CA1159273A

CA1159273A - Plant conditioning compositions containing titanium

Info

Publication number: CA1159273A
Application number: CA000391622A
Authority: CA
Inventors: Istvan Pais; Magdolna Feher; Csaba Soptei; Elemer Tomordi
Original assignee: Nitrokaelepek; Kerteszeti Egyetem
Current assignee: Nitrokaelepek; Kerteszeti Egyetem
Priority date: 1980-12-29
Filing date: 1981-12-07
Publication date: 1983-12-27
Also published as: JPS57134405A; BE891618A; NL8105864A; ES508202A0; CH654981A5; AR227570A1; RO83098A; PT74194A; HU186758B; ES8404770A1; SE8107796L; DD201844A5; AU8016182A; IE813058L; FI67533C; GB2090585A; AT377972B; PL234387A1; FI813916L; BG41123A3

Abstract

PLANT CONDITIONING COMPOSITIONS CONTAINING TITANIUM
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 kelate 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 nutriments 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

~S~2~3 The invention relates to plant condit~oning compositions conta~ning titaniuml which have an increased physico-chemical and biological stability.
It is well known that tltanium 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-old 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-biological tests for example the strains Clestridium botulinum, Aspergill~s niger, Lactobacillus lactis, Clostridium bytilicum, Ther~obacterium 20 mobile decompose ascorbic acid used for form~ng complexes.
The presence of titanium is supposed to increase this effect.
On the other hand, titanium sprayed on the sur~ace of leaves as a thin film may easily be inactivated by environmen~al 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 process.

~ . ~

~L~S~3 The invention relates to a new plant conditioning composition containing titanium, which i5 devoid of the above disadvantages, i.e. in which our-valent titanium is 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 re-sistant to microorganisms as well.
According to ~he invention there is provided a plant conditioning composition ccntaining a titanium-ascorbic acid kelate, substantially for spraying oliage or seed treatment, which comprises 0.1 to 15~0 % by weight o a titanium-ascorbic acid kelate containing 14 to 28 gOmoles 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 lS more biochemically essen~ial nutriments and/or 0.0001 to 0.001 paxts of one or more phytohormons 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, ~-nitro-benzoic acid and salts thereof, pro-pionic acid and salts thereof, and hexamethylenetetramine related to the total weight of solid ingredients.
Ascorbic acid is used in a 20 to 200-fold excess related to titanium. The above-listed stabilizers are add~d to the solution up to a concen~ration of 25 % by weight but in a concentration exceeding 2 % by weight ~, ~ i:

~3 S~3 - 2a -their ac~ivity 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 S 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 % ;n comparison with the known compositions ,.

~ . - .

~5~Z73 which do no~ contain stabilizators. The compositions can be stored for a long time without a noticea~le loss of activ~
ity, in spite of their high ascorbic acid concentration, even in very dilute aqueous solutions.
The compositions according to the invention comprise in addition to fo,ur-valent titanium ions and a 20 to 200-fold excess of ascorbic acid related to titanium and optionally further conventional additives at least 0.01% by weight of one or more compounds selected from the following group: sorbic acid, benzoic acid, p-hydroxy-benzoic acid, propionic acid~ salts of these compound,and hexamethylene-tetramine optionally in admixture with trace elements and/or vegetable nutriments. Trace elements include magnesium, iron, manganese, zinc, moly~denum and boron while the term "vegetable nutriments" is used to refer to conventional nitrogene-phos-phorus-potassium (,NPhP~ containing fertilizers, suspensions, etc.
When preparing the compositions a ~our~valent titanium salt is dissolved in water in a desired concentration, ascor~ic acid is added in a desired excess and the pH of the solution is preferably adjusted to about 5.
To the solution o~tained one or more oi the above-listed additives are added. In the absence of these additives the liquid surface is covered by colonies o~ microorganisms already after 2 weeks. Microorganisms decrease the active ingredient concentration and make the ordinary use of solutions i~possibI~. The additives according to the invention inhibit the g~owth of ~icroorganism 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%-~;

~lS~ 73 incxease in crop yield in comparison ~ith 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 macronutriments and plant hormones when added in a given amount to the complex of four-valent titanium with ascorb;c acid accelerate the plant growth.
The compositions containing macro- and micronutri-ments when applied to the plants in a low dose as leaf or spray fertilizers or used for seed dressing have a consider-able influence on the development of plants, accelerate the absorption of micronutriments, promote the effect of plant hormones below the toxic threshold value.
The plant conditioning compositions according to the inventlon comprise 0.1 to 15.0~ by weight, preferably 0.5 to 1500% by weight of a titanium-ascorbic acid kelate which contains 14 to 28 g.moles of ascorbic acid related to 1 g.
atom of four-valent titanium ions the pH value of which is adjusted to 5 t~ 7, 0.1 to 2.0 parts by mass of a bio-chemically essential nutriment related to 1 part by mass offour-valent titanium ions or a combination of su~h nutriments and/or 0.001 to 0.01~ ~f one or more phytohormones and at least 0.01% by w~ight of one or more of the compounds selected from the following group: sorbic acid and salts thereof, benzoic acid and salts thèreof, ~-nitro-benzoic 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 or further conventional additives.

~15~;~'73 As a nutriment the composition preferably contains boron, magnesium, manganese, iron, zinc, molybdenum or a water-soluble salt thereof. Macronutriments ~nclude water-soluble nitrogen~phosphoru$-potassium fertilizers.
The phytohormone components of the compositions may be auxines, giberellines, cycloquinines, heteroauxines (alpha-naphthylacetic acid-beta-indolylacetic acid), etc. Phyto-hormones include 2,4-dichlorophenoxyacetic acid and salts thereof. The compositions contain 1000 to 2000 ppm of ascorbic 10 acid in one litre of solution and the amount of ascorbic acid related to four-valent titanium is between 50,000 and 100,000 ppm. As a further additive one or more of the stabilizers referred to hereinabove 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 S00 ppm of iron related to 1000 ppm of four-valent titanium, in the orm c)f water-soluble salts.
The compositions may contain for example 25 ppm of 2,4-dich-lorophenoxyaceti~ acid or 10 ppm o~ giberellic a~id or similar 20 additives related to 1000 o 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 for 1 g.atom of titanium in water, adjusting the pH of t~e aqueous solution to S to 7 and adding the aqueous solution of micro- and macro-nutximents to the solution obtained. To this solution suitable wetting agents or adhesives and s~abilizators may be added. Stabilizing agents 30 stabilize the concentration of titanium and micro-elements _5_ ~55'i~

on the surface o~ 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 tha~ the nutriments penetrate into the ~hloroplastices o~ leaves and as a result phytosynthetic and enzyme ac~ivity are increased.
In field trials and greenhouse experiments under controlled conditions (e.g. illumination) it has been 10 established that-the use of the csmpositions according to the invention accelerates the absorption of biochemically essential nutriments. The absorption of magnesium, manganese, iron and zinc which play an important role in photosynthesis, has a direct influence on the yield o fruit trees and cereals and increases the food value as well. When spraying papilion-aceae and grasses, molybdenum and when treating beets, the presence of boron increases crop yleld, improves the conditions of carbohydrate formation and has a favourable e~fect on the formation of cell walls. In case of soils poor ~n nutriments 20 it is advisable to give also water-soluble nitrogen, phosphorus and potassium compounds to the plant conditioning compositions according to the invention.
Small concentrations of phytohormones and herbicides having a hormone activity considerably increase the growth of young plantsj seedlings and promote the growth of sprouts and buds.
The optimum doses of the plant conditioning composi-tions according to the invention are depending on the plant varieties to be treated. When treating vegetables in their 30 vegetation period, 5 to 10 lit.~ha. doses ma~ be employed Z~3 3- or 4-times~ For treating cereals after blooming a single 1 lit./ha. dose is generally sufficient. If youny seedlings are treated starting from their 3 to 4-leaf stage every 10 days, theix growth is efficiently increased.
Spraying can be performed by planes helicopters or sprayers. Before use the compositions are diluted with water to the desired concentration and-are used in an amount of 1 to 5 lit./ha. depending on the way of application. From economical point o~ view, it is advisable to connect treat-10 ments by the instant compositions with other plant protectionworks. 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 fo~r-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 lit., the pH is adjusted 20 to 5 and 1 g. of salycilic acid is added. The storability of the composition obtained is at least 2 years.
To the above composition a 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 o~ K2O 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 thè latter one contains also essential nutriments in 30 addition to the components used for conditioning plants.

~S~2~

The activity of the composition described above was tested on wheat/Rana-l in the vegetation period, in a dose of 3 x 1 g. titanium/ha. The yield of t~e treated plants was compared with that of the untreated control. The following results were obtained.
Yield 10 kg./ha. %
, Wheat treated by the above composition 47.25 121.4 10 Untreated control 38.93 100.0 Example 2 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 lit. and the pH is adjusted to about 5. To the solution 2 g. of ferrous sulfate are added.
The composition under normal condit:ions can be stored fox about 2 years without any loss in activity. The activity of the composition was tested in fielcl trials on silo maize.
The silo maize was treated with the above composition in a dose corresponding o 3 x 1 g. titanium/ha. The results obtained are given in the following table.
~ield %

Silo maize treated by the above composition 486.0 119.0 Untreated control 408.0 100.0 Example 3 A four-valent ti~anium salt corresponding to 1 g.

of ti~anium and 95 g. of ascorbic acid are dissolvad in 1 lit.
of water. The sol~tion is made up to 1 lit., the pH is adjusted to about 5 and 0.5 g. of sodium benzoate are added.
The composition obtained can be stored for more than 2 years ~.' g~73 without any loss in activity.
The activity of the composition was tested in maize germination tests (TC 3344/a variety). The following treat-men~s were carried out:
Control I: untreated control Control II: treatment carried out with a composition having the above ingredients except sodium benzoate Test solution: the composition prepared according to this example.
The compositions were used in the same dose as in Exampl~ 1.
The results obtained are given in the following table.

Mean stem %
length /cm/
_ 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 Test composition 484.0 119.2 Example 4 A four-valent, water-soluble titanium compound corresponding to 1 g. of titanium and 105 g. of asco~bi~

acid are dissolved in water. The solution is made up to 1 30 lit., the pH is ad~usted to about 5 and 0.1% by weight o _g _ ~r"
:~ .

~51~2~3 magnesium, 0.05% by weight of iron, 0.05% by weight of manganese, 0~05% by weight of zinc, 0.02% by weight of moly-bdenum and 0.05% by weight of boron are added in the form of water-soluble metal salts. The composition preserves its original activity for more than two years.
Example 5 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-soluhle salts are dissolved in water and the solution is made up to l lit. The pH is adjusted to 5 and 0.5 g. of sodium benzoate and lQ00 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 1000-fold dilution for treating apples. Paprika is treated in a 4 to 5-leaf stage three times, by spraying. The appla trees are sprayed when the petals are fallin~ and the treatment is repeated two more times, in the third and sixth week. Peach, apricot, pear and cherry can also succ~ss~ully be treated in an analogeous way. The results obtained on paprika and apples, respectively are shown in the following tables.
Paprika Test Average Pieces Ascorbic content kg. ~eight ~100 acid Treatment /plant % plants % mg.~100 g.

Control 7.46 100.0 280 100.072 100.0 Treated 9.19 123.5 324 115.7266 369.4 ~ ~ ~73 Apple Test Yield Glucose Content Variety an`d 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 6 A four-valent titanium salt corresponding to 1000 ppm of titanium, a 28-times molar excess of ascorbic acid and 0.5 g. of salycilic acid are dissolved in water and the solution is made up to 1 lit. The pH is adjusted to 5 and 10 ppm of giberellic acid and 2000 ppm of sodium dodecylbenzone-sulphonate (wetting agent~ are added.
The composition obtained was tested in wheat germi-nation tests and was used for treat:ing 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 ~5~'~73 Saintpaulis ionantha test Treatment Plant diameter Dry substance Formation of /average ofbulbs 100 plants/cm ~ ~

Control 15.753.96 23 Treated 21.204.58 48 The results show that the wheat grains treated by the compositions according to the invention germinated in a shorter time and the growth of the treated 5aintpaulis ionantha plants was accelerated in comparison with the control grains and plants, respectively. The same growth accelerating affect can be observed when ornamental plants are treated. The treated plan~s flower earlier and consequently can be sold about 2 weeks earlier than the control plants.
Example 7 A four-valent titanium salt corresponding to 2000 ppm of titanium and 100,000 ppm of ascorbic acid are dissolved in 1 lit. of water. 0.5 g. of sodium benzoate and 50b ppm of a water-soluble molybdenum salt and lOQ0 ppm of poly-ethylene-polypropylene block polymer (wetting agent) are added.
The p~ of the solution is adjusted to 5~
5 to 6-leaf lucerne plants were treated by the above compositions before every mowing once, in a dose of 2 lit./ha.
Green peas were treated by the above composition during budding and at the first by a dose of 2 lit./ha~, altogether twice. Grass was sprayed by 1 lit./ha. of the above composition once. The results of the above treatments are shown in the following ta~les.

; - 12 -~59Z~a; 3 Treating green peas Variety and Treatment Yield Average Saccharose Delicacy kg./ha, % ~T) %
Puget Control 4450 100.0 1~0.5 5.3S
Treated 5250 118.0 127.5 5.88 Grune Control 4210 100.0 136.2 5.35 Treated 5260 124.9 123.8 5.75 Lucerne test 10 Treatment Green Dry Substance Raw protein Digestable Starch Weigh~ content proteinvalue kg./m g./hg.g./kg. g./kg.g./kg.
, Cbntrol 1.25 905 128 93 301 Treated 1.87 915 171 124 316 Grass test Treatment Yield Raw protein Starch Value kg~./ha. ~ g./kg. g./kg.
:
Control 4300 100.046 110 Treated 6500 151.247 106 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 o~ lucerne in addition to the improve-: ; :
ment of quantitative and qualitative characteristics the number of roots is also considerably increased and the activity `~
of nitrogenase 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 8 A water-soluble four-valent titan~um salt corres-ponding to 1000 ppm of titanium and 900,000 ppm of ascorbic acid are dissolved in water and the solution is made up to 1 lit. The pH of the solution is adjusted to 5 and 25 ppm of - 13 ~

~159~ 73

2,4-dichlorophenoxyacetic acid sodium salt, 0.5 g. of sodium benzoate and petroleum sulfonate sodium salt (wetting agent) are added.
By the composition obtained, after dilutionl vine plants were sprayed three times in their vegetation period.
The results are shown in the following table.

Vine test Variety and TreatmentGlucose Sugar/acid g./100 ml. ~ ratio 10 "Treasure of Pannonia"
Control 8.0 100.0 13.2 Treated 9.4 117.5 19.2 "Italian Riesling"
Control 12.6 100.0 15.1 17.6 139.6 28.3 The above results show that the treatment increases the carbohydrate content of grapes and accordingly, the sugar/acid ratio is also increased.

Claims

Claims:

1. A plant conditioning composition containing a titanium-ascorbic acid kelate, substantially for spraying foliage or seed treatment, which comprises 0.1 to 15.0 %
by weight of a titanium-ascorbic acid kelate containing 14 to 28 g.moles of ascorbic acid related to 1 g.atom of titaniumr the pH of which is adjusted to S to 7, 0.1 to 2.0 parts of one or more biochemically essential nutriments and/or 0.0001 to 0.001 parts of one or more phytohormons 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-nitrobenzoic acid and salts thereof, propionic acid and salts thereof, and hexa-methylenetetramine related to the total weight of solid ingredients.

2. A composition as claimed in claim 1 which comprises as a biochemically essential nutriment a water-soluble salt of boron, magnesium, manganese, iront zinc or molybdenum.

3. A composition as claimed in claim 1 or claim 2 which comprises as a biochemically essential nutriment a nitrogen-phosphorus-potassium-containing fertilizer

4. A composition as claimed in claim 1, which comprises as phytohormons auxines, guberellines, cytochinines and heteroauxines.

5. A composition as claimed in claim 4, wherein said heteroauxines are selected from alpha-naphthylacetic acid and beta-indolylacetic acid,

6. A composition as claimed in claim 1 or 4, which comprises 2,4-dichlorophenoxyacetic acid or salts thereof as a phytohormon.

7. A composition as claimed in claim 1, claim 2 or claim 4 additionally comprising a wetting agent and/or an adhesive.