US 3539684 A
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United States Patent Office 3,539,634 Patented Nov. 10, 1970 3,539,684 BACTERICIDAL POLYMERS Merwin Frederick Hoover, Bethel Park, Pa., assignor to Calgon Corporation, Pittsburgh, Pa. No Drawing. Filed Nov. 21, 1968-, Ser. No. 777,878 Int. Cl. A01n 23/00, 9/22 U.S. Cl. 424-78 9 Claims ABSTRACT OF THE DISCLOSURE Bactericidal effects of various homopolymers and copolymers of fatty quaternary diallyl ammonium compounds are disclosed.
BACKGROUND OF THE INVENTION It has been known for years that certain quaternary ammonium compounds are excellent bactericides. Although it is very common for quarternary ammonium compounds to have bactericidal effects, it is also known that not all quaternary ammonium compounds display such abilities. It nevertheless may be said that, generally speaking, quaternary ammonium compounds having fatty tails exhibit excellent bactericidal and bacteristatic effects. See, for example, Surface Active Quaternary Ammonium Germicides by Carl Lawrence, Academic Press, Inc., 1950.
Attempts have been made to incorporate fatty quaternary ammonium groups into polymers, generally water soluble polymers. However, little success has been achieved. See also, for example, Melamed, U.S. Pats. 2,980,634 and 2,980,657. Other examples can be found in British Pat. 1,059,117 and U.S. Pat. 2,309,592. I have found that fatty quaternary ammonium groups may be incorporated into long chain water-soluble polymers when they are generally of the structure disclosed by Butler in U.S. Pat. 3,288,770. See my patent application filed Dec. 15, 1967, Ser. No. 690,793 now abandoned.
SUMMARY OF THE INVENTION I have found that water soluble polymers containing at least 0.5% by weight of a fatty alkyl diallyl quarternary ammonium compound exhibit excellent bacteristatic and bactericidal properties. The balance of the polymers of my invention may be comprised of other diallyl quaternary ammonium monomers and/or monoethylcnically unsaturated monomers.
Examples of the copolymerizable monoethylenically unsaturated comonomers are acrylamide and the Nsub stitutcd acrylamides disclosed in British Pat. 788,079. Examples are N-(Z-diethylamino-ethyl)-methacrylamide, N- (3 -dimethylamino-propyl -methacrylamide, N- 3-diethylamino-propyl)-methacrylamide, N-(2 piperidino-ethyl)- methacrylamide, N- Z-dimethylamino-ethyl -acrylamide, N-(Z-diethylaminoethyl)-acrylamide, and N-(3-dimethylamino-propyl) aciylamide, N-(2-dimethylaminoethyl)- methacrylamide, N-( 2 morpholinethyl)-methacrylarnide, N-(3-piperidino-pro-pyl) -methacrylamide and N-( 3-hexamethylene-aminopropyl)-methacrylamide. Included in this group ar monomers disclosed in U.S. Pat. 2,980,657, namely those of the formula CH2=CR O R; (R)I TAI%R 2-11 X R4 11 where R is hydrogen or methyl, R is independently hydrogen or a lower alkyl group having 0 to 4 carbon atoms,
A is a straight or branched chain alkylene group having 2 to 10 carbon atoms or a divalent saturated aliphatic group consisting of a plurality of alkylene groups of 2 to 10 carbon atoms each pair of which is connected by an ether oxygen atom, R and R may be (1) separate groups selected individually from the group consisting of alkyl groups having 1 to 12 carbon atoms, hydroxyalkyl groups having 2 to 12 carbon atoms, alkoxyalkyl groups having 2 to 12 carbons atoms, and (2) a single saturated aliphatic group which together with the N atom forms a heterocyclic group containing 5 to 6 atoms in the ring of which 4 to 5 are carbon and which may contain a second atom of the group consisting of O, N, and S, the second atom, if nitrogen, being substituted by an alkyl group having 1 to 18 carbon atoms, R; is selected from saturated and unsaturated aliphatic hydrocarbon groups having 1 to 18 carbon atoms (polyalkoxy) alkyl groups having 2 to 18 carbon atoms, hydroxyalkyl groups having 2 to 18 carbon atoms, an aralkyl or substituted aralkyl group having 7 to 24 carbon atoms, or a phenoxyalkyl group having 7 to 24 carbon atoms, X is OH or a negative, salt-forming atom or radical, and n is an integer having a value from 1 to 2. The N-3-oxohydrocarbon-substituted acrylamides, such as diacetone acrylamide, disclosed in U.S. Pat. 3,277,056, are also useful; other useful monomers include vinyl benzyl monomers of the general formula ea/ H CCHC H -CHzNR' Y R wherein R, R and R" each represents individually a monovalent radical selected from the group consisting of CH OHCH CH CHOHCH CH OHCHOHCH and alkyl of 1 to 4 carbon atoms, aryl, cycloalkyl, and arylalkyl hydrocarbon radicals, and R, R and R" collectively represent the trivalent radical of the formula /CHCH= c6 \O]E[=CH wherein, the three valences are attached to the nitrogen atom, and said R groups containing a total of not more than 12 carbon atoms in the sum of the constituent radicals, and Y is an anion, such as are discussed in Silvernail and Zembal U.S. Pat. 3,011,918. Also included are mono mers disclosed in U.S. Pat. 2,980,634 having the formula in which A is ethylene, trimethylene, or -CHRCH where R may be any alkyl or alkenyl group having from 1 to 16 carbon atoms, R and R may be (1) separate group selected individually from the group consisting of alkyl or alkenyl groups having 1 to 12 carbon atoms, hydroxyalkyl groups having 2 to 12 carbon atoms, polyalkoxy-alkyl groups having 2 to 12 carbon atoms, or (2) R and R may together reprsent the morpholino residue: (C H :O, the pyrrolidino residue, C H the piperidino residue, C H and an N-alkylpiperazine residue: (C H :NR where R" is an alkyl of 1 to 18 carbon atoms, such as methyl, ethyl, ispropyl, R is selected from saturated and ethylenically unsaturated aliphatic hydrocarbon groups having 1 to 18 carbon atoms (polyalkoxy) alkyl groups having 2 to 18 carbon atoms, alkoxyalkyl groups having 2 to 18 carbon atoms, hydroxyalkyl groups having 2 to 18 carbon atoms, and aralkyl or substituted aralkyl groups having 7 to 24 carbon atoms, or a phenoxyalkyl group having 7 to 24 carbon atoms, at least one of R R and R has at least 7 carbon atoms, and X is OH or a negative, salt-forming atom or radical preferably of monovalent character, such 3 as halide, c.g., bromide, chloride, iodide, sulfate, e.g., the methyl sulfate anion, and sulfonate, e.g., p-tolueneor cyclohexyl-sulfonate anions.
-In addition, monomers may be used such as are disclosed and discussed in Hayek US. Pat. 2,741,568, of the general formula Rz-If-Ih a where R is a member of the class consisting of hydrogen, methyl and ethyl radicals, R R and R are alkyl radicals of from 1 to 4 carbon atoms, and X is a saturated bivalent hydrocarbon radical of from 1 to 4 carbon atoms, or a bivalent hydroxyalkyl radical of 1 to 4 carbon atoms (see Formula IV in U.S. Pat. 2,810,713).
Examples of the diallyl quaternary ammonium comonomers are dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride and methyl ,8- propionamido diallyl ammonium chloride. For other examples see Butler US. Pat. 3,288,770.
The preferred polymers of my invention are copolymers of at least 0.5% by weight of a fatty quaternary diallyl ammonium chloride and the remainder dimethyl diallyl ammonium chloride and/ or acrylamide.
Surprisingly enough, I have found that the fatty quaternary diallyl ammonium monomers exhibit no significant bactericidal or bacteristatic properties. Only when water soluble polymers are prepared having at least 0.5% by weight of a fatty quaternary diallyl ammonium group is an operable composition achieved.
The following Table I illustrates the effects of my polymer compositions on Aerobacter aerogenes. The results shown were for a time kill test. All compositions are reported on a percent by Weight basis. A description of a time kill test is as follows:
TIME KILL TEST (1) A stock bacteria solution was prepared in the following manner. A beef extract neutrant broth (Ofiicial Methods of Analyses of the Association of Official Agricultural Chemists, Tenth edition, 1965, page 80, Reagent (a)) was inoculated with Aerobacter aerogenes and incubated for 24 hours at 35 C. Ten milliliters of the broth was then added to 90 milliliters of sterilized deionized water.
(2) Stock solutions of the compound to be tested were prepared such that 1 milliliter contained the desired ppm. of active compound.
(3) One milliliter of the stock bacteria solution and 1 milliliter of the stock compound solution were added to 48 milliliters of sterilized deionized water. The solution was left standing for a contact time for 3 hours.
(4) After 3 hours of contact time, 1 milliliter was withdrawn and appropriate serial dilutions performed in sterile phosphate buffered (KH PO deionized water. Then 1 milliliter of this diluted solution was plated in Trypton glucose extract agar and incubated for 24 hours at 35 C.
After incubation the plates were counted and the percent reduction (kill) calculated using a control count as reference. The control was prepared in the same manner except the compound solution was not added and the contact time was 0 hours.
TABLE I Test, Percent Formulation p.p.m. l
1. Homopolymcr of MODAAC 2. Homopolymer ofMDDAAC 3. Copolymer of 5% MODAAC, 95% of DMDAAQg 4. Copolymer of MODAAC, 25% DMDAAO 5. Copolymer of 5% MDDAAC, 95% DMDAAC o. Copolymer 0f 50% MDDAAC, 50% DMDAAC 7. Copolymer of 75% MODAAO, 25% acrylamide 8. Copolymer of 5% MDDAAC, 95% acrylamide g 9. Copolymer of 75% MDDAAC, 25% DMDAAC 10. Copolymer of 20% MODAAC, 40% DMDAAC; i 1 40% acrylamide. l 10 99 11. Copolymer of 20% MDDAAC, 40% DMDAAC, 1 99 40% acrylamide. 10 99 NorE.-MODAAC methyl n-octyl diallyl ammonium chloride; MDDAAO methyl n-dodecyl diallyl ammonium chloride; DMDAAC dimethyl diallyl ammonium chloride.
Table II illustrates the effects of the fatty quaternary diallyl ammonium chloride monomers on Aerobacter aerogenes. The results shown were for a time kill test.
TABLE II Dosage Percent Monomer in p.p.m. kill 1. Methyl n-octyl diallyl, ammonium chloride 2. n-Octyl bcnzyl diallyl, ammonium chloride. 8 3. Methyl dodecyl diallyl, ammonium chloride A contrast of Tables I and II indicates that the fatty diallyl quaternary ammonium monomers are ineffective against bacteria when compared to the polymers containing them.
It is apparent that it would be difficult to ascertain the minimum concentration below which my polymers will have no biocidal effects. However, for all practical purposes it may be assumed that at least about 0.5 part of polymer per million parts of water should be present. As is known in the art of bactericides, there is some minimum contact time below which results are negligible. Another factor which should be kept in mind when using the polymers of my invention is that they are highly cationic and will tend to lose their effectiveness in the presence of polyanionic compounds.
The polymers of this invention have utility in treating circulating water systems such as cooling towers and swimming pools to inhibit growth of algae and bacteria. The polymers may also be used to inhibit growth of algae and bacteria in ponds, reservoirs, and other bodies of stagnant water.
I do not intend to be restricted to the above specific examples and illustrations. My invention may be otherwise practiced within the scope of the following claims.
1. Method of treating an aqueous medium to inhibit the growth of bacteria therein comprising dissolving in such aqueous medium an effective amount of a random, linear, water soluble polymer consisting essentially of repeating units of the following formula where R is an alkyl group of C to C R is selected from the group consisting of H, alkyl of C to C and B-propionamid'o, and X is an anion selected from the group consisting of F C1 Br I CH SO and CH COO 2." Method of claim 1 where R is C R is CH, and X is C1 3. Method of claim 1 Where R is C R is CH and X is C1 4. Method of treating an aqueous medium to inhibit the growth of bacteria therein comprising disolving in such aqueous medium an effective amount of a random, linear, water soluble polymer of the following formula where R is an alkyl group of C to C R is selected from the group consisting of H and alkyl of C to C R is an alkyl group of C to C R is selected from the group consisting of H, R and alkyl group of C to C X is an anion independently selected from the group consisting of F C1 Br I CH SO and CH COO a is 0.5% by weight to 97.5% by weight and b is 2.5% to 99.5% by weight.
5. Method of claim 4 where- R is C R R and R are CH and X is C1 6. Method of claim 4 where R is C R R and R are CH and X is C1 7. Method of treating an aqueous medium to inhibit the growth of bacteria therein comprising disolving in such aqueous medium an effective amount of a random, linear, water soluble copolymer of the formula 0 Ha CH2 where R is an alkyl group of C to C R is selected from the group consisting of H and alkyl of C to C R is an alkyl group of C to C R is selected from the group consisting of H, R and alkyl group of C to C X is an anion independently selected from the group consisting of F C1 Br -1 CH SO and CH COO a is 0.5% by weight to 97.5% by Weight; b is from 0 to 97% by weight; 0 is from 2.5% to 9.5% by weight.
8. Method of claim 7 where R is C R R and R are CH and X is C1 9. Method of clairn 7 Where R is C R R and R are CH and X is C1 References Cited UNITED STATES PATENTS 2,595,225 5/1952 Coffman 26088.3 2,923,701 2/1960 Schuller et al. 2,980,634 4/ 1961 Melamed. 2,980,657 4/1961 Melamed. 3,147,218 9/l964 Booth et a1. 210-54 3,288,770 11/1966 Butler.
FOREIGN PATENTS 1,059,117 2/1967 Great Britain.
LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,539 ,684 November 10 Merwin Frederick Hoover It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2 lines 25 to 29 the formula should appear as 5 below:
R l H C CH (3 H FH N R same column 2, line 58, "reprsent" should read represent Column 5, lines 31 to 38, in section B of the formula, the 10 left symbol in the ring structure reading CH should read CH Column 6, line 7, "9 5%" should read 99 5% Signed and sealed this 6th day of April 1971 (SEAL) Attest:
EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER Attesting Officer Commissioner of Pan