BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the discovery that certain water-soluble reaction products of urea and formaldehyde exhibit exceptional properties in the foliar feeding of growing plants. More particularly, this invention is concerned with aqueous solutions of phosphate and potassium containing materials together with a water-soluble urea formaldehyde reaction product composition consisting essentially of unreacted urea and methylol- and methyleneurea compounds which is essentially free of unreacted formaldehyde, is non-burning, and is absorbed by plant foliage at rates more nearly equivalent to other macronutrients such as phosphorus, potassium and sulfur, than currently used nitrogen containing compositions.

2. Description of the Prior Art

The foliar feeding of plant nutrients involves the dissolution of the nutrients in water and spraying of the aqueous solution of nutrients onto the leaves of plants. Unsuccessful results from foliar fertilization in increasing yield and obtainment of better quality of crop has been reported in the past by Mederski, H. J. and Volk, G. W., Foliar Fertilization of Field Crops, Ohio Agricultural Experimental Station Research Circular 35, (August, 1956). It has been generally assumed that legume and cereal grain crops which have been adequately fertilized by ground fertilization will not produce significantly higher yields of the grain by supplemental foliar fertilization. The obtainment of mixed results employing foliar fertilization of crops is generally due to varying environmental factors, soil fertilities, inability to apply more than small quantities of foliar fertilizers without damaging plant tissue and absorption of the various plant's nutrients contained in the fertilizer by the plant at different rates. The January, 1969 issue of World Farming contains a more complete dissertation of the benefits of nitrogen- phosphorus-potassium (N-P-K) foliar fertilization and the limits of application levels beyond which leaf scorch occurs.

Various references to foliar fertilization appear in the literature. Semon United States Patent 2,663,629 is concerned with the supplemental nitrogen 'feeding of plants through leaves by applying an essential nitrogen-supplying nutrient such as urea with a diamide of an organic dicarboxylic acid as dispersing agent. Belasco et al. United States Patent 2,802,307 is concerned with a method for increasing the nutritive value of plants by application of aqueous solutions of urea and other nitrogeneous compounds to the foliage, thereby increasing the production of various crops. Martin United States Patent 3,087,806 describes a method for improving the yield of soybeans by spraying the plants periodically throughout their growth with an aqueous solution of urea phosphate. Wagner United States Patent 3,558,300, assigned to the same assignee as is the present application, describes a method for foliar feeding of field crops, including soybeans and cereal grains, with an aqueous solution of an ammonium polyphosphate to improve the stress resistance of the plants; adequate ground fertilization is employed in conjunction with the foliar feeding. Backlund United States Patent 3,640,698 describes a fertilizer urea solution containing micronutrients for treatment of plants and soil to correct micronutrient deficiencies.

Clapp et al. United States Patent 4,038,064, also assigned to same assignee as is the present application, describes the most recent advance in the foliar fertilization of field crops; the present invention constitutes an improvement in the compositions and methods described therein. Although the foliar fertilizer compositions described in United States Patent 4,038,064 result in improved yields, such compositions have at times been found to be deficient in providing an adequate supply of nitrogen during the maturation of the crop which occurs over relatively extended periods, for example, about five to ten weeks, since currently available water-soluble nitrogen sources such as urea or ammonium salts are absorbed by the plant within several days, i.e. less than one week following application, while water-insoluble products, in solid or suspension form, normally require a period of three months or longer to be absorbed, with as much as 40% of the nitrogen contained in such product remaining unabsorbed at the time of harvest.

Urea-formaldehyde compositions have also been known for many years to have been used as non-burning, slow release fertilizers in solid or suspension form, especially for ground fertilization. Background information concerning the use of such urea-formaldehyde compositions, known in the literature as "ureaform" may be found in Windsor, G. W. and Long, M. I. E., J. SCI. Food Agriculture 9:185-194 (April 1958). In addition, the use of stable urea-formaldehyde suspensions and solids as fertilizers has been an active topic in the patent literature. Hence, British Patent 976,713 discloses the production of stable suspensions of urea and formaldehyde which are suited for incorporation in an acidic fertilizer substrate to prepare mixed fertilizers. Mortenson et al. United States Patent 2,827,368 is concerned with certain chemical fertilizers which provide liberal quantities of nitrogen, potassium and phosphorus and which have little or no "burn" or plasmolysis effect on leafy plants, based on the vapor pressure of a water solution of the fertilizer ingredients. Waters et al. United States Patent 3,092,486 assigned to the same assignee as is the present application, is concerned with an ammoniating solution containing urea and formaldehyde suitable for use in the manufacture of mixed fertilizers containing water-insoluble nitrogen. O'Donnell United States Patent 3,227,543 is concerned with the production of stable, liquid urea-formaldehyde condensates and use thereof in the production of solid urea-formaldehyde fertilizer compositions containing chelating agents and/or trace elements, uniformly distributed and suspended therein in slowly releasable form. Formaini United States Patent 3,677,736, also assigned to the same assignee as is the present application, is concerned with liquid fertilizer suspensions containing ureaform having certain water insoluble nitrogen content and activity index. Kise United States Patent 2,652,377 and Moore et al. United States Patent, 3,970,625, each being also assigned to the same assignee as is the present application, are concerned with the production of a stable, aqueous solution of urea-formaldehyde reaction products and with a process for preparing an improved urea-formaldehyde concentrate particularly adapted to production of slow- release nitrogeneous fertilizers, respectively. Justice et al. United States Patent 3,462,256, assigned to the same assignee as is the present application, is concerned with the preparation of urea-formaldehyde aqueous concentrates employable as a constituent in the compositions of the present invention. Hence, the prior art has failed to recognize that certain water-soluble urea-formaldehyde reaction products are particularly useful as foliar fertilizers, and especially, the compatability of certain such urea-formaldehyde reaction products with other primary plant nutrients to provide a highly efficient, nonphytotoxic, slow- release foliar fertilizer composition.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has been discovered that certain water-soluble reaction products of urea and formaldehyde are particularly useful for foliar feeding of growing plants, and further, are absorbed by plant foliage at rates more nearly equivalent to other primary plant nutrients, such as the phosphorus and potassium components of the fertilizer, than currently used conventional water-soluble nitrogen containing fertilizers, such as urea in liquid form or ammonium salts, illustratively ammonium sulfate, as well as nitrogen-containing water-insoluble products in solid or suspension form.

In accordance with the present invention it has been discovered that certain water-soluble urea- formaldehyde reaction products essentially free of unreacted formaldehyde consisting essentially of unreacted urea, methylol- and methyleneurea compounds and having an ammoniacal nitrogen content of not more than about 5%, exhibit highly desirable properties rendering these compositions especially suitable for foliar feeding of plants. The water-soluble urea- formaldehyde reaction products employed in the compositions of the present invention when used in combination with phosphorus, potassium, and if present, sulfur macronutrient components of foliar fertilizer compositions result in reduced alkalinity and buffering of the resultant composite fertilizer ingredients. In addition to being of a non-burning character, thereby avoiding phytotoxicity and metabolic imbalance in plants, the foliar fertilizer compositions of the present invention provide for healthy plants with increased yields. Furthermore, highly efficient use of nutrient solutions by the plants is achieved by use of the compositions of the present invention since the nitrogen of the urea-formaldehyde reaction products is totally absorbed by plants within the period corresponding essentially to the period of absorption required by plants for the phosphorus and potassium, as well as sulfur containing foliar macronutrient components of the fertilizer compositions containing these nutrients.

Accordingly, the present invention provides nonphytotoxic liquid compositions capable of being applied as a foliar fertilizer to provide essentially uniform absorption of nitrogen, phosphorus and potassium and, if present, sulfur, macronutrient components thereof by the plant growth to which it is applied comprising an aqueous solution containing, on a weight basis the following primary nutrient constituents:

• a) about 3% to 35% nitrogen, present in the form of a water-soluble urea-formaldehyde reaction product essentially free of unreacted formaldehyde consisting essentially of unreacted urea, methylol- and methyleneurea compounds, said reaction product having an ammoniacal nitrogen content of not more than about 5%;
• b) about 3% to about 30% phosphorus (calculated as P₂0₅) having at least about 35% of the phosphorus present in the polyphosphate form;
• c) about 3% to about 30% of potassium (calculated as K₂0); and
• d) from about 0 to about 5% sulfur in the form of a water-soluble salt. The remainder of the composition comprises essentially water.

The urea-formaldehyde reaction product, which provides the major portion of the nitrogen constituent of the compositions of the present invention, may be obtained by several procedures. The preferred method for production of such urea-formaldehyde reaction product is described in U.S. Patent 3,462,256, the disclosure of which is hereby incorporated by reference. In accordance with this patent, the urea-formaldehyde reaction products are aqueous concentrate solutions containing about 80% to 90%, by weight partially reacted urea and formaldehyde in a mol ratio above about 1:1 and less than about 2:1 which will remain substantially clear for at least about 30 days at ambient temperatures and will not "salt out" i.e. precipitate solid material at temperatures as low as 0°C. for at least 7 days. These urea-formaldehyde reaction products are prepared by a process which comprises preparing an aqueous mixture of urea and formaldehyde having a urea: formaldehyde mol ratio above about 1:1 but less than about 2:1, adding ammonia in an amount of about 0.3% to 6%, by weight of the urea and formaldehyde, heating said mixture at a temperature between about 75°C and boiling while maintaining the pH of the mixture in the range of about 8.5 to 10, preferably 9.0 to 9.8, with strong alkali until at least about 90% of formaldehyde is in combined form, with at least about 60% of the formaldehyde in the form of methylol compounds, and then continuing said heating at a pH of 7 to 8.5, preferably 7.3 to 7.9 until at least 50%, but no more than about 80%, preferably about 60% to 70% of the formaldehyde is in the form of methylene groups. This reaction product is characterized by being essentially free of unreacted formaldehyde and contains unreacted urea in an amount generally between about 30% and 80% of that employed, methylolurea compounds such as monomethylolurea and dimethylolurea, in an amount of about 10 to 30% of the urea used, and methylene-urea compounds, such as methylenediurea and dimethylenetriurea in an amount between about 20% and 50% of the urea used, and is further characterized by having an ammoniacal nitrogen content of not more than about 5%, preferably not greater than about 3%.

The aqueous mixture of urea, formaldehyde and ammonia can be prepared from the individual components, i.e. a commercially available formaldehyde solution and urea in any convenient form. However, such compositions can also be prepared by adding urea, in liquid or solid form, to an already partially condensed urea-formaldehyde reaction product, such as UF Concentrate 85, prepared in accordance with U.S. Patent 2,652,377, the disclosure of which is hereby incorporated by reference, and the term "aqueous mixture" mentioned hereinabove is meant to include mixtures prepared in this manner.

The amount of ammonia necessary varies within the range of 0.3 to 6%, by weight of the total urea- formaldehyde. About 0.7 to 3%, by weight, is employed when the urea: formaldehyde mol ratio is in the range of 1.3:1 to 1.8:1 in accordance with preferred embodiment. The ammonia may be employed in liquid or gaseous form, either anhydrous or in aqueous solution. It is to be noted that the ammonia is not used merely to provide a desired pH, since this is the function of the strong alkali. The ammonia by itself would not maintain the pH at the desired level but rather, the presence of ammonia during the heating step results in a product having superior stability as compared with a product similarly prepared, but without added ammonia. Best results are obtained when at least about 50% of the ammonia, and preferably essentially all of the ammonia, is added before or during the first heating stage; otherwise, the order in which the components are added is of little consequence. Usually, the urea and formaldehyde are mixed in water and then ammonia is added. Sufficient water should be used to dissolve all of the components during the heating step. However, the use of more than 50% by weight of water is undesirable as it necessitates a prolonged evaporation step. Heating is preferably commenced within a few minutes after preparation of the mixture to ensure that the resulting product is uniformly stable.

The mixture is heated at a temperature between 75°C. and its boiling point, preferably between about 85°C. to 95°C.; substantially atmospheric pressure for a total time of about 30 to 180, preferably about 75 to 115 minutes. The amount of time, of course, decreases as the heating temperature increases.

The first heating stage is carried out until at least about 90% of the formaldehyde is in combined form (or, conversely, no more than 10% of free formaldehyde is present) with at least 60% of formaldehyde in the form of methylol compounds. The percentage of combined formaldehyde can be determined by the sodium sulfite method described in Formaldehyde, Walker, second edition, page 382. By effecting this test at 0°C., the amount of free formaldehyde can be determined. By effecting the same test at 80°C., combined amount of free and methylol formaldehyde can be determined. From the result of these tests, the percentages of methyl- olformaldehyde and methyleneformaldehyde can be determined. For the purpose of the present invention, all formaldehyde which is neither free nor in methylol form is considered to be in methylene form. The end point in the second heating stage can also be determined using the 80°C. sodium sulfite method, or an 80°C. alkaline peroxide method, described in Walker on page 384.

Another method for determining the end point of the heating is an acetone titration test. A 10 milliliters sample of the mixture is concentrated at reduced pressure to a urea-formaldehyde content of about 80% to 90%, preferably about 85%, and is mixed with 20 milliliters of methanol. The resulting mixture is then titrated at room temperature with acetone until it becomes turbid. If more than the predetermined amount of acetone is required, the salting out temperature of the mixture is above 0°C. The amount of acetone required to cause turbidity will vary slightly depending, for example, on the amount of water in a mixture. Products prepared in accordance with the preferred conditions require about 30 to 34 milliliters of acetone.

Any strong alkaline material may be used to control the pH during the aforedescribed heating step. In the preferred method, an alkali metal hydroxide is gradually added to the reaction mixture at a rate sufficient to maintain the pH in a range of 8.5 to 10 until the desired percentage of combined formaldehyde is achieved. Thereafter, the addition of hydroxide is discontinued and the pH drops rather quickly to below about 8.5 and remains below that level during the remainder of the heating. Usually the addition of the alkaline material is discontinued about 50% to 80% through the total heating period.

When the heating is completed, the water content of the reaction mixture may vary between about 15% and about 45% by weight, depending upon the starting materials employed. If the amount of water is greater than about 20% by weight, the mixture should be concentrated under subatmospheric pressure at about 35°C. to 90°C. until a clear solution containing at least about 80% urea and formaldehyde is obtained. If there is a hold between the heating step and evaporation step, the mixture is advantageously cooled below about 45°C. before holding. The final product should also be quickly cooled before storage. The pH of the final cooled product should be in the range of 7 to 11, preferably 9 to 10. If necessary, the product can be adjusted to this pH by addition of sufficiently strong alkaline material. It is also desirable to add a small amount, about 0.05% to 1.0% by weight of ammonia to this product to further increase stability.

The nitrogen constituent of the compositions of the invention is present in an amount between about 3% to about 35%, preferably between about 18% and 32% and is, in general, supplied totally by the water-soluble urea-formaldehyde reaction product ingredients. These constituents generally comprise unreacted urea in an amount between about 5% and 50%, preferably between about 8% and 35%, methylolurea compounds, such as monomethylolurea and dimethylolurea, in an amount between about 5% and 25%, preferably between about 10% and 20% and methyleneurea compounds, such as methylenediurea and dimethylenetriurea, in an amount between about 30% and 80%, preferably between about 40% and 70% of the total quantity of nitrogen present in the composition. Other water soluble urea-formaldehyde reaction products may also be present in minor amounts, i.e. less than about 10% of the weight of the urea-formaldehyde product. If desired, a portion of the nitrogen can also be supplied by water soluble ammonium salts, such as ammonium polyphosphate produced by reaction of superphosphoric acid with ammonia, or by ammonium sulfate.

The phosphorus macronutrient constituent of the compositions of the present invention are present in an amount between about 3% and about 30%, preferably between about 4% and 12% (calculated as P205) and is characterized by having at least about 35%, and preferably at least about 50%, of the phosphorus present in the linear "polyphosphate" form. The polyphosphate nutrient component includes the pyrophosphate, and other polymer phosphates from the tri- to the nona-phosphates and higher linear polyphosphates. Use of concentrations of the polyphosphate lower than those specified herein result in solutions which have unacceptable higher salting out temperatures and less micronutrient chelating ability. Higher concentrations of the "polyphosphate" form result in formation of metaphosphates which have lower solubilities than the linear form and are ineffectual in preventing formation of precipitates. If desired, the phosphorus constituent may be added in combined form, such as an ammonium phosphate or ammonium polyphosphate, as well as potassium polyphosphate. While the phosphorus and potassium components can be produced and added separately, they are preferably produced as potassium polyphosphate solutions in a single manufacturing operation, for example, as disclosed in U.S. Patent 3,607,018, the disclosure of which is hereby incorporated by reference; however, the potassium polyphosphate product must be dissolved in a solvent other than an aqueous ammonia solution, such as water, to ensure that the final liquid composition of the present invention contains less than about 5% nitrogen in the ammoniacal form.

The potassium and, if employed, sulfur macronutrient constituents to be employed in the compositions of the invention may also be in the form of salts containing potassium or sulfur. For example, potassium carbonate bicarbonate, etc. may be used and a single salt may be used to provide both potassium and sulfur such as potassium sulfate, or as indicated above, the salt may provide potassium and phosphorus, such as potassium polyphosphate, etc. The sulfur will commonly be present as the sulfate, associated with ammonium, potassium, calcium or a similar cation. The potassium component of the solution should be essentially free of chloride ion which may have a burning or scorching effect on the plants when applied to the foliage. Accordingly, the total chloride ion content of the composition is normally maintained below about 5%, and preferably less than about 2%.

The nonphytotoxic liquid fertilizer compositions of the invention, when employed as a foliar fertilizer, normally are employed at a pH preferably near neutral, e.g. from about 5.5 to about 8.5, and particularly from about 6.0 to about 7.2 to maintain the rate of hydrolysis at a minimum. Liquid compositions of pH values from 4 to about 11 may be used, however, depending upon the nutrient requirements of the area to be fertilized. Thus, areas deficient chiefly in phosphate could be fertilized with a more strongly acidic phosphate solution, for example, a potassium or ammonium polyphosphate with a pH from about 4 to about 6 and containing some free-phosphoric acid.

The aforementioned liquid compositions of the invention are applied to crops, turf, horticulture or silviculture by aerial application with a total volume of aqueous spray applied being from about 22 to about 670 L/ha (about 2 to about 60 gallons per acre), preferably from about 112 to about 450 L/ha (about 10 to about 40 gallons per acre). The actual volume employed may be varied somewhat, depending upon the substrate to which the solution is to be applied, season, difficulty of the application, as well as the density and moisture content of the foliage. The liquid compositions are normally applied directly to foliage when the foliage is not in a turgid growing state and when atmospheric conditions are mild, i.e. moderate temperature and humidity. In general, these compositions are diluted with water to reduce burning and permit more uniform application with larger volumes of materials and the volume selected will be sufficient to achieve complete distribution of the fertilizer of the foliage without effecting any substantial drainage of the foliage to the surface soil. The concentration of the fertilizer in the aforementioned aqueous spray will normally be at least about 2 weight percent nutrient, and should be sufficient to achieve the application of from about 4.5 to about 90 kg/ha (about 4 to about 80 pounds per acre), preferably about 11 to about 67 kg/ha (about 10 to about 60 pounds per acre) N-P-_K-S nutrients in the case of field crops; from about 45 to about 225 kg/ha (about 40 to about 200 pounds per acre), preferably from about 90 to about 180 kg/ha (about 80 to about 160 pounds per acre) N-P-K-S nutrients in the case of turf; and from about 22 to about 180 kg/ha (about 20 to about 160 pounds per acre) N-P-K-S nutrients in the case of horticulture and silviculture. For example, a mixture with less burning potential which can be directly applied to turf under all conditions can be made from urea-formaldehyde reaction product and potassium polyphosphate; hence a 20-4-4 liquid composition grade is made by mixing about 567 kg (1252 lbs) of a urea-formaldehyde reaction product, about 202 kg (445 lbs) of potassium polyphosphate (2-18-18) and about 137 kg (303 lbs) of water. Mixtures useful in foliar feeding of commerical field crops such as corn, soybeans, cotton or wheat are made from urea-formaldehyde reaction product, potassium polyphosphate and small amounts of other common fertilizer materials. A mixture useful in foliar feeding grain crops such as corn, sorghum and wheat is a N-P-K grade 15-5-5 made by blending about 172 _Kg (932 lbs) of urea-formaldehyde reaction product, about 103 kg (556 lbs) of potassium polyphosphate and about 94 kg (512 lbs) of water per 1000 kg (per ton) of product. Similarly a mixture useful for foliar feeding soybeans and other legumes is a N-P-K grade 12-7-9 made by blending about 133 kg (724 lbs) of urea-formaldehyde reaction product, about 143 kg (778 los) of potassium polyphosphate, about 14 kg (78 lbs) of potassium sulfate and about 77 kg (420 lbs) of water per 1000 kg (per ton) of product. A mixture useful for foliar feeding cotton is a N-P-K grade 10-8-9 made by blending about 109 kg (590 lbs) of urea-formaldehyde reaction product, about 164 kg (889 lbs) of potassium polyphosphate, about 7 kg (39 lbs) of potassium sulfate and about 89 kg (482 lbs) of water per 1000 kg (per ton) of product. All these mixtures are applied without dilution directly to plant foilage as fine mists. The liquid fertilizer compositions of the invention are preferably only applied annually; however, more frequent applications such as semi-annual or quarterly applications can be used, or alternatively, the applications can be less frequent, for example, biannually. Preferably, the fertilizer solution is applied during the active growing season of the crops, turf, silviculture or horticulture. Application of the compositions of the present invention is made using conventional applicators well known in the industry and is made in conjuction with conventional, adequate ground application of fertilizer containing nitrogen, phosphorous, potassium and other essential nutrients if the soil is deficient in any of these nutrients.

The plant foliage treated with the liquid compositions of the invention respond rapidly to the fertilization as evidenced by increased green coloration of the foliage within a few days to weeks after fertilization. This increased greening is generally persistent, lasting for several months or throughout the growing season and results in substantially greater rate of crop yield, or growth of turf, silviculture or horticulture. The nonburning character of the liquid compositions of the invention is evidenced by the fact that as much as about 112 kg/ha (100 pounds per acre) of nitrogen can be applied without harmful effects, while the maximum of about 56 kg/ha (50 pounds per acre) of nitrogen can be applied using urea solutions which are conventionally applied. A further advantage of the compositions of this invention is that the unreacted urea portion of the liquid composition is absorbed by the foilage within about,a week following application, while that portion of urea which is in chemical combination with formaldehyde in the form of methylolurea and methyleneurea compounds is absorbed more slowly, requiring up to about 7 to 8 weeks for complete absorption.

Minor and trace metal nutrients may also be incorporated in the aforementioned liquid foliar fertilizer compositions of the invention in minor amounts, for example from about 0.01 to 5, preferably from about 0.5 to 2.5 weight percent, to supplement the nutrition of the crops, turf, horticulture or silviculture. Aqueous solutions of water soluble salts or complexes of trace metals may be used such as boron, zinc, iron, molybdenum, manganese, magnesium, copper and mixtures thereof to correct any trace metal deficiencies. Suitable water-soluble salts include the sulfates, nitrates and halides of the aforementioned metals. In addition, various chelating agents can be used to insure solubility of these metal nutrients.

Assimulation of the liquid fertilizer compositions of the invention by the foliage can be accelerated somewhat by incorporation of minor amounts, for example from about 0.1 to 2.5 preferably from about 0.25 to 1.0 weight percent, of a surfactant. Use of the surfactant improves spreading of the liquid compositions on the foliage to achieve an even coverage and also assists in absorption of the fertilizer into the foliage. Suitable surfactants include cationic, anionic and nonionic types as well as mixtures thereof, as are well known in the art.

Various pesticides can also be incorporated with the aforementioned liquid compositions to obtain a combined fertilization-pesticidal treatment. The pesticides may be herbicides having a selective action for undesired vegetation or weed species or can be insecticides, larvicides, or miticides and may be synthetic or naturally occuring chemicals.

The selective herbicides which may be used to control undesired vegetation include: chlorophenoxy- alkano acids, esters and salts thereof such as 2,4-dichlorophenoxyacetic acid; 2,4,5-trichloro- phenoxyacetic acid; 2-methyl-4-chlorophenoxyacetic acid; 2-methyl-(4-chlorophenoxy)butyric acid; 4-(2,4-dichlorophenoxy)butyric acid; 2-(2,4,5-trichlorophenoxy) propionic acid; the alkali metal salts of the aforementioned acids or esters of these acids with C_l-C_a alkanols or C_l-C₃ glycols or glycol mono-ethers with C_l-C₅ alkoxy groups. Examples of these are sodium 2,4-dichlorophenoxy acetate; potassium-2-(2,4-5-tri- chlorophenoxy)propionate; octyl-2,4-dichlorophenoxyacetate; and mono-butoxyethylene glycol-2,4-dichlorophenoxyacetate; etc.

Other selective herbicides which can be used include C₁-C₅ alkyl-N-phenyl carbamates and alkyl thiocarbamates such as isopropyl-N-phenyl-carbamate; ethyl-N-chloromates such as isopropyl-N-phenyl-carbamate; ethyl-N-chlorophenylcarbamate; 4-chloro-2-butenyl-N-(3-chlorophenyl)carbamate; 2,3,-dichloroallyl-N,N-diisopropylthiocarbamate; ethyl-N,-N-di-n-propylthiocarbamate; methyl-N-(3,4-dichlorophenyl)-carbamate; n-propyl-N-ethyl-N-(n-butyl)-thiocarbamate; and 2-chloroallyl-N,N-diethyl- dithiocarbamate.

Urea derivatives that exhibit phytotoxicity can also be used and examples include N,N'-substituted ureas having the following substituents: phenyl, chlorophenyl, C₁-C₅ alkyl, alkoxy and chloroalkyl or chloronorbornyl.

Examples include:

• l,3-bis-(2,2,2-trichloro-l-hydroxyethyl)urea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 1-(chloro-2-norbornyl)-3,3-dimethylurea, 3-(3,4-dicnlorophenyl)-l-methoxy-l-methylurea, 3-(4-chlorophenyl)-l,l-dimethylurea, 3-(3,4-dichlorophenyl)-l-n-butyl-l-methylurea.

Amides which demonstrate selective phytotoxicity can also be used such as the C₂-C₆ alkyl, chloroalkyl, phenylalkyl, naphthylalkyl and alkenyl amides having N-phenyl, N-alkyl, N-chlorophenyl and N-alkenyl substituents. Specific examples include: N-(3,4-dichlorophenyl)-methacrylamide; N,N-dimethyl-2,2-diphenylacetamide; 1-naphthylacetamide; N-(3-chloro-4-methylphenyl)-2-methylpentanamide; and N-(3,4-dichlorophenyl)propionamide.

Dichlorobenzoic acid and its amino, C_l-C₃ alkoxy, nitro and halo derivatives can also be used such as dichloro-benzoic acid; 2,3,6-trichlorobenzoic acid; 3-amino-2,5-dichlorobenzoic acid; 2,6-dichloro- benzonictrile; 2-methoxy-3,6-dichlorobenzoic acid; etc., heterocyclic compounds such as triazine derivatives, e.g., 2-chloro-4,6-bis(ethylamino)-s-triazine and 2-chloro-4-ethylamino-6-isopropylamino-s-triazine.

Various nitrated phenyl compounds known to have selective phytotoxicity can be combined with the fertilizers such as 4,6-dinitro-o-sec-butyl phenol and its alkali metal or alkanol amine salts; 4,6-dinitro-o-cresol and N,N-di(n-propyl)-2,-6-dinitro-4-methylaniline.

Examples of suitable insecticides include the chlorinated hydrocarbons such as DDT, bis(p-chlorophenyl) trichloroethane and related compounds, e.g., methoxychlor, Dilan, bis(p-chlorophenoxy) methane, bis(p-chlorophenyl)ethanol, chlorobenzilate, and p-chlorophenyl phenyl sulfone. Other chlorinated hydrocarbons include benzene hexachloride, Lindane, Chlordane, Aldrin, Dieldrin Heptachlor and Toxaphene.

The organic phosphorus insecticides can also be used including tetraethyl pyrophosphate, tetraethyl dithiopyrophosphate, octamethyl pyrophosphoramide, Parathion, Para-oxon, Methyl Parathion, Chlorothion, o-ethyl-o-p-nitrophenyl benzenethiophosphate, Diazinon, Malathion, and Demeton.

Carbamates such as ferric dimethyldithiocarbamate; trimethylphenyl methylcarbamate; 4-(dimethyl- amino) m-tolylmethylcarbamate; 4-benzothienyl-N-methylcarbamate; s-ethyl dipropylthicarbamate; 2,3-quinoxal- medithol cyclic trithiocarbamate; 1-naphthyl-N-methylcarbamate and 2-isopropoxyphenyl N-methylcarbamate.

Various fungicides include: chloranil; 2,3-dichloro-l,4-naphthoquinone, pentachlorophenol; metallic dialkyl dithiocarbamates such as zinc or ferric dimethyldithiocarbamate, disodium ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, captan, colloidal sulfur, lime sulfur, and ammonium polysulfide.

The naturally occurring insecticides can also be used such as the various pyrethums, e.g., pyrethin I, cinerin I, pyrethrin II, cinerin II, jasmolin II, etc., and synthetically prepared and related insecticides such as allethrin, furethrin, cyclethrin, barthrin, and dimethrin, used.

The aforementioned pesticides can be admixed with any of the aforementioned fertilizer solutions in proportions such that the final aqueous material applied will provide from about 0.11 to about 5.6 kg/ha (about 0.1 to about 5 pounds per acre) of the pesticide. A preferred dosage is from about 0.56 to about 3.4 kg/ha (0.5 to about 3 pounds per acre).

The following examples will illustrate a mode of practice of the invention and serve to demonstrate results obtainable thereby.

EXAMPLE 1

The methods set forth in this Example illustrate the preparation of the urea-formaldehyde reaction product employable in the compositions of the present invention.

A. This method employs solutions of urea and formaldehyde and requires evaporation to achieve the desired nitrogen concentrations.

Into a reactor equipped with an agitator there are charged 28,988 parts of 50% urea solution at a temperature of about 40°C. Then, 9065 parts of a 50% formaldehyde solution and 1196 parts of 29% ammonia solution are added to the reaction mixture. The reaction temperature is maintained below 40°C during these charging operations. The mixture is heated to 90°C and the addition of 25% caustic is started when the temperature reaches 75°C. The caustic is added at a rate to maintain the reaction mixture at pH of 9 to 9.5. Overall addition of 648 parts 25% NaOH solution is completed in about 50 minutes after the reaction mixture reaches a temperature of 75°C. The reaction is continued at 90°C for another 30 minutes for a total of 90 minutes. The reaction mixture is cooled to 40°C and then concentrated in an evaporator at 40 mm Hg absolute pressure and at 37°C, thus producing 22,700 parts of urea-formaldehyde reaction product concentrate, which is then cooled to ambient temperature. For long term storage, an additional 0.5 wt.% ammonia as 29% NH₄0_H is admixed with the product. The final product having a a salting-out temperature below 0°C. analyzes 31 wt.% total nitrogen; has a urea-formaldehyde ratio of 1.6 and contains about 20% urea N, 15% methylolurea N and 65% methyleneurea N.

B. This method employs solid urea and a urea- formaldehyde concentrate starting material and does not require evaporation.

Into a stirred reaction vessel there are charged 13,000 parts of pebbled urea, 7786 parts of a commercially available urea-formaldehyde concentrate (UFC-85 containing about 25% urea, 60% formaldehyde, and 15% water) and 1200 parts 29% NH₄0H, the mol ratio of urea to formaldehyde being 1.6. The mixture is heated and when the temperature reaches 75°C, caustic is added in incremental amounts to maintain the pH between 9 and 9.5 over a reacton period of 60 minutes. A total of 700 parts 25 wt.% NaOH is added during this portion of the reacton period. The reaction is continued at 90°C for an additional 15 minutes and then the solution is permitted to cool to ambient temperature. The final urea-formaldehyde reaction product yield is 22,700 parts and contains 31 wt.% total nitrogen. The product has a U/F ratio of 1.6 and contains 15% urea N, 20% methylolurea N and 65% methyleneurea N.

C. This method employs liquid urea solution and a urea-formaldehyde concentrate starting material.

Into a stirred reactor there are charged 150,103 parts of 50% urea 30 solution, 44,816 parts urea-formaldehyde concentrate (UFC-85 containing 25% urea, 60% formaldehyde and 15% water) and 9273 parts of 29% NH₄0H. The temperature during the charge period is held below 40°C. and thereafter heating of the reaction mixture is continued. When the temperature reaches 75°C incremental addition of caustic is begun to maintain a pH of 9 to 9.5 over a 60 minute reaction period; a total of 4546 parts of a 25 wt.% NaOH solution is used during this portion of the reaction period. The reaction is continued at 90° for an additional 15 minutes. The urea-formaldehyde reaction product is cooled to ambient temperature and then 4580 parts of 29% NH₄0H admixed therewith to yield a total of 213,326 parts final product. The final product analyzes 21 wt.% total nitrogen and contains 15% urea N, 15% methylolurea N and 70% methyleneurea N.

EXAMPLE 2

This experiment demonstrates that water-soluble urea-formaldehyde reaction products employed in the present invention release nitrogen more slowly than urea, but faster than water-insoluble urea-formaldehyde reaction products (ureaform).

0.56 meter square test plots of Bermuda grass were treated with various nitrogeneous materials at a rate of about 45 kg/ha (40 pounds per acre). The plot treated with a nutrient solution containing 12% urea nitrogen was dark green and grew vigorously for about 5 weeks. The plot treated with the water-soluble urea-formaldehyde reaction product employable in the present invention was also dark green and grew vigorously for about ten weeks. The plot treated with water-insoluble urea-formaldehyde reaction product (ureaform) was less green and grew more slowly than the other two previously described treated plots, but was greener than the control plot which was untreated with any nitrogeneous solution.

EXAMPLE 3

This Example demonstrates the non-burning character of the urea-formaldehyde water-soluble, urea- formaldehyde reaction products employable in the present invention, relative to urea.

Bahia grass plots in Florida were treated with urea solutions containing 12% and 18% nitrogen, respectively, at rates of about 28, 56 and 84 kg/ha (25, 50 and 75 pounds per acre) of nitrogen. The 12% nitrogen solution burned about 25% of the grass foliage at about 56 kg/ha (50 pounds per acre) of nitrogen and the 18% nitrogen solution burned about 40% of the grass foliage at about 56 kg/ha (50 pounds per acre) of nitrogen. The 12% and the 18% solutions burned more than 50% of the grass foliage at about 84 kg/ha (75 pounds per acre) of nitrogen.

Solutions of the water-soluble urea- formaldehyde reaction product employed in compositions of the invention containing 20% nitrogen were applied to adjacent plots at rates of about 28, 56 and 84 kg/ha (25, 50 and 75 pounds per acre) of nitrogen. No evidence of burning or scorch of the grass foliage in any of the plots was observed.

EXAMPLE 4

This Example compares the rate of absorbence of nitrogen provided by: (a) urea; (b) typical water-soluble urea-formaldehyde reaction product employed in the compositions of the invention (UMM); and (c) water-insoluble urea-formaldehyde reaction product (ureaform).

Soybeans at mid-pod stage and corn were sprayed with a liquid nutrient composition mixture having an N-P-K grade corresponding to 12-6-6 in which the nitrogen was provided by urea, UMM and ureaform, as indicated above. The amount of nitrogen absorbed, following ten (10) days of application of the liquid nutrient compositions, is set forth in Table I below.