DE1467383A1 - Slow-acting fertilizers - Google Patents

Description

BADTSCHS AIILIlT- & SODA-FABRIK AG

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- '■' ■ 'Ludwigshafen am Rhein, March 12, 1963

Ludwigshafen am Rhein, August 1968

For a long time, "Zeit" has been in the field of agricultural chemistry Opportunities' sought, "the" delivery of plant nutrients 'to adapt' to the 'respective needs of the' plants', if used 'The' well-known 'mineral' commercial fertilizers' are available to the plants the'nutrients, 'especially'the main nutrients nitrogen and potassium »" available practically immediately after fertilization «The utilization of the" nutrients is determined by the ratio of absorption largely determined by the plants and leaching. the The removal of nutrients can, however, be carried out in humid and semi-humid conditions Do not prevent the climate or artificially irrigated areas.

In addition to the above-mentioned leaching losses, there is often the risk of concentration, damage from the directly effective salts supplied with fertilization, especially with fertilization-intensive crops cheaper »because of this. in§hssonä, <sr © SOGENA of mi;? e "Ituxuslconsum ¹¹ prevented shipyards can"Pä>, ÜR increased a regular tiah

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how it can be obtained with slow-acting fertilizers, in general the plant growth and results in better harvests in the case of cultivated plants, the yield, based on the nutrient unit supplied in each case, is higher for slow-acting fertilizers.

As slow "acting fertilizers were already difficult to dissolve Compounds are used that mainly contain the plant nutrients nitrogen, potassium, phosphorus and possibly the trace elements contained in chemically bound form. Examples are urea-formaldehyde polycondensates (UREAFORM), crotonylidenediurea (FLORASiID), potassium glasses or sparingly soluble Ammonium magnesium phosphate.

Other suggestions were the usual easily soluble salt mixtures to provide with water-insoluble coatings that the E Influence nutrient delivery. Such coatings must also be physiologically harmless and "should" borrowed by bacteria can v / earth and this if possible in a way that benefits the plants. As a side benefit, they could also include the caking of the fertilizer grains and theirs Prevent corrosive effects on other substances. The previous proposals, suitable coating agents on fertilizer granules to be applied in such a way that they have a depot effect However, it did not lead to satisfactory results.

In the French patent 1 270 910 a method for improving the effectiveness of fertilizers is described »

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.for the "mineral fertilizers in granulated or lumpy" Form with "several different organic layers, preferably "Such 'from' drying oils, covered with ground" The individual coatings v / ground on the granules at various Temperatures "and applied using various organic solvents.

In the Belgian patent specification 600.133 it is recommended that the granulated fertilizers with a solution of polyoxyalkylenes or to treat polysiloxanes in organic solvents «

A similar process is known from British patent specification 815 829, in which the fertilizer granules are pretreated with plaster of paris before the organic plastic is applied.

A major disadvantage of these known processes for the production of slow-acting fertilizers is that the "coating" is carried out using organic solvents. The removal of the organic solvents requires additional equipment. In addition, there is a risk that explosions can occur when the coated fertilizer grains are dried with hot gas streams. It is also cumbersome, "zu'erreichen changing using different chemischer'Substanzen. Also, the" effective coating nur'durch pretreatment of the fertilizer with a lipophilic "water-insoluble ¹ 'chen layer at anderen'Temperaturen'oder'mit'wasserunlöslichen inorganic materials, such as plaster of paris, is an adverse measure.

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To prevent granulated fertilizers from caking, 'are made according to the procedure of British Patent Specification 785 64-5 the granulated fertilizers with a urea-sormaldehyde precondensate sprayed. However, these coatings only prevent the individual grains from sticking to one another. The coatings however, they are completely unspecific in terms of diffusion the nutrients through the plastic skin into a watery or moist medium.

In the German patent specification. ... * .. (patent application B. 9 674 IVa / .16) is a process for improved granulation of fertilizers by adding a copolymer of methacrylic acid and methacrylate or styrene to the granulator described. As a result, the fertilizer is intimately mixed with the additive before the grains are formed. However, it can easily prove that the addition of the compounds mentioned before or during granulation is not essential Affects the rate of diffusion of the treated fertilizers. .

It has now been found that slow-acting fertilizers can be avoided by coating fertilizers with plastics of the disadvantages outlined above can be produced if you add 2 to 20 percent by weight of a mixture to the fertilizers brings, which consists essentially of

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1. 50 Ms 90 percent by weight of a free vinyl group containing Polyeii polymer with a "viscosity between 0.7 and 1.5 poise, measured as a SO ^ solution in white spirit in the Brookfield viscometer, and

2. 10 to 50 percent by weight of a drying oil that is at least Contains 2 conjugated double bonds in the molecule or a grouping that is slightly conjugated double bonds supplies, and

5. 5 to 50 percent by weight of a lipophilic aminoplast condensate,

and the coatings harden in the usual way.

Polymers "of dienes or trienes, such as butadiene, isoprene, piperylene, 3-methylbeptatriene-1, 4 * 6 » n-Decatrien-1,5,9 »in Irage, which are obtained by methods in which the polymerization takes place exclusively or partially with 1,2-addition of the monomers. Particularly useful Polymers containing free vinyl groups are obtained according to the method described in J. Polym. Sc. J [(1946) 275 described method in which Sodium was used as a catalyst and a mixture of dioxane and heptane as a solvent.

Copolymers of one or more dienes or trienes containing free vinyl groups with up to 50 percent by weight copolymerizable compounds, such as ethylene, propylene, butylene, isobutylene, vinyl acetylene or, preferably, styrene or acrylonitrile, also esters of acrylic acid or methacrylic acid with aliphatic or alicyclic alcohols with up to

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12 carbon atoms or vinyl ethers, vinyl esters, vinyl or vinylidene halides and other compounds containing polymerizable double bonds come into consideration «

The content of free vinyl groups in the polyene polymers used according to the invention is determined by measurement ₍ the absorption in the infrared range at 10.98 / U in relation to the absorption of the other unsaturated groups in question (such as the unsubstituted trans double bond at 10.34 / U); the greater this free vinyl group content, the more reactive the polyene polymers are.

Their viscosity should be between 0.7 and 1.5 poise (50% solution in white spirit, Brookfield) or with a K value (H. Fikentscher, Cellulose-Chemie JJ5 (1932) 58) from 18 to 30. The viscosity can can be reduced by adding solvents with certain properties.

Natural oils, for example wood oil, oiticica oil and ricin oil, are suitable as component (2). A grouping which easily gives two conjugated double bonds with elimination of water is, for example, -OH-CH ₂ -CH = CH ₂ -.

OH

Suitable amino plastic components (3) are the customary ones made from an aldehyde, preferably formaldehyde, and thus condensate

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cash "nitrogen-containing materials constructed uncured Harze'bzw * whose Oligoinere and in some cases also the corresponding monomers Useful amine * ^ lastvorkondensate blank check z * B _t using urea, thiourea, melamine, benzoguanamine, amelin, guanidine," dicyandiamide, Glyoxalureins, such as glyoxaldi- and monourein, H, H'-dimethyl urea, as well as substitution products and derivatives of the compounds mentioned. Such aminoplast precondensates are produced by the usual methods of aminoplast chemistry. The present invention relates to particularly suitable aminoplast precondensates which, in addition to urea or other compounds containing amino groups, optionally contain di- and / or triamino compounds of the 1,3j5-triazine series as an essential component. The aminoplast precondensate can be etherified with monohydric or polyhydric alcohols. Preference is given to precondensates whose methylol groups are wholly or partially etherified with butanol. ■

The mixtures of components (1), (2) and (3) can using the usual methods, e.g. by spraying or pouring, directly onto the granulated or lumpy fertilizers to be brought. This can be done in the usual way in fertilizer manufacturing plants existing equipment, such as agitators, rotating drums, fluidized bed apparatus, vibrating belts, Vibrating sieves, conveyor screws, Hauersohn's corners, Use case guns and spray towers. The mixes can

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can be added as a jet of liquid, in the form of fine droplets, or as an aerosol. The mixtures can be hardened by using an elevated temperature and by adding siccative compounds such as cobalt liaphthenate or radical-forming compounds such as peroxides or hydroperoxides, optionally together with accelerators such as amines or cobalt salts. A particular advantage of the specified mixtures is that the elevated temperatures can also be generated with a hot nitrogen stream instead of with a stream of hot air, without the hardening being inhibited; characterized the safety of the coating process is' substantially increased "Z _S B" is obtained by heating the coated granules or pieces to temperatures of 60 to 150 C, preferably from 105 to 12O ⁰ C, / during 2 to 20, preferably 5 minutes insoluble, elastic or hard coatings resistant to water.

It may be advisable to apply several of the same coating layers by repeating the process one or more times. This allows due to the specific chemical compositions of the coatings reflect the properties of slow-acting fertilizers in exactly the same way modified as they are determined by the agricultural experts.

The fertilizers that are coated with plastics according to the invention include, for example, inorganic salts or salt

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Mixtures ^ the alkali metals, alkaline earth metals or ammonium as a cation, phosphate, ITitrate, chloride, sulfate or carbonate contained as anion, or urea, derivatives of urea or urea salts in question, The fertilizers to be coated but can also be wholly or partially of vegetable or animal origin «

Any pre-treatment of the granulated or lump fertilizers on the one hand or the coating components on the other are just as unnecessary as the alternating application of lipophilic layers and the release of nutrients regulating layers «The coatings obtained by the process according to the invention have those physical, chemical and microbiological properties that lent precisely adjustable nutrient delivery to the different types of plants according to their growing conditions and allow different soil conditions accordingly. Another advantage of the new process is that in a single continuous operation in different Mixtures or - if desired - even with a single one Mixture can coat the fertilizers. Several coatings are also possible if you use the untreated granulate during a pass through the viewing apparatus certain proportions at successive transit points of the total mixture to be applied.

The parts and percentages mentioned in the examples are G-e-

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weight units. The following comparison examples explain the registration without limiting it.

example 1

7 parts of a copolymer of 80 parts of butadiene and 20 parts of styrene »which was obtained by the process of TJS patents 2,768,984, 2,762,851, German patent 1,040,246 or French patent 1,133,006 and which has a K value of 23.5 and 53 f ^a yinyl groups are mixed with 2 parts of wood oil and one part of a hexamethylolmelamine butylated in the cold in a strongly acidic medium with the addition of clay 1 io cobalt naphthenate.

13 nitrogen-13 ₅ ~ 21 K ₂ O mm with a grain size 2-4 heated 300 parts of a fertilizer PGO 10 minutes in a coating pan in a 110 to 120 ⁰ C with a stream of hot nitrogen. 6 parts of the above-mentioned mixture are entered, which after 5 minutes have formed a glossy coating on the hot grain that is only visibly sticky. This operation is repeated twice more and then heated for 20 minutes at the same temperature _f After cooling, one obtains a not adhesive serving the etv / a 6 fa, based on the fertilizer, by weight. The coated fertilizer is allowed to settle for two days ".

For comparison, the same coating ($ 6) is made with the butadiene-styrene copolymer performed alone. Inside the above

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the times indicated, the coating is still strongly adhesive j. for a sufficient hardening is about three times the time required Necessary (see Fig. 1, curve 1).

25 g of coated fertilizer grains are stored in 100 cm ¥ aes at normal temperature for at least 48 hours. The water resistance of the fertilizer granules coated with the plastic mixture corresponds to a rating of 1 to 2 _t that of the grains of grade 3 coated with the butadiene-styrene copolymer alone . (1 = very good, 5 = very bad)

Food delivery test (Fig. 1, curve 3):

In each case 10 g of the coated fertilizer are mixed with 475 cm of water in a 500 cm volumetric flask and stored ^{at 2O 0 O.} The solution is moved from time to time and the first sample is taken after 8 or 24 hours by pipetting out 25 cur of solution and immediately replacing it with fresh 25 cm of water. The nitrogen is determined titrimetrically in the sample taken after reduction with an Arnd * 8 alloy. This sampling is repeated at the desired time intervals. The nitrogen is measured in the same way and the total nitrogen output is calculated by adding up.

Potassium is measured after taking the same sample with the flame photometer certainly.

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As "experiments" show, the method according to the invention clearly a delay in reaching the nutrient delivery »

Example J?

7 parts of a styrene-containing butadiene polymer which was obtained with the di-sodium compound of the trainer en <x -methylstyrene in tetrahydrofuran! Solution by pressing butadiene and which had a content of 84 $ 1,2-addition product and a K value of 19 5 shows, are mixed with 2 parts of wood oil and 1 part of a butylated hexamethanol melamine with the addition of 1 ^c / o cobalt naphthenate. For comparison, the same coating (6 ^c / o) is carried out with butadiene polymer alone. Within the times given above, the coating is still strongly adhesive; about three times the time is necessary for sufficient hardening (see Fig. 1, curve 2).

The coating of the fertilizer granules and the testing in the standing test and in the nutrient release test are carried out after the description in example 1.

The standing test results in a grade of 2 to 3

As tests show, 'by' the 'inventive' method significantly delayed "the! nutrient delivery" (Fig. 1, curve 4).

Example 3

7 parts of a polybutadiene made using "ITatrium

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in a Iiösungsmittelgemisch of 1 part of dioxane and 3 parts of n-heptane was recovered and had a content of free vinyl groups of $ 80> and a K value of 23.5, was mixed with 2 parts of tung oil and 1 part of an in in acidic medium the cold Tmtylated Hexamethyiolmelamine mixed. 1 $ cobalt naphthenate is added to this mixture.

The inspection of the fertilizer granulates and the inspection in the Stand test and in the nutrient release test. takes place after, the Description in example 1.

A grade 1 to 2 is obtained in the standing test.

As tests show, the method according to the invention significantly delayed the release of nutrients (Fig. 1, Curve 5).

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Claims (2)

- 14 -. O.Z. 22 361 Patent Claim * 'A method for producing slow-acting fertilizers by coating fertilizers with plastics, characterized in that 2 to 20 percent by weight of a mixture is applied to the fertilizers which essentially consists of 1. 50 to 90 percent by weight of a polyene polymer containing free vinyl groups with a viscosity between
0.7 and 1.5 poise, measured as a 50% solution in petroleum ether in a Brookfield viscometer, and 2. 10 to 50 percent by weight of a drying oil that has at least two conjugated double bonds in the molecule or
contains a moiety that provides easily conjugated double bonds, and J>. 5 to 50 percent by weight of a lip.oph.ileu aminoplast condensate exists, and the coatings harden in the usual way. Badisehe Anilin- & Soda-labrik AG NeUÖ Untertagen (Art 7, Paragraph 1, Paragraph 2, No. 1, Clause 3 of the Amendment Act of 4.9, «TO 8098t1 / 0681