SK722021A3 - Repellent preparations against damage to cultures by animals, method of their preparation and use - Google Patents

Abstract

It is characteristic of repellent preparations against crop damage by animals in the sense of the solution that they contain calcium acetylide (calcium carbide) and lanolin. These can be in the form of suspensions, pastes or creams. Part of the solution is also the method of their preparation and their use.

Description

The field of technology

The solution concerns repellent preparations against crop damage by animals, the method of their preparation and their use.

Current state of the art

By biting leaves and shoots (mainly on plantings of forest stands), as well as by damaging tree bark (especially in the winter), it causes considerable damage, especially by wild animals. Especially the food, which is planted less than other conifers, is an attractive variety of diet for animals. Likewise, young deciduous trees (beech, oak, ash, ...) are also damaged by animals. The most widespread are bite damages caused by roe deer and deer. In recent decades, there has also been a significant increase in the number of wild animals in our country, as a result of which there has also been an increase in damage caused by animal bites.

One of several possible ways to effectively reduce these damages is provided by chemical protection in the form of taste repellents, which are applied directly to the trees. Effective chemical repellents can significantly reduce the costs associated with securing trees, as there is no need to build expensive fences or renew the planting of seedlings.

Several types of chemical repellants are currently used in Slovakia, the Czech Republic and abroad, which are more or less effective. In practice, however, it has been observed that the animal can get used to the applied repellent after a certain period of time, and it is therefore necessary to vary the repellents and alternate the active substances contained in them.

Currently used chemical anti-bite repellants can be divided into: deterrent, pain-causing, conditioned resistance and taste repellants. Essentially, these are always taste and smell active substances, while in some repellants their effects are combined.

In Slovakia and also in the Czech Republic, several repellents based on tetramethylthiuram disulfide -(CH3)2N-CS-S-S-CS-N(CH3)2, so-called thiram (TMTD), which is mainly used as a fungicide. Currently, the use of tetramethylthiuram disulfide is already prohibited. Repellents containing ichthyol, tallow oil, sand, ground limestone and fat distillation residues are also known. There are also commercially available products imitating human sweat and other natural odors, or substances identical to nature.

In recent years, mainly in the Czech Republic, the effectiveness of developmental preparations containing various burning and irritating substances (capsaicin, piperine), denatonium benzoate, so-called Bitrex as a compound with an extremely bitter taste, albumin, blood meal, fish oil, dimethyl sulfoxide (DMSO) and several plant essential oils - essential oils. The effect of some dyes as well as luminescent additives was also experimentally verified.

From the published results of foreign research, it is necessary to mention the work of Ward, J.S. and Williams, S.C. ("Effectiveness of deer repellents in Connecticut, Human-Wildlife Interactions 4 (1): 56-66, 2010) according to which a total of ten commercial preparations were tested the use of repellents based on spoiled chicken eggs and coyote urine. A study by Trent, Nolte, and Wagner ("Comparison of Commercial Deer repellents, USDA National Wildlife Research Center Staff Publications, 572, 2001) evaluated the effectiveness of 20 repellents available in the US, with products containing degrading proteins (rotten chicken eggs, spoiled slaughter waste).

The essence of the invention

It has now been found that suspensions, pastes or creams containing calcium acetylide, CaC2 and lanolin can be advantageously used as repellent preparations against damage to cultures by animals, especially woody plants. Calcium acetylide, known as calcium dicarbide, or usually as calcium carbide (CAS: 75-20-7, ES: 200-848-3) is one of the basic products of the electrochemical industry, which is produced from limestone and coke. With considerable simplification, the reduction of lime with coke can be expressed by the reaction scheme:

CaO + 3 C ^ CaC2 + CO ΔΗ298,ι = +108.0 kcal

The reaction has a distinctly endothermic character, with the necessary heat being supplied by an electric current, which is created in the form of an electric arc and also by the resistance that the contents of the furnace offer to the passage of the current. The reaction is reversible, and the temperature at which carbide starts to form is about 1700°C. The resulting carbide is dissolved in excess lime to melt. In order to convert other portions of lime into carbide, it is necessary that the temperature in

SK 72-2021 A3 furnace reached about 2,100 °C. The melt obtained at this temperature consists of 75-80% calcium carbide, the rest is calcium oxide, coke and limestone impurities and also a small amount (0.5-1%) of residual carbon.

The majority of the produced carbide is used for the production of ethene - acetylene (C2H2), a significant part of which is further processed into a number of important organic substances (acetaldehyde, acetic acid, butadiene, etc.) and cyanide compounds. It is also used in the steel industry as a reducing desulfurization agent. Approximately a quarter of the produced carbide is processed by azotization to calcium cyanamide, CaCN2, the so-called nitrogenous lime. In 1862, Fridrich Wohler discovered that the action of water on calcium carbide produces ethyne - acetylene according to the scheme:

CaC2 + 2H2O ^ Ca(OH)2 + C2H2

The use of calcium carbide acetylide for the protection of agricultural plants in Slovakia is currently permitted by current legislation, and carbide powder is used to repel moles by introducing such carbide into their burrows.

Lanolin is an amorphous, greasy substance obtained during the washing of sheep's wool. Use "ointment obtained from wool was already known in ancient Greece. Liebrich and Braun dealt with its refinement in Germany, and in 1882 they labeled this substance as "lanolin. Lanolin is a hydrophobic protection of wool fibers, so it forms a protective layer against the effects of water. Due to the absence of glycerol in this oily substance, it is justified to include it among waxes from a chemical point of view. Lanolin is a complex mixture of natural esters of higher insoluble alcohols and sterols with higher fatty acids.

Lanolin can be characterized physicochemically as follows:

color: yellow, light brown to brown specific gravity - density (at 15 °C): 0.94 - 0.97 g/cm ³ refractive index (refraction at 40 °C): 1.48 melting point: 35 - 40 ° C content of free acids: 4 - 10% content of free alcohols: 1 - 3% iodine number: 15 - 30 saponification number: 95 - 120 average molecular weight: 790 - 880 representation of fatty acids: 50 - 55%.

The aqueous emulsion obtained by degreasing wool (usually sheep's) is separated in the first stage by centrifugation and subsequent sedimentation at elevated temperature, resulting in the thickening of the "oily components". The mentioned method of rough cleaning is repeated (usually two to three times). The raw lanolin obtained in this way is further purified for pharmaceutical and cosmetic use, while the content of free fatty acids and alcohols, water, and the content of pesticides, detergents and polyaromatic hydrocarbons are minimized. Refining also changes the color of lanolin from brown to yellow and removes its characteristic "sheep smell". At room temperature, lanolin has the character of a relatively thick, hard-to-manipulate, sticky amorphous consistency, reminiscent of plum jam. Lanolin does not dissolve in water, even if mixed with water (2-3 parts of water to one part of lanolin) it forms a so-called aqueous lanolin.

It has been found experimentally that lanolin mixes with liquid hydrocarbons - for example with light hydrogenated gasoline (C4-C11), fatty acids, carboxylic acid esters - for example ethyl acetic acid (ethyl acetate), fatty acid esters and also with several chlorinated alkane derivatives, such as for example with trichloromethane (chloroform) -CHCl ₃ , tetrachloromethane (carbon chloride) - CCI4 and 1,2-dichloroethane (ethylene dichloride) -CH2CICH2CI. Some aromas can also be used for the preparation of lanolin emulsions, especially benzene (C6H6), toluene-methylbenzene (C6H5.CH3), or xylene-dimethylbenzene (C6H4(CH3)2).

The advantage of using some chlorinated alkane derivatives compared to aromatics, gasoline and also to esters is their non-flammability. However, a certain disadvantage is their considerably high specific gravity — density (1.25 to 1.6 g/cm ³ ).

Fats and oils are the source of fatty acids. These contain saturated and unsaturated fatty acids. The advantage of fatty acids is that they are represented in the form of mixtures in both animal fats and vegetable oils, which are generally available and biodegradable. The representation of individual types of fatty acids in some types of oils and fats is different, which can be seen from the following overview:

SK 72-2021 A3

The total number of carbons in a fatty acid molecule

- saturated fatty acids - unsaturated fatty acids

Type of oil, or oil

C4C6C8C10C12C14 C16 C18 C20-24 C16 C18* C18** C18*** more

Average fatty acid content (%)

Castor oil 2 8 3 87 (C18-castor oil) Coconut oil 1 9 7 45 18 9 1 1 7 2 Linseed oil 6 2 1 19 24 48 Rapeseed oil 1113 20 15 2 57 (C22-erucic) Sunflower oil 4-9 1-7 7 14-40 48-74 Soybean oil 10 2 1 1 30 50 6 Olive oil 7.5-20 0.5-5 55-83 2.5-21 Beef tallow 6 27 14 50 2

C18* - oleic acid -CHafC^hCH = CH(CH2^COOH

C18** - linoleic acid -CH3(CH2h(CH2CH = CHhfCH^COOH

C18*** - linolenic acid -CH3(CH2CH = CHHC^bCOOH.

An equally great advantage of fatty acid esters is their biodegradability. They are produced by transesterification of fatty acid triglycerides, in which propanetriol is replaced by methanol. The source of fatty acids can be more than 300 types of plants, while these are usually found in seeds and fruits.

The most important oleaginous plants and thus fatty acids are: canola, sunflower, olives, soybeans, coconuts and others. Oils and fats obtained by collecting used cooking oils from gastronomic establishments (used frying oils, etc.) can also be used as a raw material for the production of esters.

Methyl alcohol (CH3OH) is most often used for esterification of fatty acids. In addition to the methyl esters used in Europe, ethyl ester is also produced from vegetable oils (mainly in the USA). A substantial proportion of fatty acid esters is currently used as part of fuels for diesel engines, such as so-called biodiesel. In Slovakia, the so-called biodiesel MDT with a 30% share of methyl ester in conventional diesel. In the USA, fuel with 20% biodiesel content is used, while in France, a diesel mixture with 5% methyl ester is sold. Several technical designations are used for fatty acid esters. In Slovakia, the designation MERO (methyl ester of rapeseed oil) is used, while abroad the term RME (rape seed methyl ester) is used. If the source of fatty acids is not only rapeseed oil, it is more correct to use the designation FAME, which is derived from the English designation Fatty Acid Methyl Ester.

According to the STN EN 14214 standard, FAME must meet, among others, the following requirements:

• FAME content: min. 96.5 wt. % • specific weight - density at 15 °C: 860 - 900 kg/m ³ • viscosity at 40 °C: 3.5 — 5.0 mm ² /s • flash point: min. 101 °C • acidity number: max. 0.5 mg KOH/g • linolenic acid methyl ester content: max. 12.0 wt. % • content of polyolefinic (4 or more double bonds) methyl esters: max. 1.0 wt. % • free glycerol content: max. 0.02 wt. % • water content: max. 500 mg/kg.

Distilled rapeseed oil methyl ester (CAS: 67762-26-9, 67762-38-3, EINECS: 267-007-3, 267-015-4) is not toxic, it is very biodegradable - MERO biodegradability tested according to CEC L -33A-93 is approximately 98 wt. % within 21 days. In France, MERO is even classified as food due to its properties.

The mentioned solvents, in the case of their technical quality, often contain small amounts of water (especially in the case of gasoline and esters). In such a case, it is advisable to remove this water before using them for the preparation of lanolin emulsions in order to avoid possible problems with the dispersion of carbide in the emulsion (foaming of the mixture, swelling of packaging, etc.). Water reaction can be used, among other methods, to remove water

SK 72-2021 A3 with a small amount of carbide. If lanolin emulsions are prepared at an elevated temperature, a small amount of carbide can be added to the lanolin - liquid phase mixture before heating. In this case, however, it is necessary to ensure perfect ventilation of the gas phase behind the cooler. By homogenizing lanolin with the mentioned solvents, it is possible to prepare emulsions characterized by suitable rheological properties even at room temperature, while the emulsions thus obtained do not chemically react with calcium acetylide and hydrophobicize its surface. The mentioned facts enable the preparation of calcium carbide suspensions in prepared lanolin emulsions.

It was found that by changing the composition of the components in suspensions prepared in this way, it is possible to effectively change their character (rheological properties), while the prepared products can be freely liquid or even pasty. To modify the properties of lanolin emulsions, it is also possible to use the addition of one of the esters or alcohols — especially methyl alcohol, ethyl alcohol or isopropyl alcohol. It was found that for the preparation of repellent preparations against the damage of cultures by animals according to this solution, it is expedient if the content of lanolin in the prepared emulsion is higher than 10 and lower than 60 wt. %, preferably 20 to 40 wt. %. In order to achieve optimal properties of the final repellent preparations according to the solution — suspensions or pastes, it is advisable to use calcium acetylide (calcium carbide), CaC2 whose particles are smaller than 1.5 mm, in their preparation. In this context, the use of calcium carbide in the form of a fine powder, which is obtained as a by-product in the production of carbide grit, was shown to be advantageous in terms of production and economics in the preparation of repellents. Carbide powder contains approximately 98% of particles equal to or smaller than 0.025 mm. It has been experimentally demonstrated that from the point of view of the effectiveness of repellent preparations against damage to cultures by animals according to the solution and also their rheology, it is suitable if the content of calcium acetylide — calcium carbide in the final preparation is more than 5 and less than 55 wt. %, preferably 15 to 45 wt. %.

In the case of the use of repellent preparations in the sense of this solution, a combined - synergistic repellent effectiveness is achieved, which is related to the effects of taste and smell. The resistance of animals to the ingestion of treated plants is further increased by the abrasive action of solid particles and the alkaline reaction of the products of the gradual hydrolytic decomposition of calcium acetylide.

If necessary, the repellent effectiveness of the preparations according to the solution can be further enhanced by the addition of other additives such as burning and irritating substances (capsaicin, piperine, etc.), denatonium benzoate, albumin, blood meal, fish oil, dimethyl sulfoxide (DMSO), substances with luminescent effectiveness, or several plant essential oils — essential oils. The hydrophobic effect of lanolin ensures a gradual and long-term effect of the repellent.

Part of the claims for protection is also the method of preparation of repellent preparations against the damage of crops by wild animals in the sense of this solution. The preparation consists of two basic steps — preparation of lanolin emulsion and dispersion of calcium acetylide in the prepared emulsion. The preparation of the lanolin emulsion can be carried out at room temperature, or preferably at an elevated temperature. When preparing an emulsion without heating, it is necessary to ensure effective mixing of the lanolin mixture with the liquid component used. Due to the amorphous nature of lanolin, it is advisable to prefer mixing by shaking or kneading. If homogenization using a stirrer is used to prepare the lanolin emulsion, it is necessary to proceed in such a way that the lanolin is gradually added to the mixed liquid phase. Preparation can also be accelerated by melting the lanolin in advance (e.g. by heating in a water bath) and gradually adding it to the intensively mixed liquid phase. It is convenient if the liquid phase can also be heated to a temperature close to the temperature of the dissolved lanolin. The preparation of a lanolin emulsion is also possible by heating the corresponding amounts of lanolin and the liquid component used together. In the case of using a liquid component with a higher vapor tension, it is necessary to heat the mixture under a reflux condenser in a closed container.

Dispersion of calcium acetylide - calcium carbide particles in a lanolin emulsion can be carried out in devices ensuring thorough homogenization of the components forming the liquid phase. According to the nature of the resulting homogenization product (suspension, paste, cream), it is necessary to choose a suitable type of mixer, or kneader.

The method of preparation of repellent preparations against animal damage to cultures according to this solution also allows preparation in one device, which, however, must meet the conditions suitable for both the preparation of the lanolin emulsion and its subsequent homogenization with carbide. Devices of this type are mixers - mixers, for example, of the Lodige type, which also allow heating of the mixed ingredients.

Depending on the nature of the repellent preparations against crop damage by animals (suspension, paste, cream), it is necessary to choose an appropriate application method for its application.

If the preparation contains calcium acetylide (calcium carbide) only in the form of its fine particles, the preparation can also be applied as a spray. If it is necessary to adjust the rheological properties of the spray liquid, it is possible to use either a similar or chemically related substance for dilution as was used in the preparation of the lanolin emulsion, or the spray can also be diluted by adding one of the alcohols (ethanol,

SK 72-2021 A3 methanol, isopropyl alcohol, etc.), vegetable oils, or esters, for example fatty acid esters (FAME, MERO, etc.).

If, according to the solution, the repellent has the character of a thick-viscous suspension, or paste, or cream and contains carbide particles that would make its application by spraying impossible, it has been proven in practice to implement the application by coating plants. A suitable flat brush or a pair of brushes with long handles is usually used for painting - the so-called tweezer brush, or the coating is simply done by hand protected by a glove. Usually, either the entire trunk and terminal shoot, or twigs (mainly in deciduous trees) are treated, or the first bed with a terminal outgrowth - the top (especially in the case of conifers). If possible modification of the rheology of the coating material is necessary, similar substances can be used for its dilution, as already mentioned.

Examples of implementation of the invention

The following examples clarify and document the solution in question, but in no way limit the claims for its protection.

Example 1

In order to prepare a lanolin emulsion intended for the preparation of a repellent preparation against damage to cultures by animals, 110.2 g of raw lanolin Fatty acids from the French company Lanolines de la Tossee and 110.2 g of ethyl acetate were weighed into a glass cup that can be closed with a twist-up system. After the container was perfectly closed, it was placed on a laboratory shaker. After a few hours, the originally amorphous lanolin completely dissolved into a dark brown, free-flowing emulsion. An emulsion containing 50% lanolin was prepared in the above-mentioned manner.

Example 2

In order to verify the possibility of preparing a lanolin emulsion with a higher lanolin content, the following was weighed in a similar way and using components of the same quality as in example 1: 157.2 g of raw lanolin and 105.2 g of ethyl acetate. Using a laboratory shaker, 59.9 wt. % lanolin emulsion.

Example 3

In order to separate the granulometric fractions of calcium acetylide, which can be used for the preparation of samples of repellent preparations against the damage of cultures by animals, the powder of calcium carbide of technical purity was subjected to sieving. A set of standardized laboratory sieves with hole sizes of 4.2 and 1.25 mm was used for separation.

By evaluating the granulometric analysis, it was found that the crushed carbide contained:

17.8% of particles d < 4 mm,

33.8% of particles 2 < d < 4 mm,

24.2% of particles 1.25 < d < 2 mm and 24.2% of particles smaller than or equal to 1.25 mm.

Example 4

During the preparation of the lanolin emulsion by the "hot" method, the following was weighed into the boiling flask: 350 g of raw lanolin, of the same quality as in the already mentioned examples, and 650 g of benzene, C6H6. The flask was placed in a water bath, in which it was heated, under a reflux condenser, to a temperature of approximately 85 °C. During the boiling and condensation of the liquid component, the initially amorphous and relatively solid lanolin gradually dissolved, resulting in an emulsion suitable for dispersing carbide particles.

Example 5

A similar method of preparing a lanolin emulsion as in example 4 was also used using a liquid component consisting of methylbenzene — toluene, C6HS5. CH3, with the difference that in this case an oil bath was used for heating. The temperature of the bath was maintained at approximately 112 — 115 °C.

Example 6

When using dimethylbenzene xylene, C6H4. (CH3)2, the procedure for preparing the lanolin emulsion was similar to that in example 5, with the difference that the oil bath was heated using an electric cooker to a temperature of about 135°C.

Example 7

In order to verify the possibility of preparing a lanolin emulsion using technical gasoline - light

SK 72-2021 A3 of hydrogenated gasoline (C4-C11) was weighed into a glass cup that could be closed with a well-sealing twist-up cap: 108.05 g of dark brown raw lanolin, of similar quality as in the previously mentioned examples, and 107.95 g of technical gasoline . After the beaker was sealed, the mixture was stirred for several hours using a laboratory mixer.

Free-flowing approx. 50 wt. % lanolin emulsion suitable for its further processing into a repellent sample in accordance with this solution.

Example 8

In a completely analogous way as in example 7, an emulsion of crude lanolin in technical gasoline containing approx. 60 wt. % lanolin by mixing 150.8 g of lanolin and 100.5 g of white spirit, at room temperature.

Example 9

By a similar procedure as in examples 7 and 8, the preparation of approx. 80% of raw lanolin was verified, using: 130.65 g of raw lanolin and 32.85 g of technical gasoline. After several hours of mixing, a very viscous emulsion of lanolin with unsatisfactory rheological properties was obtained. In order to adjust the rheology, an additional 23 g of technical gasoline was added. By mixing, a free-flowing emulsion containing about 70% lanolin was obtained.

Example 10

In order to prepare a sample of a repellent preparation against crop damage by animals according to the solution intended for verification of its effectiveness in planting forest trees, with constant mixing, 631 g of 53.5 wt. % emulsion of lanolin in ethyl acetate gradually added 420 g of the technical calcium carbide fraction separated by sieving. The carbide used contained particles smaller than 1.25 mm. The obtained product contained approximately 40% carbide, while it had satisfactory rheological properties and was suitable for direct application by painting.

Example 11

For similar use and in an analogous way as in example 10, to 615 g 59.85 wt. % emulsion of crude lanolin in technical gasoline added 411 g of calcium carbide of similar granulometry as in Example 10. The carbide used contained particles smaller than 1.25 mm. The obtained product contained approximately 40% carbide, while it had satisfactory rheological properties and was suitable for direct application by painting.

Example 12

In order to verify the effectiveness, a sample of the repellent preparation against damage to cultures by animals was prepared, similarly to examples 10 and 11, by homogenization of 1,337 g 43.7 wt. % emulsion of raw lanolin in tetrachloromethane (carbon chloride) — CCL ₄ and 874 g fraction of technical calcium carbide (d < 1.25 mm). The obtained product contained approximately 40% carbide, while it had satisfactory rheological properties and was suitable for direct application by painting. The advantage of this preparation was its non-flammability.

Example 13

During the laboratory preparation of a lanolin emulsion suitable for the preparation of a sample of a repellent preparation in the sense of a solution, the following was weighed into a glass jar with a well-sealing twist-up cap:

156.4 g of raw lanolin, dark brown in color and

162.45 g of trichloromethane (chloroform), CHCl3.

After several hours of mixing with a laboratory shaker at room temperature, an emulsion containing approximately 49% lanolin was prepared. The product had suitable rheological properties and was used for homogenization with the powdered form of calcium acetylide — calcium carbide (CaC2).

Example 14

The possibility of preparing a lanolin emulsion using 1,2dichloroethane (ethylene dichloride), CH2CICH2CI was verified in laboratory conditions. The dissolution of lanolin was carried out at an elevated temperature, in the apparatus and under the same conditions as in example 4. The temperature of the water bath used for heating was approximately 85 °C. Under these conditions, an emulsion containing approx. 35 wt. % lanolin with satisfactory rheological properties.

Example 15

In connection with the treatment of Caucasian fir seedlings (Abies normanniana) against forest animal bites, the growth tops of the seedlings were coated using the so-called emulsion-based product applied with a tick brush

SK 72-2021 A3 of lanolin in carbon chloride, according to example 12, in order to practically check the possibility of diluting the preparation, methanol was added to its part. The product diluted in this way was more liquid and applied well.

Example 16

In order to increase the effectiveness of the repellent preparation in the sense of a solution based on a carbide suspension in a lanolin - carbon chloride emulsion, with a similar composition as in example 12, the following was further added to 100 parts by weight of the suspension:

0.5 part by weight approx. 40 wt. % solution of capsaicin in dimethylsulfoxide and 2 parts by weight of approx. 15 wt. % solution of denatonium benzoate (Bitrex) in propylene glycol.

Example 17

The treatment of growth tops of Scots pine (Pinus sylvestris L.) against gnawing by wild animals was carried out with a preparation in the sense of a solution, which contained an emulsion of raw lanolin in technical gasoline (C4-C11) and crushed calcium acetylide — carbide, containing particles smaller than 2 mm. Since the repellent used was a paste, it was applied to the tops of planted seedlings using a coating with hands protected by gloves.

Example 18

In order to prepare a lanolin emulsion based on fatty acid esters, the possibility of their preparation at room temperature and also under heat was verified in laboratory conditions. 227.6 g of raw lanolin of similar quality as in example 1 and 227.75 g of methyl ester of rapeseed oil (Agromero) were weighed into a glass jar with the possibility of its tight closure (twist-up system). The contents of the container after its perfect closure were mixed (by shaking) at room temperature (approx. 20 °C). After about 30 hours of occasional stirring, a dark brown emulsion with a larger agglomerate of still undissolved lanolin was obtained.

In order to check the possibility of preparing a similar emulsion under heat, the following was weighed into the same container: 216.85 g of raw lanolin and 217.7 g of ester (Agromero). After it was thoroughly closed, the container was placed in a water bath where it was gradually tempered to a temperature of approx. 85 °C. Within about 45 minutes, the lanolin was completely dissolved, while the mixture had the character of a free-flowing solution - melt, dark brown in color. Thorough homogenization of the mixture resulted in an emulsion containing approximately 49.9% lanolin, which acquired the character of a paste upon cooling. 25 parts by weight of powdered calcium acetylide — carbide (CaC2) obtained during dust removal at the factory was mixed with 75 parts by weight of the prepared paste intermediate.

Example 19

In order to prepare a lanolin emulsion intended for the finalization of the repellent preparation according to the solution, the mixture consisting of 78.65 parts by mass of rapeseed oil and 41.6 parts by mass of raw lanolin was heated to a temperature of about 65 °C with occasional mixing. During about an hour of heating, the originally amorphous lanolin completely melted. A dark brown lanolin emulsion containing approximately 34.6% lanolin was obtained in the above-mentioned manner. Powdered calcium acetylide - carbide containing particles equal to and smaller than 1.25 mm was added to the prepared lanolin emulsion with constant stirring. The mixing ratio of the components was: 85% lanolin emulsion and 15% carbide. After cooling, the mixture had a pasty consistency and was intended for the treatment of seedlings of deciduous trees (oak, beech) by coating their growth tops with a hand equipped with a protective glove.

Example 20

When preparing a sample of a repellent preparation in the sense of a solution, with a creamy consistency, intended for the treatment of seedlings of deciduous trees (beech, oak), a stainless steel container placed in another container with water heated using an immersion electric cooker was used. 281 g of raw lanolin of similar quality as in example 1 and 844 g of cooking-quality rapeseed oil were weighed into the container. The mixture of lanolin and vegetable oil was slowly heated with occasional stirring. Already at a mixture temperature of about 35 °C, gradual dissolution of lanolin was noticeable due to the gradual darkening of the oil phase. The complete melting of lanolin occurred at a mixture temperature of about 50 °C (at a water bath temperature of about 70 °C), after about 20 minutes of mixing. The prepared oil emulsion of lanolin was dark brown in color and had the character of a well-flowing liquid. To a perfectly homogeneous emulsion containing approx. 25 wt. % of lanolin, 375 g of powdered calcium carbide acetylide (the dust portion captured during the production of crushed carbide) was further added. 1,500 g of the repellent preparation was prepared according to the solution intended for application tests by applying it using a two-armed, so-called tweezer brush and also by hand application with a protected glove.

SK 72-2021 A3

Example 21

When preparing a similar sample as in example 20, a sample of the repellent preparation was prepared in an identical manner. The sample was prepared using:

288 g of raw sheep lanolin of the same quality as in example 1,

853 g of a mixture of fatty acid esters FAME - 10 (Meroco a. s. Leopoldov), meeting the requirements of STN 14214, according to which it can be characterized as follows:

• fatty acid methyl ester content: min. 96.5 wt. %, • density at 15 °C: min. 860, max. 900 kg/m ³ , • viscosity at 40 °C: min. 3.5; max. 5.0 mm ² /s, • flash point: 101 °C, • sulfur content: max. 10.0 mg/kg, • cetane number: min. 51.0;

• sulfate ash content: max. 0.02 wt. %.

375.45 g of powdered calcium carbide, of similar quality as in example 20, was gradually added to the raw lanolin emulsion while stirring.

Industrial applicability

It is characteristic of the repellent preparations against crop damage by animals according to the solution that they contain calcium acetylide (calcium carbide) and lanolin. Preparations can be in the form of suspensions, pastes, or even creams. The preparation process, which is part of the solution, is undemanding and its implementation does not require the use of special raw materials and equipment. The preparation consists of two basic steps - preparation of lanolin emulsion and dispersion of calcium acetylide in the prepared emulsion. Similarly, the application of preparations in the sense of a solution does not require the use of any unusual procedures, aids and equipment.

Claims (11)

1. Repellent preparations against crop damage by animals, characterized by the fact that they contain calcium acetylide - CaC ₂ and lanolin. 2. Repellent preparations against damage to crops by animals according to claim 1, characterized in that they have the nature of a suspension, paste or cream. 3. The method of preparing repellent preparations against damage to cultures by animals according to claims 1 and 2, characterized in that calcium acetylide is dispersed in a lanolin emulsion. 4. The method of preparing repellent preparations against damage to cultures by animals according to claim 3, characterized in that the lanolin emulsion contains one of the chlorinated alkane derivatives, one of the fatty acids, one of the fatty acid esters, ethyl acetate, benzene, toluene, xylene or gasoline. 5. The method of preparation of repellent preparations against animal damage to cultures according to claim 3, characterized in that the lanolin emulsion contains tetrachloromethane - CCI ₄ , trichloromethane CHCI ₃ , 1,2-dichloroethane - CH ₂ CICH ₂ CI. 6. The method of preparing repellent preparations against damage to cultures by animals according to claim 3, characterized in that the lanolin emulsion contains any of the vegetable oils. 7. The method of preparing repellent preparations against damage to cultures by animals according to claim 3, characterized in that the lanolin emulsion contains rapeseed oil methyl ester. 8. The method of preparing repellent preparations against damage to cultures by animals according to claim 3, characterized in that it contains methyl alcohol and/or ethyl alcohol and/or isopropanol. 9. The method of preparing repellent preparations against damage to cultures by animals according to claims 1 to 3, characterized in that the size of the calcium acetylide particles is smaller than 1.5 mm. 10. The method of preparing repellent preparations against damage to cultures by animals according to claims 1 and 8, characterized in that calcium acetylide is used as a dust fraction, the so-called powder obtained during the production and separation of crushed calcium acetylide. 11. Use of repellent preparations against damage to cultures by animals according to claims 1 and 2 in the form of coating plants or by spraying them.