[1]3 @ 8 3 2 2 2 2 9 United States Patent Office ,t,,ted Aug. 27, 1974 3,832,229 METHOD OF USING LATEX POLYMER FORMULATIONS FOR SEEPAGE CONTROL Paul L. Du Brow, Chicago, and Alvin L Frisque, La Grange, El., assignors to Nalco Chemical Company, Chicago, 111. 5 No Drawing. Filed Oct. 6, 1972, Ser. No. 295,633 Int. Cl. E02b 3100 U.S. Cl. 117-161 UA 10 Claims 10 ABSTRACT OF THE DISCLOSURE A method of seepage control which comprises contacting a surface with either: (1) water-in-oil emulsion containing dispersed throughout a finely-divided water-soluble vinyl addition polymer; or (2) a stable liquid disper- 15 sion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic polymer. INTRODUCT'ION 20 Water losses to the earth due to seepage have long been experienced. For example, irrigation ditches, feeder canals and drainage ditches lose great quantities of water to the ground before the water is used or before it reaches 25 its point of application. Also great quantities of water are lost due to seepage in farm ponds. In addition, it is often desirable to maintain a moisture area upon a permeable surface such as roads and highways, thus preventing the seepage of moisture into the ground below. 30 It is a known fact that water or moisture will penetrate and be absorbed by a penneable surface. More specifically, water tends to penetrate the ground upon contact. This loss of water is experienr-ed to a great extent in the Western, Southwestern and Southern portions of the United 3,- States where irrigation is a requirement for the growing @) and maintaining of any vegetable and plant life. It would be desirable to provide a metbod of seepage control by which the amount of water lost through a permeable surface, i.e., the earth, could be minimized. 40 Such a method would provide an improved method for transportation of water from both a cost and waste standpoint. It has been discovered that this method may be effected by the application of a water-in-oil emulsion con- 45 taining dispersed throughout a finely-divided water-soluble vinyl addition polymer. Of equal importance is a stable liquid dispersion of an emulsion containing anionic polymer from above and a water-soluble cationic polymer. OBJECTS 50 Therefore, an object of this invention is to provide a method of seepage control which comprises contacting a surface with a water-in-oil emulsion containing dispersed throughout a fmely-divided water-soluble vinyl addition 55 polymer. Another object of this invention is to provide a method of seepage control which comprises contacting the surface with a stable liquid dispersion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic 60 polymer. A further object of this invention is to provide a method of seepage control for irrigation ditches, drainage: ditches, farm ponds and feeder canals. Further objects will appear hereinafter. 65 T'HE INVENTION This invention involves a method of seepage control which comprises contacting a surface with a water-in-oil emulsion containing dispersed therethroughout a finely- 70 divided water-soluble vinyl addition polymer. The emulsion containing polymer comprises: 2 (A) An aqueous phase rangi ng between 75 and 95% by weight of the emulsion, which is comprised of: (1) a water-soluble Yinyl addition polymer having a concentration between 20 and 50% by weight of the emulsion, (2) water ranging between 5 and 25% by weight of the aqueous phase, (B) A hydrophobic liquid ranging betwee@n 5 and 25% by weight of the emulsion; and (C) A water-in-oil emulsifying agent having a concentration between 0.1 and 30% by weight of the emulsion. In addition, this invention involyes a method of seepage control which comprises contacting a surface with a stable liquid dispersion of a water-soluble anionic vinyl addition polymer and a water-soluble cationic polymer; the dispersion comprising: (A) A polymeric latex composed of a water-in-oil emulsion which contains dispersed therein a finely-divided water-soluble anionic vinyl addition polymer, the polymeric latex having uniformly distributed therethroughout; (B) A water-soluble cationic polymer with t@he weight ratio of (A): (B) being within the range of 1: 10 to 10: I and the total amount of (A) + (B) present within the dispersion being within the range of from 0.001 to 75% by weight. THE EMULSION CONTAINING POLYMERS In general, polymer emulsions are stable, and yet at the same time contain relatively large amounts of polymer. The polymers dispersed in the emulsion are quite stable when the particle size of the polymer is within the range of 2 millimicrons up to about 5 microns. The preferred particle size is within the range of 5 millimicrons and 3 microns. The stable water-in-oil emulsion comprises: (A) an aqueous phase; (B) a hydrophobic liquid; and (C) a water-in-oil emulsifying agent. The polymer containing emulsion of this invention is comprised of an aqueous phase ranging between 75 and 95% by weight of the emulsion. The aqueous phase is defined as the sum of the polymer and copolymer and the water present in the composition. The preferred range is between 75 and 90% by weight of the emulsion. The most preferred range is between 80 and 85% by weight of the emulsion. The present invention has a polymer concentration between 20 and 50% by weight of the emulsion. A preferred range is between 25 and 40% by weight of the emulsion. The most preferred range is between 30 and 35 % by weight of the emulsion. The polymers most commonly used in the application of this invention are acrylamide polymers which include - polyacrylamide and its water-soluble copolymeric derivatives such as, for instance, acrylic acid, methaerylic acid, maleic anhydride, acrylonitrile, and styrene. The copolymers contain from about 5 to 95% by weight of acrylamide. The molecular weights of the polymers and copolymers generally exceed 500,000. A polymer -also used in the practice of this invention is hydrolyzed polyacrylamide which has from I to 50% of the original carboxamide groups hydrolyzed to carboxyl groups. The molecular weights of hydrolyzed polyacrylamides generally range from 500,000 to I million or more. Other water-soluble vinyl polymers are described in detail in the following U.S. Pats.: 3,418,237; 3,259,570; and 3,171,805. In examining the disclosure of these patents it will be seen that the water-soluble polymers may be either cationic or anionic and, in some instances, the ionic charges are sufficiently slight so that the poly-
[2]3 mers may be considered nonionic. For exaniple, watersoluble polymers and copolymers of allyl amines, diallyl amines or dimetbylaminoethyl methacrylate are cationic. Polymers such as polyvinyl alcohol are nonionic and polymers such as polyacrylic acid or polystyrene sulfonates are anionic. All of these polymers may be used in the practice of this invention. The molecular weights of the polymers described above may vary over a wide range, e.g., 10,000 to 25 million. The preferred polymer has a molecular weight in excess of I million. The organic or oil phase of the emulsion is comprised of an inert hydrophobic liquid. The hydrophobic liqtiid comprises between 5 and 25% by weight of the emulsion. The preferred range is between 10 and 25% by weight of the emulsion. The most preferred range is between 10 and 20% by weight of the emulsion. The oil phase used in preparing these emulsions may be selected from a large group of organic liquids which include liquid hydrocarbons and substituted liquid hYdrocarbons. Preferred group of organic liquids are hydro,carbon liquids which include blends of aromatic and aliphatic hydrocarbon compounds, which contain from 4 to 8 carbon atoms. Thus, such organic hydrocarbon liquids as benzene, xylene, toluene, mineral oils, kerosenes, napthas, and in certain instances, petroleums may be used. A particularly useful oil from the standpoint of its physical and chemical properties is in the branchchain isoparaffinic solvent sold by Humble Oil and Refinery Company under the tradename "Isopar M." Typical specifications of this narrow-cut isoparaffinic solvent are set forth below in Table 1. TABLEI AUni- MaxiSpecification properties ------------- mum mum Test method Gravity, API at 60/601 F ----------- 48.0 61. 0 ASTM D 287 Color, Saybolt ---------------------- 30 ---------- ASTM D 156 Aiiiline point,' F------------------ 185 ---------- ASTM D 611 SWfur, p.p.m ------------------------------- 10 ASTM D 12661 Distillation,' F -------------------------------------- ASTM D 86 1BP ---------------------------- 400 410 Dry point ------------------------------ 495 Flash point, ' F.2................... 160 ---------- ASTM D 93 I Nephelometric mod. Pensky-Martens closed cup. Any conventional water-in-oil emulsifying agent can be used such as sorbitan monostearate, sorbitan monooleate, and the so-called low HLB materials which are all documented in the literature and are summarized in the Atlas HLB Surfactant Selector. Although the mentioned emulsifiers are used in producing good water-in-oil emulsions, other surfactants may be used as long as they are capable of producing these emulsions. The water-inoil empulsifying agent is presented in amounts ranging between 0.1 and 30% by weight of the emulsion. The preferred range is between 1.0 and 15% by weight of ,the emulsion. The most preferred range is between 12 and 15% by weight of the emulsion. The water-in-oil emulsion used in the practice of this invention exhibits the unique ability of rapidly dissolvin.into aqueous solution. The po lymer-contaiding emulsion releases the polymer in water in the presence of a surfactant in a very short period of time. Tbis inversion teebnique is described in Anderson et al., U.S. 3,624,019. This U.S. patent is incorporated herein by reference. ,Generally, the emulsion-containing polymer will be diluted with an organic liquid prior to use. In this application, the water-in-oil emulsioncontaining the vinyl addition polymer will be diluted with an organic liquid so that the final dispersion will have 0.001 to 10% by weight of the two polymers. Typically, the liquid organic solvent is added to the emulsion-containing polymer in the ratio of from 99:1 to 10:90, preferably 97:3 to 60:40. The organic liquids used for this dilution include both aromatic and aliphatic hydrocarbon compounds. Tbus, 3,832,229 4 toluene, and mineral oils, kerosene, napthas and petroleums may be used. STABLE LIQUID DISPERSION The stable liquid dispersion is a water-soluble anionic vinyl addition polymer in the form of a water-in-oil emulsion which contains dispersed therein the finelydivided water-soluble anionic vinyl addition polymer which contains uniformly distributed therethroughout a 10 water-soluble cationic polymer. The water-in-oil emulsion containing dispersed therein the finely-divided watersoluble anionic vinyl addition polymers are described above in the section The Emulsion Containin.@ Polymers. The watersoluble anionic vinyl addition polymers that 15 are used in the practice of this portion of the invention may be illustrated by the following list of polymers. TABLEII No.: Name I ---- Polyacrylic acid-sodium salt. 20 2 ---- Polymethacrylic acid-sodium salt. 3 ---- Maleic anhydride-vinyl acetate copolymer. 4 ---- Polyvinylmethyl ether-maleic anhydride copolymer. ---- Methacrylic acid-acrylamide copolymer. 25 6 ---- Polyacrylic acid. 7 ---- Isopropenyl acetate - maleic anhydride sodium salt. 8 ---- Itaconic acid-vinyl acetate. ---- Methyl styrene-maleic anhydride sodium 30 salt. 10 ---- Styrene-maleic anhydride. I I ---- Methylmethacrylate-maleic anhydride sodium salt. 35 12 ---- Acrylic acid-styrene. 1 3---- Acrylamide-acrylic acid (5% by weight). 14 ---- Acrylamide-acrylic acid (50% by weight). 15 ---- Polystyrene sulfonic acid. 16 ---- Acrylamide-acrylic acid (80% by weight). 40 The above polymers may vary in molecular weight. They may be as low as 10,000 or as high as 12,000,000 or more. In many of the more useful applications, which will be more fufly discussed hereafter, the molecular weight wiU be greater than 1,000,000. 45 The invention contemplates using as preferred watersoluble anionic vinyl addition polymers the homo- and copolymers of acrylic acid as well as the water-soluble salts thereof. THE WATER-SOLUBLE CATIONIC POLYMERS 50 T'hese polymers also may be selected from a wide variety of kncwn polymeric materials. Several of these polymers arelisted below in Table III: TABLE III 55 No.: Name 1 ---- Ethylene dichloride-ammonia condensation polymers. ---- Tetraethylene pentamine-ep ichlorohydrin condensation polymers. 60 3 ---- Epichlorohydrin - ammonia condensation polymers. 4 ---- Polyethylene imine. ---- Ethylene diamine. ---- PolydiaIlyl amine. 6,5 7 ---- Dimethylamino ethyl methacrylate. 8 ---- The methyl chloride quaternary of Number 1. ---- The benzol chloride quatemary of Number 7. 70 10 ---- Guanidine formaldehyde condensation polymers. 11 ---- Acrylamide-diallylamine (30%). The above polymers are iuustrative of typical watersuch organic hydrocarbon liquids as benzene, xylene, 75 soluble cationic polymeric materials that may be used in
[3]3,832,229 5 the practices of the invention. A preferred class of these polymers may be described as alkylene polyamines which are Mustrated by polymers 1, 2, 3, 4, 5 and 8 above. Many of the above polymers have been described with respect to the reactants firom- which they are prepared. A detailed discussion of the above polymers and other 5 cationic polymers appears in Canadian Pat. No. 731,212, the disclosure of which is incorporated herein by reference. The polymers may be employed as solutions or in the form of a water-in-oil latex emulsion. When the 10 polymers are of the vinyl addition type they may be copolymers of other ethylenicary saturated monomers. Such copolymers should contain at least 5% by weight of the cationic monomer. Once the latices containing the water-soluble anionic 15 vinyl addition polymers are prepared as described above, the stable liquid dispersion is prepared by combining the latex containing pdlymer with the - water-soluble cationic polymers by the utilization of conventional mixing techniques. Preferably, the water-soluble cationic polymers 20 are in the form of aqueous solutions which contain 5 to 40% by weight of the polymer and are added to the polymeric latex. Altematively, they may be nearly water-free After uniformly mixing the two components there results a dispersion of a water-soluble anionic vinyl addition polyiner and a water-soluble cationic polymer. The proportions of the two polymers may be varied to a considerable degree. For instance, the ratio of the watersoluble anionic vinyl addition polymer to water-soluble cationic polymer may vary between 1:10 to 10:1 on a 30 weight basis. A preferred ratio is 1:5 to 5:1. The most prefmed ratio is 1:2 to 2: 1. The amount of water-soluble anionic vinyl addition polymers plus water-soluble cationic polymers present in the finished stable dispersion may be varied over a wide 35 range of concentrations, e.g., liquid dispersions containing from 0.001 to 75% by weight are useful, although for most applications the total weight of the two polymers contained in the dispersion concentrate wiR be within the range of 5 to 40% by weight, with a very 40 beneficial dispersion being one which contains between 10 to 30% by weight of the two polymers. 'fhe finished dispersion concentrates are stable at room temperature for periods of time ranging between several days to as long as six months since they may be prepared 45 over a wide variety of concentrations. To irustrate the preparation of stable liquid dispersions, a variety of emulsions were prepared containing different water-soluble anionic vinyl addition polymers. These emulsions are set forth below in Table IV. 50 TABLERV Percent bywt. Percent Composi- ' in Polymer particle tion number Water oil Polymer emulsion size range -------------- 72 28(l) 93% acrylamide ------------- 35 0.05-7.0 microns. 17% methaerylic acid --------- ]EL ------------ 72 28(I) acrylamide ------------- 35 Do. 7 methaerylic acid -------- ------------ 72 28(T) acrylamide ------ -- 35 DO. IV ------------ 93 32 <30 microns. 67 33(I) 7 v ------------- 70 30 7 ----- 34 .01-10 microns. (1) 13 VI ------------ 71 29(I) ----- 37 <lmm. NOTE.-I=Isopar M; T=Toluene. DISPERSION A 65 To the emulsion in Table IV, Composition Number VI, there was added 30% by weight of an aqueous dispersion containing 23% by weight of an alkylene polyamine prepared from the condensation of ethylene dichloride and ammonia. The polymer was prepared using 70 the techniques set forth in Canadian Pat. No. 785,829. DISPERSION CONCENTRATE B To composition Number VI in Table IV, there was added an aqueous dispersion which contained 25% by 7-5 6 weight of an ammonia ethylene dichloride polymer of the type used in Dispersion A above, with the exception it had been quaternized with methyl chloride. To iuustrate other novel dispersion concentrates of the invention Table V is presented below: TABLE V Antonio Disper- latex, Percent Percent sion Table IV by wt. Cationto polymer by wt. C --------- I 60 209,' solution of a tetra7 40 ethylene pentamine eptchlorohydrin reaction product (Canadian Pat. 731,212). D -------- VI so Ethylene diamlne ----------- 10 E --------- v 70 75% aerylamide, 25% dimethylamino ethyl methactylate copolymer in the form of a latex twater-inoil)-See Table II, U.S. 3,624,019. All of the above dispersion concentrates were stable and were capable of being stored under a variety of conditions without interreaction of the two polymers. GenerAy, the stable liquid dispersion will be diluted with an organic liquid prior to use. As mentioned above, the preferred dispersion concentrate will have from 5 to 40% by weight of the two polymers. In this application, the stable liquid dispersion@ will be diluted with an organic liquid so that the final dispersion will have 0.001 to 10% by weight of the two polymers. Typically, the liquid organic solvent or brine water is added to the stable dispersion in the ratio of from 99:1 to 10:90, Preferably 97:3 to 60:40. The organic liquids used for this dilution include both aromatic and aliphatic hydrocarbon, cgmpounds. Thus, such organic hydrocarbon liquids as benzene, xylene, toluene, and mineral offs, kerosene, napthas and petroleums may be used. In addition to a dilution with a liquid hydrorarbon solvent, preferably a brine water may be used for dilution purposes. Typir-ally, the brine water consists of an aqueous solution of a water-soluble inorganic salt. Generally, the salts used are sodium chloride, sodium sulfate, sodium bromide, calcium sulfate and magnesium suffate. The salts are not limited to those mentioned above. Any water-soluble inorganic salt may be used. The brine water concentration may bave a salt content ranging from 0.1% to as high as a concentrated salt. The dispersion when diluted with the brine water is stable and is capable of being stored under a vaxiety of conditions without interaction of the two polymers. THE METHOD A surfactant may be added to the diluted emulsioncontaining polymer of the diluted stable dispersion as the case may be. However, generally a surfactant is not added. The concentration of the surfactant added may vary over a wide range, preferably from 0.01 to 50% by weight based on the polymer. I-lowever, generally the surfactant concentration is within the range 1.0 to 3.0% by weight based on polymer. The preferred surfactants are hydrophilic and are further characterized as being watersoluble. Any hydro-
[4]7 philic-type surfactant such as ethoxylated nonyl phenols, ethoxylated nonyl phenol formaldhyde resins, dioctyl esters of sodium sulfosuccinate, and octyl phenol polyoxyethanol can be used. Basically, any anionic, cationic or nonionic surfactant can be employed in the Pract'ce of this invention. Surfactants which could be useful in this invention are fully disclosed in U.S. Pat. 3,624,019. After the emulsion or dispersion, diluent and surfactant have been mixed together, the resulting mixture may be applied to the treating surface in any conventional method such as a ponding technique. After application of the mixture to the surface, the mixture is allowed to penetrate the surface. The solvent will evaporate and upon contact with water the polymer will swell. "is results in the plugging of the permeable surface, resulting in a reduction in water seepage. Example 1 This test involved filling of several 23/4 inch diameter plexiglass cylinders with a medium sand to a depth Of 5 inches and treating with a 3% solids of the various emulsion-containing polymers and dispersions described above. The emulsion or dispersion was added at a rate of 25 grams cylinder. After drying, a 3 inch head of water was applied to the soil. Typical results of the test are shown in Table VI below. TABLE VI Percent Test Treatment polymer See page rate 1--------------- None -------------------------------- V@: per hour. 2 --------------- Composition I ------------ i- M @er.day. 3 --------------- Composition III ---------- 3 4 --------------- Dispersion A -------------- 3 Do. 5 --------------- Dispersion C -------------- 3 Do. We
