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. Of course, mixtures of these erably from about 1500-50,000, and contain at least three and polymer classes are also contemplated. preferably more repeat units per molecule (preferably from Class I Polymers about 10-500). Moreover, the partial or complete salts of the The Class I polyanionic polymers of the present invention 10 are at least tetrapolymers, i.e., they are composed of at least polymers should be water dispersible and preferably water four different repeat units individually and independently soluble, i.e., they should be dispersible or soluble in pure selected from the group consisting of type B, type C, and type water to a level of at least about 5% w/w at room temperature G repeat units, and mixtures thereof, described in detail with mild agitation. below. However, the Class I polymers comprehend polymers Advantageously, at least about 50% (by mole) of repeat 15 having more than four distinct repeat units, with the excess units contain at least 1 carboxylate group. These species also repeat units being selected from the group consisting of type are typically capable of forming stable solutions in pure water B. type C, and type G repeat units, and mixtures thereof, as up to at least about 20% w/w solids at room temperature. well as other monomers or repeat units not being type B, C, or To summarize, the preferred polymers of the invention G repeat units. have the following characteristics: Preferred Class I polymers contain at least one repeat unit The polymers should be dispersible and more preferably from each of the B, C, and G types, one other repeat unit fully soluble in water. selected from the group consisting of type B, type C, and type The polymers should have a significant number of anionic G repeat units, and optionally other repeat units not selected functional groups, preferably at least about 90 mole from type B, type C, and type G repeat units. Particularly percent by weight, more preferably at least about 96 25 preferred polymers comprise a single type B repeat unit, a mole percent by weight, and most preferably the poly single type C repeat unit, and two different type G repeat mers are essentially free of non-anionic functional units, or two different type B repeat units, a single type C groups. repeat unit, and one or more different type G repeat units. The polymers are stable thermally and chemically for con However constituted, preferred Class I polymers contain at Venient use. 30 least about 90 mole percent (more preferably at least about 96 mole percent) of repeat units selected from the group consist The polymers should be essentially free of ester groups, ing of type B, C, and G repeat units (i.e., the polymers should i.e., no more than about 5 mole percent thereof, and most contain no more than about 10 mole percent (preferably no preferably no more than about 1 mole percent. more than about 4 mole percent) of repeat units not selected The polymers should have only a minimum number of 35 from types B, C, and G). amide-containing repeat units, preferably no more than The Class I polymers are easily converted to partial or fully about 10 mole percent thereof, and more preferably no saturated salts by a simple reaction with an appropriate salt more than about 5 mole percent. forming cation compound. Usable cations can be simple cat The polymers should have only a minimum number of ions such as sodium, but more complex cations can also be monocarboxylate repeat units, preferably no more than 40 used. Such as cations containing a metal atom and other about 10 mole percent thereof, and more preferably no atom(s) as well, e.g., Vanadyl cations. Among preferred metal more than about 5 mole percent. cations are those derived from alkali, alkaline earth, and tran The ensuing detailed description of preferred polymers sition metals. The cations may also be amines (as used herein, makes use of the art-accepted term “repeat units” to identify “amines' refers to primary, secondary, or tertiary amines, the moieties in the polymers. As used herein, “repeat unit 45 monoamines, diamines, and triamines, as well as ammonia, refers to chemically converted forms (including isomers and ammonium ions, quaternary amines, quaternary ammonium enantiomers) of initially chemically complete monomer mol ions, alkanolamines (e.g., ethanolamine, diethanolamine, and ecules, where such repeat units are created during polymer triethanolamine), and tetraalkylammonium species). The ization reactions, with the repeat units bonding with other most preferred class of amines are alkyl amines, where the repeat units to form a polymerchain. Thus, a type B monomer 50 alkyl group(s) have from 1-30 carbon atoms and are of will be converted to a type B repeat unit, and type C and type straight or branched chain configuration. Such amines should G monomers will be converted type C and G repeat units, be essentially free of aromatic rings (no more than about 5 respectively. For example, the type B maleic acid monomer mole percent aromatic rings, and more preferably no more will be chemically converted owing to polymerization con than about 1 mole percent thereof). A particularly suitable ditions to the corresponding type B maleic acid repeat unit, as 55 alkylamine is isopropylamine. These possible secondary cat follows: ions should be reacted with no more than about 10 mole percent of the repeat units of the polymer. 1. Type B Repeat Units Type B repeat units are dicarboxylate repeat units derived 60 from monomers of maleic acid and/or anhydride, fumaric OH HO HOC CO2H acid and/or anhydride, mesaconic acid and/or anhydride, Sub stituted maleic acid and/or anhydride, substituted fumaric maleic acid maleic acid repeat unit acid and/or anhydride, Substituted mesaconic acid and/or anhydride, mixtures of the foregoing, and any isomers, esters, Different monomers within a given polymerization mixture 65 acid chlorides, and partial or complete salts of any of the are converted to corresponding repeat units, which bond to foregoing. As used herein with respect to the type B repeat each other in various ways depending upon the nature of the units, “substituted species refers to alkyl substituents (pref US 9,139,481 B2 5 6 erably C1-C6 straight or branched chain alkyl groups sub vinyl, allyl, and methallylsulfonic acids or salts. The total stantially free of ring structures), and halo Substituents (i.e., amount of type G repeat units in the Class I polymers of the no more than about 5 mole percent of either ring structures or invention should range from about 0.1-65 mole percent, more halo substituents, preferably no more than about 1 mole per preferably from about 1-35 mole percent, and most preferably cent of either); the substituents are normally bound to one of 5 from about 1-25 mole percent, where the total amount of all of the carbons of a carbon-carbon double bond of the mono the repeat units in the Class I polymer is taken as 100 mole mer(s) employed. In preferred forms, the total amount of type percent. The definitions and discussion relating to 'substi B repeat units in the Class I polymers of the invention should tuted.” “salt, and useful salt-forming cations (metals, range from about 1-70 mole percent, more preferably from amines, and mixtures thereof) with respect to the type G about 20-65 mole percent, and most preferably from about 10 repeat units, are the same as those set forth for the type B 35-55 mole percent, where the total amount of all of the repeat repeat units. units in the Class I polymer is taken as 100 mole percent. Vinylsulfonic acid, allylsulfonic acid, and methallylsul Maleic acid, methylmaleic acid, maleic anhydride, meth fonic acid, either alone or in various mixtures, are deemed to ylmaleic anhydride, and mesaconic acid (either alone or as be the most preferred monomers for generation of type G various mixtures) are the most preferred monomers for gen 15 repeat units. It has also been found that alkali metal salts of eration of type B repeat units. Those skilled in the art will these acids are also highly useful as monomers. In this con appreciate the usefulness of in situ conversion of acid anhy nection, it was unexpectedly discovered that during polymer drides to acids in a reaction vessel just before or even during ization reactions yielding the novel polymers of the invention, a reaction. However, it is also understood that when corre the presence of mixtures of alkali metal salts of these mono sponding esters (e.g., maleic or citraconic esters) are used as mers with acid forms thereof does not inhibit completion of monomers during the initial polymerization, this should be the polymerization reaction. followed by hydrolysis (acid or base) of pendantester groups Further Preferred Characteristics of the Class I Polymers to generate a final carboxylated polymer Substantially free of As noted previously, the total abundance of type B, C, and ester groups. G repeat units in the Class I polymers of the invention is 2. Type C Repeat Units 25 preferably at least about 90 mole percent, more preferably at Type C repeat units are derived from monomers of itaconic least about 96 mole percent, and most preferably the poly acid and/or anhydride, Substituted itaconic acid and/or anhy mers consist essentially of or are 100 mole percent B, C, and dride, as well as isomers, esters, acid chlorides, and partial or G-type repeat units. It will be understood that the relative complete salts of any of the foregoing. The type Crepeat units amounts and identities of polymer repeat units can be varied, are present in the preferred Class I polymers of the invention 30 depending upon the specific properties desired in the resultant at a level of from about 1-80 mole percent, more preferably polymers. Moreover, it is preferred that the Class I polymers from about 15-75 mole percent, and most preferably from of the invention contain no more than about 10 mole percent about 20-55 mole percent, where the total amount of all of the of any of (i) non-carboxylate olefin repeat units, (ii) ether repeat units in the polymer is taken as 100 mole percent. repeat units, (iii) ester repeat units, (iv) non-sulfonated mono The itaconic acid monomer used to form type C repeat unit 35 carboxylic repeat units, and (V) amide-containing repeat has one carboxyl group, which is not directly attached to the units. “Non-carboxylate” and “non-sulfonated’ refers to unsaturated carbon-carbon double bond used in the polymer repeat units having essentially no carboxylate groups or Sul ization of the monomer. Hence, the preferred type C repeat fonate groups in the corresponding repeat units, namely less unit has one carboxyl group directly bound to the polymer that about 55 by weight in the repeat units. Advantageously, backbone, and another carboxyl group spaced by a carbon 40 the mole ratio of the type B and type C repeat units in com atom from the polymer backbone. The definitions and discus bination to the type G repeat units (that is, the mole ratio of sion relating to “substituted,” “salt, and useful salt-forming (B+C)/G) should be from about 0.5-20:1, more preferably cations (metals, amines, and mixtures thereof) with respect to from about 2:1-20:1, and still more preferably from about the type C repeat units, are the same as those set forth for the 2.5:1-10:1. Still further, the polymers should be essentially type B repeat units. 45 free (e.g., less than about 1 mole percent) of alkyloxylates or Unsubstituted itaconic acid and itaconic anhydride, either alkylene oxide (e.g., ethylene oxide)-containing repeat units, alone or in various mixtures, are the most preferred mono and most desirably entirely free thereof. mers for generation of type C repeat units. Again, if itaconic The preferred Class I polymers of the invention have the anhydride is used as a starting monomer, it is normally useful repeat units thereof randomly located along the polymer to convert the itaconic anhydride monomer to the acid form in 50 chain without any ordered sequence of repeat units. Thus, the a reaction vessel just before or even during the polymeriza polymers hereofare not, e.g., alternating with different repeat tion reaction. Any remaining ester groups in the polymer are units in a defined sequence along the polymer chain. normally hydrolyzed, so that the final carboxylated polymer It has also been determined that the preferred Class I poly is Substantially free of ester groups. mers of the invention should have a very high percentage of 3. Type G Repeat Units 55 the repeat units thereof bearing at least one anionic group, Type G repeat units are derived from substituted or unsub e.g., at least about 80 mole percent, more preferably at least stituted Sulfonate-bearing monomers possessing at least one about 90 mole percent, and most preferably at least about 95 carbon-carbon double bond and at least one Sulfonate group, mole percent. It will be appreciated that the B and C repeat in acid, partial or complete salt, or other form, and which are units have two anionic groups per repeat unit, whereas the Substantially free of aromatic rings and amide groups (i.e., no 60 preferred Sulfonate repeat units have one anionic group per more than about 5 mole percent of either aromatic rings or repeat unit. amide groups, preferably no more than about 1 mole percent For a variety of applications, certain tetrapolymer compo of either). The type G repeat units are preferably selected sitions are preferred, i.e., a preferred polymer backbone com from the group consisting of C1-C8 straight or branched position range (by mole percent, using the parent monomer chain alkenyl Sulfonates, Substituted forms thereof, and any 65 names of the corresponding repeat units) is: maleic acid isomers or salts of any of the foregoing, especially preferred 35-50%; itaconic acid 20-55%: methallylsulfonic acid are alkenyl Sulfonates selected from the group consisting of 1-25%; and allylsulfonic sulfonic acid 1-20%, where the total US 9,139,481 B2 7 8 amount of all of the repeat units in the polymer is taken as 100 100% by weight thereof). Various sources of vanadium may mole percent. It has also been found that even Small amounts be employed, with Vanadium oxysulfates being preferred. of repeat units, which are neither B nor C repeat units, can It has been discovered that it is most advantageous to significantly impact the properties of the final polymers, as perform these polymerization reactions in Substantially aque compared with prior BC polymers. Thus, even 1 mole percent ous dispersions (e.g., at least about 95% by weight water, of each of 2 different G repeat units can result in a tetrapoly more preferably at least about 98% by weight water, and most mer exhibiting drastically different behaviors, as compared preferably 100% by weight water). The aqueous dispersions with BC polymers. may also contain additional monomer, but only to the minor The molecular weight of the polymers is also highly vari extent noted. able, againdepending principally upon the desired properties. 10 It has also been found that the preferred polymerization Generally, the molecular weight distribution for polymers in reactions may be carried out without the use of inert atmo accordance with the invention is conveniently measured by spheres, e.g., in an ambient air environment. As is well known size exclusion chromatography. Broadly, the molecular in the art, free radical polymerization reactions in dispersions weight of the polymers ranges from about 800-50,000, and 15 are normally conducted in a way that excludes the significant more preferably from about 1000-5000. For some applica presence of oxygen. As a result, these prior techniques tions, it is advantageous that at least 90% of the finished involve Such necessary and laborious steps as degassing, inert polymer be at or above a molecular weight of about 1000 gas blanketing of reactor contents, monomer treatments to measured by size exclusion chromatography in 0.1 M Sodium prevent air from being present, and the like. These prior nitrate solution via refractive index detection at 35° C. using expedients add to the cost and complexity of the polymeriza polyethylene glycol standards. Of course, other techniques tions, and can present safety hazards. However, in the poly for Such measurement can also be employed. merizations of the polymers of the present invention, no inert Especially preferred Class I polymers include the follow gas or other related steps are required, although they may be ing repeat units: maleic from about 30-55 mole percent, employed if desired. more preferably from about 40-50 mole percent, and most 25 One preferred embodiment comprises creating highly con preferably about 45 mole percent; itaconic from about centrated aqueous dispersions of Solid monomer particles 35-65 mole percent, more preferably from about 40-60 mole (including saturated dispersions containing undissolved percent, and most preferably about 50 mole percent; methal monomers) at a temperature of from about 50-125°C., more lylsulfonic from about 1-7 mole percent, more preferably preferably from about 75-110° C., and adding vanadium from about 3-6 mole percent, and most preferably about 4 30 mole percent; and allylsulfonic from about 0.1-3 mole per oxysulfate to give avanadium concentration in the dispersion cent, more preferably from about 0.5-2 mole percent, and of from about 1-1000 ppm, and more preferably from about most preferably about 1 mole percent. This type of polymer is 5-500 ppm (metals basis). This is followed by the addition of typically produced as a partial alkali metal salt (preferably hydrogen peroxide over a period of from about 30 minutes-24 sodium) at a pH of from about 0.2-3, more preferably from 35 hours (more preferably from about 1-5 hours) in an amount about 0.3-2, and most preferably about 1. The single most effective to achieve polymerization. This process is com preferred polymer of this type is a partial Sodium salt having monly carried out in a stirred tank reactor equipped with a pH of about 1, with a repeat unit molar composition of facilities for controlling temperature and composition, but maleic 45 mole percent, itaconic 50 mole percent, methallyl any suitable equipment used for polymerization may be Sulfonic 4 mole percent, and allylsulfonic 1 mole percent. 40 employed. This specific polymer is referred to herein as the “T5” poly Another highly preferred and efficient embodiment C. involves charging a stirred tank reactor with water, followed Syntheses of the Class I Polymers by heating and the addition of monomers to give a dispersion Virtually any conventional method of free radical polymer having from about 40-75% w/w solids concentration. Where ization may be suitable for the synthesis of the Class I poly 45 maleic and/or itaconic monomers are employed, they may be mers of the invention. However, a preferred and novel syn derived either from the corresponding acid monomers, or thesis may be used, which is applicable not only for the from in situ conversion of the anhydrides to acid in the water. production of the Class I polymers of the invention, but also Carboxylate and sulfonated monomers are preferred in their for the synthesis of polymers containing dicarboxylate repeat acid and/or anhydride form, although salts may be used as units and Sulfonate repeat units and preferably containing at 50 well. Surprisingly, it has been found that incomplete mono least one carbon-carbon double bond. Such types of polymers mer dissolution is not severely detrimental to the polymeriza are disclosed in U.S. Pat. Nos. 5,536,311 and 5,210,163. tion; indeed, the initially undissolved fraction of monomers Generally speaking, the new synthesis methods comprise will dissolve at some time after polymerization has been carrying out a free radical polymerization reaction between initiated. dicarboxylate and Sulfonate repeat units in the presence of 55 After the initial heating and introduction of monomers, the hydrogen peroxide and Vanadium-containing species to reactor contents are maintained at a temperature between achieve a conversion to polymer in excess of 90%, and more about 80-125°C., with the subsequent addition of vanadium preferably in excess of 98%, by mole. That is, a dispersion of oxysulfate. Up to this point in the reaction protocol, the order the dicarboxylate and Sulfonated monomers is created and of addition of materials is not critical. After introduction of free radical initiator(s) are added followed by allowing the 60 Vanadium oxysulfate, a hydrogen peroxide solution is added monomers to polymerize. over time until substantially all of the monomers are con Preferably, the hydrogen peroxide is the sole initiator used verted to polymer. Peroxide addition may be done at a con in the reaction, but in any case, it is advantageous to conduct stant rate, a variable rate, and with or without pauses, at a fixed the reaction in the absence of any Substantial quantities of or variable temperature. The concentration of peroxide solu other initiators (i.e., the total weight of the initiator molecules 65 tion used is not highly critical, although the concentration on used should be about 95% by weight hydrogen peroxide, the low end should not dilute the reactor contents to the point more preferably about 98% by weight, and most preferably where the reaction becomes excessively slow or impractically US 9,139,481 B2 10 diluted. On the high end, the concentration should not cause peroxide addition was complete, the reactor was held at 95° difficulties in performing the polymerization safely in the C. for two hours, followed by cooling to room temperature. equipment being used. The resulting polymer dispersion was found to have less Preferably, the polymerization reactions of the invention than 2% w/w total of residual monomers as determined by are carried out to exclude Substantial amounts of dissolved 5 chromatographic analysis. iron species (i.e., more than about 5% by weight of such Example 2 species, and more preferably Substantially less, on the order of below about 5 ppm, and most advantageously under about Exemplary Synthesis 1 ppm). This is distinct from certain prior techniques requir ing the presence of iron-containing materials. Nonetheless, it 10 Apparatus: is acceptable to carry out the polymerization of the invention Same as Example 1 in 304 or 316 stainless steel reactors. It is also preferred to Procedure: Water was charged into the reactor, stirring was exclude from the polymerization reaction any significant initiated along with heating to a target temperature of 100° C. During this phase, itaconic acid, Sodium methallylsulfonate, amounts (nor more than about 5% by weight) of the sulfate 15 Sodium allylsulfonate, and maleic anhydride were added so as salts of ammonium, amine, alkali and alkaline earth metals, as to make a 70% w/w solids dispersion with the following well as their precursors and related Sulfur-containing salts, monomer mole fractions: such as bisulfites, sulfites, and metabisulfites. It has been maleic: 45% found that use of these sulfate-related compounds leaves a itaconic: 50% relatively high amount of sulfates and the like in the final methallylsulfonate: 4% polymers, which either must be separated or left as a product allylsulfonate: 1% contaminant. When the reactor temperature reached 100° C. vanadium The high polymerization efficiencies of the preferred syn oxysulfate was added to give avanadium metal concentration of 25 ppm by weight. After the vanadium salt fully dissolved, theses result from the use of water as a solvent and without the hydrogen peroxide (as 50% w/w dispersion) was added con need for other solvents, elimination of other initiators (e.g., 25 tinuously over 3 hours, using the feeding tube. The total aZo, hydroperoxide, persulfate, organic peroxides) iron and amount of hydrogen peroxide added was 7.5% of the disper Sulfate ingredients, the lack of recycling loops, so that Sub sion weight in the reactor prior to peroxide addition. After the stantially all of the monomers are converted to the finished peroxide addition was complete, the reactor was held at 100° polymers in a single reactor. This is further augmented by the C. for two hours, followed by cooling to room temperature. fact that the polymers are formed first, and Subsequently, if 30 The resulting polymer dispersion was found to have less desired, partial or complete salts can be created. than 1% w/w total of residual monomers as determined by chromatographic analysis. EXAMPLES Example 3 The following examples describe preferred synthesis tech 35 niques for preparing polymers; it should be understood, how Preparation of Tetrapolymer Partial Salts ever, that these examples are provided by way of illustration only and nothing therein should be taken as a limitation on the A tetrapolymer calcium sodium salt dispersion containing overall scope of the invention. 40% by weight polymer solids in water was prepared by the 40 preferred free radical polymerization synthesis of the inven Example 1 tion, using an aqueous monomer reaction mixture having 45 mole percent maleic anhydride, 35 mole percent itaconic Exemplary Synthesis acid, 15 mole percent methallylsulfonate sodium salt, and 5 mole percent allylsulfonate. The final tetrapolymer disper Apparatus: 45 sion had a pH of slightly below 1.0 and was a partial sodium A cylindrical reactor was used, capable of being heated and salt owing to the Sodium cation on the Sulfonate monomers. cooled, and equipped with efficient mechanical stirrer, con At least about 90% of the monomers were polymerized in the denser, gas outlet (open to atmosphere), Solids charging port, reaction. liquids charging port, thermometer and peroxide feeding This sodium partial salt tetrapolymer was used to create tube. 50 40% solids in water calcium salts. In eachinstance, apart from Procedure: Water was charged into the reactor, stirring was the Sodium present in the tetrapolymer mixture, appropriate initiated along with heating to a target temperature of 95°C. bases or base precursors (e.g., carbonates), or mixtures During this phase, itaconic acid, sodium methallylsulfonate, thereof were added to the aqueous tetrapolymer at room tem Sodium allylsulfonate, and maleic anhydride were added so as perature to generate the corresponding salts. Specifically, the to make a 50% w/w solids dispersion with the following 55 following basic reactants were employed with quantities of monomer mole fractions: the tetrapolymer to give the following salts: maleic: 45% Salt A-calcium carbonate and a minor amount of sodium itaconic: 35% hydroxide, pH 1.5. methallylsulfonate: 15% Salt B-calcium carbonate and a minor amount of sodium allylsulfonate: 5% 60 hydroxide, pH 3.5. When the reactor temperature reached 95° C. vanadium oxysulfate was added to give avanadium metal concentration Example 4 of 25 ppm by weight. After the vanadium salt fully dissolved, hydrogen peroxide (as 50% w/w dispersion) was added con Exemplary Synthesis tinuously over 3 hours, using the feeding tube. The total 65 amount of hydrogen peroxide added was 5% of the dispersion A terpolymer salt dispersion containing 70% by weight weight in the reactor prior to peroxide addition. After the polymer Solids in water was prepared using a cylindrical US 9,139,481 B2 11 12 reactor capable of being heated and cooled, and equipped least two different monomers individually and respectively with an efficient mechanical stirrer, a condenser, a gas outlet taken from the group consisting of what have been denomi open to the atmosphere, respective ports for charging liquids nated for ease of reference as B' and C'monomers; alternately, and Solids to the reactor, a thermometer, and a peroxide feed the polymers may be formed as homopolymers or copoly ing tube. mers from recurring C" monomers. The repeat units may be Water (300 g) was charged into the reactor with stirring and randomly distributed throughout the polymer chains. heating to a target temperature of 95° C. During heating, In detail, repeat unit B' is of the general formula itaconic acid, Sodium methallylsulfonate, and maleic anhy dride were added so as to make a 75% w/w solids dispersion with the following monomer mole fractions: maleic anhy 10 dride 20%; itaconic acid—60%: methallylsulfonate sodium salt 20%. When the monomers were initially added, they were in Suspension in the water. As the temperature rose, OC--- CO or OEC- - CO- or OEC- - CO - the monomers became more fully dissolved before polymer ORs OR6 Y/ O O ization was initiated, and the maleic anhydride was hydro 15 V / lyzed to maleic acid. When the reactor temperature reached Y 95° C. vanadium oxysulfate was added to yield a vanadium metal concentration of 50 ppm by weight of the reactor con tents at the time of addition of the vanadium salt. After the and repeat unit C" is of the general formula Vanadium salt fully dissolved, hydrogen peroxide was added as a 50% w/w dispersion in water continuously over two hours. At the time of hydrogen peroxide addition, not all of O the monomers were completely dissolved, achieving what is | OR O sometimes referred to as “slush polymerization’; the initially O K8 R | undissolved monomers were Subsequently dissolved during 25 I /s the course of the reaction. The total amount of hydrogen -(-CH-C-- or -(-CH-C-- O or peroxide added equaled 5% of the dispersion weight in the V V M R Ro R Ro-C reactor before addition of the peroxide. V After the peroxide addition was completed, the reaction C-OR O mixture was held at 95°C. for two hours, and then allowed to 30 O cool to room temperature. The resulting polymer dispersion O had a pH of slightly below 1.0 and was a partial sodium salt | owing to the Sodium cation on the Sulfonate monomers. The R-C-O dispersion was found to have a monomer content of less than -(-CH (4- \ 2% w/w, calculated as a fraction of the total solids in the 35 | \ / reaction mixture, as determined by chromatographic analy sis. Accordingly, over 98% w/w of the initially added mono R R.--0 mers were converted to polymer. O Class IA Polymers Class IA polymers contain both carboxylate and sulfonate 40 wherein each R, is individually and respectively selected functional groups, but are not the tetra- and higher order from the group consisting of H, OH, C-Clso straight, polymers of Class I. For example, terpolymers of maleic, branched chain and cyclic alkyl or aryl groups, C-Co itaconic, and allylsulfonic repeat units, which are per se straight, branched chain and cyclic alkyl oraryl formate (Co.), known in the prior art, will function as the polyanionic poly acetate (C), propionate (C), butyrate (C), etc. up to Co mer component of the compositions of the invention. The 45 based ester groups, R'CO groups, OR groups and COOX Class IA polymers thus are normally homopolymers, copoly groups, wherein R' is selected from the group consisting of mers, and terpolymers, advantageously including repeat units C-Co straight, branched chain and cyclic alkyl or aryl individually and independently selected from the group con groups and X is selected from the group consisting of H, the sisting of type B, type C, and type G repeat units, without the alkali metals, NH and the C-C alkyl ammonium groups, R. need for any additional repeat units. Such polymers can be 50 and Ra are individually and respectively selected from the synthesized in any known fashion, and can also be produced group consisting of H. C-Clso straight, branched chain and using the previously described Class I polymer synthesis. cyclic alkyl or aryl groups, Rs. R. Ro and R are individu Class IA polymers preferably have the same molecular ally and respectively selected from the group consisting of H, weight ranges and the other specific parameters (e.g., pH and the alkali metals, NH and the C-C alkyl ammonium polymer Solids loading) previously described in connection 55 groups, Y is selected from the group consisting of Fe, Mn, with the Class I polymers, and may be converted to partial or Mg., Zn, Cu, Ni, Co, Mo, V, W, the alkali metals, the alkaline complete salts using the same techniques described with ref earth metals, polyatomic cations containing any of the fore erence to the Class I polymers. going (e.g., VO"), amines, and mixtures thereof; and Rs and Further disclosure pertaining to the Class I polymers and Ro are individually and respectively selected from the group uses thereof is set forth in application Ser. No. 62/001,110, 60 consisting of nothing (i.e., the groups are non-existent), CH, filed May 21, 2014, which is fully incorporated by reference CH, and C.H. herein. As can be appreciated, the Class II polymers typically have Class II Polymers different types and sequences of repeat units. For example, a Broadly speaking, the polyanionic polymers of this class Class II polymer comprising B' and C repeat units may are of the type disclosed in U.S. Pat. No. 8,043,995, which is 65 include all three forms of B' repeat units and all three forms of attached hereto and is incorporated by reference herein in its C" repeat units. However, for reasons of cost and ease of entirety. The polymers include repeat units derived from at synthesis, the most useful Class II polymers are made up of B' US 9,139,481 B2 13 14 and C repeat units. In the case of the Class II polymers made going arranged in series may be employed. A wide range of up principally of B' and C repeat units, Rs. R. R. and R. Suitable reaction arrangements are well known to the art of are individually and respectively selected from the group polymerization. consisting of H, the alkali metals, NH, and the C-C alkyl In general, the initial polymerization step is carried out at a ammonium groups. This particular Class II polymer is some temperature of from about 0° C. to about 120° C. (more times referred to as a butanedioic methylenesuccinic acid preferably from about 30° C. to about 95° C. for a period of copolymer and can include various salts and derivatives from about 0.25 hours to about 24 hours and even more thereof. preferably from about 0.25 hours to about 5 hours). Usually, The Class II polymers may have a wide range of repeat unit the reaction is carried out with continuous stirring. concentrations in the polymer. For example, Class II poly 10 mers having varying ratios of B':C" (e.g., 10:90, 60:40, 50:50 After the polymerization reaction is complete, the Class II and even 0:100) are contemplated and embraced by the polymers may be converted to partial or Saturated salts using present invention. Such polymers would be produced by conventional techniques and reactants. varying monomer amounts in the reaction mixture from 15 Preferred Class II Maleic-Itaconic Polymers which the final product is eventually produced and the B' and The most preferred Class II polymers are composed of C" type repeat units may be arranged in the polymer backbone maleic and itaconic B' and C repeat units and have the gen in random order or in an alternating pattern. eralized formula The Class II polymers may have a wide variety of molecu lar weights, ranging for example from 500-5,000,000, depending chiefly upon the desired end use. Additionally, in XO can range from about 1-10,000 and more preferably from about 1-5,000. Preferred Class II polymers are usually synthesized using dicarboxylic acid monomers, as well as precursors and 25 derivatives thereof. For example, polymers containing mono and dicarboxylic acid repeat units with vinyl ester repeat units OX XO and vinyl alcohol repeat units are contemplated; however, polymers principally comprised of dicarboxylic acid repeat units are preferred (e.g., at least about 85%, and more pref 30 where X is either Horanother salt-forming cation, depending erably at least about 93%, of the repeat units are of this upon the level of salt formation. character). Class II polymers may be readily complexed with In a specific example of the synthesis of a maleic-itaconic salt-forming cations using conventional methods and reac Class II polymer, acetone (803 g), maleic anhydride (140 g), tantS. 35 itaconic acid (185g) and benzoyl peroxide (11 g) were stirred Synthesis of the Class II Polymers of the Invention together under inert gas in a reactor. The reactor provided In general, the Class II polymers are made by free radical included a Suitably sized cylindrical jacketed glass reactor polymerization serving to convert selected monomers into the with mechanical agitator, a contents temperature measure desired polymers with repeat units. Such polymers may be ment device in contact with the contents of the reactor, an further modified to impart particular structures and/or prop 40 inert gas inlet, and a removable reflux condenser. This mix erties. A variety of techniques can be used for generating free ture was heated by circulating heated oil in the reactorjacket radicals, such as addition of peroxides, hydroperoxides, azo and stirred vigorously at an internal temperature of about initiators, persulfates, percarbonates, per-acid, charge trans 65-70° C. This reaction was carried out over a period of about fer complexes, irradiation (e.g., UV, electron beam, X-ray, 5 hours. At this point, the contents of the reaction vessel were gamma-radiation and other ionizing radiation types), and 45 poured into 300 g water with vigorous mixing. This gave a combinations of these techniques. Of course, an extensive clear solution. The solution was subjected to distillation at variety of methods and techniques are well known in the art of reduced pressure to drive off excess solvent and water. After polymer chemistry for initiating free-radical polymeriza sufficient solvent and water have been removed, the solid tions. Those enumerated herein are but some of the more product of the reaction precipitates from the concentrated frequently used methods and techniques. Any Suitable tech 50 nique for performing free-radical polymerization is likely to Solution, and is recovered. The solids are Subsequently dried be useful for the purposes of practicing the present invention. in vacuo. A schematic representation of this reaction is shown The polymerization reactions are carried out in a compat below. ible solvent system, namely a system which does not unduly Step 1 interfere with the desired polymerization, using essentially 55 any desired monomer concentrations. A number of Suitable aqueous or non-aqueous solvent systems can be employed, COOH Such as ketones, alcohols, esters, ethers, aromatic solvents, water and mixtures thereof. Water alone and the lower (C- C.) ketones and alcohols are especially preferred, and these 60 COOH may be mixed with water if desired. In some instances, the Itaconic acid polymerization reactions are carried out with the Substantial acetone solvent He He exclusion of oxygen, and most usually under an inert gas Such Benzoyl peroxide initiator as nitrogen or argon. There is no particular criticality in the 5 hours o–C–O type of equipment used in the synthesis of the polymers, i.e., 65 T = 65-700 C. stirred tank reactors, continuous stirred tank reactors, plug Maleic anhydride flow reactors, tube reactors and any combination of the fore US 9,139,481 B2 15 16 -continued larly important are pesticidal actives (e.g., herbicides, insec COOH ticides, fungicides, and nematocides), especially the insecti cides and herbicides, and mixtures thereof. The well known pyrethroid and organophosphate pesticides are Suitable for COOH 5 use in the invention, as well as glyphosate herbicides. O O O More generally, the pesticides used in the invention are Acetone solution broadly selected from insecticides and herbicides. In the con Polymer text of insecticides, synthetic pyrethroids and organophos (with partial anhydride content) phates are particularly preferred. For example, permethrin 10 (C21H20C1203, (3-phenoxyphenyl)methyl 3-(2,2-dichloro Step 2 ethenyl)-2,2-dimethyl-cyclopropane-1-carboxylate, CAS #52645-53-1) and bifenthrin (C23H22ClF302, (2-methyl-3- phenylphenyl)methyl (1S,3S)-3-(Z)-2-chloro-3,3,3-trifluo COOH roprop-1-enyl-2,2-dimethylcyclopropane-1-carboxylate, 15 CAS #82657-04-3) are suitable pyrethroids. A typical orga al- + H2O -> --> nophosphate pesticide useful in the invention is malathion COOH (C10H1906PS2.2-(dimethoxyphosphinothioylthio) butane O O O dioic acid diethyl ester, CASH 121-75-5). Acetone solution More generally, the following insecticides are useful in the COOH 2O invention: antibiotic insecticides: allosamidin, thuringiensin macrocyclic lactone insecticides O COOH avermectin insecticides: abamectin, doramectin, ema O mectin, eprinomectin, ivermectin, Selamectin OH OH 25 milbemycin insecticides: lepimectin, ilbemectin, milbe Fully hydrolyzed acid form polymer, mycin Oxime, moxidectin aqueous solution spinosyn insecticides: spinetoram, spinosad arsenical insecticides: calcium arsenate, copper acetoarsen Once again, the Class II polymers should have the same ite, copper arsenate, lead arsenate, potassium arsenite, 30 Sodium arsenite preferred characteristics as those of the Class I and Class IA botanical insecticides: anabasine, azadirachtin, d-limonene, polymers set forth above. nicotine, pyrethrins (cinerins (cinerin I, cinerin II), jasmo Fertilizer Actives lin I, jasmolin II, pyrethrin I, pyrethrin II), quassia, roten A variety of liquid or solid fertilizers may be incorporated one, ryania, Sabadilla into the compositions of the invention, in lieu of or together carbamate insecticides: bendiocarb, carbaryl with synthetic resin polymers. Such fertilizers broadly benzofuranyl methylcarbamate insecticides: benfuracarb, include ammoniacal, phosphate, potassium, minerals (such carbofuran, carbosulfan, decarbofuran, furathiocarb as secondary nutrients and micronutrients), mixed NPK fer dimethylcarbamate insecticides: dimetan, dimetilan, tilizers, and mixtures thereof. hyduincarb, pirimicarb The fertilizers include ammoniacal nitrogen-containing 40 Oxime carbamate insecticides: alanycarb, aldicarb, aldoxy fertilizer, such as those selected from the group consisting of carb, butocarboxim, butoxycarboxim, methomyl. nit urea, UAN, ammonium nitrate, ammonium sulfate, urea, rilacarb, oxamyl, tazimcarb, thiocarboxime, thiodicarb, monoammonium phosphate, diammonium phosphate, thiofanox Sodium nitrate, calcium nitrate, potassium nitrate, nitrate of phenyl methylcarbamate insecticides: allyxycarb, ami Soda, urea formaldehyde, methyl ammonium phosphate, 45 nocarb, bufencarb, butacarb, carbanolate, cloethocarb, ammoniated Super phosphate, and mixtures thereof. In the dicresyl, dioxacarb, EMPC, ethiofencarb, fenethacarb, case of Solid ammoniacal fertilizers such as urea, the solids fenobucarb, isoprocarb, methiocarb, metolcarb, mexac should be ground to a fine particle size in order to assist in arbate, promacyl, promecarb, propoXur, trimethacarb, maintaining the products within the liquid matrix. Phospho XMC, xylylcarb rous fertilizers include monoammonium phosphate (MAP), 50 desiccant insecticides: boric acid, diatomaceous earth, silica diammonium phosphate (DAP), calcium phosphates (normal gel phosphate and Super phosphate), ammonium phosphate, diamide insecticides: chlorantraniliprole, cyantraniliprole, ammonium Super phosphate, ammonium polyphosphate, flubendiamide phosphoric acid, basic slag, rock phosphate, colloidal phos dinitrophenol insecticides: dinex, dinoprop, dinosam, DNOC phate, bone phosphate, ammonium Sulfate, ammonium thio- 55 fluorine insecticides: barium hexafluorosilicate, cryolite, Sulfate, and mixtures thereof. The secondary nutrient miner sodium fluoride, sodium hexafluorosilicate, sulfluramid als include calcium, magnesium, and Sulfur, either in formamidine insecticides: amitraz, chlordimeform, formet elemental form or as fertilizer compounds. Micronutrients anate, formparanate include Zinc, iron, manganese, copper, boron, cobalt, Vana fumigant insecticides: acrylonitrile, carbon disulfide, carbon dium, selenium, silicon, nickel, and mixtures thereof, which 60 tetrachloride, chloroform, chloropicrin, para-dichloroben can be in elemental form or as fertilizer compounds. Any Zene, 1,2-dichloropropane, ethyl formate, ethylene dibro normally solid fertilizers are preferably finely ground to mide, ethylene dichloride, ethylene oxide, hydrogen cya facilitate dispersion in the final liquid compositions. nide, iodomethane, methyl bromide, methylchloroform, Biocidal Actives methylene chloride, naphthalene, phosphine, Sulfuryl fluo Biocidal actives in liquid or solid form may also be incor- 65 ride, tetrachloroethane porated into the compositions of the invention, in lieu of or in inorganic insecticides: borax, boric acid, calcium polysulfide, combination with any of the above-described actives. Particu copper oleate, diatomaceous earth, mercurous chloride, US 9,139,481 B2 17 18 potassium thiocyanate, silica gel, Sodium thiocyanate, see isoxazole organothiophosphate insecticides: isox also arsenical insecticides, see also fluorine insecticides athion, ZolaprofoS insect growth regulators pyrazolopyrimidine organothiophosphate insecti chitin synthesis inhibitors: bistrifluoron, buprofezin, chlo cides: chlorpraZophos, pyrazophos rfluaZuron, cyromazine, diflubenZuron, flucycloXuron, pyridine organothiophosphate insecticides: chlorpy flufenoXuron, hexaflumuron, lufenuron, novaluron, rifos, chlorpyrifos-methyl noviflumuron, penfluoron, teflubenzuron, triflumuron pyrimidine organothiophosphate insecticides: juvenile hormone mimics: epolfenonane, fenoxycarb, butathiofos, diazinon, etrimfos, lirimfos, pirimi hydroprene, kinoprene, methoprene, pyriproxyfen, tri phos-ethyl, pirimiphos-methyl, primidophos, 10 pyrimitate, tebupirimfos prene quinoxaline organothiophosphate insecticides: juvenile hormones: juvenile hormone I, juvenile hormone quinalphos, quinallphos-methyl II, juvenile hormone III thiadiazole organothiophosphate insecticides: athi moulting hormone agonists: chromafenozide, dathion, lythidathion, methidathion, prothidathion halofenozide, methoxyfenozide, tebufenozide 15 triazole organothiophosphate insecticides: isazofos, moulting hormones: a-ecdysone, ecdysterone triaZophos moulting inhibitors: diofenolan phenyl organothiophosphate insecticides: azothoate, precocenes: precocene I, precocene II, precocene III bromophos, bromophos-ethyl, carbophenothion, unclassified insect growth regulators: dicyclanil chlorthiophos, cyanophos, cythioate, dicapthon, nereistoxin analogue insecticides: benSultap, cartap, thiocy dichlofenthion, etaphos, famphur, fenchlorphos, feni clam, thiosultap trothion, fensulfothion, fenthion, fenthion-ethyl, het nicotinoid insecticides: flonicamid erophos, jodfenphos, mesulfenfos, parathion, par nitroguanidine insecticides: clothianidin, dinotefuran, imi athion-methyl, phenkapton, phosnichlor, profenofos, dacloprid, thiamethoxam prothiofos, Sulprofos, temephos, trichlorimetaphos-3. nitromethylene insecticides: nitenpyram, nithiazine 25 trifenofos pyridylmethylamine insecticides: acetamiprid, imidaclo phosphonate insecticides: butonate, trichlorfon prid, nitenpyram, thiacloprid phosphonothioate insecticides: mecarphon organochlorine insecticides: bromo-DDT, camphechlor, phenyl ethylphosphonothioate insecticides: fonofos, DDT (pp'-DDT), ethyl-DDD, HCH (gamma-HCH, lin trichloronat dane), methoxychlor, pentachlorophenol, TDE 30 phenyl phenylphosphonothioate insecticides: cyanofen cyclodiene insecticides: aldrin, bromocyclen, chlorbicy phos, EPN, leptophos clen, chlordane, chlordecone, dieldrin, dilor, endosulfan phosphoramidate insecticides: crufomate, fenamiphos, (alpha-endosulfan), endrin, HEOD, heptachlor, HHDN, fosthietan, mephosfolan, phosfolan, pirimetaphos isobenzan, isodrin, kelevan, mirex phosphoramidothioate insecticides: acephate, isocarbo organophosphorus insecticides 35 phos, isofenphos, isofenphos-methyl, methamidophos, organophosphate insecticides: bromfenVinfos, chlorfen propetamphos Vinphos, crotoxyphos, dichlorvos, dicrotophos, dimeth phosphorodiamide insecticides: dimefox, mazidox, ylvinphos, fospirate, heptenophos, methocrotophos, mipafox, Schradan mevinphos, monocrotophos, naled, naftalofos, phos oxadiazine insecticides: indoxacarb phamidon, propaphos, TEPP, tetrachlorvinphos 40 oxadiazolone insecticides: metoxadiaZone organothiophosphate insecticides: dioxabenzofos, foSme phthalimide insecticides: dialifos, phosmet, tetramethrin thilan, phenthoate pyrazole insecticides: chlorantraniliprole, cyantraniliprole, aliphatic organothiophosphate insecticides: acethion, dimetilan, tebufenpyrad, tolfenpyrad amiton, cadusafos, chlorethoxyfos, chlormephos, phenylpyrazole insecticides: acetoprole, ethiprole, demephion (demephion-O, demephion-S), demeton 45 fipronil, pyraclofos, pyrafluprole, pyriprole, Vaniliprole (demeton-O, demeton-S), demeton-methyl (deme pyrethroid insecticides ton-O-methyl, demeton-S-methyl), demeton-S-me pyrethroid ester insecticides: acrinathrin, allethrin (bioal thylsulphon, disulfoton, ethion, ethoprophos, IPSP. lethrin), barthrin, bifenthrin, bioethanomethrin, cyclethrin, isothioate, malathion, methacrifos, oxydemeton-me cycloprothrin, cyfluthrin (beta-cyfluthrin), cyhalothrin, thyl, oxydeprofos, oxydisulfoton, phorate, Sulfotep, 50 (gamma-cyhalothrin, lambda-cyhalothrin), cypermethrin terbufos, thiometon (alpha-cypermethrin, beta-cypermethrin, theta-cyper aliphatic amide organothiophosphate insecticides: methrin, Zeta-cypermethrin), cyphenothrin, deltamethrin, amidithion, cyanthoate, dimethoate, ethoate-me dimefluthrin, dimethrin, empenthrin, fenfluthrin, fen thyl, formothion, mecarbam, omethoate, pro pirithrin, fenpropathrin, fenvalerate (esfenvalerate), thoate, Sophamide, vamidothion 55 flucythrinate, fluvalinate (tau-fluvalinate), furethrin, imi Oxime organothiophosphate insecticides: chlor prothrin, metofluthrin, permethrin (biopermethrin, phoxim, phoxim, phoxim-methyl transpermethrin), phenothrin, prallethrin, profluthrin, heterocyclic organothiophosphate insecticides: azame pyresmethrin, resmethrin (bioresmethrin, cismethrin), thiphos, coumaphos, coumithoate, dioxathion, endot tefluthrin, terallethrin, tetramethrin, tralomethrin, trans hion, menazon, morphothion, phosalone, pyraclofos, 60 fluthrin pyridaphenthion, quinothion pyrethroid ether insecticides: etofemprox, flufenprox, halfen benzothiopyran organothiophosphate insecticides: prox, protrifenbute, silafluofen dithicrofos, thicrofos pyrimidinamine insecticides: flufenerim, pyrimidifen benzotriazine organothiophosphate insecticides: pyrrole insecticides: chlorfenapyr azinphos-ethyl, azinphos-methyl 65 tetramic acid insecticides: Spirotetramat isoindole organothiophosphate insecticides: dialifos, tetronic acid insecticides: Spiromesi?en phosmet thiazole insecticides: clothianidin, thiamethoxam US 9,139,481 B2 19 20 thiazolidine insecticides: taZimcarb, thiacloprid carbanilate herbicides: barban, BCPC, carbasulam, carbeta thiourea insecticides: diafenthiuron mide, CEPC, chlorbufam, chlorpropham, CPPC, desme urea insecticides: flucofuron, Sulcofuron, see also chitin Syn dipham, phenisopham, phenmedipham, phenmedipham thesis inhibitors ethyl, propham, Swep unclassified insecticides: closantel, copper naphthenate, cyclohexene oxime herbicides: alloxydim, butroxydim, crotamiton, EXD, fenazaflor, fenoxacrim, hydramethyl clethodim, cloproxydim, cycloxydim, profoxydim, set non, isoprothiolane, malonoben, metaflumizone, niflurid hoxydim, tepraloxydim, tralkoxydim ide, plifenate, pyridaben, pyridalyl, pyrifluquinazon, cyclopropylisoxazole herbicides: isoxachlortole, isoxaflutole rafoxanide, Sulfoxaflor, triarathene, triaZamate. dicarboximide herbicides: cinidon-ethyl, flumezin, flumiclo 10 rac, flumioxazin, flumipropyn, see also uracil herbicides The foregoing insecticides, and links for a further identifi dinitroaniline herbicides: benfluralin, butralin, dinitramine, cation and description of the insecticides, can be found at ethalfluralin, fluchloralin, isopropalin, methalpropalin, http://www.alanwood.net/pesticides/class insecticides.h- nitralin, ory Zalin, pendimethalin, prodiamine, profluralin, tml, which is incorporated herein in its entirety. trifluralin A particularly preferred herbicide is glyphosate 15 dinitrophenol herbicides: dinofenate, dinoprop, dinosam, (C3H8NO5P (phosphonomethyl)aminoacetic acid, dinoseb, dinoterb, DNOC, etinofen, medinoterb CAS#1071-83-6). Other herbicides which can be used in the diphenyl ether herbicides: ethoxyfen invention include: nitrophenyl ether herbicides: acifluorfen, aclonifen, amide herbicides: allidochlor, amicarbazone, beflubutamid, bifenox, chlomethoxyfen, chlornitrofen, etnipromid, benzadox, benzipram, bromobutide, cafenstrole, CDEA, fluorodifen, fluoroglycofen, fluoronitrofen, fomesafen, cyprazole, dimethenamid (dimethenamid-P), diphenamid, furyloxyfen, halosafen, lactofen, nitrofen, nitrofluorfen, epronaz, etnipromid, fentraZamide, flucarbazone, oxyfluorfen flupoxam, fomesafen, halosafen, isocarbamid, isoxaben, dithiocarbamate herbicides: dazomet, metam napropamide, naptalam, pethoxamid, propyZamide, halogenated aliphatic herbicides: allorac, chloropon, dalapon, quinonamid, saflufenacil, tebutam 25 flupropanate, hexachloroacetone, iodomethane, methyl anilide herbicides: chloranocryl, cisanilide, clomeprop, bromide, monochloroacetic acid, SMA, TCA cypromid, diflufenican, etobenzanid, fenasulam, flufen imidazolinone herbicides: imazamethabenZ, imaZamox, acet, flufenican, ipfencarbazone, mefenacet, mefluidide, imaZapic, imazapyr, imaZaquin, imaZethapyr metamifop, monalide, naproanilide, pentanochlor, inorganic herbicides: ammonium sulfamate, borax, calcium picolinafen, propanil, SulfentraZone arylalanine herbi 30 chlorate, copper Sulfate, ferrous Sulfate, potassium azide, potassium cyanate, sodium azide, Sodium chlorate, Sulfu cides: benzoylprop, flamprop (flamprop-M), ric acid chloroacetanilide herbicides: acetochlor, alachlor, nitrile herbicides: bromobonil, bromoxynil, chloroxynil, butachlor, butenachlor, delachlor, diethatyl, dimeth dichlobenil, iodobonil, ioxynil, pyraclonil achlor, metaZachlor, metolachlor (S-metolachlor), 35 organophosphorus herbicides: amiprofoS-methyl, anilofos, pretilachlor, propachlor, propisochlor, prynachlor, bensulide, bilanafos, butamifos, 2,4-DEP, DMPA, EBEP, terbuchlor, thenylchlor, xylachlor fosamine, glufosinate (glufosinate-P), glyphosate, pipero Sulfonanilide herbicides: benzofluor, cloransulam, phos dicloSulam, florasulam, flumetSulam, metoSulam, oxadiazolone herbicides: dimefuron, methazole, oxadiargyl. perfluidone, pyrimisulfan, profluaZol 40 oxadiaZon Sulfonamide herbicides: asulam, carbasulam, fenasulam, oxazole herbicides: carboxazole, fenoxasulfone, isouron, oryzalin, penoXSulam, pyroxSulam, see also Sulfony isoxaben, isoxachlortole, isoxaflutole, monisouron, lurea herbicides pyroxasulfone, toprameZone thioamide herbicides: bencarbazone, chlorthiamid phenoxy herbicides: bromofenoxim, clomeprop, 2,4-DEB, antibiotic herbicides: bilanafos 45 2,4-DEP, difenopenten, disul, erbon, etnipromid, fentera aromatic acid herbicides: col, trifopsime benzoic acid herbicides: chloramben, dicamba, phenoxyacetic herbicides: 4-CPA, 2,4-D, 3,4-DA, MCPA, 2,3,6-TBA, tricamba MCPA-thioethyl, 2,4,5-T pyrimidinyloxybenzoic acid herbicides: bispyribac, phenoxybutyric herbicides: 4-CPB, 2,4-DB, 3,4-DB, pyriminobac 50 MCPB, 2,4,5-TEB phenoxypropionic herbicides: cloprop, 4-CPP dichlorprop pyrimidinylthiobenzoic acid herbicides: pyrithiobac (dichlorprop-P), 3,4-DP, fenoprop, mecoprop, (meco phthalic acid herbicides: chlorthal prop-P) picolinic acid herbicides: aminopyralid, clopyralid, piclo aryloxyphenoxypropionic herbicides: chloraZifop, clo al 55 dinafop, clofop, cyhalofop, diclofop, fenoxaprop, quinolinecarboxylic acid herbicides: quinclorac, quinmerac (fenoxaprop-P), fenthiaprop, fluazifop, (fluazifop-P), arsenical herbicides: cacodylic acid, CMA, DSMA, haloxyfop, (haloxyfop-P), isoxapyrifop, metamifop, hexaflurate, MAA, MAMA, MSMA, potassium arsenite, propaquizafop, quizalofop, (quizalofop-P), trifop Sodium arsenite phenylenediamine herbicides: dinitramine, prodiamine benzoylcyclohexanedione herbicides: mesotrione, Sulcotri 60 pyrazole herbicides: azimsulfuron, difenZoquat, halosulfu one, tefuryltrione, tembotrione ron, metaZachlor, metazosulfuron, pyrazosulfuron, benzofuranyl alkylsulfonate herbicides: benfuresate, etho pyroxasulfone fumesate benzoylpyrazole herbicides: benzofenap, pyrasulfotole, benzothiazole herbicides: benazolin, benzthiaZuron, fenthi pyrazolynate, pyrazoxyfen, toprameZone aprop, mefenacet, methabenzthiazuron 65 phenylpyrazole herbicides: fluazolate, nipyraclofen, carbamate herbicides: asulam, carboxazole, chlorprocarb, pinoxaden, pyraflufen dichlormate, fenasulam, karbutilate, terbucarb pyridazine herbicides: credazine, pyridafol, pyridate US 9,139,481 B2 21 22 pyridaZinone herbicides: brompyrazon, chloridazon, dimida cinmethylin, clomazone, CPMF, cresol, cyanamide, ortho Zon, flufenpyr, metflurazon, norflurazon, oxapyrazon, dichlorobenzene, dimepiperate, endothal, fluoromidine, pydanon fluridone, fluorochloridone, flurtamone, fluthiacet, indano pyridine herbicides: aminopyralid, cliodinate, clopyralid, fan, methyl isothiocyanate, OCH, oxaziclomefone, pen diflufenican, dithiopyr, flufenican, fluoroxypyr, haloxy tachlorophenol, pentoxaZone, phenylmercury acetate, pro dine, picloram, picolinafen, pyriclor, pyroxSulam, thiaz Sulfalin, pyribenzoxim, pyriftalid, quinoclamine, opyr, triclopyr rhodethanil, Sulglycapin, thidiazimin, tridiphane, trimetu pyrimidinediamine herbicides: iprymidam, tioclorim ron, tripropindan, tritac. quaternary ammonium herbicides: cyperquat, diethamduat, The foregoing herbicides, and links for a further identifi difenZoquat, diguat, morfamquat, paraquat 10 cation and description of the herbicides, can be found at thiocarbamate herbicides: butylate, cycloate, di-allate, http://www.alanwood.net/pesticides/class herbicides.html, EPTC, esprocarb, ethiolate, isopolinate, methiobencarb, which is incorporated herein in its entirety. molinate, orbencarb, pebulate, prosulfocarb, pyributicarb, In many instances, pesticides having an amphoteric or sulfallate, thiobencarb, tiocarbazil, tri-allate, Vernolate positive surface charge are preferred. Such surface charge thiocarbonate herbicides: dimexano, EXD, proxan 15 characteristics may be inherent in the pesticide employed, or thiourea herbicides: methiuron may arise by applying an appropriate cationic or amphoteric triazine herbicides: dipropetryn, indaziflam, triaziflam, trihy Surfactant onto the Surfaces of pesticide particles. Generally, droxytriazine the surfactants are used at a level of from about 0.01-10% by chlorotriazine herbicides: atrazine, chlorazine, cyanazine, weight (more preferably from about 0.1-3% by weight) based cyprazine, eglinazine, ipazine, mesoprazine, pro upon the total weight of the pesticide fraction in the overall cyazine, proglinazine, propazine, Sebuthylazine, composition taken as 100% by weight. simazine, terbuthylazine, trietazine Suitable cationic surfactants include: dieicosyldimethyl methoxytriazine herbicides: atraton, methometon, prome ammonium chloride; didocosyldimethyl ammonium chlo ton, secbumeton, Simeton, terbumeton ride; dioctadecyldimethyl ammonium chloride; dioctade methylthiotriazine herbicides: ametryn, aziprotryne, 25 cyldimethyl ammonium methoSulphate; ditetradecyldim cyanatryn, desmetryn, dimethametryn, methoprotryne, ethyl ammonium chloride and naturally occurring mixtures prometryn, simetryn, terbutryn of above fatty groups, e.g., di(hydrogenated tallow)dimethyl triazinone herbicides: ametridione, amibuzin, hexaZinone, ammonium chloride; di(hydrogenated tallow)dimethyl isomethiozin, metamitron, metribuzin ammonium metho-Sulphate; ditallow dimethyl ammonium triazole herbicides: amitrole, cafenstrole, epronaz, flupoxam 30 chloride; and dioleyidimethyl ammonium chloride. triazolone herbicides: amicarbazone, bencarbazone, carfen These cationic Surfactants also include imidazolinium traZone, flucarbazone, ipfencarbazone, propoxycarbazone, compounds, for example, 1-methyl-1-(tallowylamido-)ethyl SulfentraZone, thiencarbazone 2-tallowy14,5-dihydroimidaz-olinium methosulphate and triazolopyrimidine herbicides: cloranSulam, diclosulam, flo 1-methyl-1-(palmitoylamido)ethyl-2-octadecyl 4,5-dihydro rasulam, flumetSulam, metoSulam, penoXSulam, pyroxSu 35 imidazolinium methosulphate. Other useful imidazolinium lam materials are 2-heptadecyl-1-methyl-1(2-stearoylamido)- uracil herbicides: benzfendizone, bromacil, butafenacil, flu ethyl-imidazoliniu-m methoSulphate and 2-lauryl-lhydroxy propacil, isocil, lenacil, saflufenacil, terbacil ethyl-1-oleyl-imidazolinium chloride. urea herbicides: benzthiazuron, cumyluron, cycluron, dichlo Further examples of suitable cationic surfactants include: ralurea, diflufenZopyr, isonoruron, isouron, methabenz 40 dialkyl (C12-C22)dimethylammonium chloride; alkyl (coco thiazuron, monisouron, noruron nut)dimethylbenzylammonium chloride; octadecylamine phenylurea herbicides: anisuron, buturon, chlorbromuron, acetate salt, tetradecylamine acetate salt; tallow alkylpropy chloreturon, chlorotoluron, chloroXuron, daimuron, lenediamine acetate salt; octadecyltrimethylammonium difenoXuron, dimefuron, diuron, fenuron, fluometuron, chloride; alkyl(tallow)trimethylammonium chloride; dode fluothiuron, isoproturon, linuron, methiuron, meth 45 cyltrimethylammonium chlorid; alkyl (coconut)trimethylam yldymron, metobenzuron, metobromuron, metoxuron, monium chloride; hexadecyltrimethylammonium chloride; monolinuron, monuron, neburon, parafluoron, phe biphenyltrimethylammonium chloride, alkyl (tallow)imida nobenzuron, Siduron, tetrafluoron, thidiaZuron Zoline quaternary salt; tetradecylmethylbenzylammonium sulfonylurea herbicides: chloride; octadecyldimethylbenzylammonium chloride; dio pyrimidinylsulfonylurea herbicides: amidosulfuron, 50 leyidimethylammonium chloride; polyoxyethylene dodecyl azimsulfuron, benSulfuron, chlorimuron, cyclosulfa monomethylammonium chloride; polyoxyethylene alkyl muron, ethoxysulfuron, flaZaSulfuron, flucetosulfu (C12-C22)benzylammonium chloride; polyoxyethylene ron, flupyrsulfuron, foramsulfuron, halosulfuron, laurylmonomethyl ammonium chloride, 1-hydroxyethyl-2- imaZoSulfuron, mesosulfuron, metazosulfuron, nico alkyl(tallow)-imidazoline quaternary salt; and a silicone cat Sulfuron, orthosulfamuron, oxasulfuron, primisulfu 55 ionic Surfactant having a siloxane group as a hydrophobic ron, propyrisulfuron, pyrazosulfuron, rimsulfuron, group, a fluorine-containing cationic Surfactant having a fluo sulfometuron, sulfosulfuron, trifloxysulfuron roalkyl group as a hydrophobic group. triazinylsulfonylurea herbicides: chlorsulfuron, cinosul Amphoteric (Zwitterionic) surfactants have a positive, furon, ethametSulfuron, iodosulfuron, metSulfuron, negative, or both charges on the hydrophilic part of the mol prosulfuron, thifensulfuron, triasulfuron, tribenuron, 60 ecule in acidic or alkaline media. Any suitable amphoteric triflusulfuron, tritosulfuron Surfactant may be used. For example, aminoproprionates may thiadiazolylurea herbicides: buthiuron, ethidimuron, be employed where the alkyl chain of the aminoproprionate is tebuthiuron, thiazafluoron, thidiaZuron preferably between about C.4 and about C.12 and may be unclassified herbicides: acrolein, allyl alcohol, aminocyclo branched or linear. The aminoproprionate may also be a pyrachlor, azafenidin, bentaZone, benzobicyclon, bicyclo 65 Sodium alkylaminoproprionate. One representative commer pyrone, buthidazole, calcium cyanamide, cambendichlor, cially available product is sold under the trade name chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, MIRATAINE JC-HA. US 9,139,481 B2 23 24 Other suitable amphoteric surfactants include, diproprion applied, and the ammoniated polymer product would be ates such as Mirataine HC-HA, Sultaines such as Mirataine added to the anhydrous ammonia in a corresponding amount. ASC, betaines such as Mirataine BET-O-30, amine oxides In instances where other types of actives are used, e.g., such as Barlox 12i and amphoteric imidazoline derivatives in non-aqueous polymers, fertilizers, or biocidal actives, these the acetate form, Miranol JEM Conc, diproprionate form, can be added to the anhydrous ammonia directly or premixed Miranol C2M-SF Conc.), and sulfonates such as Miranol JS with ammonia solution before introduction into the anhy Conc. drous ammonia. The actives may be used at a level of from Other examples of amphoteric Surfactants include amino about 0.5-10% by weight, and more preferably from about acid, betaine, Sultaine, Sulfobetaines, carboxylates and Sul 1-8% by weight, based upon the total weight of the compo fonates of fatty acids, phosphobetaines, imidazolinium 10 sitions taken as 100% by weight. derivatives, soybean phospholipids, yolk lecithin, the alkali When finally mixed, the compositions of the invention may metal, alkaline earth metal, ammonium or Substituted ammo be applied to plants (foliar), the soil adjacent plants, or seeds. nium salts of alkyl amphocarboxy glycinates and alkyl The presence of anhydrous ammonia provides the usual fer amphocarboxypropionates, alkyl amphodipropionates, alkyl tilizing effect, whereas the agricultural active(s) provide fur amphodiacetates, alkyl amphoglycinates and alkyl amphop 15 ther beneficial effects. ropionates wherein alkyl represents an alkyl group having 6 I claim: to 20 carbon atoms, alkyliminopropionates, alkyl imino 1. An agriculturally useful composition comprising respec dipropionates and alkyl amphopropylsulfonates having tive quantities of anhydrous ammonia, ammonia Solution, and between 12 and 18 carbon atoms, alkylbetaines and ami an agricultural active comprising a polyanionic polymer. dopropylbetaines and alkylsultaines and alkylamidopropyl 2. The composition of claim 1, said anhydrous ammonia hydroxy Sultaines wherein alkyl represents an alkyl group being the preponderant ingredient of said composition. having 6 to 20 carbon atoms. 3. The composition of claim 1, the pH of said composition The Complete Compositions of the Invention being from about 8-13. The compositions of the invention contain three principal 4. The composition of claim 1, said agricultural active ingredients, namely anhydrous ammonia, ammonia Solution, 25 further comprising an active selected from the group consist and active(s). Generally, the anhydrous ammonia is the pre ing of one or more mineral-containing fertilizers, pesticides, ponderant ingredient in the compositions and is present at a and mixtures thereof. level of from about 60-90% by weight, more preferably from 5. The composition of claim 4, said mineral-containing about 65-85% by weight. The compositions are normally fertilizers selected from the group consisting of nitrogenous, prepared in pressurized tanks, such as conventional anhy 30 ammoniacal, and mixed NPK fertilizers, macronutrients, drous ammonia tanks. micronutrients, minerals, and mixtures thereof. Where aqueous agricultural actives are used, there are gen 6. The composition of claim 1, said polyanionic polymer erally two methods of converting the water to ammonia Solu containing maleic and itaconic repeat units. tion. First, the water fraction of a given active is separated 7. The composition of claim 6, said polyanionic polymer from the Solids fraction, and the water fraction is ammoniated 35 being dispersed in ammonia Solution. to create an ammonia Solution with only a minor amount of 8. The composition of claim 1, said polymer comprising at free water. Thereafter, the ammoniated water fraction is least four repeat units distributed along the length of the recombined with the solids fraction. Alternately, it may be polymer chain, said repeat units including at least one each of possible to directly ammoniate the water fraction without the a maleic, itaconic, and Sulfonate repeat unit. need for any Solids/liquid separation step. For example, in the 40 9. A method comprising the steps of applying to soil, anhy case of the previously described polymers in aqueous disper drous ammonia, ammonia Solution, and an agricultural active sion (e.g., the NUTRISPHERE-NR) product), the aqueous comprising a polyanionic polymer. fraction may be directly ammoniated at the end of the poly 10. The method of claim 9, said polymer comprising at mer synthesis to give the necessary conversion to ammonia least four repeat units distributed along the length of the solution. This treatment of course raises the overall pH of the 45 polymer chain, said repeat units including at least one each of polymeric product to the range of around 8-12. In this form, a maleic, itaconic, and Sulfonate repeat unit. the polymer may be directly introduced into pressurized 11. An agriculturally useful composition comprising anhydrous ammonia without encountering the previously respective quantities of anhydrous ammonia, ammonia Solu described exothermic reaction. However ammoniation of the tion, a first agricultural active comprising a polyanionic poly original water fraction is achieved, the final ammoniated 50 mer, and a second agricultural active selected from the group material should be essentially water-free, e.g., no more than consisting of one or more mineral-containing fertilizers, Syn about 5% water, more preferably no more than about 1% thetic resin polymers different than said polyanionic polymer, Water. pesticides, and mixtures thereof, said anhydrous ammonia When use is made of the preferred actives of the invention, being the preponderant ingredient of said composition and namely one or more of the previously described polymers 55 being present at a level of from about 60-90% by weight. having about 40% by weight polymer dispersed in water, the 12. The composition of claim 11, said polyanionic polymer water content of the dispersion is first converted to ammo containing maleic and itaconic repeat units. nium hydroxide or ammonia Solution by the introduction of 13. The composition of claim 12, said polyanionic polymer ammonia into the aqueous polymer dispersion. When the comprising at least four repeat units distributed along the dispersion is essentially water-free, it can be readily added to 60 length of the polymer chain, said repeat units including at anhydrous ammonia to form the final composition, usually by least one each of a maleic, itaconic, and Sulfonate repeat unit. pressure injection to overcome the pressure in the anhydrous 14. The composition of claim 11, said second agricultural ammonia tank. Usage of this type of ammoniated polymer active being a mineral-containing fertilizer. product is normally at a level of from about 12-45 ounces per 15. An agriculturally useful composition comprising acre of applied ammonia, more preferably from about 18-35 65 respective quantities of anhydrous ammonia, ammonia Solu ounces per acre, and most preferably at 30 ounces per acre. tion, a first agricultural active comprising a polyanionic poly That is, a grower would select a rate of ammonia/acre to be mer, and a second agricultural active comprising a pesticide. US 9,139,481 B2 25 26 16. The composition of claim 15, said polyanionic polymer containing maleic and itaconic repeat units. 17. The composition of claim 16, said polyanionic polymer comprising at least four repeat units distributed along the length of the polymer chain, said repeat units including at 5 least one each of a maleic, itaconic, and Sulfonate repeat unit. 18. The composition of claim 15, said second agricultural active further comprising an active selected from the group consisting of one or more mineral-containing fertilizers, Syn thetic resin polymers different than said polyanionic polymer, 10 and mixtures thereof.