HU187317B - Granulated pesticide compositions - Google Patents

Abstract

PROCEDURE FOR OBTAINING A GRANULAR PESTICIDE FORMULATION CONTAINING A METILCARBAMATE DERIVATIVE. IT CONSISTS IN THE FORMATION OF A POLYMER FILM INSOLUBLE IN WATER BY REACTION, IN AN ORGANIC SOLVENT AND IN THE PRESENCE OF PYRIDINE, OF EQUAL PARTS OF A PHENOLIC RESIN OF BENZYL ETHER AND A LIQUID AROMATIC POLYISOCIANATE; DISPERSION OF 1.0 TO 1.8 PARTS OF THIS COMBINATION IN 81 TO 96 PARTS OF UREA GRANULES; MIXTURE OF GRANULES COATED WITH 0.2 TO 11 PER 100 N-METHYLCARBAMATE OF 2,3-DIHYDRO-2,2-DIMETHYLENZOFURAN-7-ILO, BEFORE THE POLYMERIZATION IS COMBATED, AND RECOVERY OF PESTICIDE GRANULES NO AGLOMERANTES. THIS COMPOSITION HAS APPLICATIONS IN AGRICULTURE TO COMBAT PLANT PESTS.

Description

The present invention relates to an improved process for the preparation of particulate insecticidal and nematocidal compositions.

The present invention relates to the preparation of particulate insecticidal and nematocidal compositions comprising the active ingredient in combination with plant nutrients.

Granular formulations are generally prepared by applying the active ingredient, usually as a solvent or liquid dispersion, or to a particulate absorbent carrier, such as attapulgite or kaolin chalk, chopped corn cob, expanded mica. Surface-coated granules can be prepared by spraying the molten active substance on the surface of a generally non-absorbing particle. Such particles are sand, broken marble or coarse talc. However, it is also possible to form coated granules by spraying a solution of the active ingredient in a solvent or by concentrating the active ingredient, for example a wettable powder or an emulsifiable concentrate, which adheres to the granular core and forms a surface coating. The active ingredient may also be powdered in the case of non-absorbent granules, in which case well-adherent adhesives are used to facilitate adherence of the active ingredient to the granules.

Coatings have already been applied to fertilizer granules to control the release of water-soluble plant nutrients, thus avoiding unwanted effects due to nutrients being introduced too quickly into the soil. Sulfur coatings and thermal film-forming polymeric coatings have also been used as coatings for fertilizer granules for this purpose. In addition, the coatings prevent the hygroscopic fertilizers from absorbing atmospheric moisture and producing nutritional losses that are volatile upon hydrolysis, such as the release of ammonia from urea.

U.S. Patent No. 3,264,089 discloses a urea fertilizer formulation having a urethane resin coating on the surface of the granules, thereby delaying the dissolution of the active ingredient. However, the presence of a pesticide is not mentioned.

U.S. Pat. Nos. 3,264,088 and 3,223,518 have an organic polymer coating on the surface of the water-soluble fertilizer particles which retards the dissolution of the active ingredient. British Patent No. 954,555 discloses another type of fertilizer coating.

U.S. Patent No. T 912,017 discloses a urea fertilizer in which a sulfur coating inhibits the rapid absorption of urea into the soil.

U.S. Patent No. 589,926 discloses granular pesticidal compositions wherein the active ingredient is adhered to a suitable seed, such as a fertilizer seed, with a water-sensitive adhesive.

The coating of the mineral parts of an "agricultural agent" such as fertilizer and / or pesticide according to Chinese Patent N1-9685 contains a water-insoluble adhesive.

The present invention relates to a powder-free, slightly hygroscopic, non-agglomerating, insecticidal and nematicidal granulate comprising a urea core coated with a film-forming polymeric material in which an active pesticidal agent is dispersed and adheres to the active pesticidal agent. When the product is applied to the soil just before the crop emerges, they are also provided with plant nutrients and pesticides.

Thus, by using the composition of the present invention, in contrast to the prior art, a controlled delay in the release of plant food and a pesticidal effect can be achieved at the same time, resulting in time, labor and energy savings.

The urea seed granules of the present invention are less hygroscopic than uncoated urea fertilizer particles and the loss of ammoniacal nitrogen due to the absorption of atmospheric moisture.

In particular, urea granules having a diameter of 0.8 to 2.0 mm and having a weight of 1 g are suitable.

The pesticidal agent is 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate (carbofuran).

The carbofuran active ingredient can be used as a technical product, or preferably as a "powder-free base containing 75% or more active ingredients, of which 79.5% is technical carbofuran (95% active ingredient) and 20.5% is inert (chalk and surfactant). . Of course, carbofuran can also be used as a finely divided solid base formulation containing 80%, 85%, 90% or more of the active ingredient in a granular pesticide.

The composition according to the invention contains from 0.2 to 11% by weight of the active ingredient carbofuran. The amount of active ingredient in the formulations may be varied so that the level of the active ingredient for controlling the pests and the nutrient levels that help the plants to develop are properly formed in the soil. Applying a composition of the present invention to the soil that contains the most effective amount of active ingredient and plant nutrients saves time, labor, and energy, and is much more beneficial than applying them individually, which is also evident in increasing yields.

In the compositions of the present invention, the film-forming polymeric materials are cross-linked thermosetting polymers formed by the reaction of a phenylaldehyde-type polymer having a reactive hydroxyl group with a polyisocyanate. Benzyl ether phenol resins are particularly preferred. The crosslinking polymerization is catalyzed by amines such as triethylamine or pyridine. Pyridine is the preferred amine.

Benzyl ether phenol resins are described in U.S. Patent 3,485,797. They are prepared by reacting phenol and a molar excess of paraformaldehyde in a solvent to

187,317 in toluene under substantially anhydrous conditions at temperatures below 130 ° C in the presence of a catalytic amount of divalent metal salts such as zinc naphthenate dissolved in the reaction medium. These phenol-formaldehyde resins are of formula I wherein m + n is at least 2 and m / n is at least 1, while X is hydrogen or methylol, wherein the methylene / hydrogen ratio is at least 1 mole.

The polyisocyanate is a liquid aromatic polyisocyanate containing at least two isocyanate groups, such as diphenylmethane diisocyanate or a mixture of di- and triphenylmethane di- and triisocyanates.

Suitable granules may be prepared when the final product contains from 1.0 to 1.8% by weight, preferably from 1.2 to 1.8% by weight, of film-forming polymer.

The compositions of the present invention are further illustrated by the following exemplary embodiments.

Example 1

This example illustrates the preparation of a granular pesticidal composition prepared by coating a urea core.

255.6 g of urea fertilizer particles (2.38-0.84 mesh), 1.8 g of benzyl ether phenol resin in 5.7 g of methylene chloride and 0.009 g of pyridine catalyst are introduced into a 2.5 liter vessel. Stopper the vessel and shake for 30 seconds. thereafter

A solution of 1.8 g of aromatic polyisocyanate (diphenylmethane diisocyanate or di- and triphenylmethane di- and triisocyanate) in 5.7 g of methylene chloride is introduced and the whole is shaken for 30 seconds. Thereafter, 4.8 g (75% by weight of powder-free base) of carbofuran, which provides 1.2% by weight of active ingredient in the final product, and 24.6 g of kaolin nitrate are premixed and added to the vessel and shaken together for 60 seconds. The vessel was then allowed to stand for curing and the next day the product was passed through a 0.84 mm mesh sieve to obtain small portions of fine material. 285 g of uniformly coated granules are thus obtained. This is Formulation A in Table 1. Subsequently, 5 g is placed in a glass container (4.5 cm x 10 cm) which is closed and shaken for 30 seconds. During this time, the surface of the granules did not break and no dusting was observed. The compaction test of the pellets was performed by pressing a column of material 4.5 cm x 7 cm at a force of 0.8 kg / cm ^{2 for} 5 minutes. The granules do not disintegrate and remain free flowing, no agglomeration is observed.

Example 2

The procedure described in the previous example is carried out and 245 g of urea fertilizer particles (2.38-0.84 mesh) are coated using the amounts of phenolic resin and polyisocyanate in Example 1, as well as a catalyst and a solvent in methylene chloride. Thereafter, 40.0 g of carbofuran (75% dust-free base), which provides 10% by weight of active ingredient in the final product, is placed in the vessel and shaken together for 60 seconds. The vessel was allowed to stand overnight and then passed through a 0.84 mesh sieve to remove traces of fine material. The amount of pellets is 285 g and the carbofuran content is 10.8%, which is the content of preparation B in Table 1. The product is shaken in a sealed glass jar for 30 seconds, after which time the product B has no particle surface fracturing and no dust formation. In the same manner as in Example 1, a compression test was performed, the particles remaining free flowing.

Examples 9

Further formulations are shown in Table 1 below. Formulations C and D (Examples 3 and 4) were prepared in the same manner as Formulations A and B except that a thinner catalyst solution was used and each resin component was shaken for 30 seconds with urea particles for 30 seconds. Dust and compaction results are excellent. In resin component E (Example 5), each resin component was mixed for 60 seconds.

Preparation F (Example 6) was prepared by mixing both resin components and the catalyst in methylene chloride four times before shaking with the urea particles. The active ingredient (carbofuran) is not uniformly distributed in the particles, the particles are severely damaged and dust formation can be observed when shaking a 5 g dose in a glass jar for 30 seconds. The same defective coating and powder formation is also observed for C and H formulations. (Examples 7 and 8) using 75% dust-free carbofuran and mixing both resin components (at a level of 0.60%) and the catalyst in methylene chloride prior to application to the urea particles. A suitable product is obtained containing 10.8% of the active ingredient and corresponding to Preparation I (Example 9) if the level of the resin components is increased to 0.90% and mixed with a catalyst in methylene chloride before application to the granules.

Example 10

This example illustrates the preparation of a granular pest control composition wherein the urea seeds are approximately 1.25 cm in diameter and approximately 1 g in weight.

Introduce into a 2.5 liter vessel 196.29 g of granular urea, a mixture of 1.00 g of phenolic resin and 1.00 g of polyisocyanate (using diphenylmethane diisocyanate or a mixture of di- and triphenylmethane di- and triisocyanate as the polyisocyanate). and 0.01 g of pyridine catalyst in solution. The vessel is shaken for 6 seconds and 1.70 g (75% dust free base) of carbofuran are added and the vessel is shaken until the resin is deposited (about 2 minutes). In this way, uniformly

187,317 coated spheres were obtained in an amount of 199.5 g containing 0.67% carbofuran.

In the same way, 196.29 g of granular urea, 1.00 g of phenolic resin, 1.00 g of polyisocionate, 0.01 g of pyridine catalyst solution, 0.42 g of carbofuran (75% dust free base) and 0.42 of kaolin chalk using a uniformly coated product, yields 198.6 g containing 0.23% carbofuran.

Example 11

This example illustrates the preparation of a larger amount of the granular composition of the invention.

22.3 kg of urea fertilizer granules are transferred to a portable cement mixer. In a separate container, 0.15 kg of phenolic resin and 0.15 kg of polyisocyanate are mixed (diphenylmethane diisocyanate or a mixture of di- and triphenylmethane di- and triisocyanate is used as the polyisocionate), and 0.95 kg of methylene chloride and 9 g are added. pyridine catalyst solution. This mixture is added to the urea particles in the cement mixer and the whole is stirred for 30 seconds. Then 0.70 kg of carbofuran (75% dust-free base) and 0.70 kg of kaolin chalk are added to the mixture, followed by stirring for about 10 minutes while the resin hardens. The uniformly coated particles are free flowing and contain 2.34% carbofuran. This preparation corresponds to the preparation R in Table 2. Formulations S and W were similarly prepared with less carbofuran content. Compositions Y and Z are prepared from 1 g (1.25 cm diameter) urea particles in a cement mixer.

Example 12

This example illustrates the use of the composition of the invention for the ripening of fruits of banana plants.

2.2 urea granules containing 2.2% by weight of carbofuran (formulation R in Table 2) are sprayed onto the soil within a radius of 50 cm around the banana-producing plants. We call such a plant "mat". A formulation of 2.0, 2.5 and 3.0 g of active ingredient per plant is used and 20 mats are used for each level of active ingredient. For comparison, a commercially available carbofuran granulate formulation having a carbon content of 5% by weight on a sand core (5G) is used. In each case 20 to 20 mats are used and 60 mats are left untreated. The roots of the treated and untreated plants are sampled before infection with the root borer nematode (Radopholus similia) and at the end of the first, second, third, fourth, fifth and sixth months after infection. A significant reduction in nematode proliferation is observed after analysis of the samples resulting from treatment with carbofuran. These results are summarized in Table 3. The numbers in the table (thousands of nematodes / 100 g of root) are lower, the fewer the number of worms present and the greater the reduction in the number of nametodes on the treated roots compared to the number of untreated roots.

Untreated plants and plants treated with 5G commercial carbofuran obtained ripe bananas at the fifth, sixth and seventh months, while plants treated with urea granules containing 2.2% carbofuran active ingredient according to the invention can be harvested at the fifth month. In banana cultivation, the whole bunch of bananas is a "cluster" and the largest subunit of the cluster is the "gavel", consisting of the "fingers" which are the individual bananas. Treatment with urea-carbofuran particles increases the number of gums per cluster and increases the weight of the clusters. Yields of plants treated with 5G commercial carbofuran are also increasing, but not as high as those of plants treated with urea-carbofuran particles. Table 4 shows the average of three replicate experiments for treated and untreated mats. Treatment with urea-carbonfuran particles resulted in an average increase of 13.8%, 4.4%, and 17.1% of gauze per cluster at the three active substance levels (2.0, 2.5 and 3.0 g of active ingredient / mate), while the average increases were 31.3%, 17.9% and 31.7%, respectively, in kg / cluster. Treatment with 5G Commercial Carbofuran showed an average increase of 3.1%, 2.2% and 10.0% in gauze / cluster and an average of 11.1%, 15.0% and 22 kg / cluster growth, respectively. , Was 0%.

EXAMPLE 13 Urea granules of the present invention containing by weight and 2% by weight of carbofuran are used to treat freshly transplanted rice seedlings (IR 22 variety) in an amount of 0.5 kg to 1.0 kg active ingredient / ha. For comparison, a 3%% carbofuran composition applied to a sand core was also used to treat 0.5 g and 1.0 kg active ingredient / ha of freshly transplanted rice seedlings in parallel plots. Some of them received urea fertilizer treatment, while others did not receive urea fertilizer treatment. Damage caused by rice pests is done at various intervals after treatment. Leaf damage is most favorable when treated with a composition containing 0.5 kg / ha of carbofuran-urea granules, whereas at 1.0 kg / ha after 30 days, treatment with carbofuran-urea particles is essentially the same as the results of the two comparative treatments. Infection with Lepidoptera strain borer beetles in its early stages of development was minimal, as evidenced by the low percentage of dead heart phenomenon in all cases, including untreated controls. A higher percentage of the "white head" phenomenon indicates that infection with the core borer beetle started later in the growth phase, but that carbofuran carb

187,317 of the mid-grain formulation and the carbofuran-sand formulation together with urea reduce the infection. The results are summarized in Table 5, which is the average of twenty stacks / treatment. The slightly higher yield of rice is the result of treatment with the composition of the invention. The composition contains carbofuran deposited on the urea core in granular form.

Table 1

Granular carbofuran preparation with urea core

creators Preparations (weight ,,) THE B C D r: carbofuran (75% dust free base, i, 60 13.33 1.50 3.00 1.66 Urea- granules 85.19 81.66 85.20 85.20 91.38 Kaolin 8.20 8.30 6.80 1.66 Phenol resin 0.60 0.60 0.60 0.60 0.61 Polyisocyanate 0.60 0.60 0.60 0.60 0.61 Catalyst 0.01 0.01 0,003 0,003 0.01 Methylene chloride 3.80 3.80 3.80 3.80 4.07 Carbofuran (s / s, theoretical 1.20 10.0 1.1 2.3 1.25 found 10.8 1.57 Dust free is excellent excellent excellent excellent compression strength is excellent excellent excellent excellent creators Preparations (weight F G H / carbofuran (75 _o dust free base) 10.47 * 1 3.23 13.23 13.23 Urea- particles 84.52 81.76 91.76 81.16 Kaolin Fenolgyanla 0.60 0.60 0.60 0.90 polyisocyanate 0.60 0.60 0.60 0.90 Catalyst 0:01 0.01 0.01 0:01 Methylenechloride 3.80 3.80 3.80 3.80 Carbofuran (s s) theoretical 10.0 10.0 10.0 10.0 found 10.8 dust free weak weak weak good Compression strength weak weak

* technical carbofuran (96, _> )

Table 2

Carbofuran-coated urea preparations prepared in pilot plant

creators R make 5 things (weight ,,) 0 ' 1 z carbofuran (75 "dust free 2.82 1.91 1.95 0.42 0.84 base) Urea- particles 89.36 89.95 91.59 96.21 * 96.21 * Kaolin 2.82 1.91 1.95 0.42 f-cnol resin 0.60 0:59 0.60 0.49 0.49 polyisocyanate 0.60 0.59 0.60 0.49 0:49 Catalyst 0003 0.01 0.01 0:01 0.01 Methylene chloride 3.80 5.04 3.30 1.96 1.96 Mixing time (minutes) 0.5 I resin carbofuran 8 10 8 10

Resume table

creators Preparations (% by weight) R S W r Z Carbofuran% (s / s) e mclcti 2.2 1.5 1.5 0.3 0.6 found 2:34 1.77 1.87 0.35 0.69 Porinenlesség compression strength good excellent Good excellent good

* One gram of urea particles 11.25 cm in diameter,

Table 3

Eradication of Radopholus similis nematodes Thousand nematodes / 100 g of root)

... K ez- Honap, 'lelle Applied heaven active substance g / mat Commercial 5G 2.2 ", urea Matthew 2.0 2.5 3.0 2.0 2.5 3.0 0 57.9 42.5 77.5 49.2 -

(application)

1 43.3 52.3 10.5 22.0 23.0 45.3 68.3 (application) T 52.0 18.2 10.3 14.8 22.3 22.5 18.5 3 42.4 18.3 33.5 29.0 8.3 11.7 32.2 4 40.8 41.3 32.7 37.3 4.7 7.2 7.8 5 45.1 17.3 20.7 19.2 9.5 18.7 13.2 6 53.2 40.3 32.0 36.2 25.5 16.2 28.0 average 46.1 31.3 23.3 26.4 - - -

(second application)

7 50.9 21.7 23.0 26.C 21.8 60.3 24.7 average 15.4 22.8 20.7

Table 4

Banana Yield Comparison A. 2.2% urea grain tg carbofuran / mat)

treatment untreated Handled Füriszám 2.0 2.5 3.0 She was removed at 5 months 10 13 11 6 Total weight, kg 262 447 340 207 Average weight, kg bunch 26.2 34.4 30.9 34.5 ,, growth - 31.3 19.9 31.7 Average number handful / cluster 7.97 9.07 8.36 9.33 % increase - 13.8 4.4 17.1

B. 5% commercial granules (g carbofuran / mat)

treatment untreated Handled cluster number 2.0 2.5 3.0 Picked at 5, 6, 7 months 98 23 38 36 Total weight, kg 2543 665 1136 1141 Average weight kg, cluster 26.0 28.9 29.9 31.7 '\, - growth 11.1 15.0 22.0 handful / cluster 7.77 8.08 7.94 8.55 • Growth 3.1 2.2 10.0

187,317

Table 5

Application for rice seedlings

Active- Leafworm Beetle Treatment material Deflections kg / ha Leaf Damage% (Dead Heart) 19DAT * 30 DAT33 DAT67 DA ^T

I-Carbofuran

urea. 0.5 14.26 14.82 0.43 0.51 3 g of carbofuran * urea 0.5 16.59 21.90 1.30 0.99 3 g of carbofuran without urea 0.5 15,10 17.43 0.46 0.72 2% carbofuran on urea 1.0 9.75 7.25 0.15 0.67 3 g of carbofuran * urea 1.0 10.28 6.78 0.26 0.79 3 g of carbofuran without urea 1.0 6.70 7.38 0.29 0.17 untreated controls 0 32.17 36.08 1.93 0.47

Treatment Active- material A g / Λίί Borehole Beetle Decay% (ÍVhite Head) Estimated rice Yield kg / h ι 95 DAT 1, carbofuran urea 0.5 7.63 1016 3 g of carbofuran * urea 0.5 6.28 984 3 g of carbofuran without urea 0.5 13.92 924 2% carbofuran on urea 1.0 6.75 1052 3 g of carbofuran * urea 1.0 4.97 988 3 g of carbofuran without urea 1.0 11.19 988 untreated controls 0 11.02 920

* DAT = number of days after treatment

Claims (1)

Patent claims CLAIMS 1. A process for the preparation of a granular insecticide and nematocide composition comprising ⁵ to 85-98% by weight of a granulated urea core having a particle diameter of 0.8-2.4 mm and a solubility of 0.5-0 in methylene chloride. 9% by weight of a benzyl ether-phenol resin of formula (I) wherein m + n is 2 to 3, m / n is 1 to 2 ¹⁰ and X is hydrogen or methylol, wherein the hydrogen / methylene molar ratio is 1: 2 and 0.001-0.003% by weight of pyridine catalyst are mixed, - ol and the mixture 1.9% by weight of methylene chloride in 0.5 to 0.9 ^5% by weight of the diphenylmethane diisocyanate or di- and triphenylmethane added di- and triisocyanate mixture, and - the surface of the particulate core cured polymer film formed directly on the weight of 0.5 to 11 ° / ₀ in an inert carrier, preferably 0.2 to 11.0% by weight of kaolin clay dispersed in amounts of 2,3-dihydro-2,2-dimethyl-benzofuran-7 -ylmethyl carbamate and dispersing the crosslinking polymer in the film. ^b 2. A process according to claim 1, characterized in that a 1.0 to 2.5 w / θ amounts of 2,3-dihydro-2,2-dimethyl-benzofuran-7-yl-methylcarbamate active ingredient.