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Patented Dec. 17, 1
Y 2,412,557
1
UNlTED- STATE s PATENT ornce
2,412,557
LUBRICATING OILS
-. Charles M. can, Jr., Webster Groves, Mo., as»
signor to Petrolite Corporation, Ltd, Wilming
ton, Deb, a corporation of Delaware
No Drawing. .
-
Original application October 16,
1944, Serial No. 558,949. Divided and this ap
plicatlon April .20, 1945, Serial No. 589,463
,
8 Claims. (01. 252-515)
1
This application is a division of my pending . unsaturated primary or secondary amine, in
application Serial No. 558,949, ?led October 16, . which the unsaturation is ethylenic and the eth
1944, for New chemical product and method of ' ylenic carbon atom nearest to the amino nitrogen
atom is separated from said nitrogen atom by‘
manufacturing same, and relates to a new com
at least four singly bonded carbon atoms. The
position of matter comprising a lubricating oil
nature of the reaction is not clearly understood,
and a new chemical product consisting of poly
and. is not readily explainable in terms of well
amide. and polyamide compounds of relatively
known organic reactions. However, a tentative
high molecular weight. The new chemical ‘prod
theory of the'reaction mechanism and of the
not above referred to may be prepared by react
ing an alpha-beta, unsaturated acid or anhydride' 10 structure of the products will be given below.
Acidic reactants found useful in the prepara
with an unsaturated amine of the'kind to be
tion of the present products, are the alpha-beta,
described, under conditions which cause polymer
unsaturated acids and anhydrides which do not
ization of the amide or imide initially formed.
- The preparation of polymers of the reaction
contain a vinyl group, especially those contain
of multifunctional acids and multifunctional 15 ing less than 10 carbon atoms. ‘Examples of .
such acids and anhydrides are crotonlc acid,
amines, is an old and-well known art, exempli- maleic acid, citraconic acid, glutaconic acid, aco
?ed, for example, by the reaction between ethyl
nitic acid, itaconlc acid, mesaconic acid, maleic
ene diamine and adipic acid. Preferably, the
anhydrida'citraconic anhydride and itaconlc an
. new chemical product that forms part of my new
hydride.
.
_‘
,
20
composition of matter, is prepared from reactants
The .condensation of esters and amides of car
in which polyfunctionality is not dependent on
boxylic acids containing a vinyl group, such, as
the presence of more than one carboxyl radical
those
of acrylic and methacrylic acids, is rela
in the molecule,’ or more than one amino radi
tively well. known and understood. The present .
cal. If such plurality of carboxyl radicalsv of
plurality of aminoradicals are present, it is 25 products are prepared by a reaction which ap
purely, incidental. The polymers herein contem- .
plated are dependent on the functionality of the
unsaturated ethylene radical of the alpha-beta
acid or anhydride on the one hand, and on the
, polyfunctionality of the unsaturated amine on 30
the other hand, based on the presence of the
amino radical, and additionally, on the function
ality of the unsaturated ethylene radical which
parently differs from ordinary ole?ne polymeri
zation, such as is involved in’ the acrylate poly
merization. Such vinyl polymers are not con
templated herein.
These acids may be monobasic, or polybasic,
including dibasic. Because of their low cost and
‘availability in commercial quantities, maleic an
hydride, fumaric acid and citraconicanhydride,
are especially useful, and products obtained with
may enter into reaction per se, or which may
activate a hydrogen atom attached to a car 35 these reactants will be used below to illustrate‘
.the present invention.
‘
bon atom in a position alpha to, or perhaps, even
‘Suitable amines for use in preparing the new
beta to the unsaturated linkage. It happens that
dicarboxy, alpha-beta, ethylenic acids or their an
hydrides, such as maleic anhydride, are most
chemical product previously referred to are the
unsaturated primary and secondary amines, in
readily available,-and thus are most conveniently 40 whichthe unsaturatlon occurs in an aliphatic
or cycloaliphatic residue, and in which the ethyl-'
However, in combination with such
enic carbon atom nearest to the amino nitrogen
polyoarboxy acid compound, it is preferred that
is
separated from said nitrogen atom by at least
the unsaturated amine contain only. one amino
four singly bonded carbon atoms. Such amines
radical. Monocarboxy acids may be employed,
\ employed.
and similarly, unsaturated polyamino compounds 45 may be aliphatic, valicyclic, mixed aliphatic-ali
may be used, but such reactants are not com
monly available at the present time.
'
My present invention contemplates polymeric
cyclic, alkylaromatic, alicyclic-aromatic, or other
containing aliphatic, alicyclic and aromatic resi
dues, and in which the hydrocarbon residues at
tached to the amino nitrogen contain 8 or more "
compounds derivable by reaction between an
alpha=beta, ethylenic acid or-anhydride and an 50 and less than '32 carbon atoms.- As stated above,
‘2,412,557
‘ing reaction, a slow stream of oxygen or oxygen
suitable amines must have an _ethylenic unsat
uration removed by four singly bonded carbon v , ‘containing gas, such as air.
'
‘ The bene?cial effect of this operation appears
atoms from the amino nitrogen; however, in ap
plying this restriction, aromatic ring carbons are . ' to arise directly from the oxygen in the gas used.
If nitrogen, hydrogen, or other oxygen-free gases
arepassed through the mixture, the rate of p01?
merization is not. appreciably increased. Eiiorts
to be considered as‘ singly. bonded. "Examples,
of suitable amines include oleylamine, dioleyl
- amine, phenyloleylamine, oleylaniline, p-decenyl
to 11nd a catalyst comparable to oxygen have so
' cyclohexylamine,dihydroabietylamine,p-l-decen
ylaniline, N-p-decenylcyclohexylaniline, etc. Such
' far failed. ‘
amines may have one or. more amino groups per
,Whenemploying oxygen or air as a catalyst,
10 "
the-temperatures of reaction may vary over
molecule, but the preferred reactants, because
of cost, are monoamines. Where a'secondary'
rather wide limits, but best results are usually'ob
amine isv employed, it is necessary‘that only'one, ' tained within the range of 150° C. to 220° C.
of the aliphatic or cyclcaliphatic radicals at- , With reactants that boil ‘within or below this
tached ‘to the amino nitrogen be unsaturated. v15 temperature range, it is ‘desirable to carry out the '
The unsaturated amine may'contain one or more
- reaction under pressure, or to conduct the reac
carbon-to-carbon double bonds. The preferred '_
amines are aliphatic, cycloaliphatic and alkylcy-v
tion at a lower temperature until amide or imide
z formation has produced an intermediate of high
cloaliphatic amines which contain 8 or more car- '
. er boiling point. I The temperature may then be
to a higher value.v The use of oxygen
.
bon atoms and less than 32 carbonatoms' in each' 20'- increased
hydrocarbon residue. attached to the amino‘ nitro ‘ ‘containing gas' as a reaction catalyst leads to
gen. Examples‘of preferred vimines are: l-ami- ' ' some ‘concomitant oxidation which may take
no-octene-5, l-aminode‘cene-9;"oleylamine; ,lin-j ‘ ' place ,to ‘an objectionable degree, it ‘extremely
ileylamine; abietylz'amine,‘ dihydroabietylamine, 2s: high temperatures. are
used.‘ -
.
The following examples will serve to illustrate ll
erucylamine, p-IédecenyIcycIohexyIamine,"~ diole-'
how chemical products-or compounds or the kind
ylamine, n-hexadecyl-#noctadeeenylamine, unsat- _
above described‘ may be prepared or produced.»
urated secondary amines obtained as a lay-prod.
uct in the manufactureof‘primary amines from .' _
'
red oil, commercialmixtures of unsaturated-pri
- mary amines derived ‘from fatty oils, etc. '
'
v_
0mm; Pnonucr
-
-
Example
1
'
_
I
-
In preparing the new chemical product that
_ :54 partso'f crude octadecenylamine (iodin
forms part of my ew composition of matter, the
No.='78)
and 20 parts of maleic anhydride were
choice of the relat ye number of moles of the re
,heated and stirred in a vessel equipped with a gas
actants is somewhat variable. Under suitable
tube, condenser and water trap. The tem
conditions, at least one mole of alpha-beta, 35. ‘inlet
perature
was held at 190° C. for 2 hours. A slow
ethylenie acid appears to be able to combine ad
ditively with an amine having one carbon-to-car- __
bon double bond, while simultaneously condens
ingwith the amino group to yield amide or imide'
The product at this point was a red, viscous,
almost rubbery oil, which was clearly soluble in
alpha-beta ethylenic acid molecules may combine
kerosene,
additively withan amine having one double bond, ,
amine having two double bonds in a single ali
phatic chain or cycloaliphatic ring. Withsec
ondary amines containing twonnsaturated ali- '
phatic or cycloaliphatic groups, it is apparent
that four or more moles of alpha-beta, ethylenic
acid may combine. Usually, the preseht products
tion mixture, the temperature was raised slowly
to 210° C. and was held at this point for 21 hours.
linkages, Actually, experiment shows thattwo
while three or more moles may combine with an
' stream of air was then started through the reac
.
'
Cannon. Paonucr
Example 2 \
54 parts of commercial‘ n-octadecyl-n-octa
decenyl amine (iodine No.=45.4) and 10 parts of
maleic ‘anhydride were reacted as above.
The product was a dark, viscous oil when
will be prepared from reactants in which the ratio 50 warm, only partly soluble'in kerosene.
of moles of alpha-beta, ethylenic acid, to moles
Cnnmcsr. Paonncr
of unsaturated amine is within the range 0.5 to 5.
To prepare said new chemical product the de
Example 3
sired alpha-beta, ethylenic acid is reacted with
the desired unsaturated amine at a temperature
23 parts of citraoonic anhydride were substi
which may range from about 100° C. to about 250°
tuted for the maleic anhydride in previous Exam
C. for a period of several hours. The reaction
ple 1.
appears to involve both amide and imide forma
Carmen. Paonncr
tion, and-addition at or near a double ‘bond of the
unsaturatedreactants, Amidi?cation catalysts, 60
Example 4
such as traces of alkali, may be employed. Ole
?né polymerization, atalysts, such as benzoyl
40 parts of maleic anhydride were used in place
peroxide may also b; employed, but such do not,
of the '20 parts in previous Example 1. Heating
in general, greatly affect the rate of reaction and
at 210° C., while, passing a slow air stream
contribute to the formation of impurities.
through the reaction mixture, was continued for
To obtain the highest degree of polymerization
30 hours.
in the. shortest period of time, certain reaction
Cannon. Paonucr
conditions have been determined to be of great
‘importance. The determination of these reac
Example 5
tion conditions ‘actually constitutes an invention 70
within 'an invention, in thatit makes possible
24 parts of commercial fumaric acid were sub
stituted for the maleic anhydride of previous
the preparation of the most desirable products
Example 1.
with the minimum of time and effort. ‘In par
ticular, it has been found that polymerization is
The product was practically identical with that
promoted by passing through the mixture, dur 75 of, Example 1.
I
g 2,412,“?
6
5
C. The product 0! Example 4 also contains free
Cannon. Pnoirucr
carboxylic acid groups.
‘
-
Products containing free carboxylic acid groups
maybereacted with alkalies, amines, heavy metal,
oxides, etc., to yield polymeric salts which have}
_ Example 6
21.4 grams of puri?ed oleyl amine (iodine
No.=95.0) and 7.9 grams of pure maleic anhy
useful properties in addition to those 0! the
polymers alone. Salts. such as the sodium salt
of the product of Example 4, may be used as
dride were reacted in a vapor-heated vessel
' equipped with gas inlet tube, viscosimeter tube,
thermometer, water trap and condenser. The
sludge dispersers or detergents in lubricating oil.
mixture was heated at 200:2“ C. by means of 10 The lead salt of the product of Example 2 may
boiling m-cresol. During the ?rst part of the
also be used as a thickening agent and a deter
reaction a stream of dry methane was passed
through the mixture. Later a slowv stream of dry
air was substituted for the methane. The vis
cosity of the reacting mixture was determined
gent in oils.
periodically by a'procedure such as that de
scribed by Flory, J. A. C. S. 62, 105 (40). The
following table summarizes the
ob
tained at various periods, and also gives 'the
molecular weights of a few samples, as deter
‘
Viscosity
Average
a; manna)
lggm
units)
product
'
5 __________ __
Methane..-_
l. 33
9_ _ _ _ _ _ _ _ _ _ . .
_ _ _ --d0_-____
1.40
__do ____ __
1.49
l6___
mono-, dip, or polyhydric alcohols. Whensuch
carboxyl-containing products are reacted with a
long chain amine or alcohol, especially useful
20 products are obtained. which are made the sub
ject of my co-pending application Serial No.
558,950, ?led October 16, 1944.
The nature of the reaction which results in
' mined cryoscopically in benzene.
Total hours of heating casusbemgd
'
In generaLproducts of the present invention .
which contain free carboxyl groups may be‘ em
ployed as such, as the metal or amine salt, as‘
an amide, ‘or in some cases, as the esters of
the formation of the new chemical product here
25 in described, is not clearly understood, but it is
believed that the alpha-beta, unsaturated acid .
reacts with the amine group of the amine, and '
___________ -_’
also condenses, by proton transfer, with the un
saturated amine at an ethylenic carbon atom of
1,760
____________ -
27 _________________________ -_do____--
1.55w ____________ __
44 _________________________ --do ____ __
1. 63
____________ __
30 same, or at a carbon atom near the double bond.
The unsaturated amine undergoing condensation
REPLACED METHANE W 1TH AIR AT THIS POINT
2. 27
2,240
6. 23
17. 20
____________ -_
____________ __
3, 020
with a molecule of ethylenic acid, is probably _
linked by amide or imide formation to a di?erent
molecule of ethylenic acid; so a type of linear
35 polyamide is formed. When the double bond of
the unsaturated alcohol is nearer to the amino
nitrogen than allowed by the conditions previ
ously given, good yields of the desired products
The product ‘was a clear, red, extremely viscous
?uid.
‘It was soluble in benzene and mineral '
are not obtained. It is believed that this is‘ the
spirits, and partly soluble in SAE 30 Pennsyl
result of the formation of stable, cyclic, inner
40
vania motor oil.‘
amides, rather than linear ,polyamides.
The data clearly shows the e?ect- of air in in
Various possible reactions which are believed
creasing the rate of polymerization. However,
might occur in the preparation of the new chemi
it is also clear that a considerable amount of
cal product that forms part of my new composi
polymerization is obtained in the absence of
tion of matter, are- as iollows, employing an
45
oxygen. The average molecular weight of the 9
unsaturated aliphatic primary amine and an
hour sample corresponds to that. of a molecule
containing about 5 monomer units.
alpha-beta, ethylenic, monocarboxy, aliphatic
acid:
Crimean Pnonucr
50
Example 7
100 parts or inaleic anhydride and 270 parts of '
commercial oleyl amine were heated at 200° C.
until re?uxing ceased. The temperature was
then raised to 240° C. and held for 4 hours. A
' product sample at this point had a cryoscopic
molecular weight of 2,400.
-
~
'
-
'
‘
nR.cH,.cH=0H~cH,-cntnncrimiirl-nnwcmcmcoon
n[a.cm.c=cn.cn,.om.n'.charm-1011
n".cn.cni'co-
.
+ (ii-DEC
.
or
I
Carmen. PnonUc-r
Example 8
56 parts of commercial dihydroabietyl amine
were substituted for the 54 parts of octadecenyl
amine employed in Example 1. ‘
The product had practically no acid value and
was a very viscous oil, soluble in lubricating oil.
It will now be noted that one of the above prod
ucts, that of Example 2, was prepared from one
molal proportion of a dibasic acid and one molal
proportion of a monobasic secondary amine.
Such products contain some free carboxyl groups.
Analysis of the product of Example 2 indicates
that somewhat less than the theoretical number
of carboxylic acid groups remains. It is believed
that this result may arise from some decarbox
ylation at the temperature of reaction, i. e., 210°
H R. 0 H2. CH. CHLCHLCHLRQCHLNH- 0H
[
-
R". CH: H. C 0-
.
1 q +. (7l—1)HzO
Where a dicarboxylic/ alpha-beta ethylenic
acid, such. as maleic anhydride, is reacted with
- .
‘9,419,557
ical Product, Example 1, less reagent is required
a primary, unsaturated amine, it is believed that
reactions analogous to the above take place with
- for a desired improvement in viscosity index._ In
the formation of polyimides. In this case the
general, the percentages of such products which
- reaction analogous to the ?rst one above would be:
will be employed, varies from as little as 0.025%
to as much as 5%, or even more, depending upon
the use to which the oil is to be put. Thus, one
object of my invention is the preparation of such
'improved lubricating oils, or lubricating oil com
positions, by adding not less than about 0.025%.
10 or more than‘. about 5% of the hereindescribed
chemical products or compounds, to lubricating
0
0
l
I
oils, such as are used in internal combustion
1'
engines.
. Such a product would be a substituted poly? '
succinimide.
>
'
.
15
Where more than'one mole of alpha-beta, eth
ylenic acid is reacted with a. mole of unsaturated
amine,.similar reactions probably occur, with the
attachment of. two or more moles of ethylenlc acid
at points in the unsaturated chain of the amine 20
at or. near the double bond.
'
not remove all of the ole?nic groups of the un
may be hydrogenated to remove ole?nic double
bonds. Other chemical reactions maybe em
ployed to modify the properties. of the polymers.
For example, they may be treated with sulfur at
'
elevated temperatures to form 'sulfurized poly
an imide both p; the original amino hydrogen
“atoms have been removed by reaction with a
mers - useful as antioxidants‘ ‘and ?lm strength
improves for petroleum or_fatty oils, or they may
For this reason, the term
be chlorinated, or. they may 'be both sulfurized
and chlorinated to yield useful additives for heavy
. “amide” will bé'used in the‘ claims in its broad
‘sense to include groups or linkages of either the
,
saturated reactants. 'If.desi'red,‘lthese products
An imide may be looked upon as a special type
of amide, or as a kind of double amide, since in
carboxyl' group.
,
The hereindescribed new chemical products
that form parts of my new 'compositionof mat
ter, are, in general, unsaturated, as reaction does
.
duty oils.
.
.
'
I conventional monoamide or imide type.
Chemical products of the type herein contem
In the above formula, R and R" represent alkyl 30 plated are referred ‘to as' addition-condensation
slfoups which contain one or more carbon atoms,
polymers. This is in conformity with nomen
'and R’ is an alkylene 'group which may contain
clature in Organic Chemistry, Gilman, 2nd edi
one or more carbon atoms. 12 is a whole number.
tion, volume 1, page 702.
In addition to the above reactions, several
Sald products are addition polymers in the
others are conceivably possible. However, it is 35 sense that some intermolecular reaction occurs
understood that the exact reactions are a matter
without the elimination of any atoms or groups,
of speculation ,or conjecture, and may vary, de
such reaction being that involved during the cou
pending, in part, on the particular reactants se
pling of the alpha-beta, ethylenic acid to the un
lected. , Such reactions are not to be construed
saturated hydrocarbon group of the amine. Fur
as a limitation in' any respect, but are submitted‘ 40 ther, condensation occurs through the reaction of
in order to show the diverse nature of the pos
sible or probable reactions involved, and addi
tionally, to indicate the inability adequately to
portray the invention in terms of conventional
chemical formulae.
,
-
My invention consists in using the chemical
products above described as lubricating oil ad
ditives for increasing the viscosity index of such.
oils. As speci?c examples of my present inven
tion, the following examples are given of a new
composition of matter, consisting of a mixture
of mineral oil and the polyamides or polyimides
previously described.
Courosrnon or MATTER
Example 1
2% by weight of the product of previous Ex
ample 7, above, was added to a lubricating oil
having a viscosity index of 60, and a viscosity at
210° F. of 46 seconds. ' The resulting clear oil so
lution had a viscosity index of 95 and a viscosity
of 53 seconds at 210° F.
Comrosrrron or Mar-ran
the carboxylic acid group with the amino group,
yielding water as a product. In general, poly
merization of the reactants employed will be pos
sible only when both addition and‘condensation
occur.
Having thus 'described my invention, what I
claim as new and desire to secure by Letters Pat
ent is:
1. A. lubricating composition, comprising a lu
bricating oil and an unsaturated amine-alpha
beta, unsaturated carboxylic acid‘addition-con
densation polymer; said amine containing at least'
one ethylenic unsaturation and having at least
4 singly bonded carbon atoms between the eth
ylenic double bond and the nearest amine nitro
gen atom, said amine having at least one hy
drogen atom directly linked to an amino nitrogen
atom, and containing less than 32 carbon atoms
per nitrogen-attached hydrocarbon group; said
‘acid containing less than 10 carbon atoms and
free from vinyl radicals; said polymer being mixed
with said lubricating oil in an amount within the
range of .025% tdabout 5%.
,
2. A composition of matter, as de?ned in claim
Example 2
. 1, wherein all radicals attached to the amine ni
2% by weight of the product of previous Ex
trogen atom are aliphatic radicals.
ample 3, above, was added to a lubricating oil hav-.
3. A composition of matter, as de?ned in claim
ing a viscosity index of 70 and a viscosity of 210°
1, wherein all radicals attached to the amino
nitrogen atom are straight chain aliphatic radi
F. of 44.9 seconds. The resulting oil had a vis
cosity index of 90.0 and a viscosity at_210° F. of 70 cals.
,
'
48.5 seconds.
4. A composition of matter, as de?ned in claim
Greater or lesser e?ects on viscosity index than
1, wherein the amine contains a single amino
1 those illustrated above may be obtained by add
nitrogen atom and all radicals attached to said ing more or less reagent. Using a product of
amino nitrogen atom are straight chain aliphatic
higher intrinsic viscosity, such as that of Chem 76 radicals.
-
2,412,557
.
5. A composition of matter, as de?ned in claim '
1, wherein the amine contains a single amino ni
trogen atom; all radicals attached to said amino
nitrogen atom are straight chain aliphatic rad
icals, and the alpha-beta, monoethylenic acid is
l0
1, wherein the amine contains a single amino
nitrogen atom; all radicals attached to said amino
nitrogen atom are straight chain aliphatic radi
cals, and the alpha-beta, monoethylenic carboxy
acid is fumaric acid.
8. A composition of matter, as de?ned in claim
1,
‘wherein the amine contains a single amino
6. .A composition of matter, as de?ned in claim.
nitrogen atom; all radicals attached to said amino
1, wherein the amine contains a single amino
nitrogen atom are straight chain aliphatic radi
nitrogen atom; all radicals attached to said amino
nitrogen atom are straight chain aliphatic radi l0 cals, and the alpha-beta,- monoethylenic carboxy
dicarboxy.
I
cals, and the alpha-beta, monoethylenic carboxy ~
acid is maleic acid.
7. A composition of matter, as de?ned in claim
‘acid is citraconic acid.
CHARLES M. BLAIR, JR.
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