U.S. patent application number 09/508382 was filed with the patent office on 2002-05-30 for quaternary ammonium phosphate compound and method of preparing same.
Invention is credited to CHO, CHANG-MOOK, CHOI, DONG-JIN, HA, JAE-MIN, HAHN, SOON-JONG, PARK, JUN-WEON, PARK, KI-MAN, SHIN, JEONG-JOO, YOO, KWANG-HEE.
Application Number | 20020065251 09/508382 |
Document ID | / |
Family ID | 19521095 |
Filed Date | 2002-05-30 |
United States Patent
Application |
20020065251 |
Kind Code |
A1 |
HAHN, SOON-JONG ; et
al. |
May 30, 2002 |
QUATERNARY AMMONIUM PHOSPHATE COMPOUND AND METHOD OF PREPARING
SAME
Abstract
Disclosed is a quaternary ammonium phosphate compound having
formula (1) and which has an anticorrosive and a biocidal effect to
have a capability of preventing corrosion of various metals
including corrosive metal substances, e.g. carbon steels, iron
casts, stain steels, coppers, tinning steel plates or alumina and
an efficient method of preparing the same. In formula (1), R1 is a
straight or a branched alkyl or aryl radical with 1 to 27 carbon
atom(s) free of --OH group and may contain hetero-atoms, and both
R2 and R3 are methyl groups or R2 and R3 are combined to form a
heterocyclic compound with 4 to 6 of carbon atoms containing oxygen
and nitrogen.
Inventors: |
HAHN, SOON-JONG; (SEOUL,
KR) ; SHIN, JEONG-JOO; (KYUNGKI-DO, KR) ; HA,
JAE-MIN; (KYUNGKI-DO, KR) ; CHO, CHANG-MOOK;
(SEOUL, KR) ; PARK, KI-MAN; (KYUNGKI-DO, KR)
; YOO, KWANG-HEE; (KYUNGKI-DO, KR) ; CHOI,
DONG-JIN; (KYUNGKI-DO, KR) ; PARK, JUN-WEON;
(KYUNGKI-DO, KR) |
Correspondence
Address: |
BAKER & BOTTS
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
|
Family ID: |
19521095 |
Appl. No.: |
09/508382 |
Filed: |
June 12, 2000 |
PCT Filed: |
April 24, 1998 |
PCT NO: |
PCT/KR98/00099 |
Current U.S.
Class: |
514/100 |
Current CPC
Class: |
A01N 43/84 20130101;
C07D 295/037 20130101; C23F 11/141 20130101; A01N 33/12 20130101;
C07C 217/08 20130101; C23F 11/149 20130101 |
Class at
Publication: |
514/100 |
International
Class: |
A01N 057/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 10, 1997 |
KR |
97-46517 |
Claims
What is claimed is:
1. A quaternary ammonium phosphate compound having the following
formula 1 and which has an anticorrosive and a biocidal effect: 8
wherein R.sub.1 is a
p-(.alpha.,.alpha.,.gamma.,.gamma.)-tetramethyl butyl phenoxy
ethoxy ethyl group, and R.sub.2 and R.sub.3 are methyl groups.
2. A quaternary ammonium phosphate compound having the above
formula 1 and which has an anticorrosive and a biocidal effect,
wherein R.sub.1 is a tetradecyl group, and R.sub.2 and R.sub.3 are
morpholinium groups having the following formula 2: 9
3. A method of preparing a quaternary ammonium phosphate compound
having the above formula 1 comprising the step of: reacting a
quaternary ammonium hydroxide having the following formula 3 with a
phosphoric acid: 10 ,wherein R.sub.1 is a straight or a branched
alkyl or aryl radical with 1 to 27 of carbon atom(s) free of --OH
group and may contain hetero-atoms, and both of R.sub.2 and R.sub.3
are methyl groups or R.sub.2 and R.sub.3 are combined to form a
heterocyclic compound with 4 to 6 of carbon atoms containing oxygen
and nitrogen.
4. The method of claim 3, wherein said ammonium hydroxide is
prepared by reacting a quaternary ammonium chloride having the
following formula 4 with a metal hydroxide of 1.05 to 2.0
equivalents to said quaternary ammonium chloride in a solvent
containing an alcohol with 1 to 4 of carbon atom(s) at
0.about.35.degree. C.: 11 ,wherein R.sub.1, R.sub.2 and R.sub.3 are
the same as defined above.
5. A composition having an anticorrosive and a biocidal effect
comprising: a quaternary ammonium phosphate compound having the
above formula 1.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is based on application No. 97-46517 filed
in Korean Industrial Property Office on Sep. 10, 1997, the content
of which is incorporated hereinto by reference.
BACKGROUND OF THE INVENTION
[0002] (a) Field of the Invention
[0003] The present invention relates to a novel quaternary ammonium
phosphate compound and, more particularly, to a quaternary ammonium
phosphate compound having the following formula 1 and which has an
anticorrosive and a biocidal effect and an efficient method of
preparing the same. 1
[0004] In the above formula 1, R.sub.1 is a straight or a branched
alkyl or aryl radical with 1 to 27 of carbon atom(s) free of --OH
group and may contain hetero-atoms, and both of R.sub.2 and R.sub.3
are methyl groups or R.sub.2 and R.sub.3 are combined to form a
heterocyclic compound with 4 to 6 of carbon atoms containing oxygen
and nitrogen.
[0005] (b) Description of the Related Arts
[0006] A quaternary ammonium halide containing a quaternary
ammonium salt as a parental core, particularly, a quaternary
ammonium chloride has the advantages of having a high biocidal
effect and a low degree of surface tension and toxicity and hence,
it is often used for the purpose of cleaning and sterilizing
various household and industrial goods. And it is also widely used
as an additive in wood preservatives, paints, industrial
water-treating agents, cleansers and biocides because it is highly
stable.
[0007] A quaternary ammonium halide is typically prepared by using
the following reaction formula.
[0008] Reaction Formula 1
R.sub.1R.sub.2R.sub.3N+R.sub.4X.fwdarw.R.sub.1R.sub.2R.sub.3R.sub.4NX
[0009] In the above reaction formula 1, R.sub.1, R.sub.2, R.sub.3
and R.sub.4 are independently alkyl or aryl radicals and X is a
halogen compound.
[0010] Recently, quaternary ammonium chlorides, particularly,
N-alkyl-N-benzyl-N-dimethyl ammonium chloride and
N-dialkyl-N-dimethyl ammonium chloride have been the subject of
many studies. They are disclosed in U.S. Pat. Nos. 3,919,143 and
3,910,866 as polymer hardening promoters, disclosed in U.S. Pat.
No. 5,300,635 as surfactants for separation of RNA and disclosed in
U.S. Pat. Nos. 5,290,805, 5,399,762, 5,561,187 and 5,567,372 as
common biocides. U.S. Pat. No. 4,929,454 and Journal of American
Wood Preservativer's Association(1987) pages 331.about.348 by A. F.
Preston disclose a technique for preserving wood by impregnating
the quaternary ammonium chloride in the wood.
[0011] U.S. Pat. No. 4,521,412 discloses iodopropargylammonium
salts having a pesticidal effect and a method of preparing the
same, and U.S. Pat. No. 5,266,567 discloses halopropargylated
cyclic quaternary ammonium compounds and a method of preparing the
same.
[0012] But all the above-described compounds have a high biocidal
effect in a water system, but as they release halogen compounds
such as fluorine, chlorine, bromine and iodine, they are difficult
to apply to corrosive metal substances such as carbon steels, cast
irons, stain steels or coppers. Accordingly, U.S. Pat. No.
5,438,034 (1995) discloses a quaternary ammonium carbonate and a
method of preparing the same, the quaternary ammonium carbonate
having the following formula 5 and which has no metal coupler and
which can be obtained easily to be used as a wood preservative. The
method adopts directly a gaseous or solid carbon dioxide as a
carbonic acid of a reactant. 2
[0013] In the above formula 5, both R.sub.1 and R.sub.2 are alkyl
groups with 8 to 12 of carbon atoms.
[0014] U.S. Pat. No. 5,399,762 (1995) discloses a quaternary
ammonium hydroxide and a method of preparing the same, the
quaternary ammonium hydroxide being used as a wood preservative. An
aqueous solution containing 80% quaternary ammonium chloride is
used as a starting material and the equilibrium of a reaction is
shifted by raising a temperature to 40.about.90.degree. C. so that
the quaternary ammonium hydroxide can be prepared. However, if the
temperature is raised as in the above, a parental core of the
quaternary ammonium salt undergoes a Hofmann elimination and
rearrangement reaction when the parental core is exposed under a
high-temperature alkaline condition so that a yellowish-brown oily
olefin and amine compounds emitting an amine ordor are formed. The
compounds are highly hygroscopic and difficult to separate. In
addition, in drying the ammonium hydroxide, a considerable quantity
of the compound is decomposed.
[0015] Moreover, all the above-described compounds have been
developed and designed only as common biocides and except for the
quaternary ammonium hydroxide, they are limited to a structure that
a leaving group of a reactant are ion-bonded with the quaternary
ammonium salt as an anionic conjugate of the compound
[0016] In another aspect, United Kingdom Patent No. 1,199, 015
(1968) and U.S. Pat. No. 4,252,662 (1981) disclose a method of
introducing a phosphoric ester as an anionic conjugate. However,
this method adopts the phosphoric ester as a reactant and is
applied in the field of a base material of a high-pressure fluid.
And U.S. Pat. No. 4,716,037 discloses a quaternary ammonium
compound having an alkyl group with a terminal alcoholic group and
which is used in hair conditioners for the purpose of lessening
corrosion of stain steels.
SUMMARY OF THE INVENTION
[0017] It is an object of the present invention to provide a
quaternary ammonium phosphate compound having the following formula
1 and which has both a strong anticorrosive effect on a wide range
of metals and biocidal effect to be used in corrosive metal
substances such as carbon steels, iron casts, stain steels,
coppers, tinning steel plates and alumina by substituting a
dihydrogen phosphate ion(H.sub.2PO.sub.4.sup.-) for a Cl.sup.31 ion
from a quaternary ammonium chloride, and a method of preparing the
same.
[0018] Particularly, a novel quaternary ammonium phosphate compound
having the following formula 1 is characterized in that it has an
ether group including an unshared electron pair to improve an
anticorrosive characteristic greatly and to be able to form a
nonoxidative anticorrosive membrane.
[0019] A first aspect of the present invention provides a
quaternary ammonium phosphate compound having the following formula
1. 3
[0020] In the above formula 1, R.sub.1 is a straight or a branched
alkyl or aryl radical with 1 to 27 of carbon atom(s) free of --OH
group and may contain hetero-atoms and both R.sub.2 and R.sub.3 are
methyl groups or R.sub.2 and R.sub.3 are combined to form a
heterocyclic compound with 4 to 6 of carbon atoms containing oxygen
and nitrogen.
[0021] R.sub.1 is preferably
P-(.alpha.,.alpha.,.gamma.,.gamma.)-tetrameth- yl butyl phenoxy
ethoxy ethyl group, and R.sub.2 and R.sub.3 are preferably methyl
groups.
[0022] And R.sub.1 is preferably a tetradecyl group, and R.sub.2
and R.sub.3 are preferably morpholinium groups having the following
formula 2. 4
[0023] The second aspect of the present invention provides a method
of preparing a quaternary ammonium phosphate compound having the
above formula 1 having the step of reacting a quaternary ammonium
hydroxide having the following formula 3 with a phosphoric acid.
5
[0024] In the above formula 3, R.sub.1, R.sub.2 and R.sub.3 are the
same as defined above.
[0025] The quaternary ammonium hydroxide is preferably prepared by
reacting a solid quaternary ammonium chloride having the following
formula 4 with a metal hydroxide of 1.05.about.2.0 equivalents to
the quaternary ammonium chloride in a solvent containing an alcohol
with 1 to 4 of carbon atom(s) at 0.about.35.degree. C. 6
[0026] In the above formula 4, R.sub.1, R.sub.2 and R.sub.3 are the
same as defined above.
[0027] The third aspect of the present invention provides a
composition having an anticorrosive and a biocidal effect,
containing a quaternary ammonium phosphate compound having the
above formula 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] A quaternary ammonium phosphate compound having the above
formula 1 is prepared as follows. 7
[0029] A quaternary ammonium chloride contains a N-benzyl group in
a parental core of a quaternary ammonium salt and is preferably
selected from the group consisting of
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.ga- mma.)-tetramethyl
butyl phenoxy]ethoxy ethyl-N-benzyl ammonium chloride, a mixture of
N-dimethyl-N-dodecyl-N-benzyl ammonium chloride,
N-dimethyl-N-tetradecyl-N-benzyl ammonium chloride,
N-dimethyl-N-hexadecyl-N-benzyl ammonium chloride and
N-dimethyl-N-octadecyl-N-benzyl ammonium chloride, and
4-benzyl-4-tetradecyl morpholinium chloride. The metal hydroxide
contains a mono-, di- or trivalent metal, preferably a monovalent
metal, and more preferably sodium or potassium.
[0030] A step for preparing the quaternary ammonium hydroxide is a
typical equilibrium reaction so that the reaction can be optimized
by changing the ratio of equivalents of reactants, solvents and
conditions of the reaction. The step is preferably carried out in a
solvent containing an alcohol with 1 to 4 of carbon atom(s),
preferably an ethanol, and more preferably an anhydrous ethanol.
When a mixture of N-dimethyl-N-dodecyl-N-benzyl ammonium chloride,
N-dimethyl-N-tetradecyl-- N-benzyl ammonium chloride,
N-dimethyl-N-hexadecyl-N-benzyl ammonium chloride and
N-dimethyl-N-octadecyl-N-benzyl ammonium chloride is used as a
starting material, the content of water can be minimized and the
yield can be maximized by using the solid mixture having been
crystallized with a drying method such as a lyophilization method .
The metal hydroxide is preferably 1.05.about.2.0 equivalents to the
quaternary ammonium chloride. If less 1.05 equivalents, the
reaction rate is decreased and if more 2.0 equivalents,
decomposition reaction may occur. The reaction is performed at
0.about.35.degree. C. so that a Hofmann elimination and
rearrangement reaction occurring under a high-temperature alkaline
condition can be suppressed and the reaction can be finished within
8 hours. Therefore, a filtrate containing the quaternary ammonium
hydroxide is not required to separate and can be used directly in
the subsequent step so that the prior filtrate drying step, where a
considerable quantity of the quaternary ammonium hydroxide is
decomposed, can be omitted.
[0031] A reaction between a quaternary ammonium hydroxide and a
phosphoric acid is a neutralization reaction and even if some heat
is generated, another side reaction is not likely to occur and
therefore a separate cooling step is not required. If the residual
metal hydroxide remains in the solution, it reacts quickly with
dihydrogen phosphate ions preferentially and can be extracted and
removed easily in the form of a metal phosphate salt.
[0032] A quaternary ammonium chloride having the above formula 4 is
added and dissolved at room temperature in an alcohol solvent with
1 to 4 of carbon atom(s). A small quantity of a metal hydroxide
containing a mono-, di- or trivalent metal is admixed and the
solution is agitated for 1.about.8 hour(s). As the reaction is
proceeded, a metal chloride is precipitated and the solution
becomes turbid. After the reaction ends, the solution is cooled at
a low temperature of about 0.degree.C. and a white metal chloride
is completely removed. Then a filtrate containing a quaternary
ammonium hydroxide intermediate having the above formula 3 is
obtained. A phosphoric acid of equivalents corresponding to those
of the quaternary ammonium hydroxide intermediate and the residual
metal hydroxide is added with a dropping funnel at room temperature
and an acid-base reaction is proceeded. A metal phosphate is
extracted and separated with a filter. Removal of the solvent from
the obtained solution by drying gives an oily paste or a white
powdery quaternary ammonium phosphate.
[0033] A preferred embodiment of this invention will be explained
with reference to the following examples.
EXAMPLES
Example 1
[0034] Preparation of solid
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.gamm- a.)-tetramethyl
butyl phenoxy]ethoxy ethyl-N-benzyl ammonium phosphate
[0035] 50 ml of ethanol was added in a 100 ml round flask. 10.0 g
(22 mmol) of
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.gamma.)-tetramethyl butyl
phenoxy]ethoxy ethyl-N-benzyl ammonium chloride was added and
dissolved at room temperature and then 2.21 g (33 mmol, 85%) of
ground potassium hydroxide was added. Equipped with an anhydrous
calcium chloride tube, the solution was agitated at a high rate for
6 hours. Precipitates were formed in the solution after the elapse
of time. The solution was cooled in an ice bath and filtered off.
Washing of the precipitates with cold ethanol gave 1.6 g of
potassium chloride. 4.18 g (33 mmol) of 85% phosphoric acid was
admixed with the filtrate and after 1 hour, the residual potassium
phosphate was extracted and filtered. Removal of the solvent and
drying of the solid gave 11.0 g of solid
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.gamma.)-tetramethyl butyl
phenoxy]ethoxy ethyl-N-benzyl ammonium phosphate.
[0036] A result of a .sup.1H-NMR analysis of the compound is shown
as .delta. 7.60.about.7.40 (m,5H), 7.26.about.7.27 (d,2H), 6.78
(d.2H), 4.93 (s,2H), 4.12.about.3.90 (t,8H), 3.30 (s,6H), 1.69
(s,6H), 1,69 (s,6H), 1.33 (s,6H) and 0.70 (s,9H).
Example 2
[0037] Preparation of powdery
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.ga- mma.)-tetramethyl
butyl phenoxy]ethoxy ethyl-N-benzyl ammonium phosphate
[0038] 9.68 g of solid
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.gamma.)-t- etramethyl
butyl phenoxy]ethoxy ethyl-N-benzyl ammonium phosphate obtained in
example 1 was dissolved in 4 ml of boiling isopropyl alcohol and
recrystallized with a boiling ethylacetate solvent. 7.50 g of white
powdery
N-dimethyl-N-[p-(.alpha.,.alpha.,.gamma.,.gamma.)-tetramethyl butyl
phenoxy]ethoxy ethyl-N-benzyl ammonium phosphate was obtained.
[0039] The melting point of the compound was 188.about.192.degree.
C. and a result of a .sup.1H-NMR analysis of the compound is shown
as .delta. 7.60.about.7.40 (m,5H), 7.26.about.7.27 (d,2H), 6.78
(d.2H), 4.93 (s,2H), 4.12 (t,4H), 4.05 (t,2H), 3.30 (s,6H), 1.69
(s,2H), 1.33 (s,6H) and 0.70 (s,9H).
Example 3
[0040] Preparation of a mixture of N-dimethyl-N-dodecyl-N-benzyl
ammonium phosphate, N-dimethyl-N-tetradecyl-N-benzyl ammonium
phosphate, N-dimethyl-N-hexadecyl-N-benzyl ammonium phosphate and
N-dimethyl-N-octadecayl-N-benzyl ammonium phosphate
[0041] 1.2 l of ethanol was added in a 2 l two-mouthed round flask.
A mixture of N-dimethyl-N-dodecyl-N-benzyl ammonium chloride,
N-dimethyl-N-tetradecyl-N-benzyl ammonium chloride,
N-dimethyl-N-hexadecyl-N-benzyl ammonium phosphate and
N-dimethyl-N-octadecayl-N-benzyl ammonium chloride was dried in a
lyophilizer of -50.degree. C. and 5 torr. 360 g(1.02 mol) of the
mixture was added and dissolved at room temperature. 93.45 g(1.42
mol) of 85% ground potassium hydroxide was added. Equipped with an
anhydrous calcium chloride tube, the solution was agitated at a
high rate for 8 hours. Precipitates were formed in the solution
after the elapse of time. The solution was cooled in an ice bath
and filtered off. Washing of the precipitates with cold ethanol
gave 75 g of potassium chloride. 163.26 g(1.42 mol) of 85%
phosphoric acid was admixed with the filtrate and after 1 hour, the
residual potassium phosphate was extracted and filtered off.
Removal of the solvent and admixing of an ethyl acetate solvent
gave a uniform slurry. Separation and drying of the slurry gave 390
g of the mixture of N-dimethyl-N-dodecyl-N-benzyl ammonium
phosphate, N-dimethyl-N-tetradecyl-N-benzyl ammonium phosphate,
N-dimethyl-N-hexadecyl-N-benzyl ammonium phosphate and
N-dimethyl-N-octadecayl-N-benzyl ammonium phosphate.
[0042] A result of a .sup.1H-NMR analysis of the compound is shown
as .delta. 7.48.about.7.44 (m,5H), 4.52 (s,2H), 3.11 (s,6H), 3.05
(t,2H) and 0.87 (t,3H).
Example 4
[0043] Preparation of 4-benzyl-4-tetradecyl morpholinium ammonium
phosphate.
[0044] 5 ml of ethanol was added in a 50 ml round flask. 4.26 g(10
mmol) of 4-benzyl-4-tetradecyl morpholinium ammonium chloride was
added and dissolved at room temperature. 420 mg(10.5 mmol) of
ground potassium hydroxide was added. Equipped with an anhydrous
calcium chloride tube, the solution was agitated at a high rate for
8 hours. Precipitates were formed in the solution with the elapse
of time. The solution was cooled in an ice bath and filtered off.
Washing of the precipitates with cold ethanol gave 550 mg of sodium
chloride. 1.21 g(10.5 mmol) of 85% phosphoric acid was admixed with
the filtrate and after 1 hour, the residual potassium phosphate was
extracted and filtered off. Removal of the solvent and admixing of
20 ml of an ethyl acetate solvent gave a uniform slurry. Drying of
the slurry gave 4.15 g of yellowish-brown solid
4-benzyl-4-tetradecyl morpholinium ammonium phosphate
[0045] A result of a .sup.1H-NMR analysis of the compound is shown
as .delta. 7.53 (m,5H), 4.68 (s,2H), 4.10 (t, 4H), 4.00 (t,2H),
3.39 (t, 4H), 1.37.about.1.29 (m,22H), 1.38 (m,2H) and 0.88
(t,3H).
Comparative Example 1
[0046] Preparation of
N-dimethyl-N-[p-N-[p-(.alpha.,.alpha.,.gamma.,.gamma-
.)-tetramethyl butyl phenoxy]ethoxy ethyl-N-benzyl ammonium
phosphate.
[0047] Example 1 was repeated except that the solution was agitated
for 30 minutes at room temperature and that after the reaction with
the phosphoric acid, the solvent was removed and an ethyl acetate
solvent was added to obtain a uniform slurry. Filtration and drying
of the slurry gave
N-dimethyl-N-[p-N-[p-(.alpha.,.alpha.,.gamma.,.gamma.)-tetramethyl
butyl phenoxy]ethoxy ethyl-N-benzyl ammonium phosphate.
Comparative Example 2
[0048] Preparation of 4-benzyl-4-tetradecyl morpholinium ammonium
phosphate.
[0049] Example 4 was repeated except that the reaction was carried
out in an ice bath containing a saturated sodium chloride solution.
310 mg of potassium chloride was formed as an intermediate and
4-benzyl-4-tetradecyl morpholinium ammonium phosphate was finally
obtained.
Comparative Example 3
[0050] Preparation of a mixture of N-dimethyl-N-dodecyl-N-benzyl
ammonium phosphate, N-dimethyl-N-tetradecyl-N-benzyl ammonium
phosphate, N-dimethyl-N-hexadecyl-N-benzyl ammonium phosphate and
N-dimethyl-N-octadecayl-N-benzyl ammonium phosphate
[0051] Example 3 was repeated except that the quaternary ammonium
chlorides were not lyophilized and used in the form of a 50%
aqueous solution. A mixture of N-dimethyl-N-dodecyl-N-benzyl
ammonium phosphate, N-dimethyl-N-tetradecyl-N-benzyl ammonium
phosphate, N-dimethyl-N-hexadecyl-N-benzyl ammonium phosphate and
N-dimethyl-N-octadecayl-N-benzyl ammonium phosphate was
obtained.
[0052] The yields of the examples and the comparative examples are
shown below in table 1.
1 TABLE 1 Yield (%) Example 1 99 Example 2 77.5 Example 3 93.8
Example 4 88 Comparative example 1 68 Comparative example 2 49
Comparative example 3 45
[0053] As shown in table 1, the preparation method of the present
invention easily obtains a quaternary ammonium phosphate in a high
yield.
Anticorrosive Effect Test
[0054] This test was carried out for the purpose of measuring an
anticorrosive effect of the compounds obtained from examples 1, 3
and 4. An anhydrous calcium chloride and magnesium sulfate 7
hydrates were mixed in 1 l of pure water to formulate 15 ppm of
magnesium hardness. A test material was added to 20 ppm and the
final pH was adjusted to 8.5. A water tank at 40.degree. C. was
used, 100 cc of air was supplied per minute and the solution was
agitated at 150 rpm. A metal test piece used were carbon steel
(c-1020), copper, cast iron, tinning steel plate of which the
surface areas were respectively 0.21 g/dm.sup.2, 0.20 g/dm.sup.2,
0.22 g/dm.sup.2, and 0.17 g/dm.sup.2. The rate of corrosion was
analyzed from the weight loss of the test piece after 42 hours and
the measuring unit was mpy (mils per year).
Biocidal Effect Test
[0055] This test was carried out for the purpose of measuring a
biocidal effect of the compounds obtained from examples 1, 3 and 4.
A test material was diluted using a serial dilution method in a
96-multiwelled plate. 10.sup.4 cfu/ml of microbes were inoculated
in the diluted solution. After the microbes were cultivated for 48
hours at 30.degree. C., MIC (Minimal Inhibition Concentration of
microorganisms) was visually observed to decide whether or not
microbial growth occurred from the turbidity. The growth medium was
nutrient broth, DIFCO, and the strains used were as follows.
[0056] Bacteria
[0057] Enterobacter aerogenes ATCC 13048, Escherichia coli ATCC
11229, Micrococcus luteus ATCC 9431, Pseudomonas aeruginosa ATCC
15442, Shigella sonnei ATCC 9290, Staphylococcus epidermis ATCC
155, Staphylococcus aureus ATCC 6538 and Bacillus subtilis ATCC
6984.
[0058] Yeasts
[0059] Candida albicans ATCC 10231, Rhodotorula rubra ATCC 9449,
Cryptococcus neoformans ATCC 34144 and Saccharomyces cerevisiae
ATCC 9763.
[0060] Fungi
[0061] Penicillium citrinum ATCC 98404, Trichoderma viridae ATCC
1287, Rhizopus oryzae ATCC 10404 and Aspergillus niger ATCC
9642.
[0062] Test Results are Shown Below in Table 2.
[0063] Table 2.
2 Anticorrosive effect (mpy) Minimal Inhibition carbon cast tinning
Concentration (ppm) steel iron copper steel Bacteria yeasts fungi
example 4.5 1.3 0.1 1.0 6.3.about.12.5 6.3.about.12.5 25.about.100
1 example 3.7 4.6 0.2 0.3 12.5.about.25 12.5.about.25 25.about.100
3 example 5.1 0.8 0.1 0.1 6.3.about.12.5 12.5.about.25 25.about.100
4 A 7.2 6.5 0.5 0.5 12.5.about.25 12.5.about.25 25.about.100 B 6.8
7.1 0.4 0.7 6.3.about.12.5 6.3.about.25 25.about.100 C 10.5 11.1
0.3 0.6 6.3.about.12.5 12.5.about.50 25.about.100 D 18.7 13.9 0.1
0.3 -- -- -- E 7.6 5.1 0.2 0.3 -- -- -- F 33.0 25.5 0.7 1.9 -- --
-- A: N-dimethyl-N-[p-(.alpha.,.alpha.,-
.gamma.,.gamma.)-tetramethyl butyl phenoxy]ethoxy ethyl-N-benzyl
chloride B: 4-benzyl-4-tetradecyl morpholinium ammonium chloride C:
a mixture of N-dimethyl-N-docecyl-N-benzyl ammonium chloride,
N-dimethyl-N-tetradecyl-N-benzyl ammonium chloride,
N-dimethyl-N-hexadecyl-N-benzyl ammonium chloride and
N-dimethyl-N-octadecyl-N-benzyl ammonium chloride D: sodium
dihydrogen phosphate (NaH.sub.2PO.sub.4.12H.sub.2O) E:
N-dimethyl-N-cetyl-N-hydroxyethyl ammonium phosphate F: Blank (no
compound contained)
[0064] As shown in table 2, the quaternary ammonium phosphate
compounds of the present invention have a high anticorrosive effect
on carbon steels, cast irons, coppers and tinning steel plates.
This results from a synergic effect between an ether bond of an
unshared electron pair in an alkyl group of a parental core of a
quaternary ammonium and phosphate of an anion. The compound also
has a high anticorrosive effect.
[0065] The present invention provides a compound which has an
anticorrosive effect on a wide range of corrosive metal substances
e.g. carbon steels, iron casts, stain steels, coppers., tinning
steel plates and alumina and which has a biocidal effect, a
cleaning effect and a low toxicity. The compound is useful where a
strong biocidal effect is required, where a cleaning effect is
required and where low toxicity and where low skin irritability is
required and when applied to equipment, devices or apparatus made
of corrosive substances. Moreover, the compound has properties to
allow performance of a substitution reaction, and provides high
purity and low toxicity so that it can be easily used on a
commercial scale.
[0066] While the present invention has been described in detail
with reference to the preferred embodiments, those skilled in the
art will appreciate that various modifications and substitutions
can be made thereto without departing from the spirit and scope of
the present invention as set forth in the appended claims.
* * * * *