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DISINFECTING USE OF QUATERNARY SUMMARY OF THE INVENTION
AMMONIUM CARBONATES
A method for disinfecting a substrate is provided. The
Substrate is contacted with a biocidal effective amount of a
This is a continuation of application Ser. No. 08/352,899 composition comprising (a) at least one quaternary ammo
filed Dec. 9, 1994 now abandoned. 5
nium carbonate, bicarbonate, or combination thereof; (b) a
FIELD OF THE INVENTION Solvent Selected from the group consisting of water and
propylene glycol, and (c) optionally, a Surfactant.
This invention relates to the use of quaternary ammonium
carbonate compositions as low corrosion disinfectant, par DETAILED DESCRIPTION OF THE
ticularly in hard water Solvents. INVENTION
BACKGROUND OF THE INVENTION Quaternary ammonium compounds useful in the present
The biocidal activities of other quaternary ammonium invention are quaternary ammonium compounds having
compositions have been reported. The biocidal activities of 15 carbonate and/or bicarbonate anions. Preferred quaternary
ammonium carbonates have the formula
various quaternary ammonium chlorides against bacteria,
fungi, and algae are tabulated in Cationic Surfactants, E. (I)
Jungerman Ed., pp. 56-57, Marcel Dekker, Inc., 1969.
Nicholas, “Interaction of Preservatives with Wood,” Chem R1 R2
istry of Solid Wood, Advance in Chemistry Series #207, V/
N COs
Powell ed., (A.C.S. 1984) notes that didecyldimethyl ammo /V
CH, CH
nium compounds, and particularly didecyldimethylammo 2
nium chloride, are potential biocides. Preston, J.A.O.C.S.
60:567 (1983) concurs and suggests that maximum fungi
toxicity is exhibited with dialkyldimethyl compounds hav 25 wherein R is a C-Co alkyl or aryl-substituted alkyl group,
ing C-C alkyl groups. Butcher et al., Chem Abstracts or a benzyl group and R is a C-C alkyl or aryl
No. 91:152627b, suggests that the presence of an acid or a Substituted alkyl group, or a benzyl group.
base can affect the activity of didecyldimethylammonium A preferred carbonate quat is one in which R" is a C-Co
quats. alkyl or aryl-Substituted alkyl group and R is a Cs-Co alkyl
Ruseggan, in U.K. Patent Publication No. 650,304, dis group. Preferably, R and R are the same Cs-Co alkyl
closes a detergent which includes a tetra alkyl quaternary group. A most preferred carbonate quat is didecyldimethy
ammonium halide or hydroxide in which two alkyl groups lammonium carbonate wherein R' and R are a Co alkyl
contain from 6 to 9 carbon atoms in each hydrocarbon group group and most preferably an n-Co alkyl group. Dide
and the other two alkyl groups contain 3 to 9 carbon atoms cyldimethylammonium carbonate, when observed as a
each together with a weak alkali. Such compositions may 35 70-80 percent by weight solution in a 50 percent by weight
also include an alkali Substrate (See U.K. Patent Publication alcohol/50 percent by weight Solvent is a yellow/orange
No. 669,506). liquid that has a slightly fruity odor. This formulation has a
Hunter et al., U.S. Pat. No. 3,169,983, disclose glycol flash point of about 160 F., and it reacts with carboxyl
monoborate Salts of quaternary amines that are useful as containing compounds.
active biocides and fungicides in Soaps, detergents, and dry 40 The stability, and particularly the thermal stability, of
cleaning compositions. carbonate quats is far Superior to that of hydroxy quats,
It has now been discovered that quaternary ammonium making these carbonate quats Suitable for concentrating and
carbonates can be used as disinfectants, particularly in hard as Stock intermediates for further processing.
water. These compositions have low corrosion properties. 45
One or more of these carbonate quats can be used alone
Some carbonate quats can be prepared by heating trim or in combination with the corresponding bicarbonate quat
ethylamine with carbon dioxide and methanol above 200 C. (s). One or more bicarbonate quats can be used alone as well.
and at 85 to 95 atmospheres. Industrial Organic Nitrogen Preferred bicarbonate quats have the formula
Compounds, Astle Ed. p 66, Reinhold Inc, 1961. However, (II)
this reaction is limited to the methyl compound because 50
higher homologs decompose to olefins by the Hoffman R1 R2
elimination reaction. See, Organic Reactions, 11, Chptr. 5, V/
N HCO
377, Krieger Publishing Co., 1975. /M
CH, CH
Chem Abst. 110, 212114 (1989) suggests that dimethyl 2
carbonate will react with triethylamine in methanol in 55
twelve hours at 115 C. and under pressure to yield a methyl wherein R and R are as defined above.
carbonate quat ester.
Chem Abst. 114, 24824 (1991) discloses that Although certain carbonate quats can be prepared by a
6-hydroxyhexyldimethylamine reacts with dimethyl carbon variety of methods, an indirect Synthesis method that can be
ate to yield a carbonate ester quat. 60 used to prepare a variety of quaternary ammonium carbonate
compositions, including, but not limited to, quaternary
BRIEF DESCRIPTION OF THE DRAWINGS ammonium carbonate compounds, preferably C-C alkyl
or aryl-Substituted alkyl, Cs-Co alkyl quaternary ammo
FIG. 1 is a graphic illustration of the sanitizing effect of nium carbonate compounds including, but not limited to, di
a composition according to the present invention. 65 C-C alkyl quaternary ammonium carbonate compounds,
FIG. 2 is a graphic illustration of the Sanitizing effect of and most preferably didecyldimethylammonium carbonate,
a composition according to the present invention. is preferred.
6,080,789
4
reaction, but the use of a C-C normal alcohol Solvent
(III) drives the reaction sharply to the hydroxy quat.
R1 R2 The amount of metal hydroxide reactant typically is a
V/ Stoichiometric amount with respect to the quaternary ammo
N CI+ M(OH)n (ROH) s nium chloride reactant. Therefore, on a theoretical basis and
/V if the reaction were complete and unequilibrated, there
CH, CH
would be no exceSS of metal hydroxide reactant upon
R1 R2 completion of the intermediate reaction. In practice, yield
V / when using a Stoichiometric amount of metal hydroxide
MV
N OH + MCIn + M (OH)
Excess reactant will range from about 65% to about 95%, but will
CH, CH
vary, dependent, in part, upon the particular metal hydroxide
reactant.
(IV) Yield of the hydroxy quat can be further improved over
R1 R2 * conventional methods by utilization of a Stoichiometric
V/ 15
excess of metal hydroxide ranging from about 2% to about
WV
N OH + CO2 + M (OH),
Excess
He 20% excess. If an excess of metal hydroxide is used yield
CH, CH will be increased to from about 95% to about 99%, again
varying as above.
R1 R2 The unreacted metal hydroxide is soluble in the hydroxy
V/ quat/Solvent intermediate.
/M
N CO3 + (MCO3 or M2CO3 + H2O) Hydroxy quat and any unreacted metal hydroxide are then
CH, CH reacted with at least a Stoichiometric equivalent of carbon
dioxide to yield the quaternary ammonium carbonate(s), and
if any unreacted metal hydroxide were present, the metal
wherein R' and R are as defined above; preferably R' is a carbonates). The conversion of the metal hydroxide to the
C-Co alkyl or aryl-substituted alkyl group; R is a Cs-Co 25 metal carbonate is the preferred reaction of the two carbon
alkyl group; and most preferably R' is the same as R and ations and will proceed more rapidly. The metal carbonate
R" is a Cs-C alkyl group; R is a straight chain C-C, will precipitate and can be separated easily, i.e. by filtration
alkyl group; M is a mono-, bi-, tri-Valent metal, preferably or the like, leaving the stable carbonate quat(s) or carbonate
a mono-Valent metal, and most preferably an alkali metal; quat(s)/Solvent reaction product.
and m is 1 if M is mono-valent, 2 if M is di-valent, and 3 if The carbonation Step can also produce the bicarbonate
M is tri-valent.
quat or the metal carbonate quat as byproducts. The carbon
An appropriate quaternary ammonium chloride with cor ate quat alone or in combination with the bicarbonate quat
is Suitable for use in disinfectant compositions of the present
responding Substituents on the nitrogen atom Such as, for invention.
example C-C alkyl or aryl-Substituted alkyl, Cs-Co Mixing, adding, and reacting of the components in the
alkyl, and preferably a di Cs-C alkyl, quaternary ammo 35 present invention can be accomplished by conventional
nium chloride is used as a starting material and is reacted means known to those of ordinary skill in the art. The order
with a metal hydroxide to yield a corresponding quaternary of addition of reactants or Solvent in any individual Step does
ammonium hydroxide intermediate Such as, for example not affect the process. Reactants and/or Solvent can be added
C-C alkyl or aryl-substituted alkyl, C-C alkyl, and Sequentially or simultaneously in any Suitable reaction ves
preferably a di Cs-C alkyl, quaternary ammonium hydrox 40 Sel. For example, the metal hydroxide may be dissolved in
ide intermediate. The hydroxy quat intermediate(s) and any alcohol and the resultant mixture added to the chloride quat
exceSS metal hydroxide are then reacted with carbon dioxide or the chloride quat may be dissolved in alcohol and the
to yield the carbonate quat(s) and the metal carbonate. metal hydroxide added to the resultant mixture. Importantly,
Many quaternary ammonium chlorides Such as, for the method of the present invention is suitable for commer
example di Cs-C alkyl quaternary ammonium chlorides, 45 cial Scale production techniques and equipment, yet conve
are Suitable reactants to prepare the intermediate hydroxy nient for Small Scale work.
quat, but didecyldimethylammonium chloride is preferred. Typically, the reactants and Solvent of the chloride quat to
The selections of the R' and R substituents of the chloride hydroxy quat reaction (III) will be stirred and heated to from
quat reactant are determinative of the hydroxy quat about 20° C. to about 70° C. and held at that temperature for
intermediate, and therefore, of the carbonate quat product. 50 a period of from about 1 hour to about 5 hours. The reaction
Special mention is also made of processes wherein R is mixture is then cooled, first to room temperature and then to
a methyl, Cs alkyl, Co isoalkyl, Co alkyl, C12 alkyl, Ca about 0°C. where it is held for about 1 hour to about 2 hours.
alkyl, C, alkyl, or benzyl group; and R is a Co alkyl, C2 Any precipitated metal chloride is collected as is known in
alkyl, CA alkyl, or Co alkyl group. the art, i.e. Such as by filtration.
The metal hydroxide reactant is a mono-, bi-, or tri-Valent 55 Alternatively, the first reaction reactants and Solvent can
metal hydroxide, preferably a mono-Valent metal hydroxide, be stirred at a slightly elevated temperature, i.e. from about
and most preferably an alkali metal hydroxide Such as 20° C. to about 40 C., to yield the hydroxy quat/solvent
Sodium hydroxide or potassium hydroxide. Special mention mixture. Hydroxy quat can be separated as above.
is made of potassium hydroxide. The metal chloride first The carbon dioxide is generally bubbled for a suitable
Step reaction product will precipitate and is easily removed, 60 period known to those of ordinary skill in the art through the
i.e. by filtration or the like, yielding a hydroxy quat/Solvent hydroxy quat/Solvent Supernatant after the metal chloride
reaction product. The hydroxy quat can be separated there precipitate has been Separated. Alternatively, the carbon
from by drying or the like, if desired. dioxide can be added as solid dry ice directly to the hydroxy
The first reaction (III) is conducted in a solvent which quat. Typically, this time varies from about 0.5 hour to about
comprises a C-C normal alcohol. Preferably, the Solvent is 65 1 hour at ambient temperature. Any precipitated metal
ethanol, and most preferably, anhydrous ethanol. The reac carbonate is collected as is known in the art, i.e. Such as by
tion to form the hydroxy quat is typically an equilibrium filtration.
6,080,789
S 6
Suitable Solvents include water, propylene glycol, or a EXAMPLE 3
combination thereof. Carbonate quats display good toler
ance to hard water compared with other quats. Water (86.3%), EDTA Acid (Versene 100) (1%), surfac
Optionally, a surfactant may be added as well. Suitable tant (CarSonon N-9-Lonza, Inc.) (5%), and didecyldim
Surfactants include, but are not limited to, non-ionic ethylammonium carbonate (50% active) 7.7% were mixed
Surfactants, for example, amine oxides, linear alcohol to yield a biocidal composition having a pH of 9.63. Freeze/
ethoxylate, Secondary alcohol ethoxylates, ethoxylate esters, thaw stability and accelerated Stability were determined
betamines, and alkyl polyglycerides. according to the procedure of Example 1.
Other conventional additives Such as builders, colorants, Results are illustrated in Table 1.
perfumes, fragrances, or cleaners may be added as required
for application to different Substrates. TABLE 1.
Suitable Substrates include, but are not limited to, hard Stability
and Soft Surfaces, food containers, and Skin.
The amount of quaternary ammonium carbonate(s) used Example 1. 2 3
to treat a Substrate is a biocidal effective amount, i.e. that 15
Freeze/Thaw No separation No separation No separation
amount to Sanitize or disinfect the Substrate. A biocidal Stability No precipitation Precipitation present No precipitation
effective amount of at least one quat is mixed with a Suitable No darkening
Solvent Such as water or propylene glycol. The biocidal Accelerated No separation No separation No separation
effective amount will depend upon the use intended and can Stability No precipitation No precipitation No precipitation
No darkening No darkening No darkening
be determined by one of ordinary skill in the art in light of
the present detailed disclosure.
A Substrate is considered disinfected or Sanitized when
99.999% of the targeted microorganism(s) on or in the EXAMPLE 4
Substrate are killed.
Typically, the disinfectant composition can either be Sup 25
P. aeruginosa with 5% organic load was dried on Stainless
plied in a dilutable concentrated form or in a ready to use Steel carriers and then immersed in 600 ppm active of a
form. A typical concentrate will comprise from about 1% by disinfectant composition prepared according to the method
weight to about 30% by weight of quat based upon 100% by of Example 1 in 400 ppm hard water.
weight of total composition and a typical ready to use After 10 minutes contact time to the disinfectant, the
formulation will comprise from about from 10 ppm to about carriers are aseptically transferred to 10 ml of letheen broth
10,000 ppm of quat based upon total composition. (neutralizer/growth media).
Treatment of the Substrate is accomplished by any means These letheen broth tubes with the carriers are then
known to those of ordinary skill in the art including, but not incubated at 37+1 C. for at least 48 hours. After 48 hours,
limited to, dipping, Soaking, brushing, Spraying, mopping, a cloudy letheen tube indicates growth or failure and a clear
Washing, or the like. The length of treatment required will 35 tube indicates no growth or pass. Results are illustrated in
vary according to treatment conditions, the Selection of Table 2. Carrier counts were performed on 10% of the
which are known to those skilled in the art. inoculated carriers. Results are illustrated in Table 2.