US009139481 B2 (12) United States Patent (10) Patent No.: US 9,139,481 B2 Sanders (45) Date of Patent: Sep. 22, 2015 (54) ANHYDROUS AMMONIA SUPPLEMENTED 3,796.559 A * 3/1974 Windgassen ........................ 71/1 WITH AGRICULTURAL ACTIVES 3,997,319 A 12/1976 Ott 4,007,029 A * 2/1977 Kenton ............................. T1/11 (71) Applicant: Specialty Fertilizer Products, LLC, 5,210,163 A 5, 1993 Grey Leawood, KS (US) 5,536.311 A 7/1996 Rodrigues s 6,228.806 B1* 5/2001 Mehta ........................... 504,117 6,515,090 B1 2/2003 Sanders et al. (72) Inventor: John Larry Sanders, Leawood, KS 6,632,262 B2 * 10/2003 Gabrielson ....................... T1/30 (US) 7,655,597 B1 2/2010 Sanders 8,043,995 B2 10/2011 Sanders et al. (73) Assignee: Verdesian Life Sciences, LLP, Cary, 8,491,693 B2 * 7/2013 Burnham .......................... T1/11 NC (US) 2004/0211234 A1* 10/2004 Volgas et al. .................. 71 (64.1 2009/0071213 A1 3/2009 Keenan et al. (*) Notice: Subject to any disclaimer, the term of this 2009/0163365 A1 6/2009 Bentlage et al. patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. FOREIGN PATENT DOCUMENTS (21) Appl. No.: 14/285,272 RU 2051884 C1 1, 1996 (22) Filed: May 22, 2014 OTHER PUBLICATIONS (65) Prior Publication Data International Search Report and Written Opinion dated Oct. 16, 2014 in PCT/US 2014/039424, International Filing Date: May 23, 2014. US 2014/0345344 A1 Nov. 27, 2014 U.S. Appl. No. 62/001,110, filed May 21, 2014, entitled Polyanionic Related U.S. Application Data Polymers. (60) Provisional application No. 61/827,452, filed on May * cited by examiner 24, 2013, provisional application No. 62/001,913, filed on May 22, 2014. Primary Examiner — Wayne Langel (51) Int. Cl. (74) Attorney, Agent, or Firm — Hovey Williams LLP C05C3/00 (2006.01) C05B (7/00 (2006.01) (52) U.S. Cl. (57) ABSTRACT CPC. C05C3/00 (2013.01); C05B 1700 (2013.01) (58) Field of Classification Search Agriculturally useful compositions comprise individual CPC ......................................................... C05C 3700 quantities of anhydrous ammonia, ammonia Solution, and one See application file for complete search history. or more agricultural actives different than anhydrous ammo nia. The compositions may include polyanionic polymers, (56) References Cited fertilizers, and/or biocidal agents. Preferably, the composi tions are created in pressurized tanks and are applied in the U.S. PATENT DOCUMENTS same fashion as anhydrous ammonia. 2,618,547 A * 1 1/1952 Davenport et al. ... 71.43 2,976,138 A * 3/1961 Hester .............. ... 71.1 3,130,033 A * 4, 1964 Stephens ............................. 71/1 18 Claims, No Drawings US 9,139,481 B2 1. 2 ANHYDROUS AMMONIA SUPPLEMENTED polymer. Therefore, these aqueous polymer mixtures are not WITH AGRICULTURAL ACTIVES Suitable for direct injection into anhydrous ammonia even though, from a plant nutrition standpoint, such mixtures CROSS-REFERENCE TO RELATED would be highly useful. APPLICATION Similarly, other types of Solid or liquid agriculturally use ful ingredients could be advantageously mixed with anhy This application claims the benefit of Provisional Applica drous ammonia, except for the tendency of solids to segregate tion Ser. No. 61/827,452, filed May 24, 2013, and Ser. No. from anhydrous ammonia, and/or because of the presence of 62/001.913, filed May 22, 2014, both incorporated by refer Water. ence herein in their entireties. 10 There is accordingly a need in the art for new agriculturally useful compositions and methods permitting actives Such BACKGROUND OF THE INVENTION valuable fertilizers to be incorporated into anhydrous ammo 1. Field of the Invention nia without experiencing the aforementioned problems. The present invention is broadly concerned with new agri 15 culturally useful compositions comprising anhydrous ammo SUMMARY OF THE INVENTION nia Supplemented with one or more types of agricultural actives. More particularly, the invention is concerned with Broadly speaking, the compositions of the invention are Such compositions, and methods of preparing and using the liquid mixtures containing at least three components, namely compositions. In general, the products include respective anhydrous ammonia as the preponderant component, with quantities of anhydrous ammonia, ammonia Solution, and one ammonia Solution and one or more agricultural actives. The or more agricultural actives. pH of the compositions is typically from about 8-13, more 2. Description of the Prior Art preferably from about 9.5-11.5. The compositions can be Anhydrous ammonia is widely used as a fertilizer. This applied to Soil in the same manner as anhydrous ammonia, material is gaseous at normal ambient temperatures, and 25 e.g., by injection into the earth behind a coulter blade, with a therefore is maintained under pressure in tanks to keep it in a follower wheel to close the soil opening generated by the liquid form prior to application. Anhydrous ammonia is typi coulter blade. cally injected from a pressure tank into the soil below grade in As used herein, “ammonia solution” refers to weakly basic order to inhibit the volatilization of the ammonia into the solutions of ammonia in water which may be denoted by the atmosphere. Although anhydrous ammonia has no pH owing 30 symbol NH(aq), and which may be referred to in the art as to the fact that it is water-free, it is an extremely caustic ammonium hydroxide, ammonia water, ammonia liquor, material which must be handled with great care. For example, aqua ammonia, aqueous ammonia, or simply ammonia. if water is injected into anhydrous ammonia, the result is a While the term "ammonium hydroxide” suggests a base with violent and uncontrolled exothermic reaction. Although not the composition (NHOHI, it is virtually impossible to generally practiced, it has been known to mix fertilizer com 35 ponents with anhydrous ammonia prior to application thereof isolate samples of NHOH, inasmuch as these ions do not to the soil. See, e.g., U.S. Pat. No. 3,997.319, which describes comprise a significant fraction of the total amount of ammo the addition of Zinc acetate to anhydrous ammonia to form a nia in an ammonia Solution, except in the case of extremely mixed fertilizer. dilute ammonia Solutions. In recent years a series of U.S. patents have issued describ 40 A wide variety of agricultural actives are useful in the ing biodegradable polymers having significant agricultural invention, and as used herein “agricultural actives' refers to facilities, particularly when used in combination with con any ingredient which has a beneficial effect upon soil, Soil ventional fertilizers or pesticides. For example, U.S. Pat. No. amendments, fertilizers, seeds, germination of seeds, plant 6,515,090 describes dicarboxylic copolymers made up, e.g., growth, and/or harvesting of plants. For example, the actives of moieties of itaconic acid and maleic anhydride. This patent 45 may include synthetic resin polymers (e.g., monomeric poly also discloses that such copolymers may be partially neutral mers such as polyvinylic or polyaspartic polymers, or copoly ized with metal or other cations, and can be used to form mers containing two or more repeat units or moieties, such as composite products with fertilizers. These combined fertil maleic-itaconic copolymers). As used herein, the term “poly izer-copolymer products have been shown to increase the mer' or “polymers' refers to any type of polymeric species, availability of phosphorous and other nutrients for uptake by 50 Such as homopolymers containing only a single polymeric growing plants, and can be applied to soil adjacent the plants unit, or copolymers containing two or more different poly or in foliar applications. Moreover, these copolymers can be meric units; this term also embraces acid forms of the poly used to good effect in combination with various pesticides, as mers, as well as partial or complete salts thereof. described in U.S. Pat. No. 7,655,597. Polymers inaccordance Other agricultural actives include fertilizers such as ammo with the 090 and 597 patents are commercially available 55 niacal, phosphate, potassium, minerals (e.g., secondary nutri from Specialty Fertilizer Products, LLC of Leawood, Kans. ents and micronutrients), and mixed NPK fertilizers; the fer under the designations NUTRISPHERE-NR) and AVAIL(R). tilizers may be organic or manufactured, in Solid or liquid NUTRISPHERE-NR) is a 40% by weight solids aqueous form. Additionally, biocidal actives (e.g., pesticides and/or copolymer of Substantially equimolar amounts of itaconic herbicides) may also be employed. and maleic anhydride moieties partially neutralized with cal 60 cium ion (CASH877469-38-0) and having a pH of 2.5-5. DETAILED DESCRIPTION OF THE PREFERRED AVAIL(R) is a 40% by weight solids aqueous copolymer of EMBODIMENTS Substantially equimolaramounts ofitaconic and maleic anhy dride moieties partially neutralized with sodium ion The new compositions of the invention are in the form of (CASH556055-76-6) and having a pH of 6-8. 65 liquids with anhydrous ammonia being the preponderant As indicated, these synthetic polymers are provided as ingredient, generally at a level of from about 60-90% by aqueous mixtures containing approximately 40% by weight weight of the overall product, in combination with agricul US 9,139,481 B2 3 4 tural active(s) and ammonia Solution. In preferred forms, the repeat groups and the polymerization reaction conditions, to actives include one or more polyanionic polymers described create the final polymer chain, apart from end groups. below. In carrying out the invention, it has been determined that The Polyanionic Polymers certain specific families or classes of polymers are particu Generally speaking, the polymers of the invention should 5 larly suitable. These are described below as “Class I.” “Class have a molecular weight of about 500-5,000,000, more pref IA.” and “Class II' polymers.