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Патент USA US3033795

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United
ate'nt
tates
ice
1
2
for bacteria inhibition of soluble oils and soluble oil
emulsions is Z-nitro-l-butanol.
3,033,735
BACTERIA INHIBITED SOLUBLE OIL
'
3,033,785
‘Patented May ,8, ‘l 962
The nitro-butanols are effective bactericides in soluble
oil emulsions in amounts ranging from about 25 to 2500
ppm. The amount of these bactericides placed in solu
ble oils in order to obtain the proper concentration in the
formed emulsions ranges from 0.1 to about 6 percent by
COMPGSITION
Edward 0. Bennett, Houston, Tex., assignor to Texaco
Inc., a corporation of Delaware
No Drawing. Filed June 2, 1958, Ser. No. 738,990
5 Claims. (Cl. 252-—33.3)
weight based on the oil.
This invention relates to a soluble oil inhibited against
The soluble oil mainly comprises a minerallubricat
bacterial action. More particularly, it relates to a bac 10 ing oil and an emulsifying agent. The mineral oil is pref
tericide-containing soluble oil particularly useful in the
erably a naphthene base distillate oil although mixed
form of an emulsion as a metal working lubricant.
paraf?n-naphthene base distillate oils are at times effec
tively employed. . Naphthene base distillate fractions are
mixtures of mineral and vegetable oils, and an emulsify
desirable because of their better emulsi?cation properties
ing agent to lower the interfacial tension between the oil 15 and stability. In general, re?ned base oil fractions hav
and large volumes of water whereby emulsions of the oil_
ing an SUS viscosity at 100° F. between 70 and 800 are
in-water type may be easily formed. The emulsifying
used in the formulation of the soluble oils of this inven
agents commonly used include soaps of petroleum sul
:tion.
Soluble oils generally are composed of mineral oil or
fonic acids, naphthenic acids, fatty acids, rosin and tall
The emulsifying agents useful in the present invention
oil. Soluble oils usually contain coupling agents and 20 are those known ‘in the ant. Examples of these emulsi
small amounts of water to stabilize the composition prior
?ers include oil soluble metal petroleum sulfonates, alkali
to emulsi?cation. Various lubricant additives are also
metal naphthenates, and resinates, salts of fatty and car
used to correct or improve certain characteristics of the
boxylic acids, such as guanidine salts of high molecular .
soluble oil or soluble oil emulsion.
The oil-in-water emulsions are formed with water-to
oil ratios ranging from 5:1 to 100:1. The more dilute
Weight ‘fatty acids and alkylolamine salts of carboxylic
which it was intended.
employed.
acids containing at least 10 carbon atoms, alkali metal
salts of tall oil, etc. These soaps or salts are usually.
emulsions, from 25:1 to 100:1 are preferred for cutting
formed with sodium because of the lower cost and avail
oils which are used as lubricants and coolants in high
ability, but potassium is also used. Mixtures of emulsi»
speed metal turning operations.
?ers, for example a mixture of sodium naphthenate and
The soluble oil itself is shipped to the user, in a sub 30 sodium petroleum sulfonate, a mixture of sodium resinate,
stantially sterile condition. However, bacteria can be
sodium naphthenate and sodium petroleum sulfonate, and.
introduced in an emulsi?ed soluble oil either through the
a mixture of guanidine stearate and triethanolamine
water used in the preparation thereof or through contami
stearate have been found extremely useful.
nation by the workers or from the air during use. The
The total emulsi?er concentration is between 10 and
bacteria, if allowed to grow unchecked, will eventually
20 percent, by weight of the total soluble oil composition
cause breakdown of the emulsion and curtail the use for
with concentrations between 12 and 16 percent usually
'
In addition to the above occurrence, a serious odor
Minor amounts of coupling agents are also advan
problem is created by certain bacterial growth in the cut
tageously employed in the soluble oil composition to im
ting ?uid. It is believed that initially the growth of 40 prove the texture and stability thereof. Those coupling
aerobic bacteria takes place with a resulting slight break
agents useful in this invention include mono and polyhy
down of the emulsion. During shutdown periods of the
droxy alcohols, ether-alcohols, and phenols. Examples
cutting machinery, as on weekends and holidays, an
of these compounds include ethyl, isopropyl, n-propyl,
aerobic sulfate-reducing bacteria grow quickly in ‘the used
cutting ?uid due to inadequate aeration in the quiescent 4.5
system and to the conditions or material provided by
the prior growth of aerobic bacteria in the ?uid. The
isobutyl, n-butyl and n-amyl alcohols; ethylene glycol, di
ethylene glycol and propylene ‘glycol; ethylene glycol
monoethylether (Cellosolve), ethylene glycol monoiso
propylether, ethylene glycol monobu-tylether, ethylene
glycol mono-n-pentylether, ethylene glycol mono-n
hexylether, diethylene glycol monoethylether (Carbitol),
presence of large amounts of sulfate-reducing bacteria
causes severe odor problems due to the formation of sul~
?des, and the odor is particularly noticeable on Monday 50 diethylene glycol monobutylether and cresol. The con
mornings after weekend shutdown periods. ,The growth
centration of the coupling agents in the soluble oils is
of anaerobic bacteria also causes a quicker and more
usually between 0.1 and 1.5 percent by weight. A pre
severe emulsion breakdown than is caused by aerobic
ferred coupling agent is ethylene glycol monobutylether
bacteria necessitating draining and cleaning of the cut
at a concentration of about 0.6-1.0 percent by weight.
ting ?uid system and the addition of new cutting ?uid. 55
In preparing the soluble oil of this invention a small '
The problem of ?nding a satisfactory bacterial in
amount of Water is preferably used to make the soluble
hibitor for a soluble oil is made di?icult by a number of
oil ?uid and to prevent oil separation, or Strati?cation of
factors which must be considered. These factors include
the emulsion, upon mixing the soluble oil with much
toxicity, oil solubility, storage stability, emulsion degra
larger amounts of Water. The water content, to stabilize
dation, additive compatibility and growth inhibition of 60 the oil, usually falls between 1 and 4 weight'percent. HA:
harmful bacteria for a sufficient period during the life
water content of about 2 percent has been found to be
of the oil.
In accordance with the present invention a soluble oil
particularly effective in the soluble oil composition.
composition which will meet the above requirements con
taius a bacteria-inhibiting amount of a hydroxy substi
tuted nitrobutane. Examples of the bactericide com
pounds of this invention include 2-nitro—1-butanol, 3
nitro-l-butanol, 4-nitro-1-butanol, l-nitro-2-butanol, l
nitro-3-butanol, 2-nitro-2-butanol, 2-nitro-3-butanol, and
'
Other useful lubricant additives, to improve certain
characteristics of the solublev oil, are at times used in the
65
composition. These include, for example, rust preventa
tives such as tn'ethanolamine, extreme pressure and oil
- iness agents, and settling agents.
In order to determine the value of compounds, known
or expected to have bacteria destroying properties in wa
the hydroxy substituted nitro-isobutanes such as Z-nitro 70 ter solutions, as bactericides in soluble oil emulsions, a
Z-methyl-l-propanol, 3~nitro-2-methyl-2-propanol and 3~
screening test was used. This test'consisted of preparing
nitro-2-rnethyl-1-propanol. The preferred nitrop-butanol
the cutting ?uids or soluble oil emulsions and adding 100,
a
3,033,785
q
.
g
4
>
500, and 1000 p.p_.m. of each bactericide to 20 m1. of
Table I——Continued
the emulsion in test tubes.‘ The tubes were then auto
claved at 15 pounds, steam pressure for 15 minutes}
After the tubes had cooled to atmospheric temperature, ‘
0.5 ml; of a composite used cutting oil samples or inocu
No. of Eliective Days of Inhibition
100 p.p.m.
lum was ‘prepared by mixing the “spoiled” cutting oil sam
, ples of several users. .The bacterial content of the in
500 p.p.m. 1,000 p.p.m.
27
10% Phenylmercuric acetate .... __
Organic mercurial (Exact; chemi
oculum was determined and‘in every case the tubes were
inoculated with a standard known number of viable bac
cal composition not known) _ - _ ;
1,2 - Dichlorohexa?uorocyolopen -
teneal
teria. Tubes of sterile uninhibited. uninoculated emul 10
sions and uninhibited inoculated emulsions were em
Oyelohexyl chloride. _
2-Arnino-L4 naphthoquinone____.
Propyl-p-hydroxyhenzoate__.____
ployed as controls. All tubes were placed on a shaking
Butyl-p-hydroxybenzoate.---
machine making 209 oscillations per minute. Immedi
ately after inoculation of the emulsions and at 24 hour
--. ...................... __
p-Ohloro-m-xylenol _____________ __
3
6
agro
Lauryl isoquinolinium bromide__
Phenylmereuric monoethauol-am
intervals for a period of 7 days, each tube was tested for 15 monium acetate ______________ ._
Zinc salt of dimethyl dithiooarha
the presence of viable bacteria by inoculating nutrient
mic racid
broth with a small standard volume of emulsion. The
3,5-Dibromo-2-phe'nyl Inercurloxy
benzoic acid ____ _.
broth tubes were incubated for 48 hours and then ex
Sodium salt of dibromohydro‘xy
amined for bacterial growth.
Those bactericides which '
mercuri, ?uoreseein (mercuro
caused the inoculated emulsions to become sterile within 20 Phenyl mercuric salicylate_.._-_-_
the seven day test period were considered promising and
1-Hydroxy-2-(1H)-pyrid.ine'thi0ne
(zinc salt)
_ __
were subjected to further testing. Of over 250 known
l-Hydroxy- -(1H)-pyridine thlone
bactericides tested in- the above manner less than a third
(copper salt) _____
Morpholine 511i co?uoride _______ _ _
were considered promising for bacteria inhibition of sol
Rosine amine si1ic0?uor1de.__
‘
uble oils.
’
chrome) ___________ __'_________ -
n>o—‘:
O QcKaGOnNUo-gw4:
Trls(hydroxymethyl)amiuo meth
7
"mp
Effective materials found with the above test procedure
Tris(hydroxymethy1 (nitro-meth- RT] P
were further tested in an Open System Test. The pro
Nitromethane. _
cedure consisted of placing 3.0 grns. of powdered iron
Nitroethane- _
1-nitropropane_-___
and 3000 ml. of a 25:1 soluble oil emulsion containing
the experimental ‘bactericide in a one gallon jar and in 30 2-nitropromne
l-Ohloro-lanitro-propane ________ __
2-Ohloro—2-nitro-propane“_
oculating with a known quantity of bacteria. The solu
1,l-Dichloro-l-nitro-propane ..... _.
ble oil consisted of a naphthene base distillate oil having
2-Amino-2-ethyl-L3 propane-din!
an SUS viscosity at 100°5 F. of about 72, 7.5 percent so
1,4~diehlorobufane
'
dium resinate, 12.0 percent sodium petroleum sulfonate,
1.0 percent ethylene glycol monobutylether, 0.5 percent
"
WOG
2-Nitro-l-butano1 _______________ _.
triethanolamine and 2.0 percent water. The system was
then aerated for 5 days and allowed to stand quiescent
for 2 days each week. Immediately after inoculation
and twice a week, thereafter duplicate standard plate
In the aboverdata, l00‘p.p.m., 500 ppm. and 1000‘
ppm. correspond respectively to about 0.25, 1.25 and
2.50 percent by weightof the potential bactericides in the
counts were made. The inhibitors were considered ef 40 soluble oil before the formation of the 25:1 dilution emul-.
fective as long as bacteria counts remained less than
IOOO/ml.
sion.
The following table shows the results of the Open Sys
tern Test on the potential bactericides:
,
,
In addition to the above ?ndings, 3-nitro-2-pentanol
’
was found ineii‘ective in the previously described screening
'
'
test.
From the above data it can easily be concluded that
45 the compounds of the invention are exceptional aerobic
' Table I
bacteria inhibitors in soluble oil emulsions.
Some of the compounds listed in the foregoing Table I
No. of Effective Days of Inhibition
100 ppm.
500 p.p.m. 1,000 p.p.m.
o-Phenyl phenol ........ -.
Resorcino1 ____________ ..
Resoreinol dibenzoate ______ .-
_
______________________ __
'
Mercuric naphthenate __________ __
0
0
0
the solution turned clear. The solution was then able to
be added to the soluble oil.’
Obviously, many modi?cations and variations of the
invention, as hereinbefore set forth, may be made without
Zinc salt of alkyl-N-propylene
diamine-pentachloronheunl
Pentachloronbeuol
-
Tetradecylamine salt of o-phenyl
nhpnnl
’
v
Dichlornphene
'
Copper naphthenate, 8% _______ __
H
Azochloramide _________________ __
Mixture of 4 and 6 chloro-2-phenyl
‘
exco
henol ________________________ __
1N ethylene bis-phenoL.
_
Tetrachlorophenol ........... _..__
Mixture of o and p-dimethyL
onO030
aminomethyl phenol __________ __
2,4,6- ri(dimethylarninomethyl)
H
phenol ________________________ __
Beta-propio1actone-_
_.
Diethyl acid pyrophosphate
m-CresoL.
2
‘
3
Malonio arid
1,2-Dlbromo-1, dichloroethaue__-_
Hydroxylamlne H01 sol. _______ -_
Mixture of 2,8-diamiuo-10-methyl
acridinium chloride and 2,8
diamino am-idinp
Ditto, H01, sol
Dtchloro-m-xy1erm1 M
mHwe:
g5o:m20gcazomwr
60 departing from the spirit and, scope thereof, and there
fore only such limitations should be imposed as are indi
cated in the appended claims.
I claim:
g
,
1. An improved soluble oil consisting essentially of a
65 major portion of an emulsi?able mineral lubricating oil,
from 10 to 20 percent by weight of an oil-in-water emulsi
fying agent, and a bacteria inhibiting amount of Z-nitro-l
butanol.
2-Methyl-lA-naphthoquinone ___________________________ __
2-Phenyl ethylamine
50 se, decomposed in the soluble oil in storage, degraded.
soluble oil emulsion properties, or could only be incorpo
rated in the soluble oil by utilizing a special technique
which entailed adding the potential bactericide to ethylene
glycol monobutylether, which is usually incorporated as
55 a coupling agent, heating this solution to 130° F. until
Sodium o-phenylphenate.
Alkylamine o-phenyl phenol ____ __
were eifective in this test. However they were objec
tionable as either completely insoluble in soluble oil per
‘
.
2. An improved soluble oil consisting essentially of a
70 majorv portion of an emulsi?able mineral lubricating oil,
from 10 to 20 percent by weight of an oil-in-water emulsi
tying agent, and from 0.1 to about 6 percent by weight
Z-nitro-l-butanol.
3. An improved soluble oil emulsion consisting essen~
3“ 75 tially of about 5 to 100 ‘parts of‘water, about one part of
3,033,785
6
an emulsi?able hydrocarbon oil composition consisting es
of water; and from about 100 to 1000 parts per million
sentially of a major portion of a mineral lubricating oil,
of Z-nitro-I-butanol.
from 10 to 20 percent by weight of an oil-in-water emulsi
References Cited in the ?le of this patent
fying agent, and from 25 to 2500 parts per million of
2-nitro-1-butanol.
UNITED STATES PATENTS
4. An improved soluble oil emulsion as described in
2,402,487
Batchelder et a1 ________ __ June 18, 1946
claim 3 containing from about 100 to 1000 parts per
2,653,909
Frazier ______________ __ Sept. 29, 1953
million of Z-nitroJ-butanol.
2,668,146
Cafcas et a1 ____________ _.. Feb. 2, 1954
5. An improved soluble oil emulsion consisting essen
tially of about 25 to 100 parts of water; about one part of
FOREIGN PATENTS
an emulsi?able hydrocarbon oil composition consisting
421,189
Italy ________________ __ Mar. 19, 1947
essentially of a major portion of a naphthene base distil
107,419
Australia ____________ _.’_ May 25, 1939
late oil having an SUS viscosity range at 100° F. of from
70 to 800, 12 to 16 percent by weight of a sodium salt of
OTHER REFERENCES
a compound selected from the group consisting of naph- 15
Pivnick
et
al.:
“Disinfection of Soluble Oil Emulsions,”
thenic acid, sulfonic acid, rosin and mixtures thereof,
Journal of the American Society of Lubrication Engineers,
from 0.1 to 1.5 percent by weight of a coupling agent
March 1957 (pages 151—153).
selected from the group consisting of monhydroxy alco
“Fundamentals of Microbiology," by Frobisher, 5th ed.,
hols, polyhydroxy alcohols, ether-alcohols, phenols and
mixtures thereof, and from about 1 to 4 percent by weight 20 1953, by W. B. Saunders Company, page 3.
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