SE459003B - THE QUANTAS AMMONIUM LINING, THE DISINFECTANT COMPOSITION INCLUDING A WATER-SOLID SOLUTION OF A QUATERN AMMONIUM LINING, AND THE PROCEDURES FOR DISINFECTION WITH QUATERNERING AMMONIUM LINING - Google Patents

Description

459 D03 10 15 20 25 30 35 2 cyl "in all these examples was used to indicate the above-mentioned mixture of primary 10-carbon branched chains having CAS number 68551-08-6 *.

Example gel 1 Decyl alcohol + HCl> decyl chloride Approximately 500 g of decyl alcohol and about 10 g of zinc chloride are heated to about 140 ° C and dry hydrogen chloride is introduced into the mixture. The outlet vapors are condensed and captured. When the volume of the condensate remains constant (at about 60-65 ml after about 3 hours), the reaction is stopped. The organic layer in the reaction flask is washed with cold water and purified by distillation.

Example 2 Decyl alcohol + methylamine> decylmethylamine 1 mole of decyl chloride is heated in an autoclave with a concentrated solution of monomethylamine in water (isopropanol or water / isopropanol mixtures can also be used), containing about 10 moles of monomethylamine, at about 110 ° C in 8-10 h. After cooling, about 1.1 moles of sodium hydroxide are added with stirring. The organic layer is separated from the mixture, freed from isopropanol (if present) and fractionated. The yield is about 0.75-0.80 moles of decylmethylamine.

Example 3 Decyl chloride + decylmethylamine> didecylmethylamine A mixture of 1 mole of decylmethylamine and 1 mole of sodium hydroxide is heated to about 160 ° C at atmospheric pressure and 1 mole of decyl chloride is added slowly over a period of 1 hour. Heating is continued for a further 1 hour. The cooled organic mixture is washed with cold water and purified by distillation.

When n-decyl chloride is used instead of decyl chloride, the product is n-decyl-decylmethylamine. Any other n-alkyl chloride with decylmethylamine gives n-alkyl-decylmethylamine. When n-decyl chloride is used instead of decyl chloride and n-decylmethylamine is used instead of decylmethylamine, the product is di-n-decylmethylamine. 10 15 20 25 30 35 459 003 Example gel 4 Didecylmethylamine + methyl chloride> didecyldimethylammonium chloride (previously known) 1 mol of didecylmethylamine in an autoclave is mixed with approximately an equal volume of isopropanol, or 50/50 isopropanol / water as solvent. Then 1 mole of methyl chloride gas (plus 1-2% excess) is pumped into the autoclave and its contents are heated at about 80-110 ° C for about 12-15 hours.

Didecyldimethylammonium chloride, the quaternary ammonium salt product, is left in solution, its concentration being about 35-50% depending on the amount of solvent used in the reaction.

When n-decyl-decylmethylamine is used instead of didecylmethylamine, the product is n-decyl-decylmethylammonium chloride (present invention). When di-n-decylmethylamine is used instead of didecylmethylamine, the product is di-n-decyldimethylammonium chloride. When n-alkyl--decylmethylamine is used instead of n-decyl-decylmethylamine, the product is n-alkyl-decyl-dimethylammonium chloride.

Example 5 For comparative purposes (as will be seen later) mixtures of quaternary ammonium salts were prepared as follows: (a) 95% by weight of didecyl-dimethylammonium chloride, 5% by weight of di-n-decyl-dimethylammonium chloride (b) 90% by weight of didecyl-dimethylammonium chloride, 10% by weight of di-n-decyl-dimethylammonium chloride. (c) 75% didecyl-dimethylammonium chloride, 25% by weight of di-n-decyl-dimethylammonium chloride.

Example Gel 6 When methylamine was treated with an equimolar mixture of decyl chloride and n-decyl chloride by the procedure shown in Example 2, the product was a mixture of about 50% decylmethylamine and about 50% n-decylmethylamine. When this mixture of secondary amines was treated with an equimolar mixture of the same two alkyl halides by the procedure shown in Example 3, the product was a mixture of about 25% didecylmethylamine, about 25% di-ns -decyl-methylamine and about 50% decyl-n-decylmethylamine.

When this mixture of tertiary amines was quaternized with methyl chloride by the procedure shown in Example 4, the product was probably a mixture of di-alkyl-dimethylammonium chloride salts in approximately the same proportions as their original tertiary amines, namely about 25% didecyl-dimethylammonium chloride, about 25% di-n-decyl-dimethylammonium chloride and about 50% decyl-n-decyl-dimethylammonium chloride.

For comparative purposes, the antimicrobial properties of didecyl-dimethylammonium chloride, di-n--decyl-dimethylammonium chloride and the three mixtures (a), (b) and (c) As shown in Example 5, were examined using the following procedure. 1. 50 ml of solution containing the solute to be tested at the test concentration was aseptically added to pre-sterilized 125 ml Erlenmeyer flasks fitted with cotton swabs. A series of flasks containing each solute at different test concentrations were inoculated with 0.5 ml of a 1/10 nutrient broth solution of a 24-hour nutrient broth culture of Pseudemonas aeruginosa. Another series was inoculated with 0.5 ml of 1/10 nutrient broth solution of a 24-hour nutrient broth culture of Aerobacter aerogenes. After 30 minutes, a 0.5 ml aliquot was taken from each flask and added to 50 ml of sterile azolectin / Tween 80 neutralizing agent. "Tween 80" is a polyoxyethylene derivative of partial fatty acid esters of hexitol anhydrides manufactured by Atlas Power Co., Wilmington, Delaware, USA. 4. Agar plate counts were made of the aliquot solutions.

Table I shows the plate bills of the tested products. The actual microbial count can be calculated by multiplying each number by 102 The tests were performed simultaneously to minimize comparative errors due to fluctuations in the ambient conditions. The table shows that at concentrations as low as 50 ppm, at least in the case of Pseudemonas aeruginosa, didecec-dimethylammonium chloride has better activity than di-n-decyl-dimethylammonium chloride, and this is important because Pseudemonas aeruginosa is one of the most difficult microorganisms to kill.

"BTC 776", the control, is a well known and potent antimicrobial agent. It is a quaternary benzalkonium manufactured by Onyx Chemical Company, Jersey City, New Jersey, USA. 459 003 o o o o o o; o o. o o o o o o o o o o o; oo o o o; ... o o o o o o. o o o o o ... o; 3 o o.o o; oáo 2 o o: o »X2 o o o o o; oJo 3 ooo man "o ... too oooo; ox fi: 2 f: oåo ooo; o; QS o; oJo ooo; ooo; ox .. oåo ... ä fl oäoo o ... ... å o oo ~ oo ~ .Too m WS ÉS o; oo ~ To ... om ~ of. oao o. .E m ..... äwß I ml .ooa l _: mm I ~ w Û.: won vän ..: oåocuuoïwuccx ¶ .... c_xE: ÉoEE = _> ovzlvr fi> uo fl | cn fl o n Z wucomouwn uwuunnou fl å u. In addition to the use of chloride as an anion in the above compounds, it is possible, although less preferred, to use other halogens having an atomic weight greater than 30 and methosulfate or ethosulfate.

Although didecyl-quaternary ammonium compounds described above are very effective, especially against Pseudomonas aeruginosa, at low concentrations, this effectiveness can be largely destroyed in the presence of hard water or organic wastewater. In fact, it is well known that most microbiocidal quaternary ammonium compounds lose a large proportion of their antimicrobial activity in the presence of hard water or organic wastewater.

Although some hitherto known dialkyl dimethylammonium salts retain sufficient activity in the presence of these impurities to be useful as bacteriostatic or sanitary agents, they are poor disinfectants. A "sanitizer" is defined herein as a compound which reduces the concentration of microorganisms to a predetermined acceptable level without necessarily killing 100% of the organisms.

A "disinfectant" is defined herein as a compound that kills 100% of the organisms).

The effectiveness of quaternary ammonium compounds as sanitary agents in hard water is usually measured by "germicidal and detergent sanitary tests", using increasing concentrations of hardness to determine the maximum water hardness - usually expressed in ppm as calcium carbonate - at which a concentration of a predetermined amount of a quaternary compound kills 99.999% of the test organisms in the inoculum measured after contact for 30 s. This test is often also referred to as a "hard water tolerance test".

The "germicidal and detergent sensitivity test" may be adequate when the microbial contaminants involve only the minor virulent, non-pathological species of micro-organisms, or when the intention is only to reduce the microbial content to predetermined acceptable levels. levels. However, when virulent, pathological species of microorganisms constitute the pollutants alone, sanitary treatment alone is insufficient. In such a case, only disinfection (100% killing of microorganisms) can be tolerated.

The effectiveness of quaternary compounds as disinfectants is usually measured by the "use dilution test". This test measures the minimum concentration of a disinfectant that kills 100% of microorganisms on a hard surface in 10 minutes.

Although the "use dilution test" often serves as a means of comparing the effectiveness of quaternary compounds as a disinfectant, it has a serious practical shortcoming, namely that it is carried out in distilled water. Most communities in the world are in hard water areas and because hard water reduces the antimicrobial effectiveness of disinfectants, it is necessary to modify the "use dilution test" so that it takes into account the water hardness.

In order to determine the true efficacy of quaternary disinfectants in hard water, certain aspects of the "use dilution test" have been combined with certain aspects of the "germicidal and detergent sanitary test". In such a combined test, a concentration of disinfectant is selected, and using that concentration, successive "use dilution tests" are performed at incrementally increasing concentrations of hard water contaminant until the quaternary compound no longer kills 100% of the test organisms.

The maximum hard water level at which the quaternary compound passes this test is the significant measure of disinfectant effectiveness in hard water.

In accordance with the present invention, it has now been discovered that decyl-n-decyl-dimethylammonium salts (where the term "decyl" is used as above to denote a mixture of primary 10-carbon atom-branched chains with a CAS numbers of 68441-08-6 *) are highly effective disinfectants in the presence of either hard water or organic wastewater or both.

These salts have the structural formula: decyl --- N n-decyl in which R is a lower alkyl group having 1-4 carbon atoms and X is either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate, the term "decyl" being to a mixture of primary branched chain alkyl groups each having 10 carbon atoms and containing a straight chain with at least two branches, the predominant component being trimethylheptyl, and the term "n-decyl" refers to the normal decyl group.

In addition to the discovery of the effectiveness of decyl-n-decyl-dimethylammonium salts as disinfectants in hard water or organic wastewater, it has also been found that although both di-n-decyl and di-decyl-dimethylammonium salts are relatively poor disinfectants in hard water or in the presence of organic wastewater when used alone, they together show a synergistic effect, whereby the mixture also becomes an effective disinfectant both in hard water and in the presence of organic wastewater.

Decyl-n-decyl-dimethylammonium salts, as well as di-decyl and di-n-decyl-dimethylammonium salts are prepared by alkylation of a tertiary amine with a primary alkyl halide. For example, decyl-n-decyl-dimethylammonium chloride is prepared by quaternizing decyl-n-decyl-methylamine with methyl chloride.

To illustrate the present invention, the following quaternary compounds were prepared, each of these compounds being represented by the name of the two alkyl substituents followed by "DMAC" which was used as an abbreviation for dimethylammonium chloridez decyl-n- decyl-DMAC 1 d-decyl-DMAC di-n-decyl-DMAC In addition to the individual compounds listed above, the following mixtures were also prepared: 90% by weight of di-decyl-DMAC, 50% by weight of di-decyl-DMAC, SO wt% di-decyl-DMAC, 90 wt% di-n-decyl-DMAC 25 wt% di-decyl-DMAC, 25 wt% di-n-decyl-DMAC and 50 wt% decyl-n-decyl-DMAC. % di-n-decyl-DMAC wt% di-n-decyl-DMAC All of the above seven materials were subjected to "use dilution test" in distilled water, against Pseudemonas aeruginosa to determine the minimum concentration at which each kills 100% of micro Each passed the "use dilution test" at the minimum concentration of 500 ppm in distilled water.

These same seven materials, each at the above concentration of 500 ppm, were then subjected to a modified form of the "use dilution test" using the techniques of "germicidal and detergent sanitizer test", wherein, in the presence of 5% blood serum as organic contamination, the concentration of hardness was increased in steps of 50 ppm in separate experiments until the level of water hardness was reached at which the disinfectant did not kill 100% of the microorganisms.This test is clearly the best method for testing the hard water performance of the disinfectants.

The results of the tests, in which all concentrations were verified by reproduced tests, are shown in the following table: TABLE 2 Concentration of hardness in water (in ppm of hardness) against Pseudomonas aeruginosa ATCC No. 15442, with an reversal of SOO ppm of quaternary compound passed failed di-n-decyl-DMAC 250 300 di-decyl-DMAC 250 300 decyl-n-decyl-DMAC 550 600 (90% di-decyl-DMAC (10% di-n- decyl-DMAC 450 500 (50% di-decyl-DMAC (50% di-n-decyl-DMAC 500 550 (10% di-decyl-DMAC) (90% di-n-decyl-DMAC 500 550 (25% di-n-decyl-DMAC 500 550) decyl-DMAC (25% di-n-decyl-DMAC (50% decyl-n-decyl-DMAC 550 600) In distilled water, di-decyl-DMAC, di-n-decyl--DMAC and decyl-n-decyl- DMACs all have approximately the same disinfectant effectiveness.

The results in the above table clearly indicate the following: l. In the presence of hard water and organic waste water, decyl-n-decyl-dimethylammonium chloride alone is the most effective hard water disinfectant, as it can tolerate a higher concentration of hard water and organic waste water than the other quaternary associations alone. 2. When used in mixtures with each other, di-n-decyl and di-decyl-dimethylammonium chlorides, although exhibiting relatively poor efficiency alone in hard water and organic wastewater, potentiate each other to greatly increase the efficiency of the mixture. Under such conditions, and the efficiency of this mixture is further increased by the addition of decyl-n-decyl-dimethylammonium chloride.

Claims (11)

10 15 20 25 30 35 459 003 13 PATENT REQUIREMENTS k ä n n e t e c k - A quaternary ammonium compound, having the structural formula: R 1 is decyl-NC 2 - X - IR in which A is n-decyl, R is a lower alkyl group having 1-4 carbon atoms and X is either a halogen having an atomic weight greater than Methosulfate or ethosulfate, the term "decyl" refers to a mixture of primary branched chain alkyl groups each having 10 carbon atoms and containing a straight chain having at least two branches, the predominant component being trimethylheptyl, and the term " n-decyl "refers to the normal decyl group. l A compound according to claim 1, wherein the X is chlorine. A compound according to claim 1, characterized in that R is CH 3. A compound according to claim 1, characterized in that X is chlorine and R is CH3. 5. A compound according to claim 1, characterized in that it is present in aqueous solution in a disinfectant effective amount. A disinfectant composition comprising an aqueous solution of a quaternary ammonium compound, characterized in that the quaternary ammonium compound is present in an amount of at least 500 ppm, the quaternary ammonium compound being decyl-n-decyl-dimethyl-ammonium halide, the term "decyl" refers to a mixture of branched chain alkyl groups, each having 10 carbon atoms and containing a straight chain having at least two branches, the predominant component being trimethylheptyl, and the term "n- decyl ”refers to the normal decyl group. 7. A process for disinfection, characterized in that it comprises applying a quaternary ammonium compound in aqueous solution, the solution comprising a disinfectant effective amount of a quaternary ammonium compound having the structural formula: R 1 (5 - decyl -1 III __ R - in which A is n-decyl, R is a lower alkyl group having 1-4 carbon atoms and X is either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate, the term "decyl" refers to a mixture of primary branched chain alkyl groups each having 10 carbon atoms and containing a straight chain with at least two branches, the predominant component being trimethylheptyl, and the term "n-decyl" refers to the normal decyl group. A process according to claim 7, wherein X is chlorine. k ä n n e t e c k - A process according to claim 7, wherein R is CH k n n e t e c k- 3. 10. A process according to claim 7, characterized in that X is chlorine and R is CH 3. 11. ll. Process for disinfection, characterized in that it comprises applying a decyl-n-decyl-dimethylammonium halide in aqueous solution in admixture with an equal total amount of di -decyl-dimethylammonium halide and di-decyl -n--dimethylammonium- halide, which are in equal proportions, the solution comprising a disinfectant effective amount of said mixture, and wherein the term "decyl" refers to a mixture of primary branched chain alkyl groups each having 10 carbon atoms and containing a straight chain with at least two branches, the predominant component being trimethylheptyl, and the term "necdecyl" referring to the normal decyl group.