IE52344B1 - Plant conditioning compositions containing titanium - Google Patents

Abstract

The invention relates to plant conditioning compositions containing titanium, which have an increased physico-chemical and biological stability. The compositions comprise 0.1 to 15.0% by weight of a titanium- ascorbic acid chelate containing 14 to 28 g.moles of ascorbic acid related to 1 g.atom of titanium, the pH of which is adjusted to 5 to 7, 0.1 to 2.0 parts of one or more biochemically essential nutrients and/or 0.0001 to 0.001 parts of one or more phytohormones related to 1 part of titanium and at least 0.01% by weight of one or more of the compounds selected from the following group: sorbic acid and salts thereof, benzoic acid and salts thereof, p-nitro-benzoic acid and salts thereof, propionic acid and salts thereof, hexamethylenetetramine related to the total weight of solid ingredients, optionally in association with wetting agents, adhesives and/or further conventional additives.

Description

The invention relates to plant conditioning compositions containing titanium, which have an increased physicochemical and biological stability.

It is well knwon that titanium plays an important role in the vital processes of plants.

It is further known that though titanium is present in the soil in a high concentration, it is not available for the plants since titanium salts insoluble in water cannot exert their biological activity, According to the Hungarian Patent specification No 170,693 a solution containing four-valent titanium ions is reacted with ascorbic acid to provide a titanium complex suitable for treating plants. Ascorbic acid is present in the solution in a 50- to 200-fold excess related to titanium. The stability of aqueous solutions containing ascorbic acid in an excess suitable for treating plants is. however, not satisfactory.

According to micro-biologicial tests for example the strains Clostridium botulinum, Aspergillus nicer.

Lactobacillus lactis. Clostridium bytilicum.

Thermobacterium mobile decompose ascorbic acid used for forming complexes. The presence of titanium, is supposed to increase this effect. On the other hand, titanium sprayed on the surface of leaves as a thin film may easily be inactivated by environmental effects and therefore in the vegetation period the frequency of treatments should considerably be increased to ensure the desired effect. Due to the high labour costs and energy demand this has a negative effect on the economy of the process.

The invention relates to a new plant conditioning composition containing titanium, which is devoid of the above disadvantages, ie, in which four-valent titanium can be resistant to oxidation even in a very dilute solution, in the presence of a high excess of ascorbic acid, after spraying on a large area. The new compositions are resistant to microorganisms as well.

According to the present invention there is provided a plant conditioning composition which comprises a four-valent titanium-ascorbic acid chelate and a stabilizer which comprises one or more of sorbic acid or a salt thereof, benzoic acid or a salt thereof, salicylic acid or a salt thereof, p-nitrobenzoic acid or a salt thereof, propionic acid or a salt thereof, or hexamethylenetetramine.

Such a composition can take the form of a solution containing four-valent titanium ions and a high excess of ascorbic acid, along with at least 0.01% by weight of one or more of the stabilizer. The percentage amount 5 for the stabilizer is related to the solid substance content of the composition.

Ascorbic acid is suitably used in a 20 to 200-fold excess related to titanium. The above-listed stabilizers can be added to the solution up to a concentration for instance of 25% by weight but in _a concentration exceeding 2t by weight their activity is increased to a relatively low extent and therefore it is generally not economic to increase their amount over this concentration. it is a considerable advantage of the compositions according to this invention that due to their increased stability the frequency of treatments can be decreased or if the frequency of treatments is unchanged, the activity is increased by 5 to 8% in comparison with the known compositions which do not contain stabilizers.

The compositions can be stored for a long time without a noticeable loss of activity, in spite of their high ascorbic acid concentration, even in very dilute agueous solutions.

The compositions according to the invention can optionally further contain trace elements and/or vegetable nutrients. Trace elements include magnesium, iron, manganese, zinc, molybdenum and boron while the vegetable nutrients can be conventional nitrogenphosphorus-potassium (NPK) containing fertilizers, suspensions, etc.

When preparing the compositions a four-valent titanium salt can be dissolved in water in a desired concentration, ascorbic acid added in a desired excess and the pH of the solution preferably adjusted to about .

To the solution obtained, one or more of the abovelisted stabilizers are added. In the absence of these additives the liquid surface is covered by colonies of microorganisms already after two weeks. Microorganisms decrease the active ingredient concentration and make the ordinary use of solutions impossible. The additives according to the invention inhibit the growth of microorganism colonies and accordingly preserve the solutions in a condition suitable for application for a long time and in the same time result in a 5 to 8% increase in crop yield in comparison with solutions having the same active ingredient concentration but not containing the additives according to the invention.

This increase in yield is due to the increased microbiological resistance.

Micro- and macronutrients and plant hormones when added in a given amount to the complex of four-valent titanium with ascorbic acid accelerate the plant growth.

The compositions containing macro- and micronutrients when applied to the plants in a low dose as leaf or spray fertilizers or used for seed dressing have a considerable influence on the development of plants, accelerate the absorption of micronutients, promote the effect of plant hormones below the toxic threshold value ID The typical plant conditioning compositions according to the invention comprise 0.1 to 15.0% by weight, preferably 0.5 to 15.0% by weight of a titaniumascorbic acid chelate which preferably contains 14 to 28 g moles of ascorbic acid related to 1 g atom of four-valent titanium ions, the pH value of whch is adjusted to 5 to 7, 0.1 to 2.0 parts by mass of biochemically essential nutrient related to 1 part by mass of four-valent titanium ions or a combination of such nutrients and/or 0.001 to 0.01% of one or more phytohormones and at least 0.01% by weight of one or more stabilizer compounds selected from the following group: sorbic acid and salts thereof, salicylic acid and salts thereof: benzoic acid and salts thereof, p.-nitrobenzoic acid and salts thereof, propionic acid and salts thereof, hexamethylene tetramine, related to the total weight of solid ingredients, optionally in association with wetting agents, adhesives ot further conventional additives.

As a nutrient the composition preferably contains boron, magnesium, manganese, iron, zinc, molybdenum or a water-soluble salt thereof. Macronutrients include water-soluble nitrogen-phosphorus-potassium fertilizers.

The phytohormone components of the compositions may be auxines, giberellines. cytokinins. heteroauxines (alpha-naphthylacetic acid; beta-indolylacetic acid). etc. Phytohormones include 2,4-dichlorophenoxyacetic acid and salts thereof. As a further additive one or more of the stabilizers referred to herinabove are added to the solution. Of the microelements the compositions may contain for example 1000 ppm of boron. 500 ppm of manganese. 500 ppm of zinc, 1000 ppm of magnesium and i 500 ppm of iron related to 100 ppm of four-valent titanium, in the form of water-soluble salts. The compositions may contain for example 25 ppm of 2.4-dichlorophenoxyacetic acid or 10 ppm of giberellic acid or similar additives related to 1000 to 2000 ppm of titanium.

The plant protecting compositions according to the invention may be prepared by dissolving a water-soluble salt of four-valent titanium, for example titanium tetrachloride or sodium titanate and 14 to 28 g moles of ascorbic acid calculated from 1 g atom of titanium in water, adjusting the pH of the aqueous solution to 5 to 7 and adding the aqueous solution of micro- and macronutrients to the solution obtained. To this solution suitable wetting agents or adhesives and stabilizing 10 agents may be added. Stabilizing agents stabilize the concentration of titanium and micro-elements on the surface of plants, which have been sprayed by the compositions.

The compositions according to the invention are generally applied to the plants by spraying.

Experimental observations show that the nutrients penetrate into the chloroplasts of leaves and as a result phytosynthetic and enzyme activity are increased.

In field trials and green house experiments under 20 controlled conditions (eg illumination) it has been established that the use of the compositions according to the invention accelerates the absorption of biochemically essential nutriments. The absorption of magnesium, manganese, iron and zinc which play an 25 important role in photosynthesis, has a direct influence on the yield of fruit trees and cereals and increases the food value as well. When spraying papilionaceae and grasses the presence of molybdenum, and when treating beets the presence of boron increases crop yield, improves the conditions of carbohydrate formation and has a favourable effect on the formation of cell walls. In case of soils poor in nutrients it is advisable to include also water-soluble nitrogen, phosphorus and potassium compounds in the plant conditioning compositions according to the invention.

Small concentrations of phytohormones and herbicides having a hormone activity considerably increase the growth of young plants, seedlings and promote the growth oif shoots and buds.

The optimum doses of the plant conditioning compositions according to the invention depend on the plant varieties to be treated. When treating vegetables in their vegetation period, 5 to 10 litre/ha doses may be employed 3- or 4-tines. For treating cereals after blooming a single 1 litre/ha dose is generally sufficient. If young seedlings are treated every 10 days starting from their 3 to 4-leaf stage, their growth is efficiently increased.

Spraying can be performed by airplanes, helicopters or sprayers. Before use the compositions are diluted with water to the desired concentration and are normally used ίο in an amount of 1 to 5 litre/ha depending on the way of application. From an economical point of view it is advisable to connect treatments by the instant compositions with other plant protection work. The compositions according to the invention are compatible with any neutral or slightly acidic plant protecting agents .

The preparation and use of the compositions according to the invention are illustrated by the following examples.

Example 1 A four-valent titanium salt corresponding to 1 g of titanium and 100 g of ascorbic acid are dissolved in water. The solution is made up to 1 litre, the pH is adjusted to 5 and 1 g of salicylic acid is added. The storability of the composition obtained is at least 2 years.

To the above composition is soluble ammonium salt corresponding to 3% by weight of nitrogen, phosphoric acid corresponding to 4% by weight of phosphorus pentoxide and a potassium salt corresponding to 5% by weight of I^O are added, where the percentage values relate to the total weight of the solution. The storability of the composition obtained is identical with the storability of the above composition but the latter one contains also essential nutriments in addition to the components used for conditioning plants.

The activity of the composition described above was tested on wheat (Rana-1) in the vegetation period, in a dose of 3 χ 1 g titanium/ha. The yield of the treated plants was compared with that of the untreated control. The following results were obtained.

Yield (102 Kg/ha) % 10 Wheat treated by the above composition 47.25 121.4 Untreated control 38.93 100.0 Example 2 A four-valent titanium salt corresponding to 1 g of 15 titanium and 95 g of ascorbic acid are dissolved in 1 litre of water. The solution is made up to 1 litre, the pH is adjusted to about 5 and 0.5 g of sodium benzoate are added. The composition can be stored for more than two years without any loss in activity.

The activity of the composition was tested in maize germination tests (TC 3344/ a variety). The following treatments were carried out: Control I: Control II: Test solution: untreated control treatment carried out with a composition having the above ingredients except sodium benzoate the composition prepared according to this example The compositions were used in the same dose as in Example 1.

The results obtained are given in the following table.

Mean stem length (cm) % 15 Control I 4.09 100.0 Control II 4.65 113.7 Test solution 4.74 115.9 The same test was repeated in'field trials on silo maize. The following results were obtained.

Yield (102 kg/ha) % Control I 406.0 100.0 Control II 471.0 116.0 5 rest compositions 484.0 119.2 Example 3 A four-valent titanium salt corresponding to 1000 ppm of titanium, 100 000 ppm of ascorbic acid, 500 ppm of manganese, 500 ppm of zinc and 700 ppm of iron in the form of water-soluble salts are dissolved in water and the solution is made up to 1 litre. The pH is adjusted to 5 and 0.5 g of sodium benzoate and 1000 ppm of sodium ligninsulfonate (wetting agent) are added.

The composition obtained is used in a 200-fold dilution for treating paprika and in a 500 to ΐοοο-fold dilution for treating apples. Paprika is treated in a 4 to 5-leaf stage three times, by spraying. The apple trees are sprayed when the petals are falling and the treatment is repeated two more times, in the third and sixth week. Peach, apricot, pear and cherry can also successfully be treated in an analogous way. The results obtained on paprika and apples, respectively are shown in the following tables.

Paprika test Treat- ment Average kg/ plant weight % Pieces/ 100 plants % Ascor- bic acid mg/lOOg con- tent % Control 7.46 100.0 280 100.0 72 100.0 Treated 9.19 123.5 324 115.7 266 369.4 Apple test Yield Glucose content Variety and treatment kg/ha * % Starking Control 3540 100.0 9.1 Treated 5960 168.3 9.8 Jonathan Control 7262 100.0 8.3 Treated 11066 152.3 10.6 Example 4 A four-valent titanium salt corresponding to 1000 ppm of titanium, a 28-times molar excess of ascorbic acid and 0.5 g of salicylic acid are dissolved in water and the solution is made up to 1 litre. The pH is adjusted to 5 and 10 ppm of giberellic acid 2000 ppm of sodium dodecylbenzonesulphonate (wetting agent) are added.

The composition obtained was tested in wheat germination tests and was used for treating Saintpaulis ionantha plants. Wheat grains were dressed by a solution containing 0.02 ppm titanium. The Saintpaulis ionantha plants were sprayed by a 0.2% dilution of the above solution every ten days, altogether twice.

The results obtained are given in the following tables.

Wheat germination test Variety and treatment Average length of plant cm % Lublajnaja Control 10.46 100.0 Treated 12.18 116.4 Saintpaulis ionantha test Treatment Plant Dry Formation diameter substance of bulbs (average of % % ioo plants) cm Control 15.75 3.96 23 Treated 21.20 4.58 48 The results show that the wheat grains treated by the compositions according to the invention germinated ina 10 shorter time and the growth of the treated Saintpaulis ionantha plants was acclerated in comparison with the control grains and plants, respectively. The same growth accelerating effect can bve observed when ornamental plants are treated. The treated plants 15 flower earlier and consequently can be sold about two weeks earlier than the control plants.

Example 5 A four-valent titanium salt corresponding to 2000 ppm of titanium and 100 000 ppm of ascorbic acid are dissolved 20 in 1 litre of water. 0.5 g of sodium benzoate and 500 ppm of a water-soluble molybdenum salt and 1000 ppm of polyethylene-polypropylene block polymer (wetting agent) are added. The pH of the solution is adjusted to . to 6-leaf lucerne plants were treated by the above compositions before every mowing once, in a dose of 2 litre/ha. Green peas were treated by the above composition during budding and at the first by a dose of 2 litre/ha, altogether twice. Grass was sprayed by 1 litre/ha of the above composition once. The results of the above treatments are shown in the following tables.

Treating green peas Variety and treatment Yield kg/ha % Average delicacy (T) Saccha- arose % Puget Control 4450 100.0 140.5 5.35 Treated 5250 118.0 127.5 5.88 Grilne Control 4210 100.0 136.2 5.35 Treated 5260 124.9 123.8 5.75 Lucerne test Treat- ment Green weight Kg/m3 Dry substance content g/hg Raw protein g/kg Digest- able protein g/kg Starch value g/kg control 1.25 90S 128 93 301 Treated 1.87 915 171 124 316 Grass test Treatment Yield Kg/ha % Raw protein g/kg Starch value g/kg Control 4300 100.0 46 110 Treated 6500 151.2 47 106 The above results show that the yield and delicacy of green peas are greatly improved by the treatment according to the invention.

In the case of lucerne in addition to the improvement of quantitative and qualitative characteristics the number of roots is also considerably increased and the activity of nitroqenase enzyme is accelerated. When spraying grass a striking increase of green mass can be observed while the raw protein and starch values remain substantially unchanged.

Example 6 A water-soluble four-valent titanium salt corresponding W to 1000 ppm of titanium and 90,000 ppm of ascorbic acid are dissolved in water and the solution is made up to 1 litre. The pH of the solution is adjusted to 5 and 25 ppm of 2,4-dichlorophenoxyacetic acid sodium salt, 0.5 g of sodium benzoate and petroleum sulphonate sodium salt (wetting agent) are added.

By the compositions obtained, after dilution, vine plants were sprayed three times in their vegetation period. The results are shown in the following table. 23 44 Vine test Glucose Sugar/acid Variety and treatment g/100 ml % ratio Treasure of Pannonia 5 Control 8.0 100.0 13.2 Treated 9.4 117.5 19.2 Italian riesling Control 12.6 100.0 15.1 Treated 17.6 139.6 28.3 The above results show that the treatement increases the carbohydrate content of grapes and accordingly, the sugar/acid ratio is also increased.

Claims (12)

1. A plant conditioning composition which comprises a four-valent titanium-ascorbic acid chelate and a stabilizer which comprises one oc more of sorbic acid oc 5 a salt theceof. benzoic acid oc a salt theceof. salicylic acid oc a salt theceof, p-nitcobenzoic acid oc a salt theceof. pcopionic acid oc a salt theceof, oc hexamethylene-tetcamine.

2. A composition accocding to claim 1 which comprises 10 0.1 to 15.0% by weight of the chelate and at least 0.01% by weight of the stabilizec.

3. A composition accocding to claim 1 oc claim 2, wherein the chelate contains 14 to 28 g-moles of ascorbic acid foe every 1 g-atom of titanium. 15

4. A composition accocding to any preceding claim which has a pH of S to 7.

5. A composition accocding to any preceding claim which comprises 0.1 to 2.0 pacts of one oc more biochemically essential nutcients pec pact of titanium. 20

6. A composition accocding to claim 5. wherein the nutrient comprises a water-soluble salt of one oc moce of boron, magnesium, manganese, icon, zinc oc molybdenum.

7. A composition according to claim 5 or 6 wherein the nutrient comprises a nitrogen-phosphorus-potassium fertilizer.

8. A composition according to any preceding claim which 5 comprises 0.001 to O.Olt by weight of one or more phytohormones.

9. A composition according to claim 8, wherein the phytohormone comprises one or.more of an auxin, giberellin, cytokinin or heteroauxin.

10. 10. A composition according to claim 9, wherein the phytohormone comprises alpha-naphthylacetic acid Or beta-indolylacetic acid.

11. A composition according to claim 8 or 9, wherein the phytohormone comprises 2,4-dichlorophenoxyacetic acid or 15 a salt thereof.

12. A composition according to any preceding claim, substantially as described in the Examples herein.