Patentcd Apr.

22, 1947

2,419,327

UNITED STATES PATENT OFFICE

2,419,327
CORROSIONJNHIBITORS-NITRITE SALTS
OF SECONDARY AMINES

'

Aaron Wachter and Nathan Stillman, Berkeley,

-

Calif., assignors to Shell Development Com

pany, San Francisco, Calif., a corporation of

Delaware
No Drawing. Application June 28, 1943,
Serial No. 492,640
5 Claims. (Cl. 252-392)
The present invention relates to water corrosion
prevention inhibitors. More speci?cally it relates

to corrosion inhibitors particularly suitable for

use in preventing corrosion of certain metal sur

faces by water associated in relatively small

quantities with organic materials.
In the handling of various organic materials,
particularly hydrocarbons and similar organic

ready separated or intentionally maintained

therein and water which may later separate from
the gasoline and collect in the bottom of the tank.
However, part of the water which separates col
lects on the tank wall, corrodlng and damaging
the same, the corrosion products in turn contami

nating the gasoline.

Analogous corrosion problems occur in numer

ous other ?elds; for example in the lubrication of
liquid compositions, it is often necessary to trans
port and/or store such materials in metal con l0 internal combustion engines, steam engines in
cluding turbines, and other similar machinery,
tainers, as in steel or other metal pipelines, drums,
quantitiesof water are often observed as a sepa
tanks and the like. Since these materials often
rate phase within the lubricating system as a
contain varying amounts of water in solution or in
result of condensation of water from the atmos
suspension which may separate, due to tempera
ture changes, for example, internal corrosion of 15 phere, or, in the case of combustion engines, as a
result of dispersion or absorption in the lubricating
the container by separated water almost invariably
oil of water formed as a product of fuel combus
occurs to a greater or lesser degree. This problem
tion. Water in such instances corrodes the various
is especially serious when gasoline is under con
metal parts of the machinery with which it comes
sideration. In spite of all reasonable and practi
cable precautions during the manufacture of gaso 20 in contact, the corrosion products causing further
mechanical damage to bearing surfaces and the
line, when the same is transported in pipelines or
like due to their abrasive nature and catalytically
stored in drums or tanks for a period of time,
promoting the chemical degradation of the lubri
especially as is so often practiced in handling
cant. In this instance, as in the example cited
aviation gasoline, an appreciable quantity of
water separates and is found as a ?lm or in 25 above, the inhibitors known to the art have not
always been entirely satisfactory, the organic
minute droplets on the pipeline or container walls
material-soluble inhibitors being, in general, rela
or even in small pools in the bottom of the con
tively ineffective water-corrosion inhibitors, and
tainer. This brings about ideal conditions for
the water-soluble inhibitors being difficult and in
corrosion and consequent damage to the metal

surfaces of the container as well as the even more 30 most instances impracticable in their application.

serious contamination o. the gasoline or other

The same or similar problems arise in the prepa

ration and use of various coating compositions

such as greases, waxes, household oils, paints,
products.
lacquers, water-soluble paints, etc., which are
As the result of the above-described corrosion
it has become necessary for manufacturers and 35 often applied to metal surfaces for protective or
other purposes.
shippers of such products to apply various inter
It is an object of the present invention to pro
nal coatings to the container walls or to add
vide potent corrosion inhibitors which are soluble
corrosion inhibitors of one type or another to the
in both organic materials and water. A further
product being stored or shipped. It has long been
recognized, however, that one of the great dif? 40 object is to provide inhibitors of this type which
satisfactorily prevent corrosion of certain metal
culties in inhibiting this type of corrosion lies in
surfaces by water. Further objects are to pro
the fact that those inhibitors which are soluble
vide water-corrosion inhibitors which are stable
in organic materials are relatively ineffective in
at ordinary temperatures of use, easily and inex
preventing water corrosion of metal surfaces. On
theother hand, those inhibitors which are eill 45 pensively prepared 'and will not deleteriously
affect organic materials with which they are
cient in preventing this type of corrosion are but
. incorporated. Other objects, together with some
slightly, if at all, soluble in organic materials and
of the advantages to be derived in utilizing the
their, application is thus rendered quite difficult
inhibitors of the present invention, will become
for these purposes.
apparent from the following detailed description
For example, various water-soluble corrosion
thereof.
inhibitors may be utilized for preventing corrosion
It has been found, according to the present in
of gasoline storage tanks by water collecting in
vention, that certain nitrite salts of secondary
the bottom of the tank, a suitable and sufficient
amines are excellent water-corrosion inhibitors
quantity of the desired inhibitor being injected in
the bottom of the tank to inhibit both water al 55 and are soluble both in water and organic mate

material contained therein by the corrosion

amass?
d

rials. The amines preferably used in preparing

the present inhibitors include those secondary

natural gasoline, straight-run gasoline, cracked

gasolines (catalytically or thermally cracked, re

amines which have basic dissociation constants

fo'rmed, iso'merized, etc.) , Diesel fuels, range fuels,

at least approximately as high as the acidic dis-.- '

bunker fuels, lubricating oils, greases, petrolatum,

paramn wax, vegetable waxes, resins, asphalts.
paints, lacquers, enamels, etc.

- sociation constant of nitrous acids; i. e., with

nitrous acid .having a dissociation constant

K.=4x104 at 18 C., the secondary amines used

in preparing the nitrite salt should have dissocia
tion constants at least approximately Kb=4X 10-4

The inhibitors of the present invention may be

prepared, in most instances, by stoichiometric

- reaction of-an organic secondary amine with ni

at 18 C. in order to prepare salts which are stable 10 vtrous acid.

at temperatures of the order of 20 C. or more.
In certain instances the inhibitors may be pre
If the composition containing the inhibitor is to
pared in situ, as for example an oil which in
be exposed to relatively high temperatures, such
hibited water-corrosion of metal surfaces was
as may be encountered in inhibited lubricating
prepared by passing nitrous acid gas through an
oil for engines (160 C. to 180 C. for internal com 15 oil containing secondary amines in solution, thus

bustion engines, 75 C. to 90 C. for turbine oils,

forming water and 'oil-soluble secondary amine

etc), a secondary amine having a dissociation

constant su?iciently high and a suitable molec- '
ular structure to form a nitrite salt stable at these
temperatures must, of course, be selected.

nitrite salts. Other methods which have been

found more generally suitable for preparing
nitrite salts of secondary amines include the fol

'
20
Bases which are not suitable are those which

are very easily oxidized or otherwise destroyed,

either upon use or in contact with nitrous acid.

lowing:

Method I.--The hydrochloride of the organic

secondary amine is contacted with sodium nitrite
in a solution in which the corresponding organic
secondary amine inhibitor salt is insoluble, the

Secondary amines which are speci?cally suited

to yield relatively stable salts of nitrous acid are 25 reaction yielding, by double decomposition, the
members of the following classes: '
inhibitor salt as a precipitate and leaving an inor

Secondary amines of the formula,

Rl\
'

NH

or

Bil-NH

ganic chloride in solution.

Method II.-An acetone solution of'the organic
secondary amine is prepared and dry hydrogen
30 chloride gas passed therethrough. ., A reaction re

sults from which is obtained the corresponding

organic secondary amine hydrochloride, which is
wherein R1 and R: are hydrocarbon radicals
usually relatively insoluble in cold acetone and
which may be aliphatic. alicyclic. heterocyclic, or
precipitates. Silver nitrite, freshly prepared from
aromatic, and may, if desired. contain preferably 35 silver nitrate and sodium nitrite and dried with
not more than one ole?nic double bond: and R1 '
acetone, is then mixed with the secondary amine
and R2 may join to form a ring radical R3.
chloride in the acetone. A second reaction there
Speci?c examples of suitable secondary amines
upon occurs, yielding an acetone solution of the
are listed below:
'
secondary amine nitrite salt and a silver chloride
Secondary amines: methyl n-butylamine, 40 precipitate. Although in this instance both re
methyl isobutylamine, methyl tertiary-butyla- . actants are but slightly soluble in acetone, by
mine, methyl amylamine, amyl hexylamine, N
virtue of the extremely low solubility of the silver
methyl cyclohexylamine, dicyclohexylamine,
chloride in acetone, the reaction usually proceeds
Bi

methyl benzylamine; corresponding ethyl, propyl

to completion at room temperature within a peri

and higher amines: 'dibenzylamine, di- (beta 45 od of approximately one hour. The silver chloride
phenyl ethyl) ,amine; piperidine, piperazine, mor
is ?ltered from the acetone and the acetone ?l
pholine, etc.

In selecting one of the above secondary amines

_ trate evaporated to obtain the desired secondary

amine nitrite, which may be further puri?ed by

for making the corresponding salt, consideration

recrystallization from a suitable solvent.
should be given to the fact that when a salt which 50
Method III.A preferred method for. prepar
is relatively highly soluble in water-immiscible
ing
organic secondary amine nitrite salts for the
organic materials is desired, a secondary amine
purposes
of the present invention comprises slow
having a sufficient number of carbon atoms to
ly adding concentrated sulfuric acid to an ap
impart to the salt the necessary solubility should
be chosen. As a rule, for these purposes it is de 55 proximately 50% by volume aqueous solution of
acetone in the presence of the secondary amine
sirable that the nitrogen base have at least
and an excess of sodium nitrite. After the re
5 carbon atoms. For use with organic materials
action has occurred, the mixture is diluted _to
which are water-miscible to an appreciable ex
about 10 times its original volume with acetone,
tent, secondary amines having less than 5 carbon
atoms may be utilized and in some instances will 60 resulting in a solution of the secondary amine
be found preferable.
'
nitrite salt and a precipitate of insoluble salts
such as sodium sulfate and sodium nitrite. After
The several hydrocarbon radicals may contain
?ltration of the insoluble salts the acetone solu
stable and inert polar substitution radicals,
' tion is evaporated to recover the organic nitrite
though preferably not more than one each. Too
many polar radicals tend in general to reduce the 65 salt, which may be further puri?ed by recrystal
lization from a suitable solvent.
solubilities of the salts in various organic sub
stances, particularly in hydrocarbon oils and the
By using one of the above procedures, the ni
like.

Suitable polar radicals include chlorine,

ether, sul?de, alcohol, amine, etc., radicals.

Nitrous acid salts of secondary amines are suit

trite salt of the secondary amines previously

mentioned can be prepared, provided that at the
70 end of the reaction the solution of organic nitrite

able for use in preventing corrosion of metal sur-'

salt or an aqueous extract thereof has a pH of

faces by water associated in small quantities with

hydrocarbons such as liquid propane. butane, n

at least approximately 7, as the organic nitrite

salts tend to decompose in acidic solution.

pentane, lso-pentane, hexanes, iso-octanes, ben

The compounds listed in Table I below were

acne, toluene, xylenes; various gasolines, e. g., 75 prepared by Method II above.

2,419,327

by weight of the water content of the organic ma

Table I
N0: (-ontcnt, per cent w.
Compound

~----
Calculated
Analysis
I

\iorpholinonltritc.

llibcnzylmuinc nitrite...

, . . . . ..

__._

32th

laxf

20.3

34.4

The compounds listed in Table II below were

prepared by Method III described above.

Table II
NO: Content, per cent \i',
Compound

-*

'

(alculatcd
Tlieyclohcxylamiuc nitrite...
\Iorpholinc nitrite. . ....

Dibcnzylmninv nitrite.

.
.

.__..

. ..__.

20. 2

Hi. 2

3-}. 4

32. 6

__ ..

1&8

4,9

,
24.3!

24.9

3L1 i

30.0

34.8

29.8

tetrahydro-Litoxazincniirifc._......._._......... .......|

Piperiilineuitriic..,.....

_.._..

inalysis

.... ..

2,4.4?-tctran1cthyl

Methylisohutylcarlmminc nitrite

____ __r
. . . . . .,

terial are preferably utilized.

Among other suitable applications for the pres
ent inhibitors the following come into consider
ation. For slushing oils and other rust-preven
tive coatings, nitrous acid salts of secondary
amines will be found effective as corrosion inhibi
tors, for most practical applications, when incor
porated in the coatings in amounts ranging ap
proximately as follows. oil base coatings, 0.05%
to 1.0% by weight; wax base coatings, other than
petroleum wax (petrolatum) base coatings, 0.05%
to 1.0% by weight; petroleum wax base coatings,
0.05% to 5.0% based on the petroleum wax con
15 tent of the particular coating; primer coatings

for paint, 0.02% to 0.3% by weight based on the

dry constituents; lubricant compositions, such as
lubricating oils for internal combustion engines,
turbines and the like, greases, semi-greases, etc.,
20 0.005% to 0.2% by weight; general purpose oils,

such as household oils, 0.05% to 1.0%.

The optimum quantity of the present inhibitors
to be used will, of course, vary with the particular

conditions under which they are used and the

Method III is generally preferred in preparing 25 speci?c inhibitor compound utilized.
In those applications wherein water having
the compounds of the present invention in view
acidic characteristics is encountered, a small
of the superior yields which are usually obtained.
quantity of an alkalizing agent should be added,
For example, in preparing the compounds listed
when secondary amine nitrite salts are used. It
above by this method, yields in excess of 90% by
has been found that these inhibitors are relative
weight were obtained in the case of piperidine ni
ly ineffectual for inhibiting corrosion of metal
trite, while yields in excess of 75% by weight were
surfaces by water having a pH less than 6. This
obtained in preparing methylisobutylcarbamine

nitrite, morpholine nitrite and dibenzylamine ni

trite.
The presently described inhibitors are most ef

fective in preventing water-corrosion of ferrous

is another reason why the composition containing

the inhibitor should be alkaline. The desired pH
may be maintained, when necessary, by adding a
sufficient quantity of a water-soluble alkaline

compound, such as sodium hydroxide, to the wa

ter to increase the pH to at least 6, or by adding
a suf?cient quantity of a suitable nitrogen base,
preventing water corrosion of copper and copper 40 such as 3,3,5-trimethylcyclohexyl amine to the
organic material in which the inhibitor is incor
alloys.
The inhibitors of the present invention may be
porated. Best results are obtained when the pH
incorporated in any substantially neutral or al
of the water is held to a value of at least approx
imately 8, no additional advantage being ob
kaline organic material, whether solid, semi-solid
or liquid, in which they are soluble and with 45 tained above a pH of 12.
which they do not react. Thus, they may be
In all instances the action of the inhibitors de
added to hydrocarbons (which may be paraflinic,
scribed above appears to be the same. Being
ole?nic, naphthenic or aromatic) of the type de
soluble in both water and organic materials, they
scribed; or to chlorinated hydrocarbons, alcohols,
may be easily incorporated in most organic ma
ethers, esters, ketones, nitriles, amino compounds,
terials. When the material to which the inhibi
amides, non-edible fats and fatty oils, paints,
tors have been added is brought into contact
varnishes, natural waxes, oils, etc., which in the
with free water, either by means of externally in
presence of H20 do not render the water acidic.
troduced moisture or by separation of water from
When adding the inhibitors to light hydrocar
the organic material, the water takes up inhibi
bon oils such as gasoline, benzene, kerosene, et'c., 55 tor from the organic material and is rendered
.005% by weight of the nitrite salt will generally
innocuous with regard to the metal surfaces
be found satisfactory for inhibition of water
noted above. Thus, for example, in the speci?c
corrosion. The precise amount of inhibitor to be
instance wherein one of the inhibitors of the
utilized in each instance will, of course, vary with
present invention is added to gasoline which is
the particular conditions at hand and should be 60 to be stored in a tank or similar Vessel, water sep
determined experimentally, particularly when un
arating from the gasoline and either falling to
usually severe corrosion conditions are to be over
the bottom of the tank or adhering to the walls
come. However, in the majority of practical ap
of the tank takes up inhibitor from the gasoline
plications when handling substantially water-in
with which it is in contact and becomes inhibited.
soluble organic materials of this type, the addi 65
The following speci?c example serves to illus
tion of approximately .0001 % to .3% by weight of
trate the effectiveness of the presently disclosed
inhibitor will be found satisfactory.
corrosion inhibitors:
Larger amounts of inhibitor may be required

metals, aluminum, nickel, chromium, and alloys

of these metals. To a lesser extent the secondary

amine nitrite salt inhibitors are also bene?cial in

for inhibiting other organic materials, particu

EXAMPLE

larly those miscible with water, such as alcohols,

ketones, and the like, as for example methyl al

One inch square low carbon steel specimens

were placed in glass receptacles containing 20 cc.
of benzene to which had been added varying
amounts of various secondary amine nitrite in
hibitors. A corrosive consisting of either 0.05 cc.
of an aqueous solution containing 0.05% by

cohol, ethyl alcohol, propyl alcohol, acetone,

methyl ethyl ketone, methyl vinyl ketone, di
oxane, etc. In such instances quantities of in

hibitor amounting to approximately .01% to 5%

2,419,992
weight of sodium chloride or the vsame amount of
water was then sprayed through the benzene in
made after standing under the above conditions

2. A non-corrosive composition of matter com

prising an organic materiaYhavinB 0. DH of at
least approximately 7 and coming in contact with
water during the useful life thereof,'said organic
material having dissolved therein in minor pro

at room temperature for a period of seven days.

portion; but in amount sui?cient to inhibit cor-

The following results were obtained:

rosion of metal surfaces by said water, dicyclo

hexylamine nitrite.

each receptacle and on to the steel specimen.

Visual examination of the steel specimens was
'

Table III

3. Anon-corrosive composition of matter com

10 prising an organic material having a pH of at

Exp.

cone of
inhibitor

in benzene

Corrosive

PM rance of s P cimen

least approximately I, and coming in contact with

met 7 days

water during the useful life thereof, said organic .

material having dissolved therein in minor pro

Per cent by

portion, but in amount sumcient to inhibit cor

weight

15 rosion, of metal surfaces by said water, a nitrite

salt of a propyl'secondary amine, said amine salt

0. 014 Water ......... .. No rust.

0. 0014 .__..do ......... ..
Do.

00014 ._-._do _________ ._ Very lrghtrust spots.

0. 014

being stable at atmospheric temperature, soluble

NaCl in water.. No rust.

0. 0014 .___.do ......... _. Very light rust spots.

0.0013

____.clo ......... ._

orust.

0 00013 ___._do _________ .. Blight staining in spots.

00005 _--..do ......... .. Very light rust spots.

in water and in said organic material.

4. A non-corrosive composition of matter com
20 prising a water-insoluble organic liquid having a

' In the above Table III, in Experiments 1

pH of at least approximately '7, and coming in.

contact with water during the useful life thereof,

through 5, methylisobutylcarbamine nitrite was

said organic! liquid having dissolved therein in

used as the inhibitor; in Experiments 6 and 7

minor proportion, but in amount su?iclent to
piperidine nitrite was used as the inhibitor; and 25 inhibit corrosion of metal surfaces by said water,
in Experiment 8, 2,4,4,6-tetramethyl tetrahydro
a nitrite salt of a secondary amine, said secondary

amine salt being stable at atmospheric temper

1,3-oxazine nitrite was used as the inhibitor.

The stability of various representative second

ature, soluble in water and in said organic liquid.
5. A non-corrosive composition of matter com
ary amine nitrite inhibitors in water at elevated
temperatures is indicated by the following experi 30 prising a liquid hydrocarbon which may come in
ments in which aqueous solutions containing 0.01
contact with water during the useful life thereof,
said hydrocarbon having dissolved therein in
grams of inhibitor in 100 cc. of water were re?uxed
at 100 C. for a period of 6 hours.
minor proportion, but in amount sumcient to
inhibit corrosion of metal surfaces by said water,
Table IV
35 a nitrite salt of a secondary amine, said secondary

amine salt being stable at atmospheric temper

N0; Content, wt. per cent

Inhibitor

Meth lisobut lcarbamine ni-

TheoreticaI

An211ysis

ature, soluble in water and in said hydrocarbon.

Jmiatlym3
a or
Re?uxing

tritg. _____ "3i ............. --

31. 1

30. b

30. 6

Piperidine nitrite ___________ ._

Morpholine nitrite __________ __

34. 8
34. 3

29. 8
32. 6

27. 7
31. 9

dm-1,3-oxazino nitrite ..... ..

24. 3

24. 9

24. 1

Dibenzylamine nitrite ______ ..

l8. 8

19.9

19. 7

2,~i,4,6~tetramethy1 tetrahy

AARON WACHTER.

NATHAN STILIMAN.
RENCES CITED
The following references are of record in the
45 ?le of this patent:

The results in the above Table IV clearly demon

strate that little. if any, decomposition of these
inhibitors takes place in aqueous solutions even 50
at temperatures considerably above those en
countered in most corrosion inhibition problems.
We claim as our invention:
1. A non-corrosive composition of matter com

Number

UNITED STATES PATENTS

Name
Date

2,921,517

2,318,606
2,297,666
2,148,862
2,012,907
2,007,199
2,283,931
2,333,206

Rosen _____________ .._ June 8, 1943

Goebel et a1 _______ __ May 11, 1943

Wachter _________ __ Sept. 29,
Kern ____________ __ Feb. 28,
Flett ____________ __ Aug. 27,
Holt _____________ __ July 9,
Irwin _____________ __ May 26,
Sloan ____________ __ Nov. 2,

1942
1939
1935
1935
1942
1943

prising an organic material having a pH of at 55

least approximately 7 and coming in contact with
2,909,292
Howland et a1 _____ __ Jan, 12, 1943
water during the useful life thereof, said organic
OTHER
REFERENCES
material having dissolved therein in minor pro
portion, but in amount su?lcient to inhibit cor
Lucas, Organic Chemistry, American Book 00.,
rosion of metal surfaces by said water, a nitrite 60 1935, p. 284.
salt of a secondary amine, said secondary amine
Hackhs Chemical Dictionary, 3rd ed., 1944,
salt being stable at atmospheric temperature,
p. 43.
soluble in water and in said organic material.