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2,411,957
Patented Dec. 3, 17946
UNITED ‘STATE, S
OFFICE
Q‘ esst??jiiies
I
I
it
i
I’
Melvin De Groote, University City, and Bernhard
Keiser, Webster Groves, Mo., assignors to ,
Petrolite Corporation, Ltd., Wilmington, Del., a
corporation of Delaware
No Drawing. Original application June 23, 1943,
Serial No. 492,180. Divided and this applica
tion April 7, 1944,'Serial No. 530,042
10 claims? (01. 260-404)
1
* see U, s. Patent No.2,242,837, dated May 20,- 1941,
This invention relates to a new‘ chemical prod
uct or compound, and to a novel method for
manufacturing the same, our present applica'»
tion being a division of our pending application
to Shields.
Serial No. 492,180, ?led June 23,1943, now Patent
No. 2,372,254fissued March '27, 1945;
I
.,
Although any of the high molal monocarboxy
acids canv be converted into esteramides of the
kind described, by conventional procedure, it- is
our preference to ‘employ hydroxylated ester
,
amides derived from higherv fatty‘acids, rather
"fO'ne. object of our invention is’ to provide a
than petroleum. acids, rosin acids, and'vthe like.
We have found that by far the most effective
new-chemical product ‘ or compound ‘ that is
capablefof various uses, but which is particularly
adapted for use as a'demulsi?er in the resolution 10 demulsifying agents are obtained from un
saturated fatty acids having ‘18 carbon atoms.’
or crude‘ oil emulsions or the wateri-in-oil type,. I
Such unsaturated fatty acids include the higher
,Another object is to provide-a "practicable
method for manufacturing said chemical product , fatty acids, such as, oleic acid, ricinoleic acid,
'linoleic acid, linolenic acid, etc, One may. em
or
compound.
~
I
-
’
»
.
I
a
125
' Brie?y described, our new chemical product
ploy mixed fatty acids, as,_for example, the fatty
acids obtained by hydrolysis ‘of cottonseed oil,
consists of a sub-resinous or semi-resinous prodr
not. obtained by reaction between a polybasic
carboxy acid or its equivalent, such as the Van
hydride, and a hydroxylated esteramide-ofthe
soyabean oil, corn oil, etc. When our new product
or compound is intended to be used as a demulsi
her ‘for resolving petroleum emulsions of the
water-in-oil type, it is preferably obtained from
20
kind hereinafter described.’ Said hydroxylated
unsaturated fatty acids, and morespeci?cally,
esteramide is of the kind in. which the" amido ' unsaturated
fatty acids containing a hydroxyl
acyl radical is derived fromia hydroxylated'mono
carboxy acid having not over 5lecarbonatoms,
and the acyloxy radical is characterized bybeiiig
radical or unsaturated fatty'acidswhich have
been subjected to oxidation or'oxyalkylation, such
acid having at least 8 and not more. than 32
'
‘ derived‘from a monocarboxyjdetergentrforming 25
carbon
'
atoms.
‘
.
"
’
,~
.
as oxyethylation.
_,
' ,
"
I‘
5
p
U ‘
The esteramidesiof the‘ kind herein described
may be obtained in ‘any conventional manner.
They are usually derived from the hydroxylated
_
It .is Well 1 known that certain .monocarboXy
low molal acids themselves; .but if desirable, ,the
organic acids containing eight carbon atoms or
more, and not more than 32v carbon atoms, are
characterized by. the fact that they combine with
alkalies to produce soap or soap-like‘ materials.
functional equivalents'such as the anhydrides,
These detergent-forming acids include ,fatty
_acyl chlorides, or other. derivatives, maybe ‘em-H
ployed.i suitable acids ‘include, hydroxyacetic- acid
(glycollicv acid), ,hydr'0Xypr0pionic acid, “(lactic
acids, resin acids, petroleum acids, etc.» 'For'. the
polyb'asic ‘ hydroxy} acids.
acid), and others. It 'is' not intended to include
Not only‘ may alpha
sake of‘ convenience, these acids will be indicated
by the formula R'COOH. Certain derivatives of
hydroxy acids be employed, but one may also
detergent-forming acids react with'alkali to pro_-'
hydroxy butyric acid, betahydroxy propionic acid,
employ'the betahydroxy acids, for'insta'ncqbeta- .
duce soap or soap-like materials, and are the .
. etc. The objection’ to the use, of such betah'ydroxy,
obvious equivalent. of Y the unchanged or . un
acids which contain, a hydrogen atomon the
40
modi?ed detergent-forming acids;‘;for instance
alpha, carbon atom, is that they are rather ,un- ‘
instead ‘of fatty‘ acids, one rmightlem/ploy" the
stable. Thus, on heating, they, lose the elements
chlorinated» fatty vacids. ' Insteadgofthe ‘resin
of water, forming unsaturated acids. This is
acids, one might employ the hydrogenated resin ‘
acids. Instead of’ naphthenic acids,‘ one-might
45
employ brominated naphtheniciacids, etc.‘ '
'
'
The fatty‘ acidsnlare of the rtypebcommonlyQ
referred ‘to as highe'rfatty acidsyl and of'cour'se,
this is-also trueinr'egard to derivatives ‘of’ the
illustrated by the formation of acrylic acid from
betahydroxy .propionic acid; For all practical
purposes, the'two hydroxy acids'most' suitable
are lactic acid, and hydroxyacetic acid. ‘7 In some
'instances;thereare available derivativesiof acids ‘
such as ethanolacetic‘a'cid, propanolacetic acid,
kind indicated, insofar ‘that such derivatives are 50 and v,the like. See U. S. Patent No. 2,238,928,
I ‘obtained from higher fiatt’yiacids. ‘The'petroleum’
acids include I not: 5 only: naturally-“occurring
naphthenic acids,.'b:ut1 also acidsobtained by the
oxidation offwax, paraiiin; etc. Such, acids ‘may
have as many-as 32 carbon atoms. 1 For. instance,»
dated April 22, ‘1941, to Cahn and Harris, and
Y particularly Example ,51, on page 3.
Note par
ticularly Examples 64-66 on pagej‘i. .' If vsuch acids
‘ bevgconsidered as derivatives of‘ hydroxyac'etic
' acid, and ,obtai'ried hypothetically.v by an oxy-~
2,411,957
3
4
alkylation reaction involving alcoholic hydroxyl
radical of hydroxyacetic acid, and ethylene oxide,
then it is apparent that analogous compounds
previously mentioned. As illustrating such hy
droxylated esters, reference is made to the fol
lowing formulas:
would be derivable by the use of glycid. In this
connection note Examples 69 and 70 of the afore
mentioned Cahn and Harris patent. In actual’
manufacture, these particular types of acid are
obtainable by other means.
The amide of such low molal hydroxy acid may
be treated with an oxyalkylating agent, such as
ethylene oxide, propylene oxide, butylene oxide,
or the like, so as to produce a compound of the’
following type:
-
O
alkylene. OH
15
alkylene. 0 H
Actually, the alkylene radical might represent
an equivalent divalent radical, in which the car
bon atom chain is interrupted at least once by 20
oxygen, as
Having obtained a bis(hydroxyalkyl>amide of
the kind described, such compound can then be
reacted in aconventional manner with a high
molal acid or its equivalent, to give an esteramide,
In the above formulas, RCO represents the acyl
radical derived from a hydroxylated acid having
in other words,»a compound of the following type:
hydroxypropionic, hydroxybutyric, etc. OHR’CO
5 carbon atoms or less, such as hydroxyacetic,
represents the acyl radical of a hydroxylated
(I? /alkylene. O O C R’
acid, such as ricinoleic acid, hy'droxystearic acid,
R CN
orsimilar acids obtained by oxidation, such as
alkylene . O H
A procedure that is frequently more readily
adaptable is simply the reaction between a low
molal acid, such as acetic acid, and a material 3
of the kind exempli?ed by diethanolamine, di
propanolaminaor the like. For the sake of brev
ity, reference hereafter will be, made largely ,to
diethanolamine and acetic acid, although other ', .
suitable reactants have already been described.
The method of manufacturing esteramides is so
well known that no further description is re
quired; but for convenience, the following exam
ple is given in substantially verbatim form, as it
blown oleic acid or'acids obtained by the hydroly
sis of blown olein. ‘Such acyl radicals all contain
at least 8 and not more than 32 carbon atoms
and are apt to contain 18 carbon atoms. R”CO
is the-acyl radical derived from a non-hydroxy
late'd monocarboxy detergent-forming acid, par
ticularly an unsaturated acid, such as oleic acid,
linolenic acid, etc. It is understood, of course,
that a mixture of fatty acids might be employed
instead'of a single fatty acid; R'” is a hydro
carbon radical having 4 to 12 carbon atoms.
, In examining the above formulas, it is to be
notedthat comparable products might be obtain
appears in U. S. Patent No. 2,238,923, dated April '
able from ,monobutanolamine, dibutano-lamine,
22, 1941, to Cahn .hHarris:
monopropanolamine, dipropanolamine, mono
glycerylamine, diglycerylamine, or the like, in
stead'of being derived from mono-ethanolamine
or diethanolamine. Similarly, the products
Example 0
(1) 156 grams of methyl lactate and 157.5 grams of
diethanolamine were re?uxed for 3 hours at 94 degrees (1.,
the alkalinity calculated as diethanolamine dropping from 50 shown in the last two formulas are derived from
50.5% to 5.4%. To the reaction mass 78 grams of methyl
trisdiydroxymethyl)aminomethane. Similar de
lactate were added and re?uxlng was continued for 3%
hours at 95 degrees C. The alkalinity dropped to 0.9%
rivatives may be derived from 2-amino-2-ethy1
expressed as diethanolamine.
The excess methyl lactate
and the methyl alcohol which formed during the reaction
were removed by distillation at a pressure of 10 mm. and
at a temperature up to about 120 degrees C. The reac
tion product was a reddish brown, water-soluble, somewhat
viscous material and comprised largely or essentially the
lactic acid amide of diethanolamine.
_
(2) 37.3 grams of the lactic acid amide of diethanola
mine, produced in part (1)‘ hereof, and 9.8 grams of lauric
acid were heated together to 60 degrees C., _whereupon a
homogeneous solution resulted, and the heating was then
continued for 20 minutes at 140 degrees C., for 20 minutes 60
at 150 degrees C., for 20 minutes at 170 degrees C., and
for 15 minutes at 180 degrees C.
Previous reference has been‘made, however, to
the fact that our preference isv'to use hydroxy
acetic acid, due to its low cost and ready avail
ability.
~
1,3-prop'anediol and 2-amino-2-rnethyl-1,3-pro
panediol.
"
'
.
'
The hydroxylated esteramides may, of course,
be derived in any other suitable way, such as
reaction with ammonia, followed by oxyethyla
tion, or some other suitable process.
Thus, the
low molal acids themselves, or, if desirable, the
functional equivalents, such as the anhydrides,
acyl chlorides, or other derivatives, may be re
acted with ammonia, or a primary amine, such
as‘any suitable alkylamine, or an alicyclic amine,
or an aralkylamine, to give the amide or substi- ,
tuted amide; in any event, a, compound contain
ing at least one amino hydrogen atom. Suit
vIllustrating somewhat'similar types of reac
tions, see U. S. Patent No. 2,238,902, dated April
22, 1941, to Katzman and Harris; and also U. S.
Patent No. 2,257,180, dated April 30, 1941, to Munz 70
when an amine is used instead of ammonia for
and Tra'skan.
reaction with the low molal hydroxyl acid, one
.
V
In View of what has been said, it will be obvious
that hydroxylated esterarnides of the kind herein
able amines include butylamine, amylamine,
octylamine, decylamine, cyclohexylamine, benzyl
amine, phenylamine, etc. Generally speaking,
may employ a hydroxylated detergent-forming
acid such as ,ricinoleic acid, in order to insure a
employedas reactants, may be obtained in various
pluralityof available alcoholic hydroxyl groups
manners, including those described in the patents 75 for subsequent reaction with the polybasic car
2,411,957
26
non-hydroxylated detergent-forming acid, such
be treated with four moles or six moles of ethyl
as oleic acid, is employed, there still'is available
ene oxide, or even more.
under any circumstances at least one alcoholic
Previous reference has been made to the fact
hydroxyl radical, to wit, the hydroxyl radical or
‘radicals of the low molal acyl radical.
»
.
i. e., the low molal amide, instead of being treated
with two moles of ethylene oxide or the like, might
‘boxy-acid or its equivalent. However, even ifa
that the preferred compounds are derived from
- '
hydroxyacetic acid, unsaturated fatty acids, par
1 g In this connection it may be wellto point out
ticularly ricinoleic acid, etc. The type of amide
which we prefer to employ for reaction with
stituted amide so obtained can be reacted with'a '10 phthalic anhydride or the like, may be illustrated
polybasic carboxy-acid or its equivalent without ' by the following:
further modi?cation. However,» the most desir
Esteramide, Example 1
able type of compound is derived from such low
One
pound
mole of hydroxyacetic acid is re
‘molal amides as are characterized by aplurality
acted
with
one
pound mole of monoethanolamine;
of alcoholic hydroxyl radicals.- Thus, if the sub 15
and after the amide has been formed in substan
stituted amide obtained by reaction between butyl
tial yield, the mass is then reacted with one pound
amine and hydroxyacetic acid is treated with
the following: By considering the reaction involv
inghydroxyacetic acid and butylamine, the sub
mole of ricinoleic acid so as to form the ester.
ethylene oxide, glycid, or the like, and then re
The reaction is illustrated by the following equa
acted with oleic acid, or some equivalent non-hy
droxylated high molal acid, one still has available 20 tions:
a plurality of alcoholic hydroxyl radicals. How
1. HOCH2COOH+HOC2H4NH2+
.
HOCH2CONHC2H4OH
ever, on treatment of such-7 amide with ethylene
oxide, glycid, or the like, at least under certain
2. HOCH2CONHCZH4OH+HORCOOH+
HOCHzCONHCzHrOOCROH
Esteramide, Example 2
One pound mole of diethanolamine is substi
conditions, there is formed to a very minor de
gree amides of certain low molal acids of the
kind previously described; 1. e., it is exempli?ed
by ethanolacetic acid. lAS a matterof fact, how
ever, it is our preference that even under such
tuted for monoethanolamine in Example 1, pre
circumstances, i. e., even where there is a plu
rality ‘of alcoholic hydroxyl radicals present, the 30
high molal acid also contains a hydroxyl group.
This, ricinoleic acid is the preferred reactant
employed to supply the high molal acyloxy radi
cal; and in such instance, the hydroxyl radical,
which is part of the ricinoleyl radical, would .
serve as a reactive function forcombination with
ticularly as demulsi?ers, must present a rather
acids are used, in light of the fact thateither one,
a
Esteramz'de, Example 3
Monopropanolamine, dipropanolamine, mono
butanolamine, dibutanolamine, tris(hydroxy
methyl) aminomethane, bis (hydroxymethyl) ami
14, preceding, are treated by a conventional
oxyalkylation process with 1-2 moles of ethylene
phthalic acid radical ‘or its equivalent is attached
directly to the low molal acyl radical, as differ
entiated from being attached in an altogether
oxide, propylene oxide, butylene oxide, glycid, or
' the like;
different position to a ricinoleylradical or ‘an '
ethanol
(b) There
radical;
would
or be present
.
a terminal
.
. . hydroxy-i
. H
.
Esteramz‘de, Example 5
Esteramides of the kind obtained in Examples
.
'A molecular arrangement whereby
-
Examples 1-3, preceding.
‘or'possibly. both, .‘of the following structural ar
(a)
'
Oleic acid is substituted for ricinoleic acid in
peculiar structure when hydroxylated low molal
‘
.
nomethane, and the like, are substituted in
place of monoethanolamine and diethanolamine
in Examples 1 and 2, preceding.
Esteramicle, Example 4
phthalic anhydride or the like by esteri?cation.
In this connection, it may be pointed out ‘that
.such‘compounds herein contemplated, and par
rangements may occur, to wit:
ceding.
to
methyl group, or its equivalent, as, for example,
when derived from hydroxyacetic acid; .and thus
Esteramide, Example 6
Methyl lactate is employed in the manner
previously indicated to produce lactic acid de
rivatives instead of hydroxyacetic acid deriva
such a terminal radical would be distinctlyihydro
tives.
In any event, the reaction of the hydroxylated
phile in character, as compared with the ordinary, .,
methyl radical appearing in. acetic acid or the . , ester amide of the kind described with a poly
basic carboxy acid or its functional equivalent,
such as the anhydride, is a well-known reaction
Other. procedures suggest themselves for prepa
like.
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.
.
..
.,
ration ofcompounds having a plurality of-alcoe
and is nothing more or less than an esteri?cation
holic hydroxyl radicals. _ For instance, in. the case ? 60 reaction of the kind employed to produce
,of compounds derived fromt‘butylamine, cyclo
hexylamine, benzylamine, or the like, one might
phthalated castor oil, phthalated ricinoleoamide,
etc. For instance,.common comparable reactions
use glycid or the like as an oxyalkylating agent. "
are described in U. S. Patent No. 1,976,602, to
Another procedure involves preparing the amide .
from ammonia and treating such amide with an;
De-Groote, Keiser and Adams, dated October 9,
1934, and U. S. Patent No. 2,078,652, to De Groote
oxyalkylating agent, such as‘ethylene oxide, p-ro
and Keiser, dated April 27, 1937.
pylene oxide, butyleneoxide, glycid, or the like,
Brie?y stated, the molar combination of the re
actions selected depend upon the available num
ber of hydroxyl groups and may be illustrated by
to produce acompound of the following type:
'
0
alkyleneOH
"
V
the following examples:
_ .
.
BXIIIJN
alky1ene.OH
‘ 7‘
_
Actually,’t_he alkylene radical might represent an
i'equivalentédivalent ‘radical _in1 which the carbon, I
'latoiii'chairi is interrupted atTle'ast'i onoe'by oxygen;- ~
a
'
»
-
Final product, Example‘ 1
One pound mole of a polyhydroxylated ester
' - amide of the kind exemplified by ,Ev‘steramide, Ex
amples T145} preceding, is reacted:v with ‘one pound
2,411,957
7
.8
mole of phthalic anhydride at approximately
being condensed by the trap. This is a conven
tional-procedure, commonly employed in this type
led-165° C. until esteri?cation is complete, as in
dicated by the substantial elimination of one al
;or similar types of reaction. ,
Although we prefer toruse phthalic anhydride
coh-olic hydroxyl radical. The product so ob
tained has one free carboxyl radical.
as the most desirable source of the polybasic car
boxy acid, one may use other polybasic carboxy
acids or their anhydridessuch as succinic, malic,
Final product, Example 2
fumaric, citric,.maleic, adipic, tartaric, glutaric,
The same procedure is followed as in the pre
ceding Final product, Example 1, except that the 10 .diphenic, naphthalic, oxalic, ,pimelic, .suberic,
azelaic, sebacic, etc. Naturally, a simple deriva
esteramide employed is the kind exempli?ed by
tive of a polybasic acid, such as chlorophthalic
Esteramide, Example 6, instead of E'steramide,
acid, can be used as advantageously as phthalic
Examples 1-5, inclusive.
acid itself, although there isno added advantage
Final product, Example 3
in the use of the more costly chemical compounds.
15
The same procedure is followed as in Final
product, Examples 1 and 2, except that two, moles
of phthalic anhydride are employed instead of
In View of the large number of .reactants and
types of, materials described, it maybe well to
note those which we particularly prefer. It has
been. pointed out that we prefer to use unsatu
one mole; and the ?nal product is characterized
rated fatty acids as the source of the high molal
by the presence of two free carboxyl radicals.
20 acyloxy radical, and particularly the hydroxylated
fatty acids commonly available, to Wit, ricinoleic
Final product, Example 4
acid. We prefer to use phthalic acid, maleic acid,
or their anhydrides,or oxalic acid as the source
of the poly-basiccarboxy acid. We prefer to use
hydroxyaceticacid or its equivalent as the source
Insofar that some of the esteramides described
in Esteramide, Examples l~6, inclusive, may have
more than two alcoholic hydroxyl groups per
molecule, one may employ-the same type or” re
action as described in theexamples immediately
preceding, except that the maximum amount of
phthalic anhydride which can be employed from
a sto-ichiometrical standpoint is employed, and
thus, the ?nal product of reaction has a. plurality
of carboxyl groups and a substantial absence of
of the low molal acyl radical. We prefer to use
monoethanolamine or diethanolamine as the re
actant for formation of the substituted amide em
ployed for subsequent reaction to produce the
30
hydroxyl groups.
esteramide.
'
>
>
In view of what has been said, it is apparent
that the hydroxylated esteramides of the kind
described ,previouslylmay be considered, for the
sake of simplicity, as being in- the classof an
alcohol, i. e.,'a monohydric or polyhydric, alco
incl product, Erample 5
In the preceding examples, where phthalic
anhydride is used, maleic anhydride or oxalic
acid is employed. In such instances where ox~
alic acid is employed, it is desirable to use a lower ‘
temperature, in view of the fact that oxalic
acid, or most of its functional equivalents, de
compose at a temperature as high as 105°, or
:hol. If an alcohol is indicated by theformula
Y'(OH)n, where nlindicates the number 1 or
more-and if a polybasic acid body beindicated
by the formula X’»(COOH)n, where n indicates
the number 2 or more, then the reaction between
a‘monohydric alcohol and a polybasic acid will
result in a compound which may be indicated by
the following formula: X’Y'(COOH) n’, where n’
indicates the number 1 or more, and which is in
thereabcuts, and instead, a temperature‘ of
105— 12° C. should be employed. Such lower We fix reality a contraction of a more elaborate struc
tural formula, in which X’ and .Y' are joined by
temperature requires longer time for esteri?ca
a‘ carboxyl radical or residue. Assuming, how
tion to take place.
~
ever, as would-be‘ true in the majority of cases,
In certain instances, desirable productsare
that the alcohol actually would. be a polyhydric
obtained from mcnohydroxylated esteramides.
alcohol, and that the acid body would be poly
For instance, hydroxyacetic acid, or methyl lac- .
basic in nature, for instanca'if one employed a
tate, can be reacted with ethyl ethanolamine,
propyl ethanolamine, ethyl propan-olamine, pro
pyl butano-lamine, or the like, and the esteramide
diphthalate ofa polyhydroxylated esteramide of
the kind previously described, then examination
reveals that the formula might result in a com
so obtained then reacted with a non-hydroxylat
ed high molal acid, such as oleic acid. Such a OI OI bination, in which there were neither residual
product containing only one hydroxyl radical, to
wit, the hydroxyl radical of the low molal acyl
radical, can be reacted with phthalic anhydride
or the like.
‘
-
'
'
carboxyl radicals, nor residual hydroxyl radicals,
or might result in compounds in which there
were residual hydroxyl radicals, and no residual
carboxyl radicals, or compounds‘ where there
E-steri?cation can beconducted in the usual 60 might be residual carboxyl radicals and no resid
ual hydroxyl radicals; or there might‘ be both.
‘manner, simply ‘employing heat to drive off the
This is indicated by the following:
water formed._'In some instances, where an 'an~
hydride is employed, water'may not be ‘formed.
If desired, one may pass a dried, inert gas, such
- as dried nitrogen gas, through the mass to hasten
esteri?cation. E‘steri?cation is also hastened at
times by the presence of a mere'trace of a suit
in which q indicates a small whole number (one
able acid, ‘such as benzene sulfonic acid. In
in the case of a monomer, and probably not over
other instances, the reaction is most suitably
20 and usually less than 10), and m’ and n’ in
conducted in the presence of an inert high boil
dicate the number 1 or more, and m" and n”
ing solvent, such as xylene. The xylene is con
indicate zero or a small or moderately-sized whole
tinuously distilled under a re?ux condenser, con~
number, such as 'zero,’ one or more, but in any
densed by such condenser, and returned to the re
event, probably a, number not in ‘excess of 10-15.
action chamber through a trap. The xylene va
,Naturally, each residual hydroxyl. could combine
, pors carry off the water, which is removed after 75 witna. phthalic acid__ bodyor; its equivalent, or
10'
~11
1'."A sub-resinous‘esteri?cation product, of the‘
with a similarcompound ‘derived from a tribasic
acid, such ascitric acid; and in such event, there
following formula: '
would be a large number-of free or uncombined
'
carboxyl radicals present, possibly 20 or more.
Actually, the preferable type of reagent would be 01
more apt .to include less than 20, and in fact, less
than 10 free hydroxyl radicals. It is not neces
sary to remark that the residual carboxyl radicals
I
(c 0 on»...
(OH) "(Ya/Xx’)
_ .
(o o 0 .2) ml
in which :c’ and y’ are small whole numbers not
greater than 10 and m, n, and m’ are small whole
can be permitted to remain as ‘such, or can be
numbers not over 10, and including zero; Z is an
neutralized in any suitable manner, such as con 10 acidic hydrogen atom equivalent; and X is a
versioninto salts, esters, amides, amino esters,
or’any othersuitable form.. Usually,such~con
version into salt form would be by means of so- -
residue derived from a polybasic carboxy acid;
and Y is a residue derived from a hydroxylated
esteramide containing (a) one amido-linked
acyl radical derived from a hydroxylated carboxy
acid having not over 5 carbon atoms; and (b)
dium hydroxide, potassium hydroxide, calcium
hydroxide, magnesium hydroxide, ammonium 15;
at least one acyloxy radical derived from a mono
hydroxide, amylamine, butanolamine, ethanol
amine, ' diethanolamine, triethanolamine, cyclo
carboxy detergent-forming acid having at least
hexanolamine, benzylamine, aniline, toluidine,
8 and not more than 32 carbon atoms, and linked
by a divalent‘ aliphatic radical to the amido nitro
etc. Conversion into the ester would be by means
ofa monohydric alcohol, such as methyl alcohol, ,
ethyl alcohol, propyl alcohol, butyl alcohol, hexyl
alcohol, _octyl alcohol, decyl alcohol, ethylene
glycol, diethylene glycol, glycerol, diglycerol, tri
' gen atom.
2. A polar sub-resinous esteri?cation product
of the following‘formula:
'
ethylene glycol, or the like. One could employ
found that such products are soluble to a fairly
de?nite extent; for instance, at least 5% in some
(coon);
(OH)n(Yv'Xz/)
an amino alcohol so as to produce an‘ester.
We have found, however, as suggested, that the
most suitable products are sub-resinous, semi
resinous, or balsam-like products, and are prefer
ably derived from polyhydroxylated reactants,
i.‘ e.,.polyhydroxylated esteramides. We have 30
‘
(000.2)...’
in which a." and y’ are small whole numbers not
greater than 10, and m, n, and m’ are small
Whole numbers not over 10, andv including zero;
Z is an acidic hydrogen atom equivalent; and
X is a residue derived from a polybasic carboxy
,acid; and Y is a residue derived from a hy
solvent such‘ as water, alcohol, benzene, dichlor
ethyl ether, acetone, cresylic :acid, or the like.
droxylated esteramide containing (a) one amido
linked acyl radical derived from a hydroxylated
This is simply another way of stating that it is 35 carboxy acid having‘ not over 5 carbon atoms; and
preferable, ifthe product be one of the sub-resins,
(b) at least one acyloxy radical derived from
whichvare commonly referred to as an A resin, or
a monocarboxy"detergent-forming acid having
B‘ resin, .as distinguished from a C resin, which
at least 8 and not more than 32 carbon atoms,
is'a highly infusible, insoluble resin (see Ellis,
and linked by a divalent aliphatic radical to the
Chemistry ofSynthetic Resins, 1935, page 862, et
amido nitrogen atom.
3. A polar sub-resinous esteri?cation product
In recapitulating what has been said previous- -v
of the following formula:
ly, the sub-resinous, semi-resinous, or balsam
(00 on)...
like product herein contemplated may be indi
45
cated by the following formula:
(0H)»(YwX=')
seq‘)
'
,
.7
-
.
.
>
(c 0 0.2),.’
in which :1:’ and y’ are small whole numbers not
greater than 10 and m, n, ‘and m’ are small
whole numbers not over 10, and including zero;
50
Z is an acidic hydrogen atom equivalent; and
in which’ the characters have their previous
X is a residue derived from a polybasic carboxy
signi?cance, and y’ represents a small whole
acid; and Y is a residue derived from a hy-'
number not greater than 5, and 0:’ represents a
droxylated esteramide containing (a) one amido
small whole number not greater than 5; Z repre-'
acyl radical derived from a hydroxylated
sents a hydrogen ion equivalent, such as metallic 55 linked
carboxy acid ‘having not over 5 carbon atoms;
atom, organic radical, etc. '
v' >
and free from an alcoholic hydroxyl radical; and
It will be noted that compounds of the type
(b) at‘least one acyloxy radical derived from
just described having at least one hydrophobe
a higher fatty acid having at least 8 and not
nucleus aredesignated as being “polar” when
than 32 carbon atoms, and linked by a di
there is present either an unesteri?ed hydroxyl 60 more
valent aliphatic radical to the amido nitrogen
radical, or an unesteri?ed carboxyl radical, or
both. We have. found that the polar type of
4; A polar sub-resinous esteri?cation product
material is by far the most effective for demulsi
of the following formula:
?cation, and it is our preference to use such
type. Indeed, this particular type is so much 65
atom.
'
»
I
more effective for demulsi?cation than the non
polar type, that it may be considered in essence
an invention with an invention.
The chemical products or compounds above
' in which :c' and y’ are small whole numbers not
described are adapted to be used as demulsi?ers 70 greater than 10 and m, n, and m’ are small whole
numbers not over 10, and including zero; Z is an
and also as plasticizers or softening agents in
acidic hydrogen atom equivalent; and X is a
the manufacture of resin-like materials.
residue derived from a poly-basic carboxy acid;
Having thus described our invention, what we
and Y is a residue derived from a hydroxylated
‘ claim as new and desire to secure by Letters
75 esteramide containing (a) one amido-linked acyl
Patent is:
2,411,957
11
12
radical derived from a hydroxylated carboxy acid
having not over 5 carbon atoms and free'from
an alcoholic hydroxyl radical; and (b) at least
an alcoholic hydroxyl radical; and (b) at least
one ricinoleyl oXy radical, and linked by a di
valent aliphatic radical to the amido nitrogen
one acyloxy radical derived from a higher un
atom.‘
saturated fatty acid having at'least 8 and not
more than 32 carbon atoms, and linked by a
divalent aliphatic radical to the amido nitrogen
atom.
5. A polar sub-resinous esteri?cation product
of the following formula:
‘
8. A polar sub-resinous esteri?cation product
of the following formula:
in which a," and y’ are small whole numbers not
greater than 10 and m, n, and m’ are small whole
numbers not over 10, and including zero; Z is
an, acidic hydrogen atom‘ equivalent; ‘and X is a
residue derived from phthalic acid; and Y is a
residue derived from a hydroxylated esteramide
containing (a) one amido-linked acyl radical de
rived from a hydroxylated carboxy acid having
in which as’ and 2/’ are small whole numbers not
greater than 10 and m, n, and m’ are small whole
numbers not greater than 10, and including zero;
Z is an acidic hydrogen atom equivalent; and X
is a residue derived from a polybasic carboxyv
acid; and Y is a residue derived from a hydroxyl
ated esteramide containing (a) one amido-linked
not over 5 carbon atoms and free from an alco
‘holic hydroxyl radical; and (b) at least one
ricinoleyl oxy radical; and linked by a divalent I
acyl radical derived from a hydroxylated carboxy
acid having not over 5 carbon atoms and free
from an alcoholic hydroxyl radical; and (b) at
aliphatic radical to the'amido nitrogen atom.
9.- A polar sub-resinous esteri?cation product
of the following formula:
»
least one acyloxy radical derived from a higher
'
eunsaturated fatty acid having 18 carbon atoms,
(OHQAYv’Xz’)
and. linked by a divalent aliphatic radical to the
amido'nitrogen atom.
(000mm
_
(0001),», I
'6." A polar sub-resinous esteri?cation product
of the following formula:
'
~
.
.
i
in which in’ and y’ are small wholenumbers not
greater than 10 and ‘m, n, andm' are small whole
numbers not over 10, and including zero; Z is an
acidic hydrogen atom equivalent; and X .is a
residue derived from maleicacid; and Y is, a
residue derived from a hydroxylated esteramide
containingla) one amido-linked acylradical de
rived from a hydroxylated carboxy acid having
not over 5 carbon atoms and freefromvan valco-.
'
(000mm
(OH)..(Y,,IXZ')
'
(0001),.’
in which a" and y’ are small Whole numbers not
greater than 10, and ‘m, nrand m’ are small whole
numbers not over 10, and including zero; Z is an
acidic hydrogen atom equivalent; and X is a
holic hydroxyl radical; and lb) at‘ least one de
residue derived-from a. polybasic carboxy acid; >
and Y is a residue derived from a hydroxylated 40 rived from a ricinoleyl oxy radical, and linked, by
a divalent aliphatic radical to the amido nitrogen
esteramide containing (a) one amido-linked acyl
radical derived from a hydroxylated carboxy acid
having not over 5 carbon atoms and free from
an alcoholic hydroxyl radical; and (b) at least
one ricinoleyl oxy radical; and linked by a di
valent aliphatic radical to the amido nitrogen
atom.
atom.
'
'
Y is a residue derived from a hydroxylated ester
v
.
~
(oooH)m~
(000.2)“,
in which :0’ and y,’ are small whole numbers not
50 greater than 10 and m, n, and m’ are small whole
in which a," and y’ are small whole numbers not ,
greater than 10 and m, n, and m’ ‘are small whole '
numbers not over 10, and including zero; Z is an
acidic hydrogenatom equivalent; and X is a
residue derived from a dibasic carboxy acid; and
.
(OH)1|(Y1/'X=’)
p
'
,
ofthe following formula:
_7. A polar‘sub-resinous esteri?cation product
of the following formula:
V
10. A polar sub-resinous esteri?cation product
numbers not over 10, andv including zero; Z is an
acidic hydrogen atom equivalent; and X is a
residue derived‘ from oxalic acid; and Y is-a
residue derived from a hydroxylate'd- esteramide '
containing (a) one amido-linked acyl radical de-' ~
rived from a hydroxylated carboxy acid having
not over 5 carbon atoms; and free from an alco
2holic hydroxyl radical; and (b) at least one
ricinoleyl oxy radical, and linked by a divalent
amide containing (a) one amido-linked acyl rad (ill; aliphatic radical‘to the amido nitrogen'atom.
ical derived from a hydroxylated carboxy acid
~'
MELVIN DE GROOTE.
having not over 5 carbon atoms and free from
BERNHABD KEISER.
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