DE2338182C3 - Micronutrient fertilizers - Google Patents

Description

Balance it out by adding appropriate micronutrient fertilizers. Such a long-lasting one and even fertilization with trace elements can be done in different ways.

It is Z. B. has already become known that ion exchangers loaded with trace ions are to be used for the long-term and even supply of plants with micronutrients

Styrene, substituted styrenes such as methyl styrene, dimethyl styrene, ethyl styrene, chlorostyrene, vinyl anisole, p-vinylbenzylamine, -methylstyrene and vinylnaphthalene.

As acrylic acid derivatives, for example:

Acrylic acid ester, acrylonitrile, methacrylic acid ester and methacrylonitrile.

OK

Examples of polyvinyl compounds include:

Divinylbenzene, diviny'toluenes, divinylnaphthalenes, Dialkyl phthalate, ethylene glycol acryate, ethylene glycol dimethacrylate, divinyl xylene, divinyl ethylene benzene, Trivinylbenzene, trivinylnaphthalene, and trivinylcyclohexane.

The preparation of the copolymers capable of anion exchange is known. It is expedient by suspension polymerization and, if appropriate, subsequent introduction of amino groups (see German patents 9 56 449, 1045 102, 10 49 583 and 10 54 715).

Anion exchangers which can be used according to the invention are also condensation resins, the basic, contain groups capable of anion exchange. Such condensation resins are im generally by condensation of aliphatic or aromatic amines with epichlorohydrin or Formaldehyde produced. Examples of aliphatic amines are polyalkylene polyamines, such as diethylenetriamine, triethylenetetramine, Pentaäthy lenhexamine, and polyethyleneimine, as an aromatic Amine, for example m-phenylenediamine.

The production of such anion-exchanging condensation resins is known (cf. German patent specification 9 72 246 and U.S. Patent 23 89 865).

The anion exchangers are loaded with anionically chelated ions of one or more elements from the group of elements with atomic numbers 24 to 30. Under »anionically chelated Ions «are to be understood in the present case as negatively charged chclate complexes of metal cations.

The production of such chelate complexes from metal cations and chelate formers is known.

Elements of the atomic numbers 24 to 30 are the metals:

Chromium, manganese, iron, cobalt, nickel, copper and zinc.

Aminopolycarboxylic acids are suitable as chelating agents which can be used according to the invention. In particular may be mentioned:

Nitrilotriacetic acid
Ethylenediamine tetraacetic acid
Diethylene-triamine-pentaacetic acid, N-Zi-hydroxyethyl-alhylenediamine-triacetic acid
Cyclohexane-trans-1,2-diamino-tetraacetic acid
Ethylenediamine-N, N'-di- (o-hydroxyphenyl) -

cacetic acid
Ν, Ν'-Di - ^ - hydroxyethyl

ethylenediaminediacetic acid
Bis (dicarboxymethyl aminomethyl) ether
Bis (dicarboxymethyl aminomethyl) sulfide

The chelating agents which can be used according to the invention are known from the literature.

The anion exchangers are loaded using the customary methods. It happens z. B. by the fact that the anion exchanger, which is present in the form of the free base or as a salt, at temperatures between 10 and 70 C with stirring with a 0.1 to 1 () ^u / uigen aqueous solution of a chelating agent in the form the free acid or is present as a salt, and then a 0.1 to 1% strength aqueous solution of a trace element salt or trace element salt mixture is added to the mixture. After equilibrium has been established, the anion exchanger loaded with anionic chelate complexes is separated off from the solution and washed with deionized water. However, it is also possible to load the anion exchanger by stirring it with an already prepared aqueous solution of a metal chelate alkali salt. Furthermore, the loading of the anion exchanger can also be carried out particularly advantageously in the filter tube by filtering a 0.1 to 10% strength aqueous solution of a metal chelate alkali salt over it at a moderate rate. In general, 0.1 to 100%, preferably 1 to 50%, of the total capacity of the anion exchanger is loaded with anionic chelate complexes of ions of the elements of atomic numbers 24 to 30 in this way.

In a special, particularly suitable application form it is possible to initially only partially use the anion exchanger with anionic chelate complexes to load the trace element ions and then subsequently the remaining part of the exchange capacity by other macro and / or micronutrient ions, such as. B. nitrate (NO.i), dihydrogen phosphate (H2PO4), molybdate (MOO4), and borate (BO.1) to saturate.

The anion exchanger loaded by one of the processes described above can optionally also be mixed with conventional cation exchangers that are loaded with nutrient cations of the elements potassium, magnesium, calcium or with ammonium (NHi ⁺ ).

The ion exchangers loaded with various anionic chelate complexes or with free nutrient ions are expediently used in a mixture with one another. They are suitable for both long-term and even supply of useful and ornamental plants.

The useful plants include z. B. Citrus fruits, cherry (Prunus), peach (Prunus persica) and wine (vilis).

Examples of ornamental plants are:

Aechmea (Aechmea fasciata), ivy (Hedera helix), Croton (Codiaeum variegaturr.), Palm (Chamaedorea elegans), philodendron (Philodendron red emerald; Philodendron scandens; Monstera deliciosa, euphorbia (Euphorbia pulcherrima), ferns (Adiantum scutum roseum), rubber tree (Ficus elastica Decora, Ficus robusta, Ficus diversifolia, Ficus benjamina), Aphclandra (Aphelandra squarrosa dania), Maranta (Maranta Makoyana), Chrysanthemums (Yellow Delaware), anthuriums (Anthurium scherzerianum), Ericaceaen (Erica gracilis), azaleas (Rhododendron simsii), Dieffenbachia (Dieffenbachia amoena; Tropic white), Dracaenen (Dracaena terminalis, Dracaena deremensis), hibiscus (Hibiscus rosa-

sinensis), lady's slipper (Cypripedium), guzmania (Guzmania minor), pachystachys (Pachystachys), peperonia (Peperonia glabella). Antler fern (Platycerium alcicorne), Scindlapsus (Scindlapsus aureus), Spatiphyllum (Spatiphyllum vvallisii) and Vriesea (Vriesea splendens).

The fertilizers according to the invention can be of the most varied natural and synthetic Substrates in which plants grow, are mixed or incorporated into them. You let are also particularly useful as a fertilizer in hydroponics.

Furthermore, the fertilizers according to the invention can preferably be placed in non-woven plastic casings bring in and use as a "sandwich fertilizer". Such sandwich fertilizers have compared to fertilizers, which are incorporated into the substrate, the advantage of quick and convenient. Interchangeability as well as the regeneration of the exhausted ion exchanger without a salt load on the plant.

The fertilizers according to the invention can either as such or in a mixture with other fertilizers, Extenders or emulsifiers and / or crop protection agents are used.

The fertilizers according to the invention can be in the form of pearls, granules or powder. It is used according to the methods customary in agriculture and horticulture. For example, the fertilizers according to the invention can be mixed with the natural or synthetic Mix the substrate or work it into the ground by digging or plowing. You can can also be scattered as top fertilizer on the plants or their habitat.

The amount used of ion exchangers charged according to the invention can be within relatively wide ranges vary. It essentially depends on the respective nutrient requirements of the plants. Generally lying the application rates between 0.001 and 0.1 l per liter of culture medium, preferably between 0.002 and 0.05 1 per liter of culture medium.

The loading of the anion exchanger with anionic chelate complexes as well as the application and The following examples are intended to illustrate the mode of action of the fertilizers according to the invention will:

example 1

One brings 1000 ml of a pearl-shaped so-called medium-basic anion ausdier - prepared by condensation of triethylenetetramine with epichlorohydrin - in the form of the hydrochloride in one Filter tube and filtered 20 l of a 1.5% strength aqueous solution of the potassium salt of Ät! Iylenediamine-di- (hydroxyphenyl / acetic acid-iron-IIIO chelate complex about it. In this way, the ion exchanger is saturated with the iron (III) chclate complex loaded and then to remove the excess chelate complex solution with desalinated Water washed. The anion exchanger loaded in this way contains 6 g iron per 1.

Example 2

1000 ml of a bead-like, strongly basic anion exchanger is brought in which is prepared from a macroporous methyl acrylate polymer crosslinked with 5% divinylbenzene and 3 "/" trivinyl-cyclohexane by amiolysis with Ν, Ν-dimethylpropylenediamine-1,3 and subsequent quaternization with methyl chloride was, in a filter tube and filtered 20 l of a ^{1.5 u} oigcn aqueous solution of the potassium salt of the ethylenediamine-di (o-hydroxyphenyl) acetic acid-iron (III) chelate complex over it loaded with the ice (HI) chelate complex and then washed with deionized water to remove the excess chelate complex solution.

B e i s ρ i e 1 3

Bring 1000 ml of a weakly basic, pearl-shaped anion exchanger from one 5% divinylbenzene and 3 "/" trivinyl-cyclohexane crosslinked macroporous methyl acrylate polymer by aminolysc with Ν, Ν-dimethyl-propylcndiamine-1,3 was prepared, into a filter tube and filtered 10 1 of a 2.9 ° oigcn solution of the copper chelate complex the ethylenediamine-telraacetic acid over it. Then it is washed with demineralized water. The anion exchanger loaded in this way contains 34.2 g of copper per liter.

Example 4

1000 ml of the weakly basic anion exchanger described in Example 3 are at room temperature with 10 1 of a 2.5% strength aqueous solution of the copper chelate complex of nitrilotriacetic acid stirred. After equilibrium has been established, the ion exchanger loaded with the copper-chclate complex becomes separated and washed with deionized water. The anion exchanger loaded in this way contains 43.4 g copper per 1.

B e i s ρ i e 1 5

1000 ml of the weakly basic anion exchanger described in Example 3 are at room temperature with 15 l of a 2.5% strength aqueous solution of the manganese (II) chelate complex of ethylenediaminetetracetic acid stirred. After equilibrium has been established, that with the manganese (II) chelate complex loaded anion exchangers are separated off and washed with deionized water. The so laden one Anion exchanger contains 35 g of manganese per I.

Example 6

Bring 50 ml of a pcrl-shaped aminomethylated, with 2% divinylbenzene crosslinked styrene polymer, the per styrene unit 1.8 aminomethyl groups contains, into a filter tube and filtered 2 l of a 1.8 "/ (IJgCn aqueous solution of the zinc chelate complex the ethylenediamine-octraacetic acid on top. The loaded ion exchanger is then used Removal of the excess chlorate complex solution washed with deionized water. The anion exchanger loaded in this way contains 60 g of zinc per liter.

B e i s ρ i c 1 7

FTO ml of Anioncnauslauschcis described in Example 6 at 6 () ^': C with 1.5 I of a 2.4 ¹ Vo-

igen aqueous solution of the cobalt chelate complex of ethylenediamine-tetraacetic acid stirred. To Adjustment of equilibrium will be that with the cobalt chelate complex separated off loaded anion exchanger and washed with deionized water. The anion exchanger loaded in this way contains 45 g Cobalt per 1.

Example 8

1000 ml of a macroporous, weakly basic one containing tertiary amino groups is stirred Anion exchanger, which is made from a crosslinked with 8% divinylbenzene and with the addition of 60% (based on the monomer mixture) of a Ci2 hydrocarbon mixture made porous styrene polymer prepared by aminomethylation and subsequent methylation with formaldehyde-formic acid was, at 50 ° C with 101 a 3.6% solution of the nickel chelate complex of ethylenediaminetetraacetic acid. The mixture is stirred at 50 ° C. for 8 h to establish equilibrium. After that, will the anion exchanger loaded with the nickel chelate complex is separated off and washed with deionized water washed. The anion exchanger loaded in this way contains 26.3 g of nickel per liter.

stirred. 8 liters of the potassium form or the ammonium form of a cation exchanger which was produced by sulfonating a polystyrene crosslinked with 6% divinylbenzene are added to the anion exchanger loaded in this way. The fertilizer mixture thus obtained was used to fertilize hydroponics in an amount of 300 ml per m ² . This amount was sufficient to ensure the nutrition of the plants listed below without deficiency symptoms for 8 months:

Aechmea (Aechmea fasciata), anthur (Anthurium scherzerianum), Aphelandra (Aphelandra squarrosa dania), palm (Chamaedorea elegans), croton (Codiaeum variegatum), lady's slipper (Cypripedium),

Dieffenbachia (Dieffenbachia tropic white), dracaenas (Dracaena deremensis), rubber tree (Ficus robusta; Ficus diversifolia; Ficus benjamina), guzmania (Guzmania mino), ivy (Hedera helix), hibiscus (Hibiscus rosa sinensis), Philode ndron (Philodendron red

so emerald; Monsteradeliciosa; Philodendron scandens), Pr.chystachys (Pachystachys), peperonia (Peperonia glabella), antler fern (Platycerium alcicorne), Scindapsus (Scindapsus aureus), Spatiphyllium (Spatiphyllium vallisii) and Vriesea (Vriesea splendens).

»5 Normal tap water was used as the irrigation water. Expanded clay was used as the filling substrate.

Example 9

For the production of a complete fertilizer that is suitable for plants in soil cultures or in soilless cultures with anionic chelate complexes of ions of trace elements, iron, manganese, copper and To supply zinc, the procedure according to the invention is as follows:

20 1 of an aminomethylated, crosslinked with 4% divinylbenzene bead-shaped styrene polymer, the contains 1.0 aminomethyl groups per styrene unit, is suspended in water and then in succession With

700 g of phosphoric acid

10 g boric acid

335 g of ethylenediamine tetraacetic acid
240 g FeSO-4 7 H2O
24 g MnSO-4 · H2O
18 5 CuSO4 5HiO
6 g of ZnSO ₄ '-71BO
* 9 g Ajnmomummolybdate
- - 3800 g of nitric acid

Example 10
For the application described below

a weakly basic anion exchanger was used, made from a polystyrene crosslinked with 2% divinylbenzene by chloromethylation and subsequent amination with methylamine.

2001 the nitrate form of this anion exchanger were suspended in water and kept at room temperature with stirring with an aqueous solution of 100 mol of the monosodium salt of ethylenediaminetetraacetic acid iron (III) chelate complex and 10

Mol of the disodium salt of the ethylenediamine-tetraacetic acid-manganese (II) chelate complex loaded.

With a single dose of 50 ml per m ² in a cut rose forcing, the alkaline soil caused by the alkaline soil could be extensively

Any signs of chlorosis that occur are eliminated. the Damage was not observed again within a year afterwards.

Similar good results were obtained when using citrus, Kalamondine 'and Gar-

denia Jasrmnoides scores * - ". /

-L

40? 485/284

Claims (1)

Claim: Micronutrient fertilizers made from anionically chelated Ions of one or more elements with atomic numbers 24 to 30, characterized by a content of at least an anion exchanger which is loaded with the anionically chelalized ions i.st. which the assimilation of the plants is impaired (cf. Science 120, 41 [1954]). The disadvantages shown, those with soil fertilization present with anionic chelate complexes can be remedied to a certain extent by lathering the complexes beforehand be introduced into the ground in polyurethane (cf. USA.-Patent 32 45 776). But also the use of the anionic chelate complexes ίο in this form is not entirely satisfactory, because one long-term and even supply of the plant Zen with trace elements can be used in practice achieve this only incompletely. Micronutrient fertilizers from other The present invention relates to micronutrient ionically chelated ions of one or more egg fertilizers found from anionically chelated ions of a element with atomic numbers 24 to 30, soft are characterized by a content of at least one anion exchanger with the anionically chelated ions is charged. It can be described as extremely surprising that the anion exchangers loaded according to the invention much better for the long-term and even supply of plants with micronutrient ions of elements of the assignment It is therefore necessary to _{identify a deficiency in micronutrients a5} lcn 24 to 30 suitable as the previously known anionic substances in substrates which are used for plant cultivation, chelate complex fertilizers or those with corresponding Meiallions loaded cation leachers, which are the closest remedies with the same type of effect. The excellent properties of the inventions Long-term fertilizers were by no means foreseeable, because it was to be expected that also with the Einsät. ", Of ion exchangers with anionic Chelate complexes are loaded all too easily because of the good interchangeability of the chelate complexes can (see US Pat. No. 3,083,074). With these ₃₅ harmful over-fertilization of the plants occurs, laden ion exchangers can Aich Although in the present invention have a fertilizer weakly acidic or also in a neutrally reacting sub-range of advantages. In this way, you can achieve an effective micronutrient fertilization in the Gestaten, in contrast to the one loaded with micronutrients; use in weakly basic reagieren- Ionenaustausdiern equally well in weak soils but with erheblidien disadvantages bc- ₄₀ acidic, neutral or weak basisdi reacting liable. This leaves a considerable proportion of the multi-value substrates to supply the plants with trace metal ions - especially the iron ion elements. It is not to be feared that -, unused, because these ions are deposited in an alkaline substrate after the release of polyvalent metal from the exchanger in the weakly alkaline sub-cations with the formation of sparingly soluble hydroxides, strat in the form of sparingly soluble hydroxides, and thus the actual use This means that the plant can no longer be drawn sufficiently, because the anionic chelates are always available. bil enough to prevent precipitation. A Weilerhin has already known that the further advantage of the plants loaded according to the invention with the elements of atomic numbers 24 to 30 ion exchangers is that they are only added _{when the} electrolyte content is determined in the form of anionic chelate complexes and which can be poured into the water (cf. »Organic Sequestering AgeiHs, which can be regulated, removes the bound nutrients. John Wiley and Sons, Inc., New York, 1959, 455 to bun. For example, anionic iron-damaging over-fertilization with anionic chelal comchelate complexes is suitable for combating chlorosis when plexuses are avoided. The fertilizers according to the invention cilrus fruits (cf. Proc. Florida State Hart. Soc. 64, ₅₅ medium thus ensure under the best possible aus-20 (1952); ibid. 66, 49 (1954). Such chelation of the micronutrients offered a complex are water-soluble and can be administered to the plant continuously, semi-liquid fertilizer through the leaf, as a liquid fertilizer. The use of ordinal numbers 24 to 30 is desirable in many plants valuable enrichment of technology, however, associated with various disadvantages. Larger washers can be used for soil fertilization. B. du'xh mixed polymerisation of Movcrluste Do not avoid it through rain, because sorpnovinyl aromatics or acrylic acid crystals are poIytable of the soils for anionischc chelate vinyl compounds accessible copolymers, in plexes of aminopolycarboxylic acids only very slight 65 which basic, ion-exchanging groups, such as is. If one tries to reduce the washout losses by adding primary, secondary, tertiary or quaternary amino acids larger amounts of anionic chclates were introduced. As monovinyl aromatics too low. over-fertilization can easily occur, for example: or several elements with atomic numbers 24 to 30 for the long-term and uniform supply of plants with anionic chelate complexes of micronutrients. In order to create optimal growth conditions for a plant, macronutrients must be added the micronutrients are also always made available in sufficient quantities in a substrate.