at 2200 rpm for 15 minutes. 4.00 g of HPC (hydroxypropyl cellulose with a molar mass M of approximately 370 000 from Sigma-Aldrich) are subsequently added. The mixture is subsequently diluted with an additional 329.7 g of ethanol to an Aerosil® R812S content of 15%. Finally, the mixture is dispersed at 1000 rpm for 15 minutes, resulting in the dissolution of the hydroxypropyl cellulose.
This corresponds to a concentration of use with the HPC of 0.3% by weight. With a molecular weight of 370 000, this results in a product % x M of 111 000.
This dispersion exhibits the viscosity curve represented in Figure 2.
This dispersion is now bottled in spray bottles and placed under pressure with a propane/butane mixture. Good spray formation can be produced. This means that a uniform coating of a surface is possible.
This spray is now be used for the spraying of cage areas occupied by mites.
Re sul t :
After 24 h and 50% relative humidity, a mortality of 67% is achieved. This is a limited activity.
Example 3
798 g of ethanol are introduced and 2 g of HMDS
(hexamethyldisilazane) are added. 200 g of Aerosil® R812S are then incorporated with stirring using a high-speed laboratory stirrer (jacketed dispersion containers, Dispermat® dissolver from VMA-Getzmann GmbH, toothed disc with a diameter of 70 mm) and subsequently dispersed at 2200 rpm for 15 minutes. 1.66 g of HPC (hydroxypropyl cellulose with a molar mass M of approximately 1 000 000 from Sigma-Aldrich) are subsequently added. The mixture is subsequently diluted with an additional 332 g of ethanol to an Aerosil® R812S content of 15%. Finally, the mixture is dispersed at 1000 rpm for 15 minutes, resulting in the dissolution of the hydroxypropyl cellulose.
This corresponds to a concentration of use with the HPC of 0.125% by weight. With a molecular weight of 1 000 000, this results in a product % x M of 125 000.
This dispersion exhibits the viscosity curve represented in Figure 3.
This dispersion is now bottled in spray bottles and placed under pressure with a propane/butane mixture. Good spray formation can be produced. This means that a uniform coating of a surface is possible.
This spray was used for the spraying of cage areas occupied by mites.
Result:
After 24 h and 50% relative humidity, a mortality of 93% is achieved. This is a good activity.
Comparative example
798 g of ethanol are introduced and 2 g of HMDS (hexamethyldisilazane) are added. 200 g of Aerosil® R812S are then incorporated with stirring using a high-speed laboratory stirrer (jacketed dispersion containers,
Dispermat® dissolver from VMA-Getzmann GmbH, toothed disc with a diameter of 70 mm) and subsequently dispersed at 2200 rpm for 15 minutes. 6.66 g of HPC (hydroxypropyl cellulose with a molar mass M of approximately 1 000 000 from Sigma-Aldrich) are now added. The mixture is subsequently diluted with an additional 327 g of ethanol to an Aerosil® R812S content of 15%. Finally, the mixture is dispersed at 1000 rpm for 15 minutes and the HPC is dissolved.
This corresponds to a concentration of use with the HPC of 0.5% by weight. With a molecular weight of 1 000 000, this results in a product % x M of 500 000.
This dispersion exhibits the viscosity curve represented in Figure 4.
This dispersion is now bottled in spray bottles and placed under pressure with a propane/butane mixture. Due to the high viscosity, good spray formation cannot be achieved. This means that a uniform coating of a surface is not possible .
Result:
After 24 h and 50% relative humidity, a mortality of 24% is now achieved. This is a poor activity.
Claims
1. Dispersion comprising hydrophobic pyrogenically prepared silicon dioxide, alcohol and at least one additive which promotes the dispersion.
2. Dispersion according to Claim 1, characterized in that it comprises a rheology-promoting agent.
3. Dispersion according to Claim 2, characterized in that hydroxypropylcellulose is used as rheology- promoting agent.
4. Use of the dispersion according to Claim 1 as acaricide and insecticide.
5. Spray can comprising the dispersion according to Claim 1.
6. Spray can according to Claim 5, additionally comprising a propellent.
7. Spray can according to Claim 6, characterized in that propellents, such as propane, butane or a mixture of propane and butane, are used with a proportion of propellent gas of 10-80%.
8. Spray can according to Claim 6, characterized in that nitrogen is used as propellent gas.
9. Spray can according to Claim 6, characterized in that nitrous oxide is used as propellent gas.
10. Spray can according to Claim 5, characterized in that the pressure necessary for the spraying is produced by a pump system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200810006884 DE102008006884A1 (en) | 2008-01-31 | 2008-01-31 | Silica dispersion |
| PCT/EP2008/068348 WO2009095142A1 (en) | 2008-01-31 | 2008-12-30 | Silicon dioxide dispersion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2234495A1 true EP2234495A1 (en) | 2010-10-06 |
Family
ID=40532590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08871664A Withdrawn EP2234495A1 (en) | 2008-01-31 | 2008-12-30 | Silicon dioxide dispersion |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2234495A1 (en) |
| JP (1) | JP2011511749A (en) |
| DE (1) | DE102008006884A1 (en) |
| WO (1) | WO2009095142A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2026017344A1 (en) | 2024-07-15 | 2026-01-22 | Biolitec Holding Gmbh & Co Kg | Composition for controlling and combating vermin infestation and microbial load |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008006883A1 (en) * | 2008-01-31 | 2009-08-13 | Evonik Degussa Gmbh | Silica dispersion |
| FR3080741B1 (en) * | 2018-05-04 | 2020-07-31 | Ab7 Innovation | COMPOSITION INSECTICIDE CONTAINING HYDROPHOBIC SILICA |
| WO2021112206A1 (en) * | 2019-12-06 | 2021-06-10 | アース製薬株式会社 | Repellent against animals in order squamata |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1542748A1 (en) * | 1964-12-30 | 1970-07-30 | Degussa | Pest repellants |
| DE3835592A1 (en) | 1988-10-19 | 1990-04-26 | Degussa | INSECTICIDES |
| US5830512A (en) | 1992-11-03 | 1998-11-03 | Vrba; Cenek H. | Insect control compositions |
| ES2210012T3 (en) | 1999-11-18 | 2004-07-01 | Sorex Limited | PESTICIDE COMPOSITION THAT INCLUDES AN AIR AIR GEL CONTAINING SILIC HYDROPHOBE. |
| DE10231757A1 (en) * | 2002-07-13 | 2004-01-22 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Process for the preparation of a surfactant-free suspension on an aqueous basis of nanostructured, hydrophobic particles and their use |
| US20040062783A1 (en) * | 2002-09-27 | 2004-04-01 | Xavier De Sloovere | Composition for combating insects and parasites |
| DE10250328A1 (en) * | 2002-10-29 | 2004-05-13 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Production of suspensions of hydrophobic oxide particles |
| DE10315128A1 (en) * | 2003-04-03 | 2004-10-14 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Process for suppressing mold formation using hydrophobic substances and an anti-mold agent for parts of buildings |
| EP1646708A2 (en) * | 2003-05-23 | 2006-04-19 | Degussa AG | Pulverulent mixture comprising hydrogen peroxide and hydrophobized silicon dioxide |
| DE102004021532A1 (en) | 2004-05-03 | 2005-12-08 | Degussa Ag | Dispersion with insecticidal activity |
-
2008
- 2008-01-31 DE DE200810006884 patent/DE102008006884A1/en not_active Ceased
- 2008-12-30 WO PCT/EP2008/068348 patent/WO2009095142A1/en not_active Ceased
- 2008-12-30 JP JP2010544608A patent/JP2011511749A/en not_active Withdrawn
- 2008-12-30 EP EP08871664A patent/EP2234495A1/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2009095142A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2026017344A1 (en) | 2024-07-15 | 2026-01-22 | Biolitec Holding Gmbh & Co Kg | Composition for controlling and combating vermin infestation and microbial load |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009095142A1 (en) | 2009-08-06 |
| DE102008006884A1 (en) | 2009-08-06 |
| JP2011511749A (en) | 2011-04-14 |
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