DE2743485A1 - METHOD FOR PRODUCING BIOLOGICALLY EFFECTIVE GRANULES - Google Patents

Description

It is known, granules containing pesticidal agents of various kinds Manufacture size using natural mineral carriers or carriers of vegetable origin. High polymer natural substances or compounds based on plastics have also been used for this purpose.

on the technique of producing granules from mineral James A. Polon reports on carriers and their properties in Pesticide Formulations, edited by Wade Van Valkenburg, Marcel Dekker Inc., New York, 1973, pp. 186-205. Because of the engagement By using high-polymer plastics instead of natural porous carriers, attempts have been made to delay the release of the active substances. Attempts have also been made to natural carriers of mineral or vegetable origin pesticidal agents to adsorb and to subsequently coat the products obtained with more or less water-soluble substances.

The purpose of these granules is to absorb pesticidal agents, to deposit them and, after application, more or less slowly to the Submit environment. In this way, the active ingredients are intended to be of animal or vegetable origin even for a longer period of time Pests can act. The active ingredient can be released in different ways. Is the active ingredient e.g. sufficiently volatile and only slightly bound to the carrier material, it can be released through direct diffusion processes. If, on the other hand, the active ingredient is of low volatility and is the carrier material sufficiently hydrophilic, for example, moisture can wet the carrier material, penetrate it and the release active substance.

Finally, it is also possible to use the active ingredient in carrier materials to embed, which slowly disintegrate without and / or due to external influences and thus slowly release the active substance. Combinations of these processes of active ingredient release mentioned here are of course also possible.

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In the DT-OS 22 38 912 is about water-degradable polymer masses reported, which have urea-like structures in their polymeric chain molecules and in liquid or solid Form. The liquid polymer masses can be converted into hard, brittle solids by heat treatment will. These changes are due to enlarged molecules or crosslinking reactions. The biologically effective Compound can either be built into the polymer itself or encapsulated by the polymer. Because of the necessary thermal treatment at elevated temperatures, the process is limited exclusively to those active ingredients that do not enter into any irreversible reactions with the ureas or possible additives under the stated conditions.

In GB-PS 903 159 the production of pellets or smaller Granules made from a natural or synthetic wax, additives and a volatile insecticide (DDVP) are described. The insecticide is slowly released after application and reaches the environment of the harmful insects in gaseous form.

In NL-PS 6 909 123, formulations using polyethylene wax with a molar weight of approx. 2000, a density of approx. 0.5 kg / l and a melting point of approx. 100 ° - 105 ° C. The melted wax is added in the autoclave An insecticide is added to temperatures above the melting point and, after solidification, the insecticide is slowly added again dispensing formulation received.

DT-OS 2 452 217 describes the incorporation of organophosphorus insecticides in matrices based on Terper.-phenol resin. The resins with a softening point of at least 100 ° C are obtained by reacting different terpenes, such as dipentene, ß-pinene, limonene and various fractions of turpentine with phenols in the presence of a condensation catalyst. The incorporated Insecticide is thus protected from damaging external influences, such as moisture, and depending on the size of the active

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Surface and other conditions slowly released into the environment .

on the use of polyvinyl chloride, polyamide, polyurethane including plastics in pesticidal formulations, see N. Cardarelli, Controlled Release Pesticides Formulations, CRC Press Inc., 1976, pp. 139 and ff.

G.B. Aquino and M.D. Pathak, J. Econ. Entom. 69, 5, p. 686 (1976) describe experiments with insecticides in rice cultivation. Insecticides are used in gelatine capsules and as simple granules in applied to the root areas of rice plants in order to delay the release of active substances to the plants. in the This method plays a very special role in rice cultivation, as the rice plants are constantly covered with insecticides during the growing season need to be supplied, which is done in a conventional manner by repeated injections at approximately 14-day intervals.

The present invention relates to a method of production of biologically active pellets or granules., which is characterized in that one becomes a mixture of carrier and biologically active material di- or polyisocyanates or their prepolymers and Η-active compounds from the group Water and / or organic di- or poly- (hydroxy- and / or amino) compounds or mixtures thereof capable of polycondensation are mixed in, this mixture is granulated or pelletized and the resulting granules or pellets at temperatures of 10 ° to 60 ° C., preferably Cure at 20 ° to 50 ° C, especially at room temperature leaves.

As carrier materials, all are in themselves for the production of granules Usual and suitable materials can be used, such as prefabricated and comminuted solid, fully synthetic or partially synthetic organic high polymers, carriers of mineral, vegetable or animal origin as well as inorganic carriers. To maintain the soil quality, carrier substances of mineral or vegetable origin are preferred, in particular

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- 5 those that are natural to the ground or that rot easily.

Examples of mineral or inorganic carriers are all types of silica, diatomaceous earth, kieselguhr, silicates and silicate-containing substances such as clay, mica, Pumice stone, also lime, magnesium carbonates, clays, poorly soluble phosphates such as Thomas flour or all kinds of coal can be used .

As fully synthetic or partially synthetic organic high polymers can, for example, urea resins, such as urea-formaldehyde resins, Cellulose derivatives such as cellulose ethers, polyvinyl alcohols or modified polyvinyl alcohols such as partially saponified Polyvinyl acetates or propionates can be used.

Vegetable carriers are particularly suitable as carriers of vegetable origin Materials such as sawdust, crushed cereal straw, especially corn and rice straw, peat, corncob meal.

The use of mineral carriers or vegetable carriers Origin has the advantage that these carrier substances disintegrate or rot after use and so do not additionally protect the environment load, while e.g. some thermoplastic or thermosetting plastics as non-biodegradable foreign matter in the Earth lag behind. This fact is particularly important if, for example, for technical reasons, the proportion of carrier material: active ingredient must be very large.

Soil-active compounds can be used as biologically active material, such as systemic insecticides, herbicides, fungicides, nematocides or algicides as well as growth regulators or Use fertilizers and mixtures of the biologically active substances mentioned. They can be as such or resolved in organic solvents, optionally with the addition of emulsifiers, wetting agents, hydrophobizing substances or other ingredients known from formulation technology

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be used. Biocides and growth regulators which are ^{not liquid above 0} ° C. and are sparingly soluble in water are preferably used in organic solution. They are preferably added to the mixtures according to the invention - in analogy to spray powder technology - in already adsorbed form, in particular on highly active adsorption material.

Suitable di- or polyisocyanates which polyadd with the Η-active compounds to form a binder that solidifies the pellets or granules are, for example, aliphatic, aromatic, heterocyclic, cycloaliphatic and araliphatic di- or polyisocyanates, such as, for example, ethylene diisocyanate, 1,4- Tetramethylene diisocyanate, hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,4- and 2,6-toluylene diisocyanate, diphenylmethane-2,4'- and -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, chlorinated ary! polyisocyanates, phenylene diisocyanates, diphenyl diisocyanates, xylylene-1,4-diisocyanate, toluene-2,4,6-triisocyanate, xylylene-1,4-diisothiocyanate, cyclohexylene-1,2- and 1,4-diisocyanate, 4,4 * , 4 "triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate technical (PAPI ^V ').

The NCO prepolymers from those mentioned above are particularly suitable Isocyanates with, for example, diols or polyols with an average molecular weight of 500 to 10,000. For the production of such prepolymers for example di- or polyols with 3-6 hydroxyl groups per molecule or corresponding hydroxyl-containing polyesters are suitable, Polyethers, polyester amides, polycarbonates and / or polyacetals.

NCO prepolymers are reaction products of di- or polyisocyanates with diols or polyols or other compounds containing several OH groups. The di- or polyisocyanates used with a stoichiometric excess, so that the resulting reaction products are still sufficiently free Contain NCO groups (= isocyanate groups) which can react like polyisocyanates.

The preparation of the isocyanate prepolymers is described, for example

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in R. Vieweg, A. Höchtlen, Kunststoff-Handbuch, Volume VII, Polyurethane, Carl Hanser Verlag, Munich 1966, p. 45 and ff.

The polycondensation component for the isocyanates mentioned or their prepolymers is primarily an Η-active compound Mention water, in particular the water or moisture contained in the carrier substances. As additional components Examples include: polyhydric alcohols, polyhydric amines or alkanolamines. As a counterpart to the NCO prepolymers are also to mention high molecular weight polyols or polyamines, such as (poly -) - hydroxy polyethers, -polyester, -polyamides.

Examples of polyhydric alcohols are ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol isomers, hexanediol, octanediol, 2-methyl-1,3-propanediol, glycerine, butanetriol, trimethyiolpropane, Hexanetriol, pentaerythritol, mannitol, sorbitol, polyethylene glycols, polypropylene glycols, polybutylene glycols.

Examples of hydroxypolyesters that can be used result from the reaction of polycarboxylic acids with polyhydric alcohols. as Polycarboxylic acids for the production of such hydroxypolyesters include e.g. malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, maleic acid, phthalic acid, isophthalic acid and hexahydrophthalic anhydride. As polyhydric alcohols the polyhydric alcohols listed above by way of example can be used for the reaction with the polycarboxylic acids mentioned here to serve.

Examples of polyester amides result, inter alia, from the implementation of the above. polyvalent, saturated and unsaturated carboxylic acids and their anhydrides with polyhydric saturated or unsaturated amino alcohols, diamines and polyamines.

Examples of polycarbonates result, for example, from the reaction of simple diols with diaryl carbonates or phosgene.

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Examples of polyacetals result, for example, from the known reaction of diols or polyols with e.g. formaldehyde.

Examples of amines as polyaddition components are also The following di- and polyamines are also mentioned: ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine. Hexamethylenediamine, diethylenediamine, triethylenetetramine, Tetraethylene pentamine, m-phenylenediamine, p-phenylenediamine, Piperazine, methylpiperazine, diethanolamine, diisopropanolamine, Triethanolamine.

The isocyanates and Η-active compounds mentioned react depending on the choice of the components to form polyurethanes, polyureas or polyurethane-ureas and thus form the binder in situ, which connects or holds together and / or encloses the individual particles of the carrier material and the active ingredients. The rate of polymerization can be increased by adding small amounts of basic amines, alkyl tin compounds, alkali hydroxides, Phenolates and / or alcoholates can be increased as catalysts in a manner known per se. The proportions of the Polymerization components are chosen in a manner known per se, preferably so that on an isocyanate group about one OH or NH, group comes.

The stated constituents of the mixtures according to the invention are mixed well, if necessary, advantageously with the use of up to equal parts by weight of organic solvents, based on the isocyanate component, and on the known devices or devices provided for granulation, pelleting or contacting. Machines further processed.

The granules or pellets obtained are then stored for a certain amount of time Time, for example a few hours to a few days, at room temperature or, if faster curing is desired, at higher temperatures. The end of curing can easily be determined by checking the strength constants. The curing

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generally takes 1-5 days.

The composition of the granules or pellets obtained can vary within wide limits. The content of bioilids and growth regulators is generally 0.5 to 10% by weight, preferably 0.5 to 5% by weight, based on the finished product, plus optionally 1 to 10% by weight of an organic solvent including the necessary emulsifiers. at The proportion of highly active compounds can be reduced to 0.5 to 2% by weight of active ingredient. The proportion of solid fertilizer, such as organic fertilizers, urea or mineral fertilizers, for example, can be up to 50% by weight and the carrier partially replace.

The binder mixture component, consisting of di- or polyisocyanate or isocyanate prepolymers and Η-active compounds, is generally 1 to 30 wt .- ^, preferably 5 to 20 wt .- ^, in particular 6 to 12 wt .- ^. If necessary, it is dissolved or suspended used in up to equal parts by weight of an organic solvent. The organic solvents used are, for example, inert ones Solvents in question, as they are usually used in isocyanate chemistry Find use. The carrier substance (s) are accounted for in the formulations generally between about 30 and 70 wt .- $, based on the finished granulate.

The inventive method can be both hydrophobic as well as introduce hydrophilic substances in granules or pellets of the desired size in such a way that they take a long time migrate into the ground and get to the roots of plants. Pesticides that have only limited stability in water can also initially be enclosed in microcapsules and then processed into pellets or granules. As wall materials for such microcapsules are Preferably those products are to be recommended that allow the active ingredient to escape slowly or that are exposed to water or water. Soil moisture is slowly dissolved and so the active ingredient release.

The method of the present invention provides i.a.

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the following advantages:

1. Several active ingredients can be used in one operation at the same time be applied.

2. The pellets or granules produced by the process described show depot action, so that a multiple Repeated treatment by conventional methods during the season is unnecessary.

3. The plant becomes continuous for a certain period of time supplied with the necessary active ingredient.

4. The active ingredients are used almost completely. A possible additional burden on the environment through excess active ingredients is avoided.

5. By using the above natural mineral and / or vegetable carriers are only very small in the soil Amounts of foreign matter supplied that can practically be neglected.

6. By using the above binders, the fine-grained and soft mineral or vegetable carriers and the active ingredients non-dusting, abrasion-resistant pellets with high mechanical strength that do not separate during transport, storage and application, for example.

7. By including the naturally in the formulation components moisture contained in the hardening (polycondensation) process can produce completely dry granulates and pellets will.

The following examples are intended to explain the invention without, however, restricting it, since extensive variations with the substances and components to be used according to the invention and

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whose proportions are possible. The desired properties are decisive for the selection of the individual substances the granules or pellets to be produced from them.

PRODUCTION EXAMPLES:

Example 1:

21 g of sawdust with a moisture content of 15% are mixed with 20 g of kaolin and 70 g of urea (as fertilizer) and ground under inert gas on a pin mill (Condux C ST 150 type) to a particle size with an average diameter of less than 500 μm . Thereafter, a mixture of 2 g of 2-sec-butylphenyl-N-methylcarbamate and 6 g of a mixture of saturated hydrocarbons with a boiling range of 255 ° to 38O ° C (Essobayol 90) 0.5 g of the emulsifier castor oil oxethylate with 40 AeO units and 9, 5 g of kieselguhr 12/0 added, mixed and, after adding 10 g of a tolylene diisocyanate prepolymer (made from tolylene diisocyanate, trimethylolpropane, butanediol and polypropylene glycol in a molar ratio of 8: 3: 1: 1) in 12 g of xylene / ethyl glycol acetate (1: 3) mixed again.

This mixture is used to make tablets on a rotary tablet press with a pressure output of 5000 kg per punch a weight of approx. 2 g with a diameter of 20 mm. The maximum compressive strength of the tablets was after 2-3 days of storage at room temperature reached and amounted to

^ 15 kp / cm ² . If the tablets are stored in a corresponding manner at about 50 ° C., the same compressive strength can be achieved after 10-15 hours.

Example 2:

From the following ingredients: 30 g dry sawdust, 10 g kaolin, 65 g NPK mineral fertilizer 12-12-18, 5 g ethylene glycol, 2 g triazophos, 5 g of the hydrocarbon mixture from example

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(1), 1g of the emulsifier castor oil oxethylate with ho AeO units, 10 g of kieselguhr, 11 g of polymethylene polyphenyl isocyanate technical (PAPI * ') in 12 g of xylene / ethyl glycol acetate (1: 3) are pellets with a weight analogous to the method according to Example (i) of approx. 2 g and a diameter of 10 mm. The maximum compressive strength of the pellets after storage for 2 days at room temperature is> 15 kp / cm. If the pellets are stored in a corresponding manner at around 50 C, the same compressive strength can be achieved after 10-12 hours.

Example 3;

From the following ingredients: 25 g of corncob meal, 40 g of dried clay, 1 g of 2-sec-butylphenyl-N-methylcarbamate, 5 g of the hydrocarbon mixture from Example (1), 1 g of calcium idodecylbenzenesulfonate, 10 g of diatomaceous earth, 10 g of a prepolymer from Tolylene diisocyanate and hexanetriol and 8 g of methylnaphthalene are produced analogously to the process from Example (1) in an eccentric press with a pressure of 50OO kg per punch pellets with a diameter of 10 mm and a weight of 1 g. The maximum compressive strength of the pellets after storage for 1-2 days at room temperature was ^ -15 kg / cm ² .

Example 4;

From the following ingredients: 40 g sawdust with a moisture content of 20%, 10 g kaolin, 10 g urea (as fertilizer), 1 g triazophos as microcapsules in 1.5 g carboxymethyl cellulose as wall material, 8 g of the hydrocarbon mixture from example (1) , 1 g of i-dodecylbenzenesulfonic acid calcium, 10 g of diphenylmethane-4,4'-diisocyanate in 15 g of xylene / ethyl glycol acetate (1: 3) are tablets with a diameter of 20 mm and a weight in an eccentric press according to the method given in Example 3 made of 2 g. The maximum compressive strength of the tablets after about 1 day of storage at room temperature was> 15 kg / cm ² .

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Example 5:

From the following ingredients: 15g corncob meal, 45 g kaolin, 1 g pyrazophos, 4 g xylene technical., 1 g of the emulsifier castor oil oxethylate with 36 AeO units, 10 g diatomaceous earth and 10 g of the prepolymer mentioned in example (1) in 10 g Xylene / ethyl glycol acetate (1: 3), which are mixed analogously to the method according to example (1), are produced on an eccentric press with a pressure of 5000 kg per punch pellets with a diameter of 20 mm and a weight of approx. 2 g. The maximum compressive strength of the pellets after about 2 days of storage at room temperature was 15 kp / cm ² .

Example 6:

From the following ingredients: 30 g dry sawdust, 15g pumice stone, 40 g NPK mineral fertilizer 12-12-18, 4 g hexamethylenediamine, 2 g 2-sec-butylphenyl-N-methylcarbamate, 6 g xylene technical, 0.5 g Calcium i-dodecylbenzenesulfonate and 10 g of diatomaceous earth as well as 10 g of the prepolymer mentioned in example (1) in 12 g of xylcl / ethyl glycol acetate (1: 3) are applied analogously to the method from example (1) on a rotary tablet press with a pressure of 5000 kg Tablets with a weight of 2 g and a diameter of 20 mm were produced per punch. The maximum compressive strength of the tablets was reached after 1 day of storage at room temperature and was> 15 kp / cm ² .

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BIOLOGICAL EXAMPLES Example It Greenhouse trials

To demonstrate the biological effectiveness, experiments 1 and 2 were carried out in the greenhouse.

Experiment 1:

Rice plants 6 weeks old were planted in test vessels together with 1 pellet each, prepared according to Example 1, corresponding to 25 mg of 2-sec-butylphenyl-N-methylcarbamate as active ingredient. The planting with 20 rice leafhoppers (Nilaparvata lugens) took place after 3, 7, 10, 14, 17, 21, 24, 28, 31, 35, 38, 42 and 45 days after transplanting. Controls were carried out 1 day after occupation. Test plants and test animals were kept during the test period at a room temperature of +25 ⁰ C and a relative humidity of about 60%. The result is summarized in Table 1.

Table 1

Stocking by days Check after days % Mortality ⁺⁾ 3 4th 8th 7th 8th 33 10 11 67 14th 15th 53 17th 18th 63 21 22nd 67 24 25th 70 28 29 75 31 32 77 35 36 80 38 39 68 42 43 73 45 46 75

Average of 3 repetitions

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Experiment 2:

In further tests, pellets, produced according to Example 2, with 25 mg Triazophos active ingredient / pellet were carried out under the above-mentioned conditions Test 1 checked. The result is summarized in Table 2.

Table 2

Stocking by days Check after days % Mortality ⁺⁾ 3 4th 27 7th 8th 48 10 11 60 14th 15th 97 17th 18th 68 21 22nd 85 24 25th 88 28 29 98 31 32 95 35 36 72 38 39 68 42 43 87 45 46 70

+) Average of 3 repetitions

Example II:

Field trials:

On the basis of the test results obtained in the greenhouse according to Example I, field tests 3 and 4 against rice leafhoppers (Nilaparvata lugens) were carried out. The pellets were introduced as a single dose three days after transplanting (3 DAT) of the young rice plants about 5 cm deep into the root zone of the plants. The application rate / ha was 2.0 kg of active ingredient at 160,000

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Plant parts ("hills") per hectare. This corresponds to otherwise the same Ratios in experiments 3 and 4 listed below, an amount of active ingredient of 12.5 mg per pellet each according to example 1 and 2.

A 4% commercial BPMC granulate (Hopcin 4 G), active ingredient = 2-sec-butylphenyl-N-methyl-carbamate, was used as a comparison agent in experiments 3 and 4, used. The first application was customary for the site 12 days after transplanting (12 DAT) with 1.0 kg Active ingredient / ha carried out. Three further applications followed at intervals of 15 days each, so that a total of one amount of active ingredient of 4.0 kg / ha was applied.

Controls were performed at 15, 19, 27, 30, 45, 71, 75, 79 and 86 DAT (days after grafting). The results are summarized in Table 3 (Experiment 3) and in Table 4 (Experiment 4).

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TABEL

kg effective DAT % DAT Mortality (WG DAT DAT 1
Abbott) DAT ) DAT DAT middle mor 47
70 Attempt 3 fabric / ha 15th 19th DAT 30th 45 DAT 75 79 86 tality 4x1.0
2.0 95
68 24
91
27 36
59 92
89 71 75
67 0
50 58
46 * Comparison means
(BPMC granulate)
Trial formulation
according to example 1 0
77 47
87

% Mortality of Nilaparvata lugens larvae

TABEL

kg effective
fabric / ha % Mortality (WG Abbott) ²⁾ DAT
15th DAT
19th DAT
27 DAT
30th DAT
45 DAT
71 DAT
75 DAT
79 DAT
86 middle
mortality
% Attempt 4 4 χ 1, 0
2.0 16
54 0
0 17th
23 0
28 53
27 20th
60 100
100 100
80 - 38
NJ
-0
47 ςο Comparison means
(BPMC granulate)
Trial formulation
according to example 2

2)

% Mortality of Nilaparvata lugens adults

cn

Claims (4)

Patent claims: 1. Process for the production of biologically active pellets or Granules, characterized in that a mixture of carrier and biologically active material is di- or Polyisocyanates or their prepolymers and Η-active compounds from the group of water and / or organic di- or poly- (hydroxy- and / or amino) compounds or mixtures thereof capable of polycondensation are mixed in, this mixture is granulated or pelletized and the granules or pellets obtained at temperatures of 10 ° to 00 ° C, preferably at 20 to 50 C, especially at room temperature, can be hardened. 2. Biologically active granules or pellets, manufactured according to Claim 1. 3. Use of the granules or pellets according to claims 1 and 2 for pest control, especially in rice cultivation. 4. Use of the granules or pellets according to claim 1 and 2 for fertilization. 909813/0563