GB2157678A - Anti-microbial di-decyl quaternary ammonium compounds - Google Patents

Abstract

Di"decyl" or "decyl"-n-decyl- alkyl quaternary ammonium compounds of formula [decyl-@(R)2-A]X<-> wherein A is "decyl" or n-decyl, R is C1-4alkyl and X is Cl<->, Br<->, I<->, (m)ethosulphate and "decyl" is a mixture of primary alkyl groups of 10c arrows having at least two branches, are useful as disinfectants.

Description

SPECIFICATION Anti-microbial quaternary ammonium compounds This invention relates to anti-microbial quaternary ammonium compounds, and it more particularly relates to didecyl dimethyl-ammonium salts and decyl n-decyl dimethylammonium salts.

The "decyl" group of this invention, both as used in "didecyl" and in "decyl n-decyl", is derived from a decyl alcohol which has a CAS number of 68551-08-6* and is, essentially, a mixture of branched primary decanols in which there is a straight chain with at least two branches, the preponderant component being trimethylheptanol.

Since the chemical transformations which are used to transform the decanol to the decyl substitutent bonded to the quaternary nitrogen of the present compounds are comparatively mild, low energy reactions that practically preclude rearrangements, the "decyl" substituent on the quaternary nitrogen reflects the same radicals and distribution as is found in the starting decanol.

The quaternary ammonium salts of the present invention are prepared by the alkylation reaction of a tertiary amine with a primary alkyl halide. The tertiary amine is prepared by the alkylation of a secondary amine with a primary alkyl halide or by two successive alkylations of a primary amine in which the alkylating agents may be the same or different primary alkyl halides.

The quaternization of didecyl methylamine with a methyl chloride gives higher yields than the quaternization of decyl dimethylamine with decyl chloride.

Decyl n-decyl dimethylammonium chloride is prepared byquaternizing decyl n-decyl methylamine with methyl chloride.

The following examples are illustrative preparations of the compounds of this invention, the term "decyl" in all these examples being used to denote the aforesaid mixture of primary 10-carbon branched chains, having the CAS No. 68551-08-6*.

Example 1 Decyl alcohol + HC1 decyl chloride About 500 grams of decyl alcohol and about 10 grams of zinc chloride are heated to about 140"C, and dry hydrogen chloride is passed into the mixture. The effluent vapors are condensed and trapped. When the volume of the condensate remains constant (at about 60-65 ml. after about 3 hours) the reaction is halted.

The organic layer in the reaction flask is washed with cold water and purified by distillation.

Example 2 Decyl alcohol + methylamine < decyl methylamine One mol of decyl chloride is heated in an autoclave with a concentrated solution of monomethylamine in water (isopropanol or water/isopropanol mixtures may also be used), containing about 10 moles of monomethylamine, at about 1 10 for 10 hours. After cooling, about 1.1 moles of caustic soda is added with stirring. The organic layer is separated from the mixture, stripped of isopropanol (if present), and fractionated. The yield is about 0.75-0.80 moles of decyl methylamine.

Example 3 Decyl chloride + decyl methylamine ) didecyl methylamine A mixture of one mole of decyl methylamine and one mole of caustic soda is heated to about 1600C at atmospheric pressure, and one mole of decyl chloride is added slowly over a period of one hour. Heating is continued for about one more 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 decyl methylamine. Any other n-alkyl chloride with decyl methylamine will yield n-alkyl decyl methylamine. When n-decyl chloride is used instead of decyl chloride and n-decyl methylamine is used instead of decyl methylamine, the product is di-n-decyl methylamine.

Example 4 Didecyl methylamine + methyl chlorides didecyl dimethylammonium chloride.

One mole of didecyl methylamine in an autoclave is mixed with about an equal volume of isopropanol, or 50/50 isopropanol/water, as solvent. Then one mole of methylchloride gas (+1-2% excess) is pumped into the autoclave and the contents therein heated at about 80"-1 1 O"C for 12-15 hours.

Didecyl dimethylammonium chloride, the quaternary ammonium salt product, is left in solution, its concentration being about 35-50% depending upon the quantity of solvent used in the reaction.

When n-decyl decyl methylamine is used instead of didecyl methylamine, the product is n-decyl decyl dimethylammonium chloride. When di-n-decyl methylamine is used instead of didecyl methylamine, the product is di-n-decyl dimethylammonium chloride. When n-alkyl decyl methyalmine is used instead of n-decyl decyl methylamine, the product is n-alkyl decyl dimethylammonium chloride.

Example 5 Mixtures of quaternary ammonium salts were prepared as follows: (a) 95% didecyl dimethylammonium chloride, 5% di-n-decyl dimethylammonium chloride by weight.

(b) 90% didecyl dimethylammonium chloride, 10% di-n-decyl dimethylammonium chloride, by weight.

(c) 75% didecyl dimethylammonium chloride, 25% di-n-decyl dimethylammonium chloride, by weight.

Example 6 When methylamine was treated with an equimolar mixture of decyl chloride and n-decyl chloride by the method shown in Example 2, the product was a mixture of about 50% decyl methylamine and about 50% n-decyl methylamine. When this mixture of secondary amines was treated with the equimolar mixture of the same two alkyl halides by the method shown in Example 3, the product was a mixture of about 25% didecyl methylamine, about 25% di-n-decyl methylamine and about 50% decyl-n-decyl methylamine.When this mixture of tertiary amines was quaternized with methyl chloride by the method shown in Example 4, the product presumptively was a mixture of di-alkyl dimethylammonium chloride salts in approximately the same proportion as their parent tertiary amines, namely about 25% didecyl dimethylammonium chloride, about 25% di-n-decyl dimethylammonium chloride, and about 50% decyl-n-decyl-dimethylammonium chloride.

The antimicrobial properties of didecyl dimethylammonium chloride, di-n-decyl dimethylammonium chloride and the three mixtures (a), (b) and (c) shown in Example 5, were investigated using the following procedure.

1. 50 ml. of solution containing the solute to be tested at test concentration was added aseptically to previously sterilized cotton-stoppered 125 ml. Erlenmeyerflasks.

2. One set of flasks containing each solute at various test concentrations was inoculated with 0.5 ml. of a 1/10 nutrient broth solution of a 24-hour nutrient broth culture of Psuedomones aeruginosa. Another set was inoculated with 0.5 ml. of 1/10 nutrient broth solution of a 24-hour nutrient broth culture of Aerobacter aerogenes.

3. After 30 minutes, a 0.5 ml. aliquot was removed from each flask and added to 50 ml. of sterile azolectin/"Tween 80" neutralizer. "Tween 80" is a polyoxyethylene derivative of fatty acid partial esters of hexitol anhydrides which is produced by Atlas Power Co., Wilmington, Delaware, U.S.A.

4. Agar plate counts were made from the aliquot solutions.

Table I shows the plate count of the products that were tested. The actual microbial count can be calculated by multiplying each number by 102.

The tests were performed simultaneously in order to minimize comparative errors due to fluctuations in ambient conditions. The table shows that at concentrations of as iittle as 5 ppm, at least with regard to Pseudomonas aeruginos, the didecyl dimethyl ammonium chloride has better activity than the di-n-decyl dimethyl-ammonium chloride, and this is important because Pseudomonas aeruginos is one of the most difficult microorganisms to kill.

"BTC 776" the control, is a well known and potent anti-microbial. It is a benzalkonium quaternary manufactured by the Onyx Chemical Company, Jersey City, New Jersey, U.S.A.

TABLE I P.A. = Pseudomonas aeruginos I = Didecyl Dimethyiammonium Chloride A.A. = Aerobacter aerogenes II = Di-n-decyl Dimethylammonium Chloride Concentration "BTC 776" II I I = 95% 1 = 90% I = 75% in p.p.m. Control II 5% II 10% II 25% P.A. A.A. P.A. A.A. P.A. A.A. P.A. A.A. P.A. A.A. P.A. A.A.

1 26.0 17.0 2 30.0 8.5 20.0 8.5 11.5 13.5 5 52.5 20.0 10.0 0 5.5 1.5 199.0 13.5 92.5 5.0 3.0 0 5 6.5 0 0 61.0 4.0 13.5 1.5 1.5 0 5 23.5 14.5 10 17.5 5.5 1.0 0 0 0 45.5 0 21.5 0 0 0 10 31.0 1.0 0 0 0 12.5 0 1.5 0 10 36.5 9.0 6.0 0 15 8.0 1.0 0 0 0 0 3.0 0 0 0 0 0 15 10.0 0 0 0 0 0 0 0 0 15 3.0 0 0 20 1.5 0 0 0 0 0 0 0 0 0 0 20 1.0 0 0 0 0 Although the didecyl-dimethylammonium chloride of this invention is a potent microbiocide at relatively low concentrations, as shown above, its biodegradability is much lower than di-n-decyl dimethylammonium chloride. However, when it is mixed with relatively small amounts of certain compounds such as di-n-decyl dimethylammonium chloride, its biodegradability is increased beyond what could be expected from the sum of contributions of the compounds.

In accordance with the above, the biodegradability of (1) didecyl dimethylammonium chloride, (2) di-n-decyl dimethylammonium chloride, and (3) physical mixtures of these two quaternary ammonium salts were determined. The extent of biodegradation was ascertained by the shake flask method. The actual extent of biodegradation of the mixture was compared to the amount of biodegradation that should have occurred according to calculations based on the concentration and biodegradability of the pure components in the mixture.

The tests were carried out in the following manner: A mixed microbial culture obtained from sewage treatment plan activated sludge was used as the inoculant. Ten milliliters of this culture and 0.3 gm. of yeast extract were added to flasks containing 1 liter of a mineral salts medium.

The mineral salts medium consisted of the following mixture: ammonium chloride 3.0 gm.

dipotassium phosphate 1.0 gm.

potassium chloride 0.25 gm magnesium sulfate. 7H2O 0.25 gm.

sodium bicarbonate 0.25gm.

Fe S04 0.002 gm.

water, q.s. 1 liter The flasks were kept at room temperature on a gyratory shaker operating at sufficient speed to assure good aeration.

For acclimation, 10 milliliters of culture were transferred serially every three days to one liter of fresh medium containing gradually increasing concentrations of the quaternary ammonium salt that was being tested, namely, 0, 0.5., 2.0,4.0, 6.0, 8.0, and 10.0 mg. per liter.

After 21 days of acclimation, the test was begun at the initial concentration of 10 mg. per liter of total quaternary ammonium compound.

Thereafter, a sample was drawn from the flask on the sixth day after the test was begun and analysed chemically for total quaternary ammonium compound concentration.

The test results are embodied in the following Table 2.

TABLE 2 INITIAL CONCENTRATION 10 mg/liter TOTAL QUATERNARY AMMONIUM SALT CONCENTRATION AFTER 6 DAYS (RESIDUE OF NON-BIODEGRADED QUATERNARY AMMONIUM SALT) COMPOUND OR MIXTURE FOUND CALC'D Didecyl dimethylammonium chloride (I) 4.6 mg. 4.6 mg.

Di-n-decyl dimethylammonium chloride (II) 0.0 mg. 0.0 mg.

95%1/5% II 2.1 mg. 4.4 mg.

90%1/10% li 2.2mg. 4.1 mg.

75%1/25% II 2.0 mg. 3.5 mg.

ACTUAL BIODEGRADABILITY 54% II 100% 95%1/5% II 79% 90%1/10% II 78% 751/25% II 80% All the tests shown in Table 2 were performed simultaneously in order to minimize the influence of any errors due to fluctuations in ambient conditions.

Table 2 shows the total concentration of quaternary ammonium compound not biodegraded in this test after 6 days, both for the pure materials and for three different mixtures. It also shows the quantities that were to be expected and calculated from the known biodegradability of the pure materials. For example, in the mixture of 90% didecyl dimethylammonium chloride and 10% di-n-decyl dimethylammonium chloride, a total concentration of 10 mg. per liter would contain 9.0 mg. of didecyl dimethylammonium chloride and 1.0 mg. of di-n-decyl dimethylammonium chloride. The didecyl dimethylammonium chloride would be 54% biodegraded, leaving a residue of 46% (of the 9.0 mg.) that was not biodegraded, or about 4.1 mg. The didecyl dimethylammonium chloride, being 100% biodegradable, would have no residue of nonbiodegraded quaternary ammonium salt.Therefore, using the calculated amount of nonbiodegraded quaternary ammonium salt in 1 liter of solution as a measure, the amount would be expected to be 4.1 mg.

which is the sum of both expected residues. In fact, what was actually found was only 2.2 mg. of quaternary salt- about 50% of the expected calculated amount. Approximately the same result (about 50% of calculated amount) was found for the 95%i/5%11, and the 75%1/25%11 mixtures. These results clearly show the unexpected co-biodegradation between the two quaternary ammonium salts.

The concentration of quaternary ammonium salt after biodegradation was determined by the method of M.E. Auerbach, Industrial and Engineering Chemistry, Analytical Edition, 15, pp. 492-3 (1944). This method was developed especially for low concentrations of quaternary ammonium salts.

Practical experience has shown that chemicals which exhibit from 60% to 70% biodegradation in these laboratory tests would be better than 90% removed during biological treatment of sewage. It should, therefore, be expected that chemicals which are biodegraded about 80% should, under practical conditions during the biological degradation of sewage, be almost completely removed during treatment.

If a minimum of 90% removal by biological treatment under practical conditions of treating sewage is taken as a standard, then it is clear that the addition of as little as about 5% of the unbranched di-n-decyl dimethylammonium quaternary salt to the branched didecyl dimethyl quaternary ammonium salts of this invention will significantly increase the biodegradability of the didecyl compound from a less than satisfactory to a very satisfactory level.

It is to be noted that not every compound that is fully biodegradable will promote the biodegradation of didecyl dimethylammonium chloride. Sucrose, for example, which, like the di-n-decyl dimethylammonium chloride, is completely biodegradable, will not influence the biodegradation of the didecyl dimethylammonium chloride. Experiments shows that the biodegradability of the branched dialkyl quaternary ammonium compound in the presence of sucrose is about 54%m where, as shown above, the addition of even 5% of 100% biodegradable di-n-decyl dimethylammonium chloride raises the biodegradability of the branched dialkyl quaternary salt from about 54% to about 79% of total quaternary.

In addition to the use of chloride as the anion in the above compounds, it is possible, although less preferred, to use the other halogens having an atomic weight greater than 30 as well as methosulfate or ethosulfate.

Although the didecyl quaternary ammonium compounds described above are very effective, especially against Pseudomonas aeruginosa, at low concentrations, this effectiveness may be largely detroyed in the presence of hard water or organic soil. It is well known, indeed, that most microbiocidai quaternary ammonium compounds lose a large portion of their antimicrobial activity in the presence of hard water or organic soil.

Although certain heretofore known dialkyl dimethylammonium salts retain enough activity in the presence of these contaminants to be useful as bacteriostatic agents or sanitizers, they are inferior 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 which kills 100% of the organisms).

The effectiveness of quaternary ammonium compounds as sanitizers in hard water is usually measured by the "Germicidal and Detergent Sanitizers Test", whereby increasing concentrations of hardness are used in order to determine the maximum water hardness - ordinarily in terms of ppm. as calcium carbonate - in which a concentration of a predetermined amount of a quaternary will kill 99.999% of the test organisms in the inoculum after 30 seconds of contact. This test is also often referred to as the "Hard Water Tolerance Test." The "Germicidal and Detergent Sanitizers Test" may be adequate when the microbial contaminants involve only the less virulant, non-pathological species of microorganisms, or when the intent is merely to reduce the microbial content species of microorganisms are the contaminants, then mere sanitization is insufficient.In such a case, only disinfection (100% kill of microorganisms) is tolerable.

The effectiveness of quaternaries as disinfectants is usually measured by the "Use Dilution Test". This test measures the minimum concentration of a disinfectant which will kill 100% of the microorganisms on a hard surface in 10 minutes.

Although the "Use Dilution Test" often serves as a means for comparing the effectiveness of quaternaries as disinfectants, it has a serious practical shortcoming; namely, it is performed in distilled water. Most communities in the world, are in hard water areas, and since hard water reduces the anti-microbial effectiveness of disinfectants, it is necessary to modify the "Use Dilution Test" so that it will take water hardness into consideration.

In order to determine the actual effectiveness of quaternary disinfectants in hard water, certain aspects of the "Use Dilution Test" have here been combined with some aspects of the "Germicidal and Detergent Sanitizers Test". In such combined test a concentration of disinfectant is seiected and, using that concentration, successive "Use Dilution Tests" are performed at increasing stepwise concentrations of hard water contaminant until the quaternary fails to kill 100% of the test organisms. The maximum hard water level at which the quaternary 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 (wherein the term "decyl", is used as above to denote a mixture of primary 10-carbon atom branched chains having a CAS member of 68441-08-6*) are highly effective disinfectant agents in the presence of either hard water, organic soil, or both.

These salts have the structural formula:

wherein R is a lower alkyl group of from 1 to 4 carbon atoms and Xis either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate, the term "decyl" referring to a mixture of primary branched chain alkyl groups each of which has 10 carbon atoms and contains a straight chain having at least two branches, and the term "n-decyl" referring 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 soil, 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 soil when used by themselves, when they are combined, they exert a synergistic effect on each other whereby the mixture also becomes an effective disinfectant both in hard water and in the presence of organic soil.

The decyl-n-decyl dimethylammonium salts, as well as the 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.

In order 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 is used as an abbreviation for dimethylammonium chloride: decyl-n-decyl DMAC di-decyl DMAC di-n-decyl DMAC In addition to the above single compounds, the following mixtures were also prepared: 90% by weight of di-decyl DMAC, 10% of weight of di-n-decyl DMAC 50% by weight of di-decyl DMAC, 50% by weight of di-n-decyl DMAC 10% by weight of di-decyl DMAC, 90% by weight of di-n-decyl DMAC 25% by weight of di-decyl DMAC, 25% by weight of di-n-decyl DMAC and 50% by weight of decyl-n-decyl DMAC.

All of the above seven materials were subjected to the "Use Dilution Test", in distilled water, against Pseudomonas aeruginosa, in order to determine the minimum concentration at which each would kill 100% of the microorganisms. Each passed the "Use Dilution Test" at the minimum concentration of 500 ppm in distilled water.

These same seven materials, each in the aforesaid concentration of 500 ppm, were then subjected to a modified form of the "Use Dilution Test", using the techniques of the "Germicidal and Detergent Sanitizers Test", whereby, in the presence of 5% blood serum as organic contaminant, the concentration of hardness was increased in steps of 50 ppm in separate experiments until the level of water hardness was reached in which the disinfectant failed to kill 100% of the organisms. This test is clearly the best method for testing the hard water performance of disinfectants.

The results of the tests, wherein all concentrations were verified by replicate tests, are shown in the following table: TABLE 3 Concentration of Hardness in Water (In ppm of Hardness) Against Pseudomonas aerugenosa ATCC &num;15442, Using 500 ppm of Quaternary 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-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 DMAC all have approximately the same disinfectant effectiveness.

The results shown in the above table clearly indicate the following: 1. In the presence of hard water and organic soil, decyl-n-decyl dimethylammonium chloride, by itself, is the most effective hard water disinfectant because it can tolerate a greater concentration of hard water and organic soil than the other quaternaries by themselves.

2. When used in admixtures with each other, di-n-decyl and di-decyl dimethylammonium chlorides, although showing relatively poor effectiveness by themselves in hard water and organic soil, potentiate each other to greatly increase the effectiveness of the mixture under such conditions, and the effectiveness of this mixture is further enhanced by the addition of decyl-n-decyl dimethylammonium chloride.

Claims (9)

1. A quaternary ammonium compound having the structural formula:

wherein A is either decyl or n-decyl, R is a lower alkyl group of from 1 to 4 carbon atoms and X is either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate, the term "decyl" referring to a mixture of primary branched chain alkyl groups each of which has 10 carbon atoms and contains a straight chain having at least two branches, and the term "n-decyl" referring to the normal decyl group.

2. The compound of claim 1 wherein X is chlorine.

3. The compound of claim 1 wherein R is CH3.

4. The compound of claim 1 wherein Xis chlorine and R is CH3.

5. The compound of claim 1 in aqueous solution.

6. The compound of claim 1 wherein A is decyl and wherein the compound is in admixture with di-n-decyl dimethylammonium halide in a ratio of between about 3:1 and about 20:1.

7. The solution of claim 5 wherein the compound is decyl-n-decyl dimethylammonium halide and contains up to about 550 ppm of hardness as measured in terms of ppm of calcium carbonate.

8. A disinfectant composition comprising an aqueous solution of a quaternary ammonium compound wherein the quaternary ammonium compound is present in an amount of at least 500 ppm, said quaternary ammonium compound being either (a) decyl-n-decyl dimethylammonium halide, (b) a mixture of di-decyl dimethyalmmonium halide and di-n-decyl-dimethylammonium halide, or (c) a mixture of di-decyl dimethylammonium halide, di-n-decyl dimethylammonium halide and decyl-n-decyl dimethylammonium halide, the term "decyl" referring to a mixture of branched chain alky groups, each of which has 10 carbon atoms and contains a straight chain having at least two branches, and the term "n-'decyl" referring to the normal decyl group.

9. A method of disinfection which comprises applying to undesired bacteria a disinfectingly effective amount of quaternary ammonium compound having the structural formula:

wherein A is either decyl or n-decyl, R is a lower alkyl group of from 1 to 4 carbon atoms and Xis either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate or ethosulfate, the term "decyl" referring to a mixture of primary branched chain alkyl groups each of which has 10 carbon atoms and contains a straight chain having at least two branches, a preponderant component of said mixture being trimethylheptanyl, and the term "n-decyl" referring to the normal decyl group.

9. A method of disinfection which comprises applying to undesired bacteria a disinfectingly effective amount of a quaternary ammonium compound having the structural formula:

wherein A is either decyl or n-decyl, R is a lower alkyl group of from 1 to 4 carbon atoms and Xis either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate, the term "decyl" referring to a mixture of primary branched chain alkyl groups each of which has 10 carbon atoms and contains a straight chain having at least two branches, and the term "n-decyl" referring to the normal decyl group.

10. The method of claim 9 wherein X is chlorine.

11. The method of claim 9 wherein R is CH3.

12. The method of claim 9 wherein Xis chlorine and R is CH3.

13. The method of claim 9 wherein said quaternary ammonium compound is in an aqueous solution.

14. The method of claim 13 wherein said solution contains up to about 550 ppm of hardness as measured in terms of ppm of calcium carbonate.

15. A method of increasing the biodegradability of the compound of claim 1 when A is decyl which comprises admixing said compound with di-n-decyl dimethyiammonium halide in a ratio of between about 3:1 and about 20:1.

Amendments to the claims have been filed on 14 September 1984, and have the following effect: (a) Claims 1 and 9 above have been textually amended.

(b) Textually amended claims have been filed as follows:

1. A quaternary ammonium compound having the structural formula

wherein A is either decyl or n-decyl, R is a lower alkyl group of from 1 to 4 carbon atoms and Xis either a halogen having an atomic weight greater than 30, methosulfate or ethosulfate, the term "decyl" referring to mixture of primary branched chain alkyl groups each of which has 10 carbon atoms and contains a straight chain having at least two branches, the preponderant component of said mixture being trimethylheptanyl, and the term "n-decyl" referring to the normal decyl group.