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United States Patent (19) 11 Patent Number: 4,782,078 Crawford Et Al United States Patent (19) 11 Patent Number: 4,782,078 Crawford et al. (45) Date of Patent: Nov. 1, 1988 (54). HALOPHORBIOCIDAL COMPOSITIONS 4,526,751 7/1985 Gartner ........................... 424/150 X 75 Inventors: Roger A. Crawford, Wadsworth; OTHER PUBLICATIONS Robert H. Juda, Akron, both of Ohio; Paritosh M. Chakrabarti, Daniels et al. J.A.C.S., 28, pp. 573 and 574. Pittsburgh, Pa. Primary Examiner-Richard L. Raymond 73) Assignee: PPG Industries, Inc., Pittsburgh, Pa. Assistant Examiner D. B. Springer Attorney, Agent, or Firm-Irwin M. Stein 21 Appl. No.: 819,453 22 Filed: Jan. 16, 1986 57 ABSTRACT 51) int. Cl." ............................................. A01N 43/36 Halophor biocidal compositions, e.g., bromophors, 52 U.S. Cl. ................. 514/424; 548/543 comprising a complex of N-alkyl substituted-2-pyrroli 58 Field of Search ......................................... 514/424 done, e.g., N-methyl pyrrolidone, halide ion, e.g., so dium bromide, and halogen, e.g., bromine, are de (56) References Cited scribed. U.S. PATENT DOCUMENTS 3,907,720 9/1975 Field et al. ............................ 52/54 7 Claims, No Drawings 4,782,078 1. 2 HALOPHOR BOCIDAL COMPOSITIONS DETAILED DESCRIPTION OF THE INVENTION DESCRIPTION OF THE INVENTION N-alkyl substituted-2-pyrrolidones that may be used 5 as the organic carrier for the halogen, e.g., bromine, are The present invention relates to solid biocidal bro those represented by the above graphic formula I. More nine- and iodine-containing compositions and, in par particularly, those pyrrollidones wherein R is methyl ticular, relates to complexes of bromine and/or iodine and R1-R5 are hydrogen or methyl are preferred. Ex with N-alkyl substituted-2-pyrollidones. amples of the aforedescribed pyrrollidones are N-methyl The halogens, i.e., chlorine, bromine and iodine, are O pyrrolidone, N-methyl-3-methyl pyrrolidone, N-meth recognized as excellent biocidal materials and are used yl-3-ethyl pyrrolidone, N-methyl 4-methyl pyrrollidone, extensively, particularly in the food processing and N-methyl-5-ethyl pyrrollidone, N-methyl-3,4-dimethyl handling industries, to prevent bacteriological contami pyrrolidone, N-methyl-3,5-dimethyl pyrrolidone, N nation of foodstuffs. Halogen sanitizers are also used in methyl-4,4-dimethyl pyrrolidone, N-methyl-3,3,5- controlling potentially harmful organisms in potable 15 trimethyl pyrrolidone, N-ethyl pyrrolidone. N-propyl water, swimming pools, hospitals, and wherever harm pyrrolidone, N-ethyl-3-methyl pyrrolidone, and N ful organisms can present a contamination problem. butyl pyrrollidone. Numerous proposals have been made to provide bio N-methyl pyrrolidone is a commercially available cidal compositions which involve the complexing of product. It may be prepared by the reaction of gamma halogen, e.g., bromine and iodine, with various com 20 butyrolactone and methylamine. 2-pyrrolidones may be pounds which have the property of liberating the halo prepared by the reaction of butyrolactone and ammo gen under conditions of use. These compositions are nia. The 2-pyrrolidones may be alkylated by first form generally referred to in the art as halophors, e.g., iodo ing the alkali metal salt thereof and then reacting it with phors and bromophors, and their disinfectant and ger an alkyl halide. The N-(C1-C4) alkyl-2-pyrrolidones micidal activity is derived essentially from the free halo 25 may be prepared by the aforesaid alkylation method or gen which the compositions liberate. by reaction of gamma-butyrolactone with the corre Complexes of iodine with cross-linked N-vinyl lac sponding alkylamine in the manner in which N-methyl tams, e.g., N-vinyl-2-pyrrolidone or N-alkyl-N-vinyla pyrrollidone is prepared. mide, polymers are described in U.S. Pat. No. 3,907,720. The added bromide or iodide (halide) ion used in the European Patent Application No. 107,277 describes an preparation of the halophor contemplated herein is antimicrobial film consisting essentially of 30 to 80 provided usually by the bromides or iodides of the alkali weight percent vinyl acetate and 20 to 70 weight per metals, sodium, lithium or potassium, or the bromides or cent N-vinyl pyrrolidone copolymer combined with iodides of the alkaline earth metals calcium and magne iodine and/or bromine. Pyrrolidone-2 has been reacted sium. Preferably, the aforesaid alkali metal halide is with bromine in chloroform to produce the addition 35 soluble or at least partially soluble in the organic car product, pyrollidone-2 hydrotribromide, having the rier, i.e., the N-alkyl substituted pyrrollidone-2 or the alkyl derivatives thereof. Lithium or sodium bromide empirical formula, (C4H7NO)3 HBr Br2). N-methyl are preferred. Sodium bromide is economically pre pyrrolidone-2 has been reacted with hydrogen bromide ferred. The halide may be represented by the formula, and bromine to form a complex having the empirical MX, wherein M is the alkali metal, sodium, lithium or formula (C5H10NO)2 HBr Br2). See, "Lactam Com potassium and X is iodine or bromine, e.g., MBr or MI. plexes of Bromine-Hydrogen Bromide' by W. E. Dan The amount of added halide used with the N-alkyl iels etal, J. Org. Chem, Vol. 28, pp. 573-574 (Feburary, substituted-2-pyrrolidone carrier can vary. In general, 1963). the mole ratio of added halide ion to elemental halogen The present invention provides a composition com 45 in the halophor composition, e.g., bromide:bromine prising a complex of bromine and/or iodine, an N-alkyl (Br2), may vary from 1:1 to 1:12, more usually from 1:1 substituted-2-pyrrollidone organic carrier, and alkali or to 1:3. Preferably, the mole ratio is about 1:2. Depend alkaline earth metal bromide or iodide ion. The result ing on the halide (bromide or iodide) ion and halogen ing composition, i.e., the halophor, is easily handled and (bromine or iodine) used, the halophor (bromophor or has exceptional stability. More particularly, the organic 50 iodophor) may contain one or more of the following carrier is represented by the following graphic formula: halide or interhalide species: Br3 and Br2 multiples thereof, e.g., Brs, Br7-, Brg etc; Br2 and Br2 mul tiples thereof, e.g., Bra, BréI; Br2 and Br2 or I2 (I) multiples thereof, e.g., Br32, Brs2, BrA, and is : 55 Bris, etc; and I3, and I2 multiples thereof, e.g., I5, R.---R, I7 -, etc. R5-C CcO The amount of halogen, e.g., bromine, complexed / N / with the pyrrolidone-added halide mixture may vary N widely. Usually the amount of halogen present in the R 60 halophor as available elemental halogen, e.g., Br2 or 12, will vary from about 10 to about 50, e.g., 25 to 40 wherein R is a C1-C4 alkyl, and R, R2, R3, R4 and Rs weight percent. are each selected from the group consisting of hydrogen In accordance with a preferred embodiment of the and C1-C2 alkyl. The iodide or bromide used to pre present invention, the added halide, i.e., alkali metal pare the complex is typically an alkali metal or alkaline 65 halide, is first admixed with, or preferably dissolved in, earth metal iodide or bromide, e.g., sodium or lithium the pyrrolidone organic carrier and subsequently halo iodide or bromide, or calcium or magnesium bromide or gen, i.e., bromine and/or iodine, introduced into the iodide. admixture or solution. While not wishing to be bound 4,782,078 3 4 by any theory, it is believed that the halogen added to liters) of bromine (Br2) were added slowly with stirring the pyrrollidone carrier-added halide mixture reacts over thirty minutes to the reaction flask. The tempera predominantly with the alkali metal halide to form ture of the contents of the reaction flask increased dur polyhalo species rather than reacting irreversibly with ing addition of the bromine to between 41 C. and 46 C. the pyrrollidone carrier, thereby providing a product 5 The reaction mixture was maintained in that tempera which yields significant quantities of available halogen, ture range while cooling with the exception of one e.g., bromine, for those applications, e.g., biocidal appli cooling excursion to 37 C. After all of the bromine had cations, requiring same. In a preferred embodiment, the been added, the temperature of the reaction mixture pyrrolidone carrier and halide, e.g., lithium or sodium continued to rise slowly. Cooling was continued until bromide, are substantially free of water. Most prefera 10 the temperature dropped to 44' C. at which point the bly, the system is anhydrous, which, it is believed, leads reaction mixture temperature decreased slowly. The to enhanced stability of the halophor prepared in accor product was a crystalline solid at room temperature. dance with the present process. Halophors described herein can be readily produced This product was stored in a glass bottle at 30° C. for 16 by combining the pyrrolidone, alkali metal halide, and 15 weeks after which the test was terminated. Periodically bromine (and/or iodine) under suitable complexing a sample was removed from the bottle and tested by conditions. For bromophors, it is preferred that liquid thiosulfate titration for the amount of available bromine bromine be combined with a mixture, e.g., solution, of remaining in the stored composition. Results are tabu the pyrrolidone carrier and alkali metal bromide, e.g., lated in Table I. The bromophor composition com sodium or lithium bromide. The reaction between liquid 20 prised 52.1 weight percent of N-methyl pyrrolidone, 9.9 bromine and the pyrrolidone-added halide liquid mix weight percent lithium bromide and 38.0 weight per ture is generally highly exothermic and hence the reac cent of added bromine. tion mixture should be vigorously stirred and cooled as TABLE I needed as the bromine is added slowly.
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