WO2007003388A2

WO2007003388A2 - Compositions supplying essential elements for preventing and correcting nutritional deficiencies in plants

Info

Publication number: WO2007003388A2
Application number: PCT/EP2006/006425
Authority: WO
Inventors: Lucio Filippini; Marilena Gusmeroli; Silvia Mormile; Domenico Portoso
Original assignee: Isagro S.P.A.
Priority date: 2005-07-05
Filing date: 2006-06-30
Publication date: 2007-01-11
Also published as: ITMI20051269A1; EP1899282A2; WO2007003388A3

Abstract

Compositions are described for supplying one or more essential elements, comprising one or more essential elements selected from potassium, iron, calcium, magnesium, manganese, copper, zinc, molybdenum, boron or nitrogen, and copolymeric compounds containing acid functions, obtained by the copolymerization of mono- or oligosaccharides with acids or their mono-unsaturated mono / polycarboxylic derivatives and/or with mono-unsaturated sulfonic acids and/or mono -unsaturated phosphonic acids and their use for preventing and correcting nutritional deficiencies in plants.

Description

COMPOSITIONS SUPPLYING ESSENTIAL ELEMENTS FOR PREVENTING AND CORRECTING NUTRITIONAL DEFICIENCIES IN PLANTS

The present invention relates to compositions which supply essential elements for preventing and correcting nutritional deficiencies in plants.

In particular, the present invention relates to compositions which supply essential elements for use in agriculture, for the prevention and cure of physiological alterations or nutritional unbalances in plants.

It is known from literature ("Principles of plant nutrition" Konrad Mengel and Ernest A. Kirkby Ed. Kluvert Academic Publishers) that plants need 16 essential elements for growth: three of thee essential nutrients (car- bon, hydrogen and oxygen) are mainly extracted from the air and water, the remaining thirteen elements must be absorbed through the roots from the surrounding soil. They include: calcium, magnesium, sulfur, nitrogen, phosphorous, potassium, iron, manganese, copper, zinc, molyb- denum, chlorine and boron. Each of these sixteen nutrients is indispensable for the growth, development and overall health of plants, even those commonly called microelements, i.e. those elements of which only minimum quantities are necessary. The rapid growth and development of fertilizers enriched with microelements in the Sixties' was followed by a more detailed study on the problems indicated above for obtaining a deeper understanding of nutritional requirements, both mineral and water of various crops, combined with an analysis of the fertility of the soil, an analysis of the irrigation water and a greater knowledge of new agronomical application techniques. In order to minimize its environmental impact and optimize the use of available resources, modern agriculture in recent years has developed an effective "crop culture" .

This field also comprises a study of plant interactions, nutrients and pathogen agents which, due to their complexity, have not yet been completely understood. Although often neglected, nutrition has always represented a fundamental component for disease control. Most terrains and environments dedicated to cultivations contain a large number of pathogens which can be more virulent on plants with nutritional deficiencies and consequently more susceptible to external attacks . A correct crop nutrition must therefore be based on products having a maximum efficiency, distributed in adequate dosages, appropriate times and with equally efficient methods.

Commercial products compensate nutritional deficien- cies by providing the necessary microelements in the form of salts or chelated with compounds which prolong their persistence in the soil, in the most bioavailable form possible for the specific crop in the specific terrain. It is in fact known that the consistency and geophysical composition and pH of the soil, combined with the meteorological variables, strongly influence the physico- chemical form of the elements also abundantly present in the soil, suppressing the mobility and consequently the bioavailability of the same essential nutrients. The main chelating-complexing molecules currently present on the market for agricultural use are: ethylene- diaminotetra-acetic acid (EDTA) , hydroxyethylenediamino- triacetic acid (HEDTA) , diethylenediaminopenta-acetic acid (DTPA), ethylenediamino-di- (o-hydroxyphenyl) acetic acid (EDDHA) , ethylenediamino-di- (o-hydroxy-4-sulfo- phenyl) acetic acid (EDDHSA), ethylenediamino-di- (o- hydroxy-4 -methyl-phenyl) acetic acid (EDDHMA), ammonium ligninsulfonate (LSA) .

Only products with a high stability constant in ter- rains with an alkaline pH (EDDHA, EDDHSA, EDDHMA) are able to exert their function as nutrition-suppliers to crops. This first limit is also associated with a high treatment cost, due to the cost of the substrate itself, whose synthesis comprises the formation of at least two isomeric forms (ortho-ortho and ortho-para) with considerable differences in the chelating capacity and stability of the chelated product. Furthermore, administration by means of "fertirrigation" (distribution of fertilizers together with the irrigation water) , "nutrirrigation" (distribution of necessary and indispensable nutritional elements through the irrigation water) and leaf application, is not possible for all the above chelated products, due to the phytoxicity effects instability of the products to light. The Applicant has now surprisingly found a new group of compositions which supply essential elements or nutritive substances vital for the prevention and treatment of deficiencies and for the overall development of plants.

An object of the present invention therefore relates to a composition which supplies essential elements for vegetal physiology, and consequently aimed at preventing and treating physiological alterations or nutritional unbalances in plants, which does not have the disadvantages of the products according to the state of the art. An object of the present invention therefore relates to a composition which supplies essential elements, comprising one or more elements selected from potassium, iron, calcium, magnesium, manganese, copper, zinc, molybdenum, boron or nitrogen, and copolymeric compounds con- taining acid functions, obtained by the copolymerization of mono- or oligosaccharides with acids or their mono- unsaturated mono/polycarboxylic derivatives and/or with mono-unsaturated sulfonic acids and/or mono-unsaturated phosphonic acids . Nitrogen is preferably present in the form of ammonia or in the form of quaternary ammonium salts .

The copolymeric compounds containing acid functions are generically defined hereafter as "acid-saccharide copolymers" . A considerable advantage of the compositions which supply essential elements according to the present invention, with respect to the chelating-complexing agents currently on the market, is their high selectivity. They can in fact be administered either through the leaf or via the root by means of burial or an injector spade, they can be used in fertirrigation even in terrains with an alkaline pH and in particular and effectively, by means of micro-irrigation systems such as hoses and drippers, without any phytotoxicity . A further advantage is that the above compositions which supply essential elements allow excellent results to be reached with a limited treatment cost.

Furthermore, the compositions which supply essential elements according to the present invention have a negli- gible environmental impact and an excellent toxicological profile, thanks to their characteristics and biodegrad- ability. This allows their insertion in modern nutritional programs and, in particular, in integrated production programs . Examples of mono-oligosaccharides are: glucose, saccharose, fructose, leucrose, palatinose, lactose, maltose, mannose, sorbitol, mannitol, gluconic acid, glucuronic acid, alkyl ethers, hydroxyalkyls and carboxyalkyls of saccharides . Examples of unsaturated mono/polycarboxylic acids and their derivatives are acrylic acid, methacrylic acid, maleic anhydride, acrylamide, allylsulfonic acid, methal- lylsulfonic acid, vinylsulfonic acid, vinylphosphonic acid. These "acid-saccharide copolymers" have particular dispersing and sequestrating properties and are completely biodegradable.

For purely illustrative purposes and without limiting the present invention in any way, "acrylic-saccharide copolymers" described and claimed in patents EP0289895, WO9517442 and WO9401476 and in the patents cited therein, can be used as "acid-saccharide copolymers" .

The copolymeric compounds containing acid functions, obtained by the copolymerization of mono- or oli- gosaccharides with acids or their monounsaturated mono/polycarboxylic derivatives and/or with monounsaturated sulfonic acids and/or with monounsaturated phos- phonic acids, can be selected from copolymers obtained by the copolymerization of glucose and acrylic acid; fruc- tose and acrylic acid; palatinose and acrylic acid; leucrose and acrylic acid; saccharose, acrylic acid and methallylsulfonate; saccharose, acrylic acid, methallyl- sulfonate and acrylamide,- saccharose, maleic anhydride, phosphorous acid and sodium hydrogen sulfite,- or saccha- rose, maleic anhydride, iron ammonium sulfate (II) .

A further object of the present invention relates to the use of said composition which supplies essential elements, comprising one or more essential elements selected from potassium, iron, calcium, magnesium, manganese, cop- per, zinc, molybdenum, boron or nitrogen, in particular nitrogen in the form of ammonia or in the form of quaternary ammonium salts, and "acrylic-saccharide copolymers", in agriculture as a nutritional product, i.e. a product capable of preventing and treating physiological altera- tions or nutritional unbalances in plants. The Applicant has now found that compositions which supply essential elements, comprising one or more essential elements and "acrylic-saccharide copolymers", unlike other commercial fertilizers, have an excellent compati- bility with commercial cupric fungicidal products, such as for example, Kentan DF (copper hydroxide at 25%) , copper oxychloride, copper hydroxide, Airone (1:1 mixture of copper oxychloride : copper hydroxide), Bordeaux mixture (copper sulfate neutralized with lime) , Carlit (mixture of Benalaxil 2.5%, Fosetil Aluminum 35%, Mancozeb 35%) and with those claimed in patent application MI 2001A002430.

A further object of the present invention relates to a process for the preparation of a composition which sup- plies essential elements, comprising an essential element and "acid-saccharide copolymers" , according to the following scheme :

Copol . + Elem. -> Elem. supplier wherein Copol. refers to the compounds previously defined as "acid-saccharide copolymers" and Elem. refers to an acid, base or salt of one or more essential elements selected from nitrogen, potassium, iron, calcium, magnesium, manganese, copper, zinc, molybdenum and boron, such as, for example, boric acid, copper sulfate, calcium hy- droxide, iron sulfate, zinc sulfate, calcium carbonate, magnesium carbonate.

The compositions which supply essential elements comprising various essential elements and "acid- saccharide copolymers", object of the present invention, can be obtained by mixing two or more supplier compositions of essential elements comprising an essential element and "acid-saccharide copolymers", or by the direct synthesis of said composition which supplies essential elements comprising various essential elements and "acid- saccharide copolymers"

When compositions comprising two essential elements and "acid-saccharide copolymers" are to be obtained, for example, it is possible to operate according to the following reaction scheme: Copol. + Elem.l + Elem.2 —» Elem.l - Elem.2 - Supplier wherein Copol. refers to the compounds previously defined as "acid-saccharide copolymers" and Elem.l and Elem.2 have the same meanings as Elem. provided that Elem.l is different from Elem.2. Operating analogously, it is possible to obtain compositions which supply essential elements comprising various essential elements and "acid-saccharide copolymers" .

The reaction can be carried out in water at a tem- perature ranging from 0 to 80⁰C, in the presence of or without an inorganic base, such as for example, ammonium hydroxide, potassium hydroxide, sodium hydroxide, depending on the element or elements to be used.

In these compositions which supply essential ele- ments, the quantity of essential elements with respect to the quantity of acrylic-saccharide copolymer preferably varies within the range of 0.01 to 20 mg of essential element per g of acrylic-saccharide copolymer.

Even more preferred are the ratios 1 mg elem./lO g copolymer or 0.04 mg elem./10 g copolymer or 0.18 mg elem./10 g copolymer.

The compositions which supply one or more essential elements, object of the present invention, can be applied, for example, on vegetables, fruit (pomaceous and drupaceous etc.), citrus fruits, vines, strawberries, kiwis, tobacco, legumes, cereals, floral and ornamental plants, nurseries, golf courses, sports fields, tree- lined areas, topsoil and lawns.

A further object of the present invention relates to a method for the prevention and treatment of physiological alterations or nutritional unbalances in plants and for increasing their resistance against external pathogen attacks by the application of a composition which supplies essential elements according to the present inven- tion. The quantity of composition which supplies one or more essential elements according to the present invention to be applied for obtaining the desired effects can vary in relation to various factors, such as for example, the element or elements which are to be agronomically applied, the "acid-saccharide copolymers" used, the crop to be nourished, the type of soil, the degree and nature of the deficiency, the climatic conditions, the application method, the formulation adopted. This information can be easily obtained in technical literature, for example, in "Il programma di fitonutri- zione ragionata" - Nutex or in "Azoto, agricoltura, am- biente" - Assofertilizzanti - Federchimica (1991) or in "Mineral nutritive" Agrotecnica (1989) . For practical used in agriculture, the above compositions which supply one or more essential elements can be used directly in the form of aqueous solutions and/or solid preparations, in relation to the essential elements and "acid-saccharide copolymers" considered, or as liquid formulations or solids containing said compositions which supply essential elements and other compounds capable of supplying nourishment to plants, or for modulating their physiological processes and also ensuring protection against phytopathogen agents or insects or other para- sitic species, through direct biocide actions or by the induction of the specific innate defense responses of each crop .

The quantity of composition which supplies one or more essential elements which can be used for practical uses in agriculture, can vary from 0.01 g to 20 g of composition per square metre of agrarian soil.

The application of the aqueous solution or liquid or solid formulations can be effected either through the leaves or roots by burial or an injector spade, in fer- tirrigation also in terrains with an alkaline pH and, in particular and effectively, by means of micro-irrigation systems such as hoses and drippers .

Solid or liquid formulations can therefore be used in the form of dry powders, wettable powders, emulsifi- able concentrates, micro-emulsions, pastes, gelatins, granulates, microgranules, solutions, suspensions, etc.

Within the scope of the present invention, these liquid or solid formulations can consequently relate to said compositions suppliers of essential elements or their mixtures with other compounds capable of nourishing plants, or modulating physiological processes, as well as ensuring protection against phytopathogen agents or insects and other parasitic species, through direct biocide actions or by the induction of the specific innate de- fense responses of each crop. The selection of the type of mixture and formulation depends on the specific use.

The mixtures are prepared in the known way, for example, by diluting or dissolving the active substance with a solvent means and/or a solid diluent, optionally in the presence of surface-active agents.

Solid diluents, or carriers, which can be used are, for example: silica, kaolin, bentonite, talc, infusorial earth, dolomite, calcium carbonate, magnesia, chalk, clays, synthetic silicates, attapulgite, seppiolite. Liquid diluents which can be adopted are, for example, water, aromatic or paraffinic organic solvents, alcohols, esters, ketones, amides.

Sodium salts, potassium salts, calcium salts, tri- ethanolamine salts of: alkylnaphthalenesulphonates, con- densed alkylnaphthalenesulphonates, phenylsulphonates, polycarboxylates, alkylsulphosuccinates, sulphosucci- nates, alkylsulphates, ligninsulphates, polyethoxylated fatty alcohols, alkylarylsulphonates, polyethoxylated al- kylphenols, polyethoxylated esters of sorbitol, polypro- poxy polyethoxylates (block polymers) , can be used as surface-active agents.

The compositions which supply one or more essential elements, according to the present invention, can also contain special additives for particular purposes, such as for example, antifreeze agents: propylene glycol, or adhesive agents, such as gum Arabic, polyvinyl alcohol, polyvinyl pyrrolidone, etc.

If necessary, it is possible to add other compatible active principles to the compositions such as, for exam- pie other fungicides, phytoregulators, antibiotics, herbicides, insecticides and fertilizers.

The compositions which supply one or more essential elements, object of the present invention, do in fact have an excellent compatibility with commercial NPK fer- tilizing products (based on nitrogen, phosphorous and potassium) , allowing their simultaneous administration.

The following examples are provided for a better understanding of the invention, which are for purely illustrative and non-limiting purposes of the present inven- tion.

EXAMPLE 1

Preparation of Polymer A.

A mole of glucose is dissolved in a solution at 30% of sodium hydroxide under stirring at 0⁰C. 0.07 moles of H₂O₂ are subsequently added, the temperature being maintained at O⁰C. 3 moles of acrylic acid are then added dropwise to the alkaline solution of sugar and hydrogen peroxide with a consequent increase in the temperature to about 75°C. The mixture is further heated to 85°C, trig- gering the exothermic reaction which brings the tempera- ture to 105⁰C. As soon as the maximum temperature is reached, the reaction mixture is immediately cooled to 2O⁰C, obtaining an extremely viscous solution. The content of active substance in the solution is 48%, deter- mined by acidification. EXAMPLE 2

Preparation of the supplier composition comprising iron and Polymer A (Composition Al) .

1.2 1 of NH₄OH at 30% are added to an aqueous solu- tion of 2 Kg of Polymer A. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable per- centage concentration of iron. EXAMPLE 3

Preparation of the supplier composition comprising calcium and Polymer A (Composition A2) .

360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer A brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homo- geniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mix- ture appears as a solution already ready for use. EXAMPLE 4

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer A (Composition A3) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer A. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements. EXAMPLE 5

Preparation of the supplier composition comprising boron and Polymer A (Composition A4) . 1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer A at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 6 Preparation of the supplier composition comprising copper, calcium and Polymer A (Composition A5) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer A. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O and 0.1 Kg of CaCl₂*2H₂O in 3 1 of H₂O. The reaction mixture immediately becomes light blue-coloured, due to the presence of a light precipitate which is formed. The reaction mix- ture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of copper and calcium. EXAMPLE 7 Preparation of the supplier composition comprising iron, calcium and Polymer A (Composition A6) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer A. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 1.20 Kg of FeNH₄ (SO₄) ₂*12H₂O and 0.1 Kg of CaCl₂*2H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish colour, it then passes through a considerable densifying phase and finally re- dissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of iron and calcium. EXAMPLE 8

Preparation of the supplier composition comprising ammo- nium and Polymer A (Composition A7) .

An aqueous solution of 1 Kg of Polymer A in acid form is neutralized by the addition of NH₄OH and the solution thus obtained is already ready for agronomical use according to consolidated fertilization practice. EXAMPLE 9

Preparation of the supplier composition comprising ammonium, potassium and Polymer A (Composition A8) .

An aqueous solution of 1 Kg of Polymer A in acid form is brought to pH 11 by the addition of NH₄OH and then neutralized with a solution of KCl. The solution thus obtained is already ready for agronomical use according to consolidated fertilization practice. EXAMPLE 10 Preparation of Polymer B An aqueous solution of glucose (100 g in 100 ml of water) are prepared separately and 57 g of H₂O₂ at 30% and an aqueous solution of acrylic acid (72 g in 200 g of a solution of NaOH at 20%) are added. The two solutions described above are added dropwise over a period of about 50 minutes into the reactor in which 100 g of water at 85⁰C are already present. In the meantime, the temperature rises to 97⁰C and, at the end of the addition, the temperature is left to stabilize at its maximum value to complete the reaction. The pH value of the reaction me- dium is kept constant at 9.0 during the whole process. At this point, the mixture is immediately cooled to about 20⁰C. The content of active substance of this polymeric solution is 32%. EXAMPLE 11 Preparation of the supplier composition comprising magnesium and Polymer B (Composition Bl) .

An aqueous solution of 2 Kg of Polymer B is brought to pH 10-11 by the addition of a concentrated solution of KOH. The basic solution thus obtained is slowly added un- der vortical stirring to the solution heated to about 40⁰C of 0.3 Kg of MgSO₄.7H₂O. A gelatinous white precipitate is formed, which slowly redissolves.

The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of magnesium. EXAMPLE 12

Preparation of the supplier composition comprising zinc and Polymer B (Composition B2) .

An aqueous solution of 2 Kg of Polymer B is brought to pH 10-11 by the addition of a concentrated solution of NH₄OH. The basic solution thus obtained is slowly added under vortical stirring to the solution heated to about 40⁰C of 0.3 Kg of ZnSO₄.7H₂O. A white precipitate is formed, which makes the solution turbid. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of zinc. EXAMPLE 13 Preparation of the supplier composition comprising copper and Polymer B (Composition B3) .

An aqueous solution of 2 Kg of Polymer B is brought to pH 10-11 by the addition of a concentrated solution of KOH. The basic solution thus obtained is slowly added under vortical stirring to the solution heated to about 40⁰C of 0.3 Kg of (CH₃COO)₂Cu-XH₂O. A light blue precipitate is formed, which makes the solution turbid. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of copper. EXAMPLE 14

Preparation of Polymer C.

A solution of 29 g of fructose in 171 g of water is charged into the reactor and heated to 80⁰C. An aqueous solution of 8 g of acrylic acid neutralized with 300 g of NaOH at 20% and contemporaneously 57 g of H₂O₂ at 30% are added dropwise over a period of about 80 minutes. During the reaction the pH is kept constant at 9.0 and the temperature rises to a maximum of 90⁰C. At the end of the addition of the two solutions, the reaction mixture is immediately cooled to room temperature. The content of active substance of this polymer solution is 35%. The biodegradability is 88%. EXAMPLE 15 Preparation of the supplier composition comprising iron and Polymer C (Composition Cl) .

1.2 1 of NH₄OH at 30% are added to an aqueous solution of 2 Kg of Polymer C. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mix- ture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable percentage concentration of iron. EXAMPLE 16 Preparation of the supplier composition comprising cal- cium and Polymer C (Composition C2) . 360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer C brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homo- geniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mixture appears as a solution already ready for use. EXAMPLE 17 Preparation of Polymer D. A solution of 108 g of palatinose in 220 g of water is charged into the reactor and 108 g of acrylic acid and 57 g of H₂O₂ at 30% are added. The reaction mixture is initially heated to 60-65⁰C under stirring and then the heating is suspended allowing the exothermy of the reac- tion to bring the temperature to 80⁰C. During the reaction the pH is kept constant at 9.0 and the temperature is kept under control at around 80⁰C for 60 minutes. After 1 hour the reaction mixture is cooled to room temperature. The content of active substance of this poly- meric solution is 31%. The biodegradability is 97%. EXAMPLE 18

Preparation of the supplier composition comprising iron and Polymer D (Composition Dl) .

1.2 1 of NH₄OH at 30% are added to an aqueous solu- tion of 2 Kg of Polymer D. The basic solution thus ob- tained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 31 of H₂O. The reaction mixture immediately becomes a reddish-brown colour, it then passes through a considerable densifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable percentage con- centration of iron. EXAMPLE 19

Preparation of the supplier composition comprising calcium and Polymer D (Composition D2) .

360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer D brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homogeniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mix- ture appears as a solution already ready for use. EXAMPLE 20

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer D (Composition D3) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer D. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements . EXAMPLE 21

Preparation of the supplier composition comprising boron and Polymer D (Composition D4) . 1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer D at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 22

Preparation of the supplier composition comprising copper, calcium and Polymer D (Composition D5) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer D. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O and 0.1 Kg of CaCl₂*2H₂O in 3 1 of H₂O. The reaction mixture immediately becomes light blue-coloured, due to the presence of a light precipitate which is formed. The reaction mix- ture is stirred for a night and then brought to the de- sired volume with H₂O up to the most suitable percentage concentration of copper and calcium. EXAMPLE 23

Preparation of the supplier composition comprising iron, calcium and Polymer D (Composition D6) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer D. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 1.20 Kg of FeNH₄ (SO₄) ₂*12H₂O and 0.1 Kg of CaCl₂*2H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish colour, it then passes through a considerable densifying phase and finally re- dissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable percentage concentration of iron and calcium. EXAMPLE 24 Preparation of the supplier composition comprising ammo- nium and Polymer D (Composition D7) .

An aqueous solution of 1 Kg of Polymer D in acid form is neutralized by the addition of NH₄OH and the solution thus obtained is already ready for agronomical use according to consolidated fertilization practice. EXAMPLE 25 Preparation of the supplier composition comprising ammonium, potassium and Polymer D (Composition D8) .

An aqueous solution of 1 Kg of Polymer D in acid form is brought to pH 11 by the addition of NH₄OH and then neutralized with a solution of KCl. The solution thus obtained is already ready for agronomical use according to consolidated fertilization practice. EXAMPLE 26 Preparation of Polymer E. A solution of 108 g of leucrose in 220 g of water is charged into the reactor and 108 g of acrylic acid and 57 g of H₂O₂ at 30% are added. The reaction mixture is initially heated to 60-65⁰C under stirring and then the heating is suspended allowing the exothermy of the reac- tion to bring the temperature to 80⁰C. During the reaction the pH is kept constant at 9.0 and the temperature is kept under control at around 8O⁰C for 60 minutes. After 1 hour the reaction mixture is cooled to room temperature. The content of active substance of this poly- meric solution is 31%. The biodegradability is 97%. EXAMPLE 27

Preparation of the supplier composition comprising iron and Polymer E (Composition El) .

1.2 1 of NH₄OH at 30% are added to an aqueous solu- tion of 2 Kg of Polymer E. The basic solution thus ob- tained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable per- centage concentration of iron. EXAMPLE 28

Preparation of the supplier composition comprising calcium and Polymer E (Composition E2) .

360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer E brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homogeniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mix- ture appears as a solution already ready for use. EXAMPLE 29

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer E (Composition E3) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer E. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements, or filtered on a buchner after crumbling the solid with the help of EtOH. EXAMPLE 30 Preparation of the supplier composition comprising boron and Polymer E (Composition E4) .

1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer E at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 31

Preparation of the supplier composition comprising copper, calcium and Polymer E (Composition E5) . 1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer E. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O and 0.1 Kg of CaCl₂*2H₂O in 3 1 of H₂O. The reaction mixture imme- diately becomes light blue-coloured, due to the presence of a light precipitate which is formed. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of copper and calcium. EXAMPLE 32

Preparation of the supplier composition comprising iron, calcium and Polymer E (Composition E6) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer E. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 1.20 Kg of FeNH₄ (SO₄) ₂*12H₂O and 0.1 Kg of CaCl₂*2H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish colour, it then passes through a considerable densifying phase and finally re- dissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable percentage concentration of iron and calcium. EXAMPLE 33

Preparation of the supplier composition comprising ammonium and Polymer E (Composition E7) .

An aqueous solution of 1 Kg of Polymer E in acid form is neutralized by the addition of NH₄OH and the so- lution thus obtained is already ready for agronomical use according to consolidated fertilization practice. EXAMPLE 34

Preparation of the supplier composition comprising ammonium, potassium and Polymer E (Composition E8) . An aqueous solution of 1 Kg of Polymer E in acid form is brought to pH 11 by the addition of NH₄OH and then neutralized with a solution of KCl. The solution thus obtained is already ready for agronomical use according to consolidated fertilization practice. EXAMPLE 35

Preparation of Polymer F

36,3 g of saccharose and 36.3 g of sodium methallyl- sulfonate are added under stirring to a solution of 224 g of acrylic acid in 381.6 g of water, neutralized with 64 g of aqueous NaOH at 45%. This is followed by the addition of 8.8 g of mercaptoethanol, 0.02 g of iron (II) sulfate in 10 g of water and 3 g of H₂O₂ at 35% with associated exothermy which brings the temperature to 101⁰C which then drops. When the temperature reaches 75⁰C 2 g of hydroxylammonium chloride in 15 g of water and 14.3 g of H₂O₂ at 35% are added and the mixture is heated to 95°C for 2 hours. At this point a further 15 g of H₂O₂ at 35% are added and when the temperature returns to 70⁰C, it is neutralized with 204 g of aqueous NaOH at 45% and the polymerization continues for a further 30 minutes at 70⁰C. The final polymeric solution is a clear yellow colour with a content of dry substance of 41.1%, a viscosity of 80 mPa.s. and a pH of 6.6. The non-reacted acrylic acid is equal to 0.006% and the non-reacted sodium methallylsulfonate 0.143%. EXAMPLE 36

Preparation of the supplier composition comprising iron and Polymer F (Composition Fl) .

1.2 1 of NH₄OH at 30% are added to an aqueous solu- tion of 2 Kg of Polymer F. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable per- centage concentration of iron. EXAMPLE 37

Preparation of the supplier composition comprising calcium and Polymer F (Composition F2) .

360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer F brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homo- geniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mix- ture appears as a solution already ready for use . EXAMPLE 38

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer F (Composition F3) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer F. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements. EXAMPLE 39

Preparation of the supplier composition comprising boron and Polymer F (Composition F4) . 1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer F at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 40 Preparation of Polymer G

116.2 g of saccharose, 58.1 g of sodium methallyl- sulfonate and 205.4 g of an aqueous solution of ac- rylamide at 40%, are added under stirring to a solution of 82.2 g of acrylic acid in 414.8 g of water, neutralized with 21.1 g of aqueous NaOH at 50%. This is followed by the addition of 8.8 g of mercaptoethanol, 0.02 g of iron (II) sulfate in 10 g of water and 3 g of H₂O₂ at 35% with associated exothermy which brings the temperature to 70⁰C. At this point 2 g of hydroxy1ammonium chloride in 15 g of water and 14.3 g of H₂O₂ at 35% are added and the mixture is heated to 95°C for 2 hours. When the temperature returns to 45⁰C, it is neutralized with 67.3 g of aqueous NaOH at 50%. The final polymeric solution is a clear brown colour with a content of dry substance of 36.8%, a viscosity of 35 mPa.s. and a pH of 7.0. EXAMPLE 41

Preparation of the supplier composition comprising iron and Polymer G (Composition Gl) . 1.2 1 of NH₄OH at 30% are added to an aqueous solution of 2 Kg of Polymer G. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable percentage concentration of iron. EXAMPLE 42

Preparation of the supplier composition comprising calcium and Polymer G (Composition G2) . 360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer G brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homo- geniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mixture appears as a solution already ready for use. EXAMPLE 43

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer G (Composition G3) . 1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer G. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements . EXAMPLE 44

Preparation of the supplier composition comprising boron and Polymer G (Composition G4) .

1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer G at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 45 Preparation of Polymer H

243 g of water, 160 g of saccharose, 47.9 g of maleic anhydride, 0.57 g of phosphorous acid and 2 g of sodium hydrogen sulfite are charged into a reactor and the mixture is kept under stirring at 80⁰C for an hour under a stream of nitrogen. 70.5 g of aqueous NaOH at 50% are slowly added and a solution of 133.6 g of acrylic acid in 141.9 g of water are dosed over a period of 5 hours at 80⁰C, and a solution of 8.1 g of H₂O₂ at 35% in 37.6 g of water and a solution of 2.85 g of sodium sulfate in 40 g of water are added simultaneously over a period of 6 hours. The polymerization is continued for a further 2 hours . The final polymeric solution has a con- tent of dry substance of 37.7%, a viscosity of 155 mPa.s. EXAMPLE 46

Preparation of the supplier composition comprising iron and Polymer H (Composition Hl) .

1.2 1 of NH₄OH at 30% are added to an aqueous solu- tion of 2 Kg of Polymer H. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable per- centage concentration of iron. EXAMPLE 47

Preparation of the supplier composition comprising calcium and Polymer H (Composition H2) .

360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer H brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homogeniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mix- ture appears as a solution already ready for use. EXAMPLE 48

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer H (Composition H3) .

1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer H. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements. EXAMPLE 49

Preparation of the supplier composition comprising boron and Polymer H (Composition H4) . 1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer H at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 50

Preparation of Polymer I

185 g of water, 108.9 g of saccharose, 77 g of maleic anhydride, 2.2 mg of iron (II) ammonium sulfate and 112.8 g of aqueous NaOH at 50% are charged into a re- actor and the mixture is heated to boiling point. At this stage a solution of 77 g of acrylic acid and 54.4 g of sodium methallylsulfonate in 94 g of water are dosed over a period of 4 hours and a solution of 34 g of H₂O₂ at 35% and 12 g of sodium persulfate in 66 g of water over a pe- riod of 5 hours. The polymerization is continued at reflux temperature for an hour, after which the mixture is neutralized with 93.6 g of aqueous NaOH at 50%. The final polymeric solution is a clear brown colour, it has a content of dry substance equal to 43% and a viscosity of 74 mPa.s. During the polymerization the development of CO₂ is observed. EXAMPLE 51

Preparation of the supplier composition comprising iron and Polymer I (Composition II) . 1.2 1 of NH₄OH at 30% are added to an aqueous solution of 2 Kg of Polymer I. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish- brown colour, it then passes through a considerable den- sifying phase and finally redissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left to rest for a night and is then brought to the desired volume with H₂O up to the most suitable per- centage concentration of iron. EXAMPLE 52

Preparation of the supplier composition comprising calcium and Polymer I (Composition 12) . 360 ml of a 10 M solution of CaCl₂.2H₂O are added to an aqueous solution of 2 Kg of Polymer I brought to pH 10 by the addition of a solution at 30% of ammonium hydroxide. After vortical stirring by means of a Turrax homo- geniser and the addition of a suitable quantity of water up to the desired concentration of Ca, the reaction mixture appears as a solution already ready for use. EXAMPLE 53

Preparation of the supplier composition comprising copper, zinc, manganese and Polymer I (Composition 13) . 1.2 1 of NH₄OH are added to an aqueous solution of 2 Kg of Polymer I. The basic solution thus obtained is slowly added under vortical stirring to the solution formed by the dissolution of 0.1 Kg of CuCl₂*2H₂O, 0.1 Kg of CaCl₂*2H₂O and 0.1 Kg of MnSO₄*H₂O in 3 1 of H₂O. The reaction mixture is left under stirring for 24 hours and brought to the desired volume with H₂O up to the most suitable percentage concentration of the microelements . EXAMPLE 54 Preparation of the supplier composition comprising boron and Polymer I (Composition 14) . 1.3 Kg of B(OH)₃ dissolved in 3 1 of H₂O are added to an aqueous solution of 2 Kg of Polymer I at pH 6-7. The reaction mixture is stirred for a night and then brought to the desired volume with H₂O up to the most suitable percentage concentration of boron. EXAMPLE 55

Preparation of the supplier composition comprising iron and Polymer BEIXON (Composition Beixon+Fe) .

1.2 1 of NH₄OH at 30% are added to an aqueous solu- tion of 2 Kg of acrylosaccharidic polymer named Beixon (44% aqueous solution) , bougth from CHT-ITALIA. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 1.727 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture immediately becomes a reddish-brown colour, it then passes through a considerable densifying phase and finally re- dissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left under stirring for a night and is then brought to the desired volume with H₂O up to obtain percentage concentration of iron about 2-3%.

Elemental Analysis : Carbon=4.75%; Nitrogen=2.84%; Iron=2.12%; Sodium: 1.55%; Sulfur=2.61% EXAMPLE 56 Preparation of the supplier composition comprising iron and Polymer BIOTEX (Composition Biotex+Fe) .

0.22 1 of NH₄OH at 30% are added to an aqueous solution of 2 Kg of acrylosaccharidic polymer named Biotex (11% aqueous solution), bougth from Prochimica Novarese. The basic solution thus obtained is slowly added under vortical stirring, by means of a Turrax homogeniser, to the solution formed by the dissolution of 0.86 Kg of FeNH₄ (SO₄) ₂*12H₂O in 3 1 of H₂O. The reaction mixture im- mediately becomes a reddish-brown colour, it then passes through a considerable densifying phase and finally re- dissolves and stabilizes in the form of a brown-coloured soluble compound. The mixture is left under stirring for a night and is then brought to the desired volume with H₂O up to the most suitable percentage concentration of iron.

With an analogous procedure, the following compounds can be obtained:

• Composition A9 : Zn + Polymer A

• Composition AlO : Mg + Polymer A

• Composition All: Cu + Polymer A

• Composition Al2 : Fe + Mn + Polymer A

• Composition A13 : Ca + Mg + Polymer A • Composition A14 : B+ Mo + Polymer A • Composition A15 : Zn + Mn + Polymer A

• Composition A16 : Fe + Mn + B + Zn + Polymer A

• Composition A17 : Mg + Mo + Polymer A

• Composition A18: K + Mn + Polymer A • Composition A19 : K + Fe + Polymer A

• Composition B4 : Fe + Polymer B

• Composition B5 : NH₄ + Polymer B

• Composition B6 : Ca + Polymer B

• Composition B7 : B + Polymer B • Composition B8 : NH₄ + K + Polymer B

• Composition B9 : Cu + Ca + Polymer B

• Composition BlO : Fe + Ca + Polymer B

• Composition B12 : Fe + Mn + Polymer B

• Composition B13 : Ca + Mg + Polymer B • Composition B14 : B + Mo + Polymer B

• Composition B15 : Zn + Mn + Polymer B

• Composition B16 : Fe + Mn + B + Zn + Polymer B

• Composition B17 : Mg + Mo + Polymer B

• Composition B18: K + Mn + Polymer B • Composition B19 : K + Fe + Polymer B

• Composition C3 : B + Polymer C

• Composition C4 : NH₄ + Polymer C

• Composition C5 : K + Polymer C

• Composition C6 : Cu + Polymer C • Composition C7 : NH₄ + K + Polymer C • Composition C8 : Fe + Ca + Polymer C

• Composition C9 : Mn + Polymer C

• Composition ClO: Cu + Zn + Mn + Polymer C

• Composition CIl: Mg + Polymer C • Composition Cl2 : Fe + Mn + Polymer C

• Composition Cl3 : Ca + Mg + Polymer C

• Composition C14 : B + Mo + Polymer C

• Composition C15: Zn + Mn + Polymer C

• Composition C16 : Fe + Mn + B + Zn + Polymer C • Composition Cl7 : Mg + Mo + Polymer C

• Composition C18 : K + Mn + Polymer C

• Composition C19: K + Fe + Polymer C

• Composition D9 : Cu + Polymer D

• Composition DlO: Cu + Mn + Polymer D • Composition DIl: Fe + Mn + Polymer D

• Composition D12 : Ca + Mg + Polymer D

• Composition D13 : B + Mo + Polymer D

• Composition D14 : Zn + Mn + Polymer D

• Composition D15 : Fe + Mn + B + Zn + Polymer D • Composition D16: Mg + Mo + Polymer D

• Composition Dl7 : K + Mn + Polymer D

• Composition D18: K + Fe + Polymer D

• Composition D19: Mg + Polymer D

• Composition E9 : Cu + Polymer E • Composition ElO: Cu + Mn + Polymer E • Composition Ell: Fe + Mn + Polymer E

• Composition E12 : Ca + Mg + Polymer E

• Composition E13 : B + Mo + Polymer E

• Composition E14 : Zn + Mn + Polymer E • Composition E15 : Fe + Mn + B + Zn + Polymer E

• Composition E16 : Mg + Mo + Polymer E

• Composition E17 : K + Mn + Polymer E

• Composition E18 : K + Fe + Polymer E

• Composition E19: Mg + Polymer E • Composition F5 : Cu + Polymer F

• Composition F6 : Cu + Mn + Polymer F

• Composition F7 : Fe + Mn + Polymer F

• Composition F8 : Ca + Mg + Polymer F

• Composition F9 : B + Mo + Polymer F • Composition FlO: Zn + Mn + Polymer F

• Composition FIl: Fe + Mn + B + Zn + Polymer F

• Composition F12 : Mg + Mo + Polymer F

• Composition F13 : K + Mn + Polymer F

• Composition F14 : K + Fe + Polymer F • Composition F15 : Mg + Polymer F

• Composition G5 : Cu + Polymer G

• Composition G6 : Cu + Mn + Polymer G

• Composition G7 : Fe + Mn + Polymer G

• Composition G8 : Ca + Mg + Polymer G • Composition G9 : B + Mo + Polymer G • Composition GlO: Zn + Mn + Polymer G

• Composition GIl : Fe + Mn + B + Zn + Polymer G

• Composition G12: Mg + Mo + Polymer G

• Composition G13 : K + Mn + Polymer G • Composition G14 : K + Fe + Polymer G

• Composition G15: Mg + Polymer G

• Composition H5 : Cu + Polymer H

• Composition H6 : Cu + Mn + Polymer H

• Composition H7 : Fe + Mn + Polymer H • Composition H8 : Ca + Mg + Polymer H

• Composition H9 : B + Mo + Polymer H

• Composition HlO: Zn + Mn + Polymer H

• Composition HIl: Fe + Mn + B + Zn + Polymer H

• Composition H12 : Mg + Mo + Polymer H • Composition H13 : K + Mn + Polymer H

• Composition H14 : K + Fe + Polymer H

• Composition H15 : Mg + Polymer H

• Composition 15 : Cu + Polymer I

• Composition 16: Cu + Mn + Polymer I • Composition 17: Fe + Mn + Polymer I

• Composition 18 : Ca + Mg + Polymer I

• Composition 19: B + Mo + Polymer I

• Composition 110: Zn + Mn + Polymer I

• Composition 111: Fe + Mn + B + Zn + Polymer I • Composition 112: Mg + Mo + Polymer I • Composition 113 : K + Mn + Polymer I

• Composition 114: K + Fe + Polymer I

• Composition 115 : Mg + Polymer I

• Composition Ca + Beixon • Composition Ca + Biotex

• Composition Mg + Beixon

• Composition Mg + Biotex

• Composition Zn + Beixon

• Composition Zn + Biotex • Composition Mn + Beixon

• Composition Mn + Biotex

• Composition B + Beixon

• Composition B + Biotex

• Composition Ti + Beixon • Composition Ti + Biotex

• Composition NH₄ + Beixon

• Composition NH₄ + Biotex

• Composition Fe+Zn+Mn + Beixon

• Composition Fe+Zn+Mn + Biotex

EXAMPLE 57

Efficacy test of ferric chlorosis on tobacco in sand. Table 1

Tobacco cultivar Brygth (first two real leaves) were transplanted in plastic glasses having a volume equal to 161 cm³, filled with 180 g of sand. After overcoming the transplant crisis, each thesis was treated with 20 ml of a solution of the compounds under examination (normalized at 6% of Fe) every 10 days (three applications) and maintained every three days with 20 ml of demineralized water. This quantity is calculated so that there is no overflow of liquids from the vase. The theses were placed in a greenhouse at a temperature of about 24°C - 60-65% R. H. - 16H of light. 10 days after the last treatment, each thesis was visually assessed as leaf and/or root development and the chlorophyll content indexes (SPAD values) effected on the last three leaves (average of 5 surveys per leaf) , by means of a "Chlorophyll Meter - SPAD 502" Minolta instrument. Table 1:

* average of three leaves ** overall visual assessment (range 0-10) *** evident symptoms of phytotoxicity EXAMPLE 58 Efficacy test of ferric chlorosis on tobacco in basic soil. Table 2

Tobacco cultivar Brygth was transplanted in plastic glasses having a volume equal to 855 cm³, filled with 600 g of soil at pH 8.0/8.2. After 20 days, each thesis was treated with 25 ml of a solution of the compounds under examination (normalized at 6% of Fe) every 10 days (three applications) and maintained every three days with 30 ml of demineralized water. This quantity is calculated so that there is no overflow of liquids from the vase. Dur- ing the first two applications, a mineral fertilizer Composition NPK at 3g/L was administered, together with the iron, to all the theses. The theses were placed in a greenhouse at a temperature of about 24⁰C - 60-65% R. H. - 16H of light. 10 days after the last treatment, each the- sis was visually assessed as leaf and/or root development and the chlorophyll content indexes (SPAD values) effected on the last three leaves (average of 5 surveys per leaf) , by means of a "Chlorophyll Meter - SPAD 502" Minolta instrument. Table 2 :

* average of three leaves

** overall visual assessment (range 0-10)

*** less developed root development

EXAMPLE 59

Efficacy test of ferric chlorosis on tomatoes in sterile soil. Table 3

Tomatoes cultivar Marmande (first two real leaves) were transplanted in plastic glasses having a volume equal to 855 cm³, filled with 600 g of sterile soil (very sandy) . After overcoming the transplant crisis, each the- sis was treated with 20 ml of a solution of the compounds under examination (normalized at 6% of Fe) every 10 days (three applications) and maintained every three days with 20 ml of demineralized water. This quantity is calculated so that there is no overflow of liquids from the vase. The theses were placed in a greenhouse at a temperature of about 24°C - 60-65% R. H. - 16H of light. 10 days after the last treatment, each thesis was visually assessed as leaf and/or root development and the chlorophyll content indexes (SPAD values) effected on the last three leaves (average of 5 surveys per leaf) , by means of a "Chlorophyll Meter - SPAD 502" Minolta instrument. Table 3 :

* average of three leaves

Claims

1. A composition which supplies essential elements, comprising one or more essential elements selected from potassium, iron, calcium, magnesium, manganese, copper, zinc, molybdenum, boron or nitrogen, and co- polymeric compounds containing acid functions, obtained by the copolymerization of mono- or oligosaccharides with acids or their mono-unsaturated mono/polycarboxylic derivatives and/or with mono- unsaturated sulfonic acids and/or mono-unsaturated phosphonic acids.

2. The composition according to claim 1, characterized in that the nitrogen is in the form of ammonia or in the form of quaternary ammonium salts .

3. The composition according to claim 1, characterized in that the mono-oligosaccharides are selected from glucose, saccharose, fructose, leucrose, palatinose, lactose, maltose, mannose, sorbitol, mannitol, gluconic acid, glucuronic acid, alkyl ethers, hy- droxyalkyls and carboxyalkyls of saccharides.

4. The composition according to claim 1, characterized in that the unsaturated mono/polycarboxylic acids and their derivatives are selected from acrylic acid, methacrylic acid, maleic anhydride, ac- rylamide, allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, vinylphosphonic acid.

5. The composition according to claim 1, characterized in that the copolymeric compounds containing acid functions, obtained by the copolymerization of mono- or oligosaccharides with acids or their monounsatu- rated mono/polycarboxylic derivatives and/or with monounsaturated sulfonic acids and/or with monoun- saturated phosphonic acids, are selected from copolymers obtained by the copolymerization of glucose and acrylic acid; fructose and acrylic acid; palati- nose and acrylic acid; leucrose and acrylic acid; saccharose, acrylic acid and methallylsulfonate; saccharose, acrylic acid, methallylsulfonate and ac- rylamide,- saccharose, maleic anhydride, phosphorous acid and sodium hydrogen sulfite; or saccharose, maleic anhydride, iron ammonium sulfate (II) .

6. The composition according to claim 1, characterized in that it also comprises other compatible active principles such as other fungicides, phytoregula- tors, antibiotics, herbicides, insecticides and fertilizers .

7. The composition according to claim 6, characterized in that the fungicides are commercial cupric fungicides .

8. The composition according to claim 6, characterized in that the cupric fungicidal product is selected from Kentan DF (copper hydroxide at 25%) , copper oxychloride, copper hydroxide, Airone (1:1 mixture of copper oxychloride : copper hydroxide), Bordeaux mixture (copper sulfate neutralized with lime) , Car- lit (mixture of Benalaxil 2.5%, Fosetil Aluminum 35%, Mancozeb 35%) .

9. The composition according to claim 6, characterized in that the fertilizers are commercial NPK fertiliz- ing products (based on nitrogen, phosphorous or potassium) .

10. The composition according to claim 1, characterized in that the quantity of essential elements with respect to the quantity of acrylic-saccharide copoly- mer varies within the range of 0.01 to 20 mg of essential element per g of acrylic-saccharide copolymer.

11. The composition according to claim 10, characterized in that the ratio between the quantity of essential elements and the quantity of acrylic-saccharide copolymer is equal to 1 mg elem./lO g copolymer or 0.04 mg elem./10 g copolymer or 0.18 mg elem./10 g copolymer.

12. Use of a composition which supplies essential ele- ments, comprising one or more essential elements se- lected from potassium, iron, calcium, magnesium, manganese, copper, zinc, molybdenum, boron or nitrogen, and copolymeric compounds containing acid functions, obtained by the copolymerization of mono- or oligosaccharides with acids or their mono- unsaturated mono/polycarboxylic derivatives and/or with mono-unsaturated sulfonic acids and/or mono- unsaturated phosphonic acids, according to any of the claims from 1 to 11, as nutritional products in agriculture for the prevention and treatment of physiological alterations or nutritional unbalances in plants .

13. Use according to claim 12, characterized in that the composition is used in the form of an aqueous solu- tion and/or solid preparation, or in a liquid or solid formulation.

14. Use according to claim 12, for supplying nutrition to plants, or for modulating their physiological processes, and/or for the control of phytopathogen agents or insects and other parasitic species, through direct biocide actions and/or by the induction of the specific innate defense responses of each crop .

15. A process for the preparation of a composition which supplies essential elements, comprising an es- sential element according to any of the claims from 1 to 11, according to the following reaction:

Copol . + Elem. -» Elem. supplier wherein Copol. represents the compounds previously defined as copolymeric compounds containing acid functions or acid-saccharide copolymers and the term Elem. represents an acid, base or salt of an essential element selected from nitrogen, potassium, iron, calcium, magnesium, manganese, copper, zinc, molybdenum and boron.

16. A process for the preparation of a composition which supplies essential elements comprising various essential elements according to any of the claims from 1 to 11, characterized in that it comprises the mix- ing of two or more compositions which supply essential elements comprising an essential element and acid-saccharide copolymers.

17. A process for the preparation of a composition which supplies essential elements comprising two or more essential elements according to any of the claims from 1 to 11, according to the following reaction:

Copol. + Elem.l + Elem.2 → Elem.1-Elem.2- Supplier wherein the term Copol . represents the compounds previously defined as copolymeric compounds contain- ing acid functions or acid-saccharide copolymers and the terms Elem.l and Elem.2 have the same meanings as Elem. provided that Elem.l is different from Elem.2.

18. The process according to claim 15 or 17, character- ized in that the acid, base or sale of an essential element is selected from boric acid, copper sulfate, calcium hydroxide, iron sulfate, zinc sulfate, calcium carbonate, magnesium carbonate.

19. The process according to claim 15 or 17, character- ized in that the reaction is carried out in water, at a temperature ranging from 0 to 80⁰C.

20. The process according to claim 19, characterized in that the reaction is carried out in an inorganic base selected from ammonium hydroxide, potassium hy- droxide, sodium hydroxide.

21. A method for the prevention and treatment of physiological alterations or nutritional unbalances of plants and/or for increasing their resistance against external pathogen attacks by the application of a composition supplier of essential elements according to one of the claims 1-11.

22. The method according to claim 21, characterized in that the application is effected in the form of an aqueous solution and/or solid preparation, a liquid or solid formulation through the leaves or roots by burial or an injector spade, in "fertirrigation" also in terrains with an alkaline pH and, in particular and effectively, by means of micro- irrigation systems such as hoses and drippers.

23. The method according to claim 21, characterized in that the composition supplier of essential elements has an application dosage ranging from 0.01 g to 20 g of composition per square meter of agrarian soil.