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Патент USA US3085918

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United States Patent 0
3,085,908
1 ,.
we
Patented Apr. 16, 1963
2
1
differ, markedly from the paints and coatings heretofore
3,085,908
used as corrosion protectants.
AMINOSILICON TREATED METALS AND METH
ODS OF'TREATMENT AND PRODUCTION
Edward L. Morehouse and, Arthur N. Pines, Snyder,
'
Suitable for use in our process are the aminoalkylalk
oxysilanes and the aminalkylpolysiloxanes, including co
polymeric materials which contain both aminoalkylsi
N.Y., assignors to Union Carbide Corporation, a cor
loxane units and hydrocarbylsiloxane units. Each, of these
poration of New York
materials contains the group:
No Drawing. Filed May 26, 1959, Ser. No. 815,794
36 Claims. (Cl. 117-127)
(>N——R—SiE)
This invention relates to a process for treating metal 10
surfaces to improve their resistance to corrosion and to
wherein R is a divalent saturated aliphatic or saturated
high temperature oxidation, and particularly to a process
or unsaturated cyclic hydrocarbon radicalhaving a chain
employing aminoalkyl silicon compounds to provide pro
of at least 3 carbons and wherein nitrogen is attached to
tective coatings for metals. This invention also relates
to articles having metal surfaces coated with aminoalky] 15 at least a third carbon removed from silicon, wherein
each of the free bonds of the‘ nitrogen atom is bonded
silicon materials. It has been found that by treating or
to a member from the class consisting of hydrogen, hydro
coating a metal, as for example copper, with an amino— I
carbyl, cyanoalkyl, aminoalkyl and [—-(CH2),,SiE], and
alkyl silicon compound having the amino group attached
wherein at least one free bond of silicon is attached to
to silicon through at least three carbon atoms, as for
example gamma-aminopropyltriethoxysilane, the coated 20 a group from the class of alkyl and silicon through Si—0
bonds and the remaining free bonds of silicon are at
tached to hydrocarbyl. Hydrocarbyl is intended to mean
a monovalent group composed of carbon and hydrogen.
The use of organic amines, particularly the high molecu- ’
Typical of the aminoalkylalkoxysilanes which may be
lar weight organic amines, as corrosion inhibitors is
employed for our coating are those compounds repre
25
known. In most instances they are dissolved in a suit
sented by the structural formula:
able solvent and are applied by coating or spraying on
metal becomes resistant to corrosion .under a wide'vari
,ety of conditions.
metal surfaces. Among the organic amines employed for
this purpose are hexadecylamine, octadecylamine, N-octa
decylpropylene diamine-1,3, as well as their fatty acid
derivatives. It is, also known that certain paints have
been suggested for this purpose. However, the use of
organic amines, paints, and the like as corrosion inhib
itors for metals has left much to be desired. By way of
illustration, while the above compounds furnish some
wherein R" represents an alkyl group such as methyl,
ethyl, propyl, and butyl, and the “like, or an aryl group
such as phenyl, naphthyl and tolyl and the like, X repre
35.
degree of protection against corrosion to certain few
sents an alkoxy group such as methoxy, ethoxy, and
metals under atmospheric conditions, they have been in
propoxy groups and the like, R is a divalent radical as
etfective as corrosion inhibitors at elevated temperatures
described above, and preferably having a carbon chain of
for any metal. For example, the ferrous metals when
from 3 to 4 carbons, (b) is an integer having a value
coated with these compounds, such as N-octadecylpro
of from 0 to 2 and preferably a value of from 0 to 1, (d)
pylene diamine-l,3, are resistant to corrosion under at 40 is'an integer having a value of from 1 to 2, and the sum
mospheric conditions. However, when the coated metals
of (d+b) is not greater than 3. Illustrative of such
are subjected to even brief contact at elevated tempera
aminoalkylalkoxysilanes are gamma-aminopropyltrieth—
tures, the corrosion inhibiting properties of the organic
amine are lost. These organic amines are thermally un
stable at elevated temperatures and decompose. Also, it
oxysilane, gamma-aminopropyltripropoxysilane, gamma
45
is to be emphasized that these amines are not etfective
with other metals, as for example copper and its alloys,
. since these amines promote corrosion thereof.
-
aminopropylmethyldiethoxysilane, gamma-aminopropyl
ethyldiethoxysilane, gamma-aminopropylphenyldiethoxy
silane, delta-aminobutyltriethoxysilane, delta-aminobutyl~
methyldiethoxysilane,
ane,
delta - aminobutylethyldiethoxysil
delta- aminobutylphenyldiethoxysilane,
gamma~
Accordingly, it is an object of this invention to pro
50 aminobutyltriethoxysilane, gamma - amino'butylmethyldi
vide a process for improving the corrosion resistant prop
‘ ethoxysilane, and the like. The aminoalkylalkoxysilanes
erties of metals, particularly those metals which are ‘
readily oxidized, such as copper, and which as far as it
in copending US. applications Serial Nos. 483,421 and '
is known are not effectively protected by known organic
615,466, ?led January 21, 1955, now Pat. No. 2,832,754,
are disclosed and claimed as new compositions of matter
and October 12, 1956, now Pat. No. 2,930,809, respec
We have found that metals having a coating of an 55 tively. Processes for producing these compounds are also
corrosion inhibitors.
'
aminoalkyl silicon compound having the amino group
disclosed and claimed in said copending applications.
attached to silicon through at least three carbon atoms,
Typical of the aminoalkylpolysiloxanes which may be
applied either as a monomer or polymer, have improved
used for our coating are those polysiloxanes which con
resistance to corrosion. For example, we have found
tain the structural unit:
that most metals (including copper) can be made re
sistant to oxidation at ambient temperature and at tem
peratures thereabove and therebelow by coating such
metals with such an aminoalkyl silicon compound. In
addition we have found that sucheoated metals are re
sistant to corrosion caused by contact with vapors or 65
liquids which are either acidic, neutral, or basic in nature. '
These coatings are normally transparent and do not
have an adverse effect on the appearance of the metal.
They leave no oily residual ?lm. ‘In these ways they
wherein R, R'?, and (b) have the same values described
above. Such polysiloxanes are prepared by the hydroly
sis and condensation of those aminoalkylalkoxysilanes
>
3,085,908
3
.
4
meric chains. Thus we can also employ as our starting
described above or by the cohydrolysis and cocondensa
tion of such aminoalkylalkoxysilanes with other hydro
lyzable silanes and can include aminoalkylpolysiloxanes
aminoalkyl silicon compound such linear end-blocked
aminoalkylpoly-siloxanes as monoethoxy end-blocked
gamma-aminopropylethylpolysiloxane or methyldiethoxy
of the trifunctional variety (i.e. where b=0), amino
silyl end-blocked delta-aminobutylrnethylpolysiloxane or
alkylalkylpolysiloxanes and .aminoalkylarylpolysiloxanes
of the difunctional variety which include cyclic or linear
monoethoxydimethylsilyl end-blocked gamma-aminopro
polysiloxanes (i.e. where b=1) and linear aminoalkyl
dialkyldisiloxanes, aminoalkyldiaryldisiloxanes and ami
noalkylalkylaryldisiloxanes of the monofunctional' variety
linear aminoalkylalkylpolysiloxanes and aminoalkylaryl
produced by the cohydrolysis cf difunct-ional, trifunctional
and monofunctional aminoalkylsilanes.
alkoxy groups, or by the cohydrolysis and condensation
pylphenylpo'lysiloxane and the like.
The end-blocked
polysiloxanes useful in our process can be prepared by
(i.e. Where b=2) as well as the mixture of compounds 10 the equilibration of cyclic aminoalkylsiloxanes with silicon
compounds containing predominantly silicon-bonded
of trialkylalkoxysilanes with aminoalkylalkyldiethoxy
silanes or aminoalkylaryldiethoxysilanes. Hydroxyl end
Suitable aminoalkylpolysiloxanes of the trifunctional
variety can be more speci?cally depicted as containing the
15
blocked linear polysiloxanes can also be prepared by
heating linear or cyclic aminoalkylpolysiloxanes with
water.
Typical copolymeric’ aminoalkylpolysiloxanes which
can be employed in our process can be depicted as con
20 taining the structural unit:
wherein R has a value previously described, Z represents
an hydroxyl and/or alkoxy group, and (c) has an average
1
BL
.
' value of from 0 to 1 and can be as high as 2 but prefer
L
rrm-n-sioH)
ably from 0.1 to 1. Aminoalkylpolysiloxanes of this 25
variety which are essentially free of silicon-bonded alkoxy
or hydroxyl groups (i.e. where c=0) can be prepared by
2
the complete hydrolysis and complete condensation of
wherein R, R", and (b) have the values described
aminoalkyltrialkoxysilanes, whereas aminoalkylpolysilox
above-the group R" need not be the same in the si
anes in which Z represents predominantly,silicon-bonded 30 loxane unit and/ or in the siloxane molecule-and at least
alkoxy groups can be prepared by the partial hydrolysis
one other siloxane unit, which unit can be a different
and complete condensation of the same star-ting silane.
On the other hand, aminoalkylpolysiloxanes in which Z
species of ‘the above unit or it- may be a unit represented
structurally as follows:
represents predominantly silicon-bonded hydroxyl groups
can be prepared by the essentially complete hydrolysis 35
and partial condensation of the same aminoalkyltrialk
oxysilanes. By way of illustration, a gamma-aminopro
pylpolysiloxane containing silicon-bonded ethoxy groups
can be prepared by hydrolyzing gamma-aminopropyltri
ethoxysilane with an amount of water insufficient to re
2
40
act with all of the silicon-bonded, ethoxy groups present
on the starting silane and subsequently condensing the
hydrolyzate so formed to produce the desired polymer.
wherein R'” represents an alkyl group, such as methyl,
ethyl, propyl, and butyl, and the like, or an aryl group
such as phenyl, naphthyl, and tolyl, and the like, or an
Suitable aminoalkylpolysiloxanes of the difunctional
variety which include cyclic and linear polysiloxanes can 45 ole?nic group, such as vinyl and cyclohexenyl and the
like, and (e) is an integer having a value of from 0 to 2.
be more speci?cally depicted by the structural formula:
Likewise R’” need not be the same in the siloxane unit
and/or in the siloxane molecule. . The copolymeric ma
terial described herein include copolymers having two or
50 more di?erent units. The copolymers suitable for use ,,
in our process can contain various combined siloxane
units such as trifunctional aminoalkylsiloxane units
wherein R, and R" have the values previously described
(where b=0) with trifuncticnal alkyl-, aryl-, ole?nic- or
mixed alkyl-, ole?nic- and arylsiloxane units (where
and (f) is an integer having a value of at least 3 and
can be as high as 7 for the cyclic aminoalkylpolysiloxanes
e=0) or with difunctional alkyl-, aryl-, ole?nie, or mixed
and higher for the linear arninoalkylpolysiloxanes. Such
alkyl, ole?nic- and arylsiloxane units (where e=1).
cyclic and linear aminoalkylpolysiloxanes can be pre
There copolymers can also contain various combined si
pared by the hydrolysis and condensation of aminoalkyl
alkyldialkoxysilanes or aminoalkylaryldialkoxysilanes.
loxane units, difunctional aminoalkylsiloxane units (where
b=l) with trifunctional alkyl-, aryl-, ole?nic- or mixed
In carrying out the hydrolysis and condensation proce
alkyl-,
ole?nic- and arylsiloxane units (where Ve=0) or
60
dures there is produced a product comprising a mixture
with difunctional alkyl-, aryl-, ole?nic-, and arylsiloxane
of cyclic and linear polysiloxanes from which the desired
units (where e=l).
polysiloxane can be recovered. Illustrative of the cyclic
Those copolymers which contain trifunctional amino’
aminoalkylsiloxanes suitable for use in our coating process
alkylsiloxane units and other siloxane units are preferably
are the cyclic tetramer of gamma-arninopropylmethyl
siloxane, the cyclic tetramer of delta-aminobutylphenyl
siloxane and the like. Illustrative of linear aminoalkyl
polysil-oxanes suitable for use in our coating process are
gamrna-aminopropylmethylpolysiloxane, gamma - amino
propylethylpolysiloxane, delta - amin-obutylmethylpolysi
loxane, gamma-aminobutylmethylsiloxane, and the like.
Included among the linear aminoalkylpolysi'loxanes
which may be ‘employed in our process are the alkyl,
alkoxy and hydroxyl end-blocked polysiloxanes which‘
contain from i to 3 of such groups bonded to the ter
minal silicon atoms of the molecules comprising the poly
prepared by the cohydrolysis and cO-condensation of the
corresponding alkoxysilane starting materials. Such co
polymers can contain silicon-bonded alkoxy and/or hy
droxyl groups or they can comprise essentially completely
condensed materials. The linear and cyclic copolymeric
70 siloxanes can be prepared by the method just described
65
or by the separate hydrolysis and condensation of an ami
noalkylalkyldialkoxysilane or aminoalkylaryldialkoxysil
ane and the dialkyldialkoxysilane, diole?nicdialkoxysih
ane, alkylaryldialkoxysilane, mono-alkyl-mono-ole?nic
dialkoxysilane, mono-arylmono-ole?nic-dialkoxysilane, or
3,085,908
6
drolysis ‘and condensation thereof either alone or with
diaryldialkoxysilane to cyclic aminoalkylsiloxanes and
other hydrolyzable silanes.
N-cyanoalkyl-aminoalkyl silicon compounds are pre
pared by the reaction of an aminoalkyl silicon compound
cyclic dialkylsiloxanes, alkylarylsiloxanes, diole?nicsilox
anes, mono - alkyl-mono - ole?nicsiloxanes, mono-ary-l
mono-ole?nicsiloxanes or diarylsiloxanes and subsequent
ly equilibrating mixtures of such cyclic siloxanes to linear
copolymers. Such linear copolymers can also contain
chain-terminating or end-blocking groups such as alkyl,
alkoxy or hydroxyl groups.
with an unsaturated nitrile in the presence of a catalyst.
The metals whose resistance to corrosion can lbe im
proved by treating with the above listed aminoalkyl sili
con compounds are those metals in the electromotive
series which lay below and include magnesium. Alloys
While the primary aminoalkyl silicon compounds have
of these metals similarly have their corrosion resistance
been described in detail and are preferred in the treat 10 improved by this treatment. The metals and alloys tested
ment of metals to form a protective coating thereon, the
include aluminum, brass, bronze, copper, chromium, iron,
corresponding secondary and tertiary aminoalkyl silicon
compounds, i.e., those in which one or both of the hydro
gen atoms bonded to nitrogen of the generically and speci
?cally depicted primary aminoalkyl silicon compounds is
magnesium, nickel, lead, silver, silverplate, sterling silver,
ternplate (tin plate), tin, beryllium bronze and zinc. ‘Ex
15 cellent corrosion protection was provided by the coatings
for all metals. In the instance of nickel, the metal nor
mally has such outstanding protection to the types of cor
rosion studied in our tests that'appreciable improvements
replaced by a hydrocarbon, cyanoalkyl or aminoalkyl
group, can be employed, as hereinbefore disclosed, with
good results.
.
Secondary and/or tertiary aminoalkyl silicon com
pounds _containing the unit:
were not detected in our tests.
20
By the present invention, the corrosion resistance of
such metals is improved by applying a continuous, thin
?lm of the aminosilicon compound over the surface of
,the metal and curing the ?lm to form a bonded coating
on the surface of the metal.
in which the nitrogen atom thereof is bonded to an amino
alkyl or cyanoalkyl group are known as N-aminoalkyl—
aminoalkyl and N-cyanoalkyl-aminoalkyl silicon com
pounds and can be employed in their monomeric form as,
The method by which an
25 aminoalkyl silicon compound is applied to a metal is not
critical and any method can be employed that results in
the deposition of a continuous ?lm; coatings may be ap
plied employing solvent solution, dispersion in liquid sys
tems, or by using undiluted aminoalkyl silicon materials.
for example, a substituted alkoxysilane,'or in their poly
Coatings have also been made by spray application from
30
meric form as well as in the form of a copolymer con
aerosol bombs. The preferred method is applying coat
taining hydrocarbon-substituted siloxane units. As is ob-'
ing from aqueous solutions, where there is solubility, and
vious, such N-aminoalkyl- and N-cyanoalkyl-substituted
from
organic solvent solutions such as alcohol and ether
aminoalkyl silicon compounds when in their polymeric
solvent systems. For example, solvents which can be
or copolymeric form comprise, for example, oils or resins
35 used include methanol, ethanol, propanol, isopropanol,
of the type described above.
butanol, 2-ethyl-hexanol, monornethylether of ethylene
The aminoalkyl substituents, which are bonded to the
glycol,
methylene chloride, trichlorethylene, mixed sol
nitrogen atom of aminoalkyl‘ silicon compounds to form
vent systems such as toluene-monomethylether of ethyl
products useful in the present invention, contain ‘at least
ene glycol, alcohols and ethers, such as diisopropylether
one nitrogen atom which is either primary, secondary or
and alcohols and freon-type propellants such as perchloro
40
tertiary, and include such groups as beta-aminoethyl,
per?uoromethanes and ethanes.
gamma-aminopropyl, gamma-aminoisobutyl, omega-ami
The systems used for coating can contain varying
nohexyl, N-gamma-aminopropyl-gamma-aminopropyl and
amounts of the aminoalkyl silicon compound. The
the like. Typical of such N-aminoalkyl-aminoalkylsili
amount of the aminoalkyl silicon compound present in a
con compounds are:
45 system is not critical and can vary over a wide range. We
N-gamma-arninopropyl-gamma-aminopropylmethyldi
ethoxysilane,
N-beta-aminoethyl-gamma-aminopropyltrimethoxysilane,
N-beta-aminoethyl-gamma-aminoisobutyltriethoxysilane,
N-gamma-aminopropyl-delta-aminobutylmethyldieth
oxysilane
and the like as well as the polymers prepared by the hy
drolysis and condensation thereof either alone or with
other hydrolyzable silanes.
N-aminoalkyl-arninoalkyl silicon compounds are pre
pared by the reaction of diamines such as ethylene or
propylene diamine with chloroalkyl silicon compounds.
The cyanoalkyl substituents which are bonded to the
nitrogen atom of aminoalkyl silicon compounds to form
products useful in the present invention contain at least
one cyano grouping and include such groups as beta
cyano-ethyl, gamma-cyanopropyl, delta-cyanobutyl and
the like. Typical of such N-cyanoalkyl-aminoalkyl sili
con compounds are:
-
N-beta-cyanoethyl-gamma-arninopropyltriethoxysilane,
N - gamma-cyanopropyl-gamma-aminosiobutylmethyldi
ethoxysilane,
N-delta-cyanob utyl-delta-aminobutyltriethoxysilane
have employed with good results systems containing from
0.05 percent up to 10 percent by weight. We can employ
systems containing greater amounts‘ of the aminoalkyl
silicon compound. The concentration employed is largely
a matter of cost and convenience‘.
After dipping or spraying of the aminoalkyl silicon
compound on the metal, the coating is cured by heating
to temperatures of from about 125° to 600° F. and above
or simply ‘by allowing the coated metal to stand at am
55 bient temperature. With certain metals, as for example,
copper, it is preferable that the coating be cured by the
use of elevated temperatures. By curing of the coating,
as used herein, is meant the ?xing or bonding of the coat
ing to the surface treated. It appears that a chemical
60 bond or bonds are established by a reaction between the
aminoalkyl silicon compound and the metal surface. Al
though we do not wish to be bound by any one theory, it
appears that the bond is constituted either by complexing
or chelating through the amine with the metal surface or
65 by bonding to the metal through the carbonfunctional
side chain attached directly to the silicon together with a
bonding through Si—O-— metal linkages.
The thickness of the ?lm applied is not narrowly criti- cal and may vary from very small thicknesses to rela
70 tively large ones such as those in excess of one inch. Film
thicknesses ranging from 0.01 to 0.10 mil are preferred
although from an economic point of view, small ?lm
thickness, as small as 0.005 mil, can be employed. The
and the like, as well as the polymers prepared by the hy 75 thickness of the coating may be regulated by the aPPlica
3,085,908
tion was obtained. This resin solution was diluted with
tion; i.e. the concentration of the solvent solution and the
number of applications can be varied to regulate thick
ness. Even relatively thick ?lms can be obtained by mul
anhydrous alcohol to give the silicone treating solution
consisting of 1 part resin solution to 5 parts by weight
tiple application from dilute solutions. Being able to
provide such surface protection to metals by the use of
anhydrous alcohol.
extremely thin ?lm is an important aspect of this inven
tion and a distinct advance in the art of protective coat
ings for metals.
The improved properties of our coated materials were
found by the following tests. In all tests coated metal
strips were used as experimental specimens. These strips
-
A copper strip 11/2 x 6 inches) was prepared for coat
ing by scouring with an alkaline cleanser. It was then
?ushed with water and dried. A portion of this metal
strip was then immersed in the silicone treating solution,
removed, and allowed to drain and air dry. This strip was
10 then hung in the 250° C. air circulating oven for 4 hours.
After this time it was removed. Where the strip had been
with water, and dried. Aminoalkyl silicon compounds
aminoalkyl silicone treated, the surface was bright and
had its original luster. Where the copper strip had not
were applied from alcoholic solution and cured. In gen
been treated, it was dark and oxidized.
were cleaned by scouring with an alkaline cleanser, ?ushed
eral coating thickness for the following tests ranged from 15
0.03 to 0.05 mil.
(1) Resistance to oxidation at ambient temperatures.-—
Both coated and uncoated metal strips were exposed to
laboratory and outside industrial atmosphere. Periodic
EXAMPLE II
Aminoalkyl Silicone Compounds as Coatings for Metals
to Provide Protection From Oxidation at Ambient
Temperatures
comparative observation of the treated and untreated 20
Four 11/2 x 6 inch steel panels were thoroughly scoured
strips were made and the degree of rusting, pitting, and/or
with alkaline cleaner, washed, then dried. Two panels
discolorationwas recorded. In addition, similar observa
were then partially dipped in a 5 percent gamma-amino
tions were made on the following aminoalkyl silicon
propylsilicone in ethanol. The other two panels were
treated metal surfaces: copper plated carbon electrodes,
silver tableware, chromium bumpers for cars, ?rearms, 25 partially dipped in a 5 percent copolymer of delta-amino
and bronze railings. In these instances it was not con
venient to heat cure at elevated temperatures the amino
butyl-methyl- and phenylsilicone in ethanol. One panel
coated with the silicone polymer and one coated silicone
copolymer were treated 5 minutes at 150° C. in an air
circulating oven. There was no visible change in panel
and vbrass strips were placed in the 250-275° C. air cir 30 appearance. The remaining panels were treated one-half
hour at 250° C. in an air circulating oven. Under these
culating oven. The effectiveness of the aminoalkyl sili
250° C. conditions, the treated areas had yellowed some
con treatment was evaluated by visual observation of the
alkyl silicon compound to the metal surface.
(2) Resistance to high temperature 0xia‘ation.—Copper
resistance of the metal surface to darkening by oxidation.
what. All four panels were then exposed to overnight
In addition, aminoalkyl silicon treated copper-clad cook
industrial atmosphere. Since it was fall, there was a rea
at 500° F. without discoloration, and (b) in normal use
areas on the panels were'heavily coated with a ?lm of red
iron oxide rust. The aminoalkyl silicone-treated areas
had not signi?cantly changed in appearance. There was
ing utensils and copper ash trays have been: (a) cured 35 sonable amount of dew. In the morning all untreated
without showing signs of darkening due to cooking heat
or extinguishing of cigarettes.
(3) Resistance to vapor and liquid phase attack under
essentially 100 percent protection to atmospheric cor
alkaline, neutral, and acid conditions-Metal specimens 40 rosion.
EXAMPLE III
were placed in glass beakers containing the ‘below listed
chemical solutions. These beaker tests which were per
Four steel panels were prepared exactly as in Example
formed on a laboratory bench gave accelerated corrosion
II for the following tests. Two panels were partially
conditions. Resistance to corrosion was evaluated by: 45 clipped in 5 percent monooleate salt of Duomeen T 1 in
(1) visual observation of metal darkening or pitting by
ethanol. Two panels were partially dipped in 5 percent
comparison to an untreated specimen, and (2) in item at,
dioleate salt of Duomeen T in ethanol. These treatments
weight losses due to copper dissolving in ammonia water
gave the panels a greasy ?lm. One panel each of the
were made and the degree of protection afforded by the
mono- -and dioleate salts were then heated for 5 minutes
aminoalkyl silicon compound was calculated.
50 at 150° C. ‘This heat treatment somewhat darkened the
coated panel area.
(a) Corrosive water (see Table III)
(b) Alkaline sul?de water
(0) Acid sul?de water '
(d)
(e)
(I)
(g)
Ammonia water
Salt water
Salt spray chamber
Aerated water
The remaining panels were heated one-half hour at 250°
C. in an air circulating oven. This heat treatment mark
‘edly darkened the panels. All four panels were then ex
55 posed to overnight industrial atmosphere. Since itwas
fall, there was a reasonable amount of dew. When ex
amined, only the 150° C. panel partially coated with the
monooleate salt of Duomeen T showed a small amount of
protection against corrosion. All other panels were badly
60 corroded and offered essentially no protection to cor
rosion.
Examples II and III show commercially available or
The following examples are illustrative of this inven
ganic corrosion preventatives are essentially completely
tion:
ineffective as corrosion preventatives for metals by com
65 parison with the aminoalkyl silicone compounds of this
EXAMPLE I
invention under the same test conditions.
Resistance to Oxidation
Table I below summarizes several other tests showing
Gamma-aminopropylsilicone was prepared by charging
220 gm. gamma-aminopropyltriethoxysilane and 130 gm. 70 .lDuomeen T monpoleate and dioleate salts are commer
cially‘available anti-corrosion agents. Duomeen. '1‘ has the
anhydrous ethanol into a 1000 ml. ?ask equipped with
following formula :
stirrer, reflux condenser, thermometer, and separatory
funnel. In a period of 15-20 minutes, 50 grams water
where R is an allcyl group derived from the fatty acids in
tullow. F. would have carbon chains predominantly 16 and
was added withstirring. The contents were heated to
18 units long. The olente and dioleate soaps are the
re?ux for one-half hour. One pint of water-White solu 75 equivalently neutralized soaps of the Duomeen T base.
3,085,908
9
protection from atmospheric corrosion as aiiorded by
the aminoalkyl silicone coatings of this invention. In
all instances uncoated metal surfaces were simultaneously
gamma-aminopropyltriethoxysilane.
used as control to observe e?’ect. In all instances there
was superior resistance to corrosion a?orded by the 5
aminoalkyl silicone coating.
10
dizing nature of copper and the effective protection against
oxidation at high temperature a?orded by a coating of
'
EXAMPLE VI
A 5 percent solution of metaphenylenediamine and a
TABLE I.-—AMINOALKYL SILICONE COMPOUNDS AS COATINGS FOR METALS TO PROVIDE PROTECTION FROM
ATMOSPHERIC CORROSION
>
‘
Metal surface
_ to which silicone
Silicone compound used as metal coating 1
Corrosive atmosphere
coating is applied
(1) Gamma-aminopmpyl iliomm
Clean alumininum panel ______ __ Industrial atmosphere.
(2) Gamma-aminopropyltriethoxysilane ______________________________ --
(3) Gamma-aminopropyl ilir'one
(4) Gamma-aminopropyl ilimno
Clean copper strips ____________ -_
Do.
__---d?
>
,
Do.
_ Copper-plated carbon electrode _ Laboratory atmosphere.
(5) Oleate salt of 10 percent gamma-aminopropylmethyl modi?ed di-
Chromium-plated bumpers“..- Winter streets, ice, snow, rain, salt.
methyl copolymer oil (MW 10,000).
_
(6) Delta-aminobutylmethyl
llimne
‘Cleaned steel panels. ___________ __ Industrial
atmosphere.
(7) 1:1 Copolymer of delta-aminobutylmethylsilicone and phenylslli- .-_--do _____________ __
Do.
cone.
(8)
_
l
-
1:1 Copolymer oi delta-aminobutylmethylsilicone and dimethylsili-
_____do _ _ _ _ . _ _ _ _ _
00118.
(9) Same
composition as in Example 7 and slabove ___________________ -_ Shotgun barreL
(10) Gemma-aminopropyl “WW
Bronze railingi.
_ _ _ _ __
Do.
____ __ Rain and Snow in a duck blimp
Lobby of research laboratory.
11) 1:1 Copolymer of gamma-amlnopropylsillcone and phenylsilicon ___ Silver teaspoon__.._
_ Domestic usage.
12) I'I’N(CHi)3slO3/2]0.5(¢siO3/2)0.4 (Me2s1o)0.1 ........................ ._ Cleaned steel panels ___________ __ Industrial atmosphere.
(13) HzN (CH2)sSiOa/:lo.s(¢$i0m)o.s(MerSlO)o.:. -
--__rio
(14) HIN(CH2)3Slo3/2]0.5(¢SIO3I2)0.3(C5H115103.!)0.‘
(15) HsN(CH?aSiOa/slot(¢SlO3/2)o.s(CsHsSiOa/2)03-
-__--,d?
-____?n
(16) HzN(CH2)sSiOmlo.s(¢S{0s/2)o.2(MezSi0)o \
(17) HzN(cHshsiowlo.:(¢S10a/2)o.r(MeiSiO)cs-__
----_fl"
. .....do
(18) Multipolymers:
-
D0,
Do.
D0_
Do.
Do,
[HzN(CHz)sSlO3/z]
[MGSiOs/x]
[MesSiO]
[qbSiOs/z]
[dnSl-O]
Mole-percent
Mole
Y Mole
Mole
Mole
percent
percent
0. 46
0. 08
0. 25
0.32
0. 18
0. 10
0. l2
0. 31
0. 37
percent percent
_
0. 18
0.03
I)(,_
0. 24
0. 29
0. 03
0. 04
D0_
DO_
5 were applied from 5-10 percent solution in alcohol by either dipping or brushing. No. 5 was applied by wiping
1 Silicones in all examples except N0.
Examples 1, 6, 7, 8, and 11 were given a 10-15 minute bake at 150° C. before exposure to corrosive
100% silicone on chromium bumper. Coatings in
atmosphere. Other coatings received no heat treatment.
areas on treated specimens, which served as controls, corroded badly. Substantially
Nora-In all instances the uncoated specimens or uncoated
no corrosion was observed on the treated metals.
'
EXAMPLE IV
Aminoalkyl Silicone Compounds as Coatings for Metals
to Inhibit...High Temperature Oxidation
A copper panel was scoured with an alkaline cleanser,
5 percent solution of parahydroxydiphenylamine was pre
pared by dissolving the organic amine in ethanol. Cop
per strips of equivalent size and cleanliness as described
in Examples IV and V were immersed in these organic
amine solutions. The panels were removed from the
solutions and allowed to drain. These two panels were
rinsed with water, and placed in a 250° C. air circulating _
oven for 1 hour. After this period it was removed. Ex: 50 placed. in a 150° C. oven for a 5 minute cure.
These
copper panels were then placed in a 250° C. air circulat
ing oven for 1 hour. After this period they were re
moved; visual examination revealed the panels had com
pletely darkened. There was no bright, shiny metal in
evidence. These two panels were replaced in the 250°
C. oven for anadditional 68 hours. When removed from
the oven, they were completely coated with a black cop
per oxide that could be flaked off the surface.
This example illustrates the ineffectiveness of coatings _
A similarly sized and cleaned piece of copper as described
in Example IV was immersed in the alcohol solution. 60 of organic amines on copper for protection from air oxi
dation at 250° C.
The panel was removed from the solution and allowed
EXAMPLE VII
to drain dry. It was then placed in a 150° C. oven for
a 5 minute cure. Thereafter it was placed in a 250° C.
A 5 percent toluene solution of 100 cstk. dimethyl
air circulating oven for one hour. After this period it
silicone was prepared. This solution was applied on a
was removed. Examination revealed it had not dark 65 clean copper panel by brushing and was allowed to air
ened. No perceptible oxidation occurred. The copper
dry. It was placed in the 150° C. ovenfor 5 minutes.
was bright and shiny. The sample was returned to the
It was then placed in the 250° C. oven for 3 hours. When
aminationrevealed it had completely darkened; there was
no bright, shiny copper surface present. The entire metal
surface had oxidized under these conditions.
EXAMPLE V
A 5 percent by weight solution of gamma-aminopropyl- .
triethoxysilane was prepared by adding 5 grams of the
aminoalkyl silicon compound to 95 grams of ethanol.
250” C. oven for an additional 3 hours. It was again
examined and there was no evidence to indicate oxida
the panel was removed, the. copper panel had turned
dark. Similarly, the conventional silicone resins having
tion of the copper had occurred. This coated copper 70 an R to Si ratio of about 1.55 and consisting of phenyl
panel was heated at 250° C. in the air circulating oven
and methyl groups attached to silicon and used as insulat
for one week. Again when it was removed, no black
ing and protective coatings were without effect on the
oxide was observed. The bright, shiny copper surface
prevention of air oxidation of copper at 250° C. I I
was essentially unchanged.
Examples IV and V demonstrate respectively the oxi 75 It is thus demonstrated that not only are organic amines
3,085,908
11
creases, and the results obtained are listed:
VI) but also that conventional silicones are also ineffec
tive to protect metals from’ air oxidation at high temper
atures.
12
The thinner coatings were calculated from weight in
ineffective as protective coatings. for metals (Example
Thickness of coating
.
(rrnils)
Table II below lists the aminoalkyl silicon monomers,
polymers, and copolymers that were tested on bright cop
Silicone in solution (weight percent) :
per metal at 250—275° C. in a manner similar to the tests
described in Example V. The results indicated all amino
alkyl silicone compounds having an amino group attached
to silicon through at least three carbons a?orded protec 0
tion from 250° C. air oxidation. Superior results were
obtained using gamma~aminopropyltriethoxysilane and
5
2
0.04
0.014
0.5
_ 0.0035
0.1
___
0.05
Nil
0.0018
0.0012
delta-aminobutyltriethoxysilane and their polymers. Sub
stantial improvements with respect to no treatment or
All of these copper specimens when placed in a 275°
C. air circulating oven for one-half hour showed im~
provement over the untreated sample. As the coating.
organic amine treatment, were obtained using the other
aminoalkyl silicone compositions. In addition, gamma
aminopropylsilicone, when applied to a copper panel, one
part of which was left untreated, provided a protective
thickness decreased below 0.003 mil, protection against
‘these severe oxidation conditions was impaired.
coating to the treated portion of the panel when exposed
In no
instance, however, did any specimen turn the dark color
to 1200" F. for a period of ten minutes in a mu?le fur 20 of the strongly oxidized, uncoated metal. It is thus seen
nace. The untreated portion was rapidly and completely
that even very thin coatings are effective in inhibiting
oxidized.
oxidation on an otherwise highly oxidizable metal such
as copper.
25
A brass panel 1 x 5 inches Was scoured with alkaline
cleanser and washed to give a clean surface. A portion
TABLE II.—AMINOALKYL SILICONE COMPOUNDS AS
COATINGS FOR THE PROTECTION OF COPPER METAL
FROM 250° C. AIR OXIDATION
Silicone compound used as coating on copper metal:
v30
_
(1) NH1(CHz)aSi(OEt)a——Gamma-aminopropyltnethoxysilane
(2) NH¢(CH2)4Si(0Et)3——Delta amincbutyltriethoxysilane
(3) ¢-N(CHa)(CH¢)4Si(OEt);-—N phenyl N methyl delta-amino’
butyltriethoxysilane
(4)
EXAMPLE IX
of this panel was immersed in 10 percent delta-amino
butyltriethoxysilane in ethanol. The panel was removed
and allowed to air dry. The panel was then placed in a
275° C. air circulating oven for 136 hours. When re
moved from the oven, the untreated area of the panel had
become a deep yellow color. The coated area of the
35 panel retained its original brass tone.
CH3
CH=C\N(CHz)aSi(OEt);—N-gamma-aminopropyltrieth
EXAMPLE X
oxysilyl 2,5 dimethyl pyrrole
Clean brass panels cleaned as described in Example IX
CH=C
were respectively partially dipped in 10 percent solution
\
.
CH3
40 of delta-aminobutylmethyldiethoxysilane in ethanol and
5 percent alcohol solutions of delta-aminobutylmethyl
(5) HN[(CHz)aSi(OEl2)3]z—BiS (gemma-triethoxysilylpropyDamine
(6) Polymer of deltn-aminobutylmethylsihcone
'
silicone
and cdelta-aminobutyl-silicone. Each of these
(7) Polymer of No. 1-Gamma-aminopropylsilicone
panels was treated exactly as that described in Example
(8) Polymer of No. 2——Delta-aminobutylsihcone
(9) Polymer of No. 3-N phenyl N methyl delta-aminobutylsilicone
IX. When these panels were removed from the 275° C.
(l0) Polymer of No. 4—Gamma-(2,5-dimethyl pyrryl) propylsilicone
45 oven, the untreated ‘brass area had signi?cantly darkened
(ll) Copolymer of delta-aminobutylsilicone and phenylsihcone
(12) Copolymer of delta-aminobutylmethylsilioone and phenylsili
in color, and the aminoalkyl silicone coated areas still
cone
(l3) Oopolymer of gamma-aminopropylsilicone and vinylsiliconei
retained their original lbr-a-ss appearance.
Examples IX and X clearly demonstrate that amino
1 The copolymer of gamma-aminopropylsilioone and vinylsilicone was
prepared by charging to a 1 liter 3-neck round-bottom ?ask. equipped 50
with re?ux condenser, agitator, thermometer, and dropping funnel:
'95 grams vinyltriethoxysilane
110 grams gamme-arninopropyltriethoxysllene
1‘
The mixture was slurried and over a period of 20 minutes, 50 grams 0 55
water were added. The solution was then heated to re?ux at 80° C.
and maintained at this temperature for 45 minutes.
The following lists the properties for the product:
Theoretical
Percent solids _________ __
24. 6
Percent silicon
Percent NHz_---Bromine numben
7. 3
2. 8
_-
20. 6
oxidation of brass.
In the following two examples corrosive water con
taining 100 ppm. each of chloride, sulfate, and bicar
130 grams anhydrous ethanol
Analysis
alkyl silicone compounds prevent the high temperature
Found
25. 3
7. 5
1.98
20. 0
bonate ions, all present as sodium salts, was used. This
solution is particularly corrosive media for steel and
other metals.
EXAMPLE x1
A 1% x 6 inch SAE 1020 steel panel was scoured free
60 of all grease with an alkaline cleanser. -It was then
partially immersed in a 200 cc. beaker containing corrosive
water. In 20 hours this uncoated steel panel had badly
discolored and there was much rust present in the water.
Table III below lists all the metals studied in the corro
65 sive water test. All metals were scoured clean and
dipped in either a 5 percent polymer or copolymer or a
10 percent monomer solution in ethanol. The panels
were drained then cured 1 hour at‘ 150° C. The panels
were then placed in 2-3 inches of corrosive water and
EXAMPLE VIII
70 the rate of corrosion visually observed over a 4-day
Several copper panels were dip-coated in alcohol solu
period. Under the test conditions the uncoated metals
tions of gamma-amtnopropylsilicone, the concentration
readily corroded whereas the coated metals were inhibited
of which was varied to obtain coatings of different thick
from corrosion. The x marks in Table III indicate
nesses. Although undiluted silicone compounds may be
applied to the surface, this technique gives heavy coatings. 75 speci?c tests of aminoalkyl silicone coated metals. The
.
3,085,908
blanks in the table indicate these combinations were not
tested.
14
by momentarily dipping in 18 percent HCl. It was then
scoured to remove all traces of corrosion products, and
TABLE III
I Coated metals found to be inhibited against corrosion when immersed in corrosive I
water for {our days
Silicon compound used as coatings onmetals
Copper
Aluminum
Zinc '
Steel b
'
Magnesium
Terne plate
(tin plate)
A. Monomers:
(1) Gamma-aminopropyltriethoxysiiane- _ -
(2) Delta-aminobutyitriethoxysilane-_
(3;
Bcta-aminophenylethyltriethoxysilane
(4
Delta-aminobutylmethyldiethoxysilane ________ __
.
(5) N-betacyanoethyl deli:a-aminobutyltriethoxysilane_.__
B. Polymers:
NMH
.
Gamma-amlnopropylsllicone (Polymer 01 1) _____________ __
Delta-aminobutylsilicone (Polymer of 2) ____ __
Beta-arninophcnylethylsilicone (Polymer of 3) _ _
Delta-aminobutylmethylsilieone (Polymer of 4) _
1:1 copolymer of No. 1 and ¢Si(OEt)3= __________ -_
1:1 ‘copolymer of No. 2 and ¢Si(0Et); ___________ -
X
Copolymer of 1 mole of No. 2 and 3 moles ¢Sl(OEt)z
X
lzl'copolymer of No. 1 and ¢MeSl(0Et)z __________ __
1:1 copolymer of No. 4 and ¢Si(0Et)a.___
1:1 copolymer of No. 4 and MezSKOEt), __________________ .1...
' Contains 100 p.p.m. each of chloride, bicarbonate, and sulfate as the
sodium salts.
b Corrosive water studies on steel were run for 20 hours.
‘
e The copolymer 0 i phcnylsilicone and gamrnaraminopropylsihcone was
prepared by the following method-To a 2,000 mi. ?ask equipped with a
stirrer, re?ux condenser, thermometer, and separatory funnel there was
charged:
G rams
1 mole phenyltriethoxysilane ................ -_
‘240
1 mole gamma-aminopropyltriethoxysilane__
220
Anhydrous
260
cob
_________________________________ -_
In a period of 15 to 20 minutes, 100 g water was a
d after the
30-minute re?ux period,_there was obtained one quart of water white
solution.
Found
Percent silicone solids _________________ __
Amino content (by acid tltration)-_
Silicon content _________________ _-
29. 0
Theory
Amino/silicon ratio calculated _________ _ _
s
,1. Aluminum blank _________ _
Coated aluminum ________ - _
11. Zinc magnesium and cop-
silicones: To a 1 liter round-bottomed ?ask equipped with a re?ux con
denser and thermometer, the following was added:
'
Grams
HaN(OH¢)aSi(OEti~
50 perceiiéta solids solution of silicone resin 1 in toluene at 110
120
1 Resin composition= (Mesiog 1:) u_u(MezSlO) o,45(¢Si03/g) ms
(¢zSiO)o.os.
This mixture was re?uxed 7 hours at 115° C. The product, approxi
mately 580-590 g., had the following properties: Viscosity, 29 cps.; per
cent solids (1 hr. at 150° C.), 49.4 percent.
1. 90
7. 3
6. 8
0. 47
0. 50
The following qualitative observations were made:
' Metals underiectzrrosive water
discussed herein by the hydrolysis and condensation method. Copoly
mers have also been prepared by the following method of equilibration
Preparation by equilibration of HzN(CH2)zSl(OEt)s with condensed
29. 2
1. 95
-
By varying the monomers of combination of monomers essentially all
of the polymer and copolymer formulations were thus prepared. This
preparation typi?es the preparation of the monomers and polymers
Observations
Reacts almost immediately to evolve
gas and increase alkalinity of cor
rosive water from pH 7.0 to greater
than pH 10.
No gas evolution, no pH change.
Readily corrodiblc metals, corrosion
thereafter dried by placing in acetone then wiping clean
with absorbent paper.
It was then placed in a 200 cc.
beaker containing 0.05 percent sodium sul?de. Within 1
minute the copper metal immersed in the water had
darkened. Within 11/2 hours marked vapor phase attack
had also occurred.
" EXAMPLE XIII
A 1 inch x 5 inch copper panel cleaned exactly as in
per blanks.
occurs within 16 hours.
Coated zinc magnesium After 48 hours no visible evidences of
Example
XII was completely immersed in 5 percent
55
and copper.
corrosion.
gamma-aminopropylsilicone in ethanol. It was removed
and allowed to drain. It was then placed in a. 150° C.
Alkaline sul?de water as used in our tests consists of
oven for 5 minutes. Then, it was placed in 0.05 percent
a 0.05-0.1 percent sodium sul?de solution. This solu
sodium sul?de solution. After 11/2 hours contact there
tion is strongly alkaline having a pH greater than 10.
was neither liquid phase nor vapor phase discoloration.
60
Even though it is basic, by a dissociation mechanism, an
The copper had exactly the same appearance as prior to
atmosphere of H28 is present over the solution. The
dipping in the corrosive medium.
solution's disagreeable smell is direct proof for the acid
Examples XII and XIII clearly show the eifectiveness
gas. This test solution was chosen since it can measure
of aminoalkyl silicone coatings in preventing corrosion
both alkaline aqueous corrosion and vapor phase acid
corrosion simultaneously. It was necessary to only par
tially immerse a metal panel in a beaker containing the
corrosive solution and visually observe the progress of
corrosion in both areas over a 2-day period.
It is well known in the art that alkaline solutions readily
dissolve silicone materials, and it was, therefore, totally
unexpected that coatings of 0.00l-0.05 mil thickness pro
of metals vfrom alkaline sul?de water.
vides such excellent protection under these conditions.
EXAMPLE XII
In the table the x marks indicate the combinations of
metals and coatings tested. The blank spaces mean these
Table IV summarizes the silicon compounds coated
on various metals which were evaluated in this test. It
was observed most uncoated metals were almost imme
diately corroded by this medium. However, in all the in
stances where the aminoalkyl silicone coatings were used,
good corrosion protection was supplied by the coatings.
A 1 inch x 5 inch copper metal strip was cleaned 75 combinations were not tested.
3,085,908
16'.
[ml Q1.
TABLE IV
Coated metals found to be inhibited against corrosive attack when
immersed in 0.05—0.1% sodium sul?de water
’ Silicon compounds used as coatings on metals
Copper
Aluminum
Lead
Tin
Magne5 urn
Brass
Silver
A. Monomers:
(1)
(2)
(3)
(4)
(5)
(6)
Gamma~aminopropyltrlethoxysilape
De1ta-aminobutyltriethoxysilane-_
__
Beta-aminophenylethyltriethoxysilane__.
Delta-aminobutylmethyldiethoxysilane
Bis(gamma~triethoxysilylpropyl)amine.__
N-beta-cyanoethyl gamma-aminopropyltriethoxysilane_
B. Homopolymcrs:
H
Gamma-aruinopropylsiliccne (polymer of No. l) ______________________ ..
Delta-aminobutylsilicone (polymer No. 2)
Beta-aminophenylethylsilieone (polymer of No. 3)
Dclta-aminobutylinethylsilicone (polymer of No. 4)
Bis(gamma)propylsilicone)amine (polymer of N0. 5).
C. Copolymers:
NNM‘N9N0 4
1:1 copolymer No. 1 and 4>Si(OEt); ___________________________________ _.
1:1 copolymer of No. 2 and ¢Si(0Et)n
1:3 copolymer of N0. 2 and ¢Si(OEt)3 ________________________________ -.
1:1 copolyrner of No. 4 and ¢MeSi(0Et)~
D 1:1 copolymcr of No. 4 and MegSi(OEt)g._-_
. Ter
E. Multipolymers:
mole-percent
0. 46
O. 32
0. 18
[MeSi 0 m]
mole
percent
0.
0.
0.
[MezSiO]
mole
percent
0. 03
0. 03
0. 04
MN
NM
N
acidic sul?de water. ~ The pH of these solutions were
In Table IV the copper and magnesium specimens
were prepared by acid treating the surface prior to scour 40 4.0, 2.5, 1.5. After 100 minutes’ exposure in these solu
tions, the aminoalkyl silicone coated copper strips were
ing. All other metals with the exception of silver were
bright and shiny and showed no signs of darkening.
scoured with an alkaline cleanser. The silver surface was
However, uncoated copper strips oxidized and turned
degreased with perclene (tetrachlorethylene).
~
black
in less than 5 minutes’ contact with these solutions.
The following observations were made during this
' study: Untreated copper, lead, silver, and brass all cor 45 Therewas no vapor phase attack of coated copper even
roded and darkened in 1-2 minutes in the sul?de solu
tion. Within 1-1/2 hours there was marked vapor phase
corrosion on the copper. Unprotected aluminum reacted
to evolve gas almost immediately. However, the use of
aminoalkyl coatings inhibited these corrosions: Coated 50
copper never did show vapor phase attack. Silver was
essentially untarnished even after 24 hours’ exposure and
with some coatings the aluminum showed no attack even
after 2 days’ contact in this atmosphere. Vapor phase
corrosion occurred rapidly with the uncoated copper
strips.
EXAMPLE XV
Four copper panels were prepared having an exposed
surface area of 12 sq. cm. by the procedure described in
Example XII. Three of these panels were coated by
immersing in 5-10 percent aminoalkyl silicone solutions.
after three days’ exposure. These coated metals showed
The panels were withdrawn from the solution and excess
complete resistance to liquid phase corrosion-for the fol 55 coating solution blotted from the coated panel. These
lowing periods: copper, 4 hours; lead, 2 hours; brass, 2
treated panels were cured by heat treating them one
hour at 150° C. ‘By reweighing these panels, the amount
hours; tin, 2 days; magnesium, 2 days.
Acid sul?de water as used in our tests comprises a 0.10
of silicone coating present on the panel was determined.
percent solution of hydrogen sul?de in distilled water.
All four panels were completely immersed in beakers con
In addition, there was admixed portions of concentrated 60 taining 0.3-0.4 percent NH4OH. Ammonium hydroxide
vHCl so that solutions having a pH of 4.0 to 1.5 were ob
saturated air, saturated by passing through a gas wash
tained. By partially immersing an aminoalkyl silicone
ing bottle containing 0.3-0.4 percent NH4OH was sup
coated copper panel in the beaker, corrosion due to
plied to the beakers. After three hours the panels were
both aqueous and vapor phase could be observed. It is
removed from the NIH4OH water and obtained their dry
well known that acidic systems facilitate'the solution of 65 weights. These panels were then returned to their re
' alkaline substances. It was thereforev totally unexpected.
spective beakers for an additional four-hour corrosion
to ?nd aminoalkyl silicone coatings resistant to corrosion
period.
'
in acidic sul?de solutions.
During this last exposure period the uncoated copper
EXAMPLE XIV
specimen became heavily coated with a blue-gray oxide
70 ?lm (verdigris) which effectively prevented its further
One-inch by ?ve-inch copper strips were scoured with
corrosion. At the end of the test, the specimens coated
alkaline cleanser, washed, and" dried. They were com
pletely immersed in 5 percent gamma-aminopropylsili
with the silicone polymers showed only slight corrosive
attack. The specimen coated with the silicone ester had
cone in ethanol, air dried, then ‘cured 30 minutes at 150°
C. ‘These strips were then placed in beakers containing 75 darkened over its snrface-—probably the start of an oxide
3,035,903‘
coating.
follows:
18
consisting of delta-aminobutylmethyl- and phenylsilicone
The results of those tested are tabulated as 7'
units. It was then cured in the 150° C. oven for 1 hour.
\
The panel was then placed in a 200 cc; beaker contain
Coating
ing 5 percent salt water. In 1 hour there was no evi
dence of corrosion. After 16 hours this panel showed no
corrosive attack with the exception of a small area at
Weight loss. (mg/12
sq. cm. copper)
Coating on copper specimen
Weight
Thick
(g.)
I ness
'
1st3hr.
Blank (no coating) ............................. ._
29. 6
Delta-aminobutyltriethox-
(1)
.
ysilane ___________________ -_
silaue.
For7hr.
(mils)
‘
Delta-aminobutylsilicone.___
Delta-aminobutylmethyl-
0.0019
0.020
18.8
25.5
0.0029
0. 0039
0.034
0. 044
1.5
l. l
2.3
2. 6
silicone.
‘
the air-salt water interface.
Examples XVI and XVII clearly demonstrate the pro
tection afforded magnesium from salt water corrosion by
10 applying a coating of 0.05 mil thickness of aminoalkyl
silicone compound in ‘accordance with the present in
vention.
~
EXAMPLE XVIII
' Three 1 x 5 inch copper panels were cleaned by giving
15 them an 18 percent HCl acid dip.
They were then
The panels were im
scoured until they were clean.
1 Insoluble oxides coated onto metal.
mersed in acetone, removed, and wiped dry. Two panels
The percent protection afforded ‘by the coating may
1 were coated by immersing them respectively in a 5 per
be calculated according to this formula:
cent gamma-aminopropylsilicone solution in ethanol and
20 a 5 percent copolymer of gamma-aminopropylsilicone
Rate uncoated-rate coated
Percent protection=
and phenylsilicone in ethanol. These panels were allowed
Rate uncoated
X100
to dry by standing overnight at room temperature. The
uncoated copper panel and the two aminoalkyl silicone
coated panels were then placed in the 9-5" F. salt spray
Since rate=weight loss per unit time and each re
ported weight loss occurred in the same period (3 hours):
.
29.6.'—wt. loss
Percent protection- _
25 chamber. Air which atomized at 20 percent salt solu
tion, was admitted to the chamber at 15 p.s.i.g.' After
X 100
‘29‘6
24 hours’ treatment, it was observed that there was good
protection for the coated panels. The uncoated panel
It is not possible with the above data to directly cal
culate the protection during the 7-hour exposure to cor 30 showed green corrosion at this time. ‘These tests clearly
show aminoalkyl silicone coatings inhibit salt spray cor
rosion since the uncoated specimen was coated with
oxide ?lm which makes its weight loss meaningless. If
rosion to copper metal.
it is assumed that corrosion would occur in the same rate
EXAMPLE XIX
during the additional 4-hour period, a total weight'loss
for the uncoated copper would be 69.2 mg.
Percent protection=
69.2-wt. loss
69.2
Therefore: . 35
X 100
Calculated data are listed for 3 and 7 hour corrosion
periods.
Percent protection
from corrosion rn-—
Coating on copper specimen
3 hours
7 hours
Delta-aminobutyltriethoxysilane
36. 5
03.0
Delta-aminobutylsilicone _____ _.
95. 0
96. 6
Delta-aminobutylmetltylsilicone
90. 5
90. 3
>
Two chrome plate steel panels (plated in accordance
with automotive bumper speci?cations) we're degreased
with trichloroethylene. One panel was dip~coated in 5
percent delta-aminobutylmethyl-phenyl silicone copoly
mer in alcohol. This panel was air dried then cured 5
40 minutes at 150° F. Both panels were then placed in the
salt spray chamber which was maintained at 100° F. Air
saturated with water was aspirated at 14 p.s.i.g. into a 20
percent salt solution which created the salt fog. After
35 days’ exposure to these conditions, the aminoalkyl
45 coated panel was essentially 100 percent free of rusting.
The uncoated chrome panel was rusting badly.
EXAMPLE XX
Four 11/2 x 3 inch carbon steel panels were scoured with
alkaline cleanser until they were bright and shiny and free
This example clearly shows aminoalkyl silicone mon- -
omer, polymer, and copolymer coatings on copper metal
effectively inhibit corrosion in aerated NH4OH water.
Although de?nite protection was provided by amino
alkyl monomer ?lms, superior results were ,obtained by
using polymers and copolymers. This invention teaches
both coating thicknesses and degree of polymerization
regulates the resistance to solubility of these coatings to
alkaline sul?de solution. Better protection is provided
by the thicker and more insoluble coatings.
of all grease. With a soft cloth, these panels were dried.
A thin ?lm of the listed formulation was wiped onto the
surface of the respective strips. Each strip was then
placed in a 200 cc. beaker ?lled with distilled water. All
55 beakers were aerated at room temperature for 24-72
I
hours. Visually observed and noted, the extent of cor
rosion was:
V60
Panel
>
Formulation
Amount I
No.
ofrustl
EXAMPLE XVI
‘A commercially pure (Mg, 96 percent; -Al, 3 percent;
Zn, 1 percent) 11/2 x 3 inch magnesium panel was cleaned
by pickling it in dilute H2SO4 then scouring the surface
Petroleum oil ‘I (15 g.) and the % oleate salt of deltaammobutylmethylsilicone cyclic trimer and
until clean. The panel was dried after ?rst giving it an
acetone rinse. This panel was placed in a 200 cc. beaker
tetramer (5 g.).
B
' '
Petroleum oil 1 (control) ........................... __
D
No costing (control) _______________________________ -_
D
Paraffin oil (18 g.) and the % stearate salt of 50 per-
B
cent delta-aminobutylmethyl-modi?ed dimetliyl
silicone oil (3.1 g.).
'
containing some 5 percent salt solution. Within 1 hour
there was evidence of corrosion.
panel was badly corroded.
After 16 hours this
-
70
1 A =nil or trace; B =small; C =medium;' D =large.
3 Gulf Security Oil “A’F-an uninhibited petroleum oil.
EXAMPLE XVII
EXAMPLE XX-I
Four aluminum panels were cleaned by scouring with
A magnesium panel cleaned exactly as described in ’
an alkaline cleanser, ?ushed with water and dried. Three
Example XVI was dipped in acetone and allowed to dry.
This panel was then immersed in a 5 percent copolymer 75 of these panels were respectively immersed in 10 percent
~
'
3,085,908
to
-
2Q
Si-O bonds and the remaining free bonds of silicon
are attached to hydrocarbyl, and curing said aminoalkyl
resin solids in toluene solutions of the following multi
polymers:
silicon compound on said surface to form an adherent
coating thereon.
[H2N(CH2)aSiO3/z] [MeSiOsn] [MezSiO]
mole-percent
molemolcpercent
percent
[¢Si0a/2l
mole-' ~
percent
l¢2S1O
percent
0. 46
0. 08 .
0. 25
0. l8
0. O3
0. 32
0. 18
0. 10
0. l2
0.31
0. 37
0. 24
0. 29
0. 03
0. O4
Panels were allowed to air dry, heat cured at 150° C.
tive series and alloys thereof, which comprises applying
for one hour, all four panelswere then placed In a 3
percent aerated salt solution. Within two hours there was
evidence of corrosion on the untreated aluminum panel. >
The coated aluminum panels were not corroded under
these conditions. Some of the coated panels withstood
?ve days’ immersion in the salt solution without corrosion.
EXAMPLE XX-Il
Admixtures comprising:
(a) 5 grams N-beta-aminoethyl-gamma-aminopropyltri
methoxysilane
to the surface of said substrate to form a ?lnr thereon-an“
aminoalkylsilane of the formula:
.
R:
wherein R is a member selected from the group consist- 1
ing of the divalent saturated aliphatic hydrocarbon, the
20 saturated cyclic hydrocarbon and the unsaturated cyclic
hydrocarbon radicals having a chain of at least 3 car
bons and wherein nitrogen is attached to at least a third
carbon removed from the silicon, R” represents a hydro
-
9.5 grams distilled water
85.5 grams absolute ethanol
(b) 5 grams Nabeta-aminoethyl-gamma-aminoisobutyl
methyldiethoxysilane
carbon group‘selected from the class consisting of the
25 alkyl and the aryl groups, X represents an alkoxy group
selected from the class consisting of methoxy, ethoxy and
9.5 grams distilled water
85.5 grams absolute ethanol 1
(c) 5 grams N-gamma-aminopropyl-gamma-aminobutyl
triethoxysilane
'
propoxy, -(b) is an integer having a value of from 0 to
2, (d) is an integer having a value of from 1 to 2, and
the sum of (d+b) is not greater than 3, and curing said
30 aminoalkylsilane on said surface to form an adherent
9.5 grams distilled water
85.5 grams absolute ethanol
coating thereon.
. substrate selected from the group consisting of the met
als lying below and including magnesium in the electro
motive series and alloys thereof,‘which comprises apply
clean copper panels. The resulting six panels were air
dried for a period of about two hours and were then
placed in an oven heated at a temperature of 15.0“ C.
for a period of ?fteen minutes to cure the silicon com
a
'
'5. A process for providing a protective coating for a
. were prepared and each admixture employed to treat two
pounds.
, '
2. A process as de?ned in claim 1, wherein said ?lm
is air-dried to cure said aminoalkyl silicon compound.
3. A process as de?ned in claim 1, wherein said amino—
alkyl silicon compound is applied in a solvent solution.
4. A process for providing protective coating for a
substrate
selected from the group consisting of the metals
10
lying below and including magnesium in the electrome
mole
ing to the surface of said substrate to form a ?lm thereon
‘an aminoalkylpolysiloxane containing the unit:
R1:
_
One set of panels treated with the above admixtures 40
was then placed in an air circulating oven maintained at
a temperature of 250° C. along with a clean untreated
panel. After a period of 16 hours the four panels were
removed from the oven and examined. It was noted that
the three treated panels retained their initial copper color
while the untreated panel has become completely black.
The remaining set of treated panels along with a clean
untreated panel were immersed in an 0.1 percent solution
2
wherein R is a member selected from the group consist
ing of the divalent saturated aliphatic hydrocarbon, the
saturated cyclic hydrocarbon and the unsaturated cyclic
45
hydrocarbon radicals having a'chain of at least 3 car
bons and wherein nitrogen is attached to at least a third
carbon removed from the silicon, R” represents a hydro
of sodium sul?de. It was noted that the untreated panel
‘turned black in color almost instantly while the treated
panels retained their initial color.
' carbon group selected from the class consisting of the
50
This application is a continuation-in-part of our co- .
pending United States application Serial No. 672,873
?led July 19, 1957, now abandoned.
What is claimed is:
l. A process for providing a protective coating for a
substrate selected from the group consisting of the metals
lying below and including magnesium in the electromotive
series and alloys thereof, which comprises applying to
the surface of said substrate to form a ?lm thereon an
alkyl and the aryl groups, and (b) is an integer having
a’ value of from 0 to 2, and curing said aminoalkylpoly
siloxane on said surface to form an adherent coating
thereon.
I
,6. A process for providing a protective coating for a
substrate, from the group consisting of the metals lying
below and including magnesium in the electromotive se
ries and alloys thereof, which comprises applying to the
surface of said substrate to form a ?lm thereon an amino
alkylpolysiloxane containing the structural unit:
aminoalkyl silicon compound which contains the group: 60
wherein R is a member selected from the group con
wherein R is a member selected from the group consist
sisting of the divalent saturated aliphatic hydrocarbon,
the saturated cyclic hydrocarbon and the unsaturated 65 ing of the divalent saturated aliphatic hydrocarbon, the
saturated cyclic hydrocarbon and the unsaturated cyclic
cyclic hydrocarbon radicals having a chain of at least
3 carbons and wherein nitrogen’ is attached to at least a
third carbon removed from silicon, wherein each of the
free bonds of the nitrogen atom is bonded to a member
hydrocarbon radicals having a chain of at least 3 car
bons and wherein nitrogen is attached to at least a third
carbon removed from the silicon, Z represents a mem
from the class consisting of hydrogen, hydrocarbyl, cyano 70. ber selected from the group consisting of hydroxyl and
alkoxy radicals, and (c) has an average value of from
alkyl, aminoalkyl and [—(CH2),,Si~=—], wherein (a) is
0 to Land curing‘said aminoalkylpolysiloxane on said
an integer of at least 3, and wherein at least one free
surface to form an adherent coating thereon.
.
bond of silicon in each of said (>N-—R-—Si5) and said
7. A process for providing a protective coating for a
[—-(CH2),,SiE] groups is attached to-a group selected
substrate selected from the group consisting of the met
from the class consisting of alkyl and silicon through
3,085,908
21
22
carbon removed from silicon, wherein each of the free
bonds of the nitrogen atom is bonded to a member from
als lying below and including magnesium in the electro
motive series and alloys thereof, which comprises apply
the class consisting of hydrogen, hydrocarbyl, cyanoalkyl,
ing to the surface of said substrate to form a ?lm there
on an organopolysiloxane containing amino groups at
tached to silicon through a carbon linkage of at least
aminoalkyl and [-~'(CH2),,SiE], wherein (a) is an in
teger having a value of at least 3, and wherein at least
one free bond of silicon in each of said (>N——-'R—SlE)
3 carbons, the remainder of the groups attached to sili
and said [—‘(CH2),,SiE] groups is attached to a group
con being selected from the group consisting of methyl,
from the class of alkyl and silicon through Si—0 bonds
ethyl, propyl, butyl, phenyl, naphthyl, tolyl, vinyl and
and the remaining free bonds of silicon are attached to
cyclohexenyl groups, and curing said organopolysiloxane
10 hydrocarbyl, and heating said ?lm to cure the aminoal
on said surface to form an adherent coating thereon.
kyl silicon compound on the surface of the copper.
8. A process for providing a protective coating for a
16. A process for providing a protective coating for
substrate selected from the group consisting of the met
aluminum which comprises applying to the surface of
als lying below and including magnesium in the electro
said aluminum to form a ?lm thereon an aminoalkyl sili
motive series and alloys thereof, which comprises ap
plying to the surface of said substrate gamma-amino 15 con compound which contains the group:
propyltriethoxysilane, and curing said gamma-aminopro
pyltriethoxysilane on said surface to form an adherent
coating thereon.
wherein R is a member selected from the group con
lying below and including magnesium in the electromo
tive series and alloys thereof, which comprises applying
bons and wherein nitrogen is attached to at least a third _
to the surface of said substrate gamma—aminopropylsilox
ane, and curing said gamma-aminopropylsiloxane on
bonds of the nitrogen atom is bonded to a member from
sisting of the divalent saturated aliphatic hydrocarbon,
9. A process for providing a protective coating for a
substrate selected from the group consisting of the metals 20 the saturated cyclic hydrocarbon and the unsaturated cy
said surface to form an adherent coating thereon.
clic hydrocarbon radicals having a chain of at least 3 car
carbon ‘removed from silicon, wherein each of the free
25
als lying below and including magnesium in the electro
motive series and alloys thereof, which comprises apply
. ing to the surface of said substrate delta-aminobutyltri
the class consisting of hydrogen, hydrocarbyl, cyanoalkyl,
aminoalkyl and [-—'(CH2)aSlE], wherein (a) is an in
teger having a value of at least 3, and wherein at least
one free bond of silicon in each of said (>N——-R-—SlE)
and said [-—(CH2),,SiE] groups is attached to a group
10. A process for providing a protective coating for
a substrate selected from the group consisting of the met
30 from the class of alkyl and silicon through Si-—O bonds
ethoxysilane, and curing said delta-aminobutyltriethoxy
silane on said surface to form an adherent coating there
on.
11. A process for providing a protective coating for
a substrate selected from the group consisting of the met
als lying below and including magnesium in the electro
motive series and alloys thereof, which comprises apply
ing to the surface of said substrate delta-aminobutyl
siloxane, and curing said delta-aminobutylsiloxane on
said surface to form an adherent coating thereon.
12. A process for providing a protective coating for
a substrate selected from the group consisting of the met
als lying below and including magnesium in the electro
motive series and alloys thereof, which comprises applying to the surface of said substrate delta-aminobutyl 45
and the remaining free bonds of silicon are attached to
hydrocarbyl, and heating said ?lm to cure the aminoalkyl
silicon compound on the surface of the aluminum.
17. A process for providing a protective coating for
chromium which comprises applying to the surface of
said chromium to form a ?lm thereon an aminoalkyl sili
con compound which contains the group:
wherein R is a member selected from the group consist
ing of the divalent saturated aliphatic hydrocarbon, the
saturated cyclic hydrocarbon and the unsaturated cyclic
hydrocarbon radicals having a chain of at least 3 car
bons and wherein nitrogen is attached to at least a third
carbon removed from silicon, wherein each of the free
methylsiloxane, and curing said delta-aminobutylmethyl
bonds of the nitrogen atom is bonded to a member from
siloxane on said surface to form an adherent coating
thereon.
13. A process for providing a protective coating for
a substrate selected from the group consisting of the met 50
teger of at least 3 and wherein at least one free bond of
als lying below and including magnesium in the electro
motive series and alloys thereof, which comprises apply
the class consisting of hydrogen, hydrocarbyl, cyanoalkyl,
aminoalkyl and [-—=(CH2),,SiE], wherein (a) is an in
silicon in each of said (>N-—R—Siz) and said
[_“(CH2)aSiE]
groups is attached to a group from the class of alkyl and
ing to the surface of said substrate N-aminoalkyl-gamma
silicon through Si-~O bonds and the remaining free bonds '
aminopropyltrialkoxysilane, and curing said N-aminoal
of silicon are attached to hydrocarbyl, and heating said
kyl-gamma-aminopropyltrialkoxysilane on said surface to 55 ?lm to cure the aminoalkyl silicon compound on the sur—
form an adherent coating thereon.
face of the chromium.
14. A process for providing a protective coating for
18. A process for providing a protective coating for
a substrate selected from the group consisting of the met
steel which comprises applying to the surface of said
als lying below and including magnesium in the electr0~
steel to form a ?lm thereon an aminoalkyl silicon com
motive series and alloys thereof, which comprises apply 60 pound
which contains the group:
ing to the surface of said substrate a copolymer con
taining gamma-aminopropylsiloxane units and vinylsilox
ane units, and curing said copolymer on said surface to
form an adherent coating thereon.
wherein R is a member selected from the group consist
of the divalent saturated aliphatic hydrocarbon, the
l5. Aprocess for providing a protective coating for 65 ing
saturated cyclic hydrocarbon and the unsaturated cyclic
copper which comprises applying to the surface of said
hydrocarbon radicals having a chain of at least 3 car
copper to form a ?lm thereon an aminoalkyl silicon com
bons and wherein nitrogen is attached to at least‘ a third
pound which conains the group:
carbon removed from silicon, wherein each of the free
bonds of the nitrogen atom is bonded to a member from
70 the class consisting of hydrogen, hydrocarbyl, cyanoal
wherein R is a member selected from the group consist
kyl, aminoalkyl and [-—-(CH2),,SiE], wherein (a) is an
ing of the divalent saturated aliphatic hydrocarbon, the
saturated cyclic hydrocarbon and the unsaturated cyclic
hydrocarbon radicals having a chain of at least 3 car
bons and wherein nitrogen is attached to at least a third 75
integer of at least 3 and wherein at least one free bond
of silicon in each of said (>N-R-Siz) and said
3,085,908
23
and silicon through Si-O bonds and the remaining free
.bonds of silicon are attached to hydrocarbyl, and heating
said ?lm to cure the aminoalkyl silicon compound on the
surface of the steel.
steel which comprises applying to the surface of said
steel a solvent solution of gamma-aminopropylsiloxane to
form a ?lm thereon, and heating said ?lm to a temperature
.
19. A process for providing a protective coating for
bronze which comprises applying to the surface of said
of about 150° C. to cure the siloxane on the steel.
24. A metal having a cured surface coating thereon of
an aminoalkyl silicon compound containing the following
bronze to form a ?lm thereon an aminoalkyl silicon c0m-,
pound which contains the group:
(>N-—R—-Sis )
24
‘temperature of at least 150° C. to cure the silane on the
copper.
23. A process for providing a protective coating on
groups is attached to a group from the class of alkyl
10
wherein R is a member selected from the group consisting
grouping:
'
wherein R is a member selected from the‘ group consist
of the divalent saturated aliphatic hydrocarbon, the satu
ing of the divalent saturated aliphatic hydrocarbon, the
rated cyclic hydrocarbon and the unsaturated cyclic hydro
saturated cyclic hydrocarbon and the unsaturated cyclic
carbon radicals having a chain of at least 3 carbons and 15 hydrocarbon radicals having a chain of at least 3 carbons
wherein nitrogen is attached to at least a third carbon re
and wherein nitrogen is attached to at least a third carbon
moved from silicon, wherein each of the free bonds of
removed from silicon, wherein each of the free bonds of
the nitrogen atom is bonded to a member from the class
the nitrogen atom is bonded to a member from the class
consisting of hydrogen, hydrocarbyl, cyanoalkyl, amino
consisting of hydrogen, hydrocarbyl, cyanoalkyl, amino
alkyl and [--(CH2),,SiE], wherein (a) is an integer of 20 alkyl and [—(CH2)aSiE], wherein (a) is an integer of .
at least v3 and wherein at least one free bond of silicon
at least 3 and wherein at least one free bond of silicon
in each of said (>N—~R-—Si2) and said [—-'(CH2) aSiE]
in each of said (}>N--R--Siz) and said [—CH2),,SiE]
groups is attached to a group from the class of alkyl
groups is attached to a group from the class of alkyl and
silicon through Si—O bonds and the remaining free bonds
25
bonds of silicon are attached to hydrocarbyl, and heat
of silicon are attached to hydrocarbyl.
ing said ?lm to cure the aminoalkyl silicon compound on
25. An article ‘having a surface of metal selected from
the surface of the bronze.
the group consisting of the metals lying below and in
and silicon through Si—O bonds and the remaining free - '
20. A process for providing a‘ protective coating for
a silver surface which comprises applying to‘ the silver
cluding magnesium in the electromotive series and alloys
pound which contains the group:
ing grouping:
thereof, said surface having a cured coating thereon of
surface to form a ?lm thereon an aminoalkyl silicon com 30 an aminoalkyl silicon compound containing the follow
wherein R is a member selected from the group consisting 35
of the divalent saturated aliphatic hydrocarbon, the satu
rated cyclic hydrocarbon and the unsaturated cyclic hy
wherein R is a member selected from the group consisting
of the divalent saturated aliphatic hydrocarbon, the satu
drocarbon radicals having a chain of at least 3 carbons
and wherein nitrogen is attached to at least a third carbon
rated cyclic hydrocarbon and the unsaturated cyclic hy
removed from silicon, wherein each of the free bonds of 40 drocarbon radicals having a chain of at least 3 carbons and
wherein nitrogen is attached to at least a third carbon re
the nitrogen atom is bonded to a member from the class
moved from Silicon, R" represents a hydrocarbon group
consisting of hydrogen, hydrocarbyl, cyanoalkyl, amino
selected from the class consisting of the alkyl and the aryl
alkyl and [-—(CI-I2),,SiE], wherein (a) is an integer of
groups, X represents an alkoxy group such as methoxy,
at least 3 and wherein at least one free bond of silicon in
cthoxy, and propoxy groups, and (b) is an integer having a
each of said (>N—R—Siz) and said [—-CH2),,Si_=_]
groups is attached to a group from the class of alkyl and
45 value of from 0 to 2, (d) is an integer having a value from
silicon through Si—-O bonds and the remaining free bonds
of silicon are attached to hydrocarbyl, curing the amino
alkyl silicon compound on the surface of the silver.
I 26. An article having .a surface of metal selectedyfrom
1 to 3, and the sum (d-l-b) is not greater than 3.
the group consisting of the metals lying below and includ
21. A process for providing a protective coating for 50 ing magnesium in the electromotive series and alloys
thereof, said surface having a cured coating thereon of
brass which comprises applying to the surface of said
an aminoalkyl silicon compound containing the follow
brass to form a ?lm thereon an aminoalkyl silicon com
ing grouping:
pound which contains the group:
55
wherein R is a member selected from the group consisting
of the divalent saturated aliphatic hydrocarbon, the satu
rnrr-a-siogl122
rated cyclic hydrocarbon and the unsaturated cyclic hy
wherein R is a member selected from the group consisting
drocarbon radicals having a chain of at least 3 carbons
of the divalent saturated aliphatic hydrocarbon, the satu
and wherein nitrogen is attached to at least a third carbon 60 rated cyclic hydrocarbon and the unsaturated cyclic hy
removed from silicon, wherein each of the free bonds of
drocarbon radicals having a chain of at least 3 carbons
the nitrogen atom is bonded to a member from the class
and wherein nitrogen is attached to at least a third carbon
consisting of hydrogen, hydrocarbyl, cyanoalkyl, amino
alkyl and [——(CH2)aSi-5], wherein (a) is an integer of
removed from silicon, R" represents a hydrocarbon group
selected from the class consisting of the alkyl and the aryl
at least 3 and wherein at least one free bond of silicon 65 groups and (b) is an integer having a value of from 0 to 2.
27. An article having a surface of metal selected from
groups is attached to a group from the class of alkyl and
the group consisting of the metals lying below and in
in each of said (>N-‘—R—Si§) and said [—CH2)aSi—_—-]
silicon through Si—O bonds and the remaining free bonds
cluding magnesium in the electromotive series and alloys
of silicon are attached to hydrocarbyl, heating said ?lm
thereof, said surface having a cured coating thereon of an
to cure the aminoalkyl silicon compound on-the surface of 70 organopolysiloxane containing amino groups attached to
the brass.
silicon through a carbon linkage of at least three carbons,
22. A process for providing a protective coating on
the remainder of the groups attached to silicon being
copper which comprises applying to the surface of said
selected from the group consisting of methyl, ethyl,
copper a solvent solution of garnma-aminopropyltriethoxy
propyl,
butyl, phenyl, naphthyl, tolyl, vinyl ‘and cyclo
75
silane to form a ?lm thereon, and heating said ?lm to a
3,085,908
25
26
sisting of the metals lying below and including magnesium
in the electromotive series, a copolymeric aminoalkyl
siloxane composed of the following structural units:
hexenyl and curing said organopolysiloxane on said sur
face to form an adherent coating thereon.
28. An article having a surface of metal selected from
the group consisting of the metals lying below and in
If?!
cluding magnesium in the electromotive series and alloys
thereof, said surface having a cured coating thereon of a
[Hm (0112) ,s10 glb
polymeric aminoalkylpolysiloxane containing the struc
2
wherein R” represents a member selected from the group
consisting of the alkyl and the aryl groups, (a) is an
integer having a value of at least 3, and (b) is an integer
tural units:
having a value of from 0 to 2; and
,
2
wherein R is a member selected from the group consisting
of the divalent saturated aliphatic hydrocarbon, the satu 15 wherein (e) is an integer having a value of from 0 to 2.
rated cyclic hydrocarbon and the unsaturated cyclic hy
34. A copolymeric aminoalkylpolysiloxane composed
drocarbon radicals having a chain of at least 3 carbons
and wherein nitrogen is attached to at least a third carbon
of the following structural units:
removed from silicon, R" represents a hydrocarbon group
consisting of the alkyl and the aryl 20
groups and (b) is an integer having a value of from 0 to
If;
[Hm (CH1) .SiOtP
’ selected from the class
2; and
'
2
'
wherein R" represents a member selected from the group
consisting of the alkyl and the aryl groups, (a) is an in
25 teger having a value of from 3 to 4, and (b) is an integer
having a value of from 0 to 2; and
e
III
'
R SiOtE
2
wherein R’" represents a hydrocarbon group selected
_ [viesiotg]
2
from the class consisting of methyl, ethyl, propyl, buwl,
phenyl, naphthyl, tolyl, vinyl and cyclohexenyl, and (e)
30 wherein (e) is an integer having a value of from 0 to 2.
35. The method of obtaining a tarnish resistant coating
on a metal normally tarnishable by ambient conditions
comprising coating the metal with a solution of an amino
is an integer having a value of from 0 to 2.
29. An article having a surface of metal selected from
the group consisting of the metals lying below and includ
ing magnesium in the‘ electromotive series and alloys
alkyl alkoxysilane having the formula
thereof, said surface being modi?ed by having a coating 35
of an aminoalkyl silicon compound which is attached
I
H2N- (CH2) n—$i—-(O R) 3--:
thereto through the reaction product of the amino group
where R is an alkyl group containing from 1 to 10 carbon
with the metal surface, said aminoalkyl silicon compound
atoms R’ is omitted when x is 0 and when present is an
having the grouping:
$1!
4.0 alkyl group containing from 1 to 10 carbon atoms and n
wherein R is a member selected from the group consisting
of the divalent saturated aliphatic hydrocarbons, the satu
rated cyclic hydrocarbon and the unsaturated cyclic hy
drocarbon radicals having a chain of at least 3 carbons
and wherein nitrogen is attached to at least a third carbon
is an integer selected from the group consisting of 3 and
4, in an organic solvent and curing the silane.
36. The method of obtaining a tarnish resistant coating
on a metal normally tarnishable by ambient conditions
comprising coating the metal with a solution of an amino
alkylalkoxysilane having the formula:
removed from silicon, wherein each of the free bonds of
II‘!
the nitrogen atom is bonded to a member from the class
HaN-(OHg) n-st-(O R) H
consisting of hydrogen, hydrocarbyl, cyanoalkyl, amino
alkyl and [—-(CH2),,SiE], wherein (a) is an integer of 50 where R is an alkyl group containing from -1 to 10 carbon
at least 3, and wherein at least one free bond of silicon
in each of said (>N——R,—SiE) and said [—-CH2),,Si-=-]
groups is attached to a group from the class of alkyl and
atoms, R’ is omitted when x is 0 and when present is from
the group consisting of —(CH2),,NH2 and an alkyl group
containing from 1 to 10 carbon atoms, at has a value se
lected from the group consisting of 0 and 1 and n is an
55 integer selected from the group consisting of 3 and 4, in
of silicon are attached to hydrocarbyl.
an organic solvent and curing the silane. '
1
30. An article as de?ned in claim 29 wherein said
coating has a thickness of from 0.01 to 0.10 mil.
References Cited in the ?le of this patent
3-1. An article having a surface of copper, said copper
silicon through Si-—O bonds and the remaining free bonds
having a coating of gamma-aminopropyltriethoxysilane
cured thereon.
32. An article having a surface of copper, said copper
having a coating of gamma-aminopropylsilicone cured
thereon.
'
'
33. As a coating for metal selected from the class con
UNITED STATES PATENTS
2,709,569
2,762,823
Roush _______________ _._ May 31, 1955 Q
2,832,754
Speier _______________ __ Sept. 11, 1956
Jex et al ______________ __ Apr. 29, 1958
2.855.381
Sommer ______________ __ Oct. 7. 1958
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