DE2743485B2 - Process for the production of biologically effective granulates - Google Patents

Description

Granules containing pesticidal agents are known different sizes using natural mineral carriers or carriers of vegetable origin. Also high polymer Natural substances or compounds based on plastic were used for this purpose

About the technology of producing granules from mineral carriers and their properties reports James A. Polon in Pesticide Formulations, edited by Wade Van Valkenburg, Marcel Dekker Inc, New York, 1973, pp. 186-205. By using high-polymer plastics instead of natural ones porous supports, attempts have been made to delay the release of the active substances. It was too tries to use pesticides on the above-mentioned natural carriers of mineral or vegetable origin To adsorb means and the products obtained subsequently with more or less strong to envelop water-soluble substances.

The purpose of these granules is to absorb pesticidal agents, to deposit and after application more or less slowly to the environment. This is how the active ingredients are meant to be too can act on animal or vegetable pests for a longer period of time. The levy the active ingredient can be done in different ways. Is the active ingredient z. B. sufficiently volatile and only slightly bound to the carrier material, so he can can be released by direct diffusion processes. If, on the other hand, the active ingredient is not very volatile and is that Carrier material sufficiently hydrophilic, so can, for. B. acting moisture wet the carrier material, penetrate into this and release the active substance.

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

In DE-OS 22 38 912 is reported on by water-degradable polymer compositions in their polymer chain molecules have urea-like structures and are in liquid or solid form can. The liquid polymer masses can be converted into hard, brittle solids by heat treatment be transferred. These changes are on Molecular enlargements or due to crosslinking reactions. The bioologically active compound can either be incorporated into the polymer itself or encapsulated by the polymer. Because of the thermal treatment required for this at elevated temperatures, the process remains exclusive limited to those active ingredients that do not cause irreversible reactions under the conditions mentioned enter with the ureas or possible additives.

In GB-PS 9 03 159 the production of pellets or smaller granules from a natural or synthetic wax, additives and a volatile insecticide (DDVP). The insecti Zid is slowly released and gets there after application gaseous in the environment of the insect pests.

In NL-PS 69 09123, 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 ⁰ C described. An insecticide is added to the melted wax in the autoclave at temperatures above the melting point and, after solidification, a formulation which slowly releases the insecticide is added from it obtain.

DE-OS 24 52 217 describes the incorporation of organophosphorus insecticides in matrices based on terpene-phenol resin. The resins with a softening point of at least 100 ^° C. are obtained by reacting various terpenes such as dipentene, / J-pinene, limonene and various turpentine fractions with phenols in the presence of a condensation catalyst. The incorporated insecticide will be like this against damaging external influences, such as B. Moist activity, protected and depending on the size of the active Surface and other conditions slowly released into the environment.

About the use of polyvinyl chloride, polyamide, polyurethane and other plastics in pesticides

For formulations see N. Cardarelli, Controlled Release Pesticides Formulations, CRC Press Ine, 1976, p. 139 and ff.

G.B. Aquino and M.D. Pathak, J. Econ. Entom. 69.5, p. 686 (1976) describe experiments with insecticides im Rice cultivation. Insecticides are used in gelatine capsules and as simple granules in the root areas applied by rice plants in order to delay the release of the active substance to the plants. in the Rice growing plays a very special role in this method Role, since the rice plants have to be continuously supplied with insecticides during the growing season, which is done in a conventional manner by repeated spraying at about half a day intervals The present invention is a Process for the production of biologically active soil granules or pellets from a mixture of Carrier and biologically active soil material, characterized in that diisocyanates or polyisocyanates or their prepolymers and hydrogen-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 resulting Granules or pellets can harden at temperatures of 10 to 60 ⁰ C, preferably at 20 to 50 ⁰ C, in particular at room temperature

As carrier materials, all are in themselves for the production

3 4

from Graiv.üaten customary and suitable materials phenylene diisocyanates,

usable as prefabricated and crushed solid, diphenyl diisocyanates,

fully synthetic or partially synthetic organic high xylylene-M-diisocyanate,

polymeric, mineral, vegetable or toluene- ^ e-triisocyanate carriers,

of animal origin and inorganic carriers. 5 xylylene-l ^ -diisothiocyanate,

To maintain the soil quality, carriers are cyclohexylene-l ^ -and-M-diisocyanate,

of mineral or vegetable origin preferred, ^ '^ "- triphenylmethane triisocyanate,

especially those that are natural or slightly polymethylene polyphenyl isocyanate

rot. technical (PAPI).

The mineral or inorganic carrier substances are ι ο

for example all types of silica, diatoms - the NCO prepolymers are particularly suitable

earth, kieselguhr, silicates and silicate-containing substances the above isocyanates with z. B. Di- or

such as clay, mica, pumice stone, lime, magnesium polyols with an average molecular weight of 500 to

carbonates, clays, poorly soluble phosphates such as Tho- 10000. For the production of such prepolymers

flour or all kinds of charcoal can be used. 15 are also suitable, for example, di- or polyols with 3-6

As fully synthetic or partially synthetic organic hydroxyl groups per molecule or equivalent High polymers can, for example, urea resins, hydroxyl-containing polyesters, polyethers, polyester

such as urea-formaldehyde resins, cellulose derivatives, amides, polycarbonates and / or polyacetals,

such as B. cellulose ethers, polyvinyl alcohol or modified NCO-Prlpolpolymer are reaction products of

adorned polyvinyl alcohols, such as. B. partially saponified polyvi- 20 di- or polyisocyanates with di- or polyols or

nylacetate or propionate can be used. other compounds containing several OH groups

As carriers of plant origin are suitable before fertilizing. The di- or polyisocyanates are with

all vegetable materials such as sawdust, shredded a stoichiometric excess is used so that

tes cereal straw, especially maize and rice straw, the resulting reaction products are still sufficient

Peat, corncob semolina. Contain 25 free NCO groups (= isocyanate groups), The use of mineral carriers or which can react like polyisocyanates. Carriers of vegetable origin has the advantage that the production of isocyanate prepolymers is z. B.

these carriers disintegrate after use or are described in R. Vieweg, A. Höchtlen, Kunststoff-

rot and so do not pollute the environment, manual, Volume VII, Polyurethane, Carl Hanser Verlag,

while z. B. some thermoplastic or duroplasti- 30 Munich 1966, p. 45 and ff.

see plastics as non-biodegradable polycondensation components for those mentioned

Foreign matter remains in the earth. This fact isocyanates or their prepolymers is primarily considered

is particularly important when z. B. to mention from Η-active compound water, in particular

For technical reasons, the quantitative ratio of carrier to the water or water contained in the carrier.

material 2 </ active ingredient must be very large. 35 Moisture Further components are e.g.

The following can be mentioned as biologically effective soil material: polyvalent alcohols, polyvalent amines

soil active compounds, such as. B. systemic or alkanolamines. As a counterpart to the

Insecticides, herbicides, fungicides, nematicides or NCO prepolymers are also high molecular weight polyols Algicides as well as growth regulators or or polyamines, such as (poly-) - hydroxy-poly- Fertilizers and mixtures of the organic ethers, polyesters and polyamides mentioned.

Use soil-active substances. Examples of polyhydric alcohols are ethylene glycol

can be used as such or dissolved in organic solutions of col, propylene glycol (1,2) and - (13), butylene glycol iso-

agents, optionally with the addition of emulsifiers, mers, hexanediol, octanediol, 2-methyl-l, 3-propanediol,

Wetting agents, hydrophobizing substances or an- glycerine, butanetriol, trimethylolpropane, hexanetriol,

whose ingre- 45 pentaerythritol, mannitol, sorbitol, polyethylene glycols, poly-

used. Bioilids and growth propylene glycols, polybutylene glycols.

gulators which are not liquid above 0 ° C and which give examples of hydroxypolyesters that can be used in water

Are poorly soluble, are preferred in organic resulting from the reaction of polycarboxylic acids with

Solution used they are preferred - in polyhydric alcohols. As polycarboxylic acids for Analogous to the spray powder technology - in already adsor- 50 production of such hydroxypolyesters are suitable

bated form, especially on highly active adsorbents, etc. z. B. malonic acid, succinic acid, glutaric acid,

tion material, in the mixtures according to the invention adipic acid, pimelic acid, maleic acid, phthalic acid,

given. Isophthalic acid and hexahydrophthalic anhydride. as

As di- or polyisocyanates, which deal with the polyhydric alcohols for the reaction with the here

Η-active compounds to one of the pellets or ss mentioned polycarboxylic acids can, for. B. the above

Polyadding granules solidifying binders, polyhydric alcohols listed as examples

For example, aliphatic, aromatic, and NEN are suitable.

heterocyclic, cycloaliphatic and araliphatic examples of polyester amides result from α a. from the

Di- or polyisocyanates, such as, for example, reaction o. G. polyvalent, saturated and unsaturated

60 saturated carboxylic acids and their anhydrides with multiple

Ethylene diisocyanate, saturated or unsaturated amino alcohol

1,4-tetramethylene diisocyanate, oils, diamines and polyamines.

Hexamethylene diisocyanate, examples of polycarbonates result, for. B. from the

1,12-dodecane diisocyanate, reaction of simple diols with diaryl carbonates

2,4- and 2,6-toluylene diisocyanate, 65 or phosgene.

Diphenylmethane-2,4'-and 4,4'-diisocyanate, examples of polyacetals result, for example, from Naphthylene-14-diisocyanate, known reaction of diols or polyols with

chlorinated aryl polyisocyanates, e.g. B. formaldehyde.

Examples of amines as polyaddition components also include the following di- and Called polyamines:

Ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine,
Hexamethylenediamine, diethylenediamine,
Triethylene tetramine, tetraethylene pentamic,
m-phenylenediamine, p-phenylenediamine,
Pjperazine, methylpiperazine, diethanolamine, diisopropanolaniin,
Triethanolamia

The isocyanates and Η-active compounds mentioned react, depending on the choice of components, to form polyurethanes, polyureas or polyurethane-ureas and thus form the binder in situ that connects or holds together and / or encloses the individual particles of the carrier material and the active ingredients can be increased in a manner known per se by adding small amounts of basic amines, alkytin compounds, alkali hydroxides, phenolates and / or alcoholates as catalysts. The proportions of the polymerization components are chosen in a manner known per se, preferably such that there is about one OH or NH ₂ group for each isocyanate group

The mentioned constituents of the mixtures according to the invention are mixed well, if necessary advantageously under Use of up to equal parts by weight of organic solvents, based on the isocyanate component, and on the known devices provided for granulation, pelleting or compaction or machines are further processed

The granules or pellets obtained are then stored for a certain time, for example a few hours up 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 hardening generally takes 1-5 days.

The composition of the granules or pellets obtained can vary within wide limits. Of the The content of bioids 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 one Solvent including necessary emulsifiers. In the case of highly effective compounds, the Reduce proportion to 0.5 to 2% by weight of active ingredient. The proportion of solid fertilizers, such as. B. organic Fertilizers, urea or mineral fertilizers can, for example, be up to 50% by weight and the Partially replace the carrier material.

The proportion of the binder mixture, consisting of dioder Polyisocyanate or isocyanate prepolymers and Η-active compounds are generally 1 to 30 % By weight, preferably 5 to 20% by weight, in particular 6 up to 12% by weight. If necessary, it is dissolved or suspended in up to equal parts by weight of an organic solvent Used as organic solvents are z. B. such inert solvents as they are in the isocyanate chemistry usually find use. The carrier substance (s) are included in the formulation ranges generally between about 30 and 70% by weight, based on the finished granulate

With the method according to the invention, both hydrophobic and hydrophilic substances can be used in Bring granules or pellets of the desired size in such a way that they only get into the ground after a long time migrate and get to the roots of the plants. Pesticides that have only limited stability in water can also initially be used in Microcapsules are enclosed and then processed into pellets or granules. as Wall materials for such microcapsules are preferred to recommend products that allow a slow release of the active ingredient or that are slowly dissolved by water or soil moisture and thus release the active ingredient.

The method of the present invention provides, inter alia. the following advantages:

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

2. The manufactured according to the procedure outlined Pellets or granules show a depot effect, so that treatment is repeated several times after conventional methods superfluous during the season

3. The plant is continuously supplied with the necessary active ingredient for a certain period of time provided

4. The active ingredients are used practically in full. A possible additional burden on the Environment caused by excess active ingredients is avoided.

5. By using the above natural mineral and / or vegetable carriers, only very small amounts of foreign matter enter the soil which can practically be neglected.

6. By using the above Binders arise from the fine-grained and soft mineral ones or vegetable carriers and the active ingredients non-sticking, abrasion-resistant pellets with high mechanical strength, which z. B. Do not segregate storage and application during transport.

7. By including the moisture naturally contained in the formulation components Completely dry granulates and pellets can be used in the hardening (polycondensation) process getting produced.

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 as well as whose proportions are possible. The decisive factors for the selection of the individual substances are desired properties of the granules or pellets to be produced therefrom.

Manufacturing 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 ST150 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-methyIcarbamat and 6 g of a mixture of saturated hydrocarbons of boiling range 255 to 38O ⁰ C (Essobayol 90) 0.5 g of

Emulsifier castor oil oxyethylate with 40 AeO units and 9.5 g of diatomaceous earth 12/0 added, mixed and after Addition of 10 g of a tolylene diisocyanate prepolymer (made from toluylene diisocyanate, trimethylolpropane, butanediol and polypyropylene glycol in a molar ratio 8: 3: 1: 1) in 12 g xylene / ethyl glycol acetate (1: 3) mixed again.

From this mixture tablets with a pressure of 5000 kg per punch are produced on a rotary tablet press with a weight of approx. 2 g and a diameter of 20 mm. The maximum compressive strength of the tablets was reached after 2-3 days of storage at room temperature and was > i5kp / 'cm ² . On storage of the tablets in a corresponding manner at about 50 ⁰ C, the same compressive strength can be attained already after 10-12 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 1, Ig of the emulsifier castor oil oxethylate with 40 AeO units , 10 g of diatomaceous earth, 11 g of technical polyethylene polyphenyl isocyanate (PAPI®) in 12 g of xylene / ethyl glycol acetate (1: 3) are produced analogously to the method according to Example 1, pellets with a weight of approx. 2 g and a diameter of 10 mm of the pellets after 2 days of storage at room temperature is> 15 kp / cm ² . If the pellets are stored in a corresponding manner at about 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, calcium iodecylbenzenesulfonic acid, 10 g of diatomaceous earth, 10 g of a prepolymer of toluene diisocyanate and hexane triol and 8 g of methylnaphthalene are produced analogously to the process from Example 1 in an eccentric press with a pressure of 5000 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 calzhim, 10 g of diphenylmethane-4,4'-diisocyanate in 15 g of xylene / ethyl glycol acetate (1: 3) are given according to the example 3 Procedure in an eccentric press tablets with a diameter of 20 mm and a weight of

2 g produced. The maximum compressive strength of the tablets after about 1 day of storage at room temperature was> 15 kg / cm ² .

Example 5

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

ίο was> 15 kp / cm ² .

Example 6

From the following ingredients: 30 g dry sawdust, 15 g pumice stone 40 g NPK mineral fertilizer 12-12-18.4 g hexamethylenediamine, 2 g 2-sec-butylphenyl-N-methylcarbamate, 6 g xylene techn, 0.5 g i- Calcium dodecylbenzenesulfonate and 10 g of diatomaceous earth as well as 10 g of the prepolymer mentioned in Example 1 in 12 g of xylene / ethyl glycol acetate (1: 3) are made analogous to the method from Example 1 on a rotary tablet press with a pressure of 5000 kg per punch tablets with a weight of 2 g and a diameter of 20 mm. The maximum compressive strength of the tablets was reached after 1 day of storage at room temperature and was> 15 kp / cm ² .

Biological examples

Example I.
Greenhouse trials

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

Attempt 1

Rice plants 6 weeks old were together with 1 pellet each, produced according to Example 1, corresponding to 25 mg 2-sec-butylphenyl-N-methylcarbamate as active ingredient, in Test pots planted The stocking 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 each 1 day after Occupying carried out test plants and test animals were during the test period at one Maintained room temperature of + 25 ° C and a relative humidity of about 60%. The result is summarized in Table 1.

Table 1

Stocking by days Check after days % Mortality
taf) 3 4th 8th 7th 8th 33 10 11th 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.

Attempt 2

In further tests, pellets, prepared according to Example 2, with 25 mg Triazophos active ingredient / pellet were included the o. Conditions of experiment 1 checked. The result is summarized in Table 2.

Table 2 Check after days % Mortali
kind *) Stocking by days 4th 27 3 8th 48 7th 11th 60 10 15th 97 14th 18th 68 17th 22nd 85 21 25th 88 24 29 98 28 32 95 31 36 72 35 39 68 38 43 87 42 46 70 45

*) Average of 3 repetitions.

10

Example II
Field trials

On the basis of the test results worked out in the greenhouse according to Example I, the Field experiments 3 and 4 against rice leafhoppers (Nilaparvata lugens) carried out. The pellets were called Single application three days after transplanting (3 DAT) the young rice plants approx. 5 cm deep into the

ίο Introduced the root zone of the plants. The application rate / ha was 2.0 kg of active ingredient at 160,000 planting sites ("hüls") per hectare. This corresponds to otherwise the same Ratios in the experiments 3 and 4 listed below an amount of active ingredient of 12.5 mg per each Pellet, produced according to example 1 and 2.

A 4% commercial BPMC granulate (Hopcin 4 g), active ingredient = 2-seo-butylphenyl-N-methyl-carbamate, 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 an 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).

Table 3

Attempt 3

kg

Active ingredient / ha DAT 15

Mortality ") (WG Abbott)

DAT DAT 19 27

DAT
30th

DAT DAT
45 71

DAT DAT
75 79

DAT
86

Medium mortality

Comparison mean 4 χ 1.0 95 24 0 36 92 47 75 0 58 47

(BPMC granulate)

Trial formulation 2.0 68 91 77 59 89 87 67 50 46 70

according to example 1

')% Mortality of Nilaparvaia lugens larvae. Table 4

Attempt 4 kg % Mortality ¹ ) (WG Abbott) DAT DAT DAT DAT DAT DAT Middle h Really 30th 45 71 75 79 86 Mortality "i fabric / ha DAT DAT DAT 0 53 20th 100 100 f. 15 19 27 / 0 Ji Comparison means 4x1.0 16 0 17th 28 27 60 100 80 - 38 ί ^; (BPMC granulate) I. Trial formulation 2.0 54 0 23 47 I. according to example 2

¹ J Vo mortality Nilaparvata lugens adults.

Claims (2)

Patent claims: 1. Process for the production of biologically active soil granules or pellets from a Mixture of carrier and biological soil-swirling material, characterized in that the mixture is di- or polyisocyanate or their prepolymers and hydrogen-active Compounds from the group of water and / or organic di- or polyhydroxy and / or amino) compounds or mixtures thereof capable of polycondensation, this mixture granulated or pelletized and the resulting granules or pellets at temperatures of 10 to Allow to harden at 60 ° C 2. Use of the prepared according to claim 1, biologically effective granules or pellets for pest control.