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Патент USA US3057897

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Unite
grates latent G‘ ,,ice
1.
3,057,892
Patented Oct. 9, 1962.
1
2
3 057 892
Where both propylene and butylene oxides are employed
in a single oxyalkylation step, they can be added step
CERTAIN PULYOXYAhKiKLENE GLYCOL ESTERS
Melvin De Groote, St. Louis, Mo., assignor to Petrolite
Corporation, Wilmington, Del., a corporation of Dela
wise or as a mixture.
. The present invention is primarily concerned with the
preparation of new, novel, and useful esters of glycol
mixtures where the ?nal properties of the materials are
N0 Drawing. Original application Apr. 17, 1958, Ser.
controlled at least in part, and in any event signi?cantly,
No. 729,054. Divided and this application June 36,
by the introduction of hydrophilic segments internally
1959, Ser. No. 823,309
into the otherwise hydrophobic polyalkylene glycol.
1 Claim. (Cl. 260-407)
10 Rather than being ineffective in the determination of ?nal
This application is ‘a division of my co-pending applica
properties, it has been found that the internal hydrophilic
tion Serial No. 729,054, ?led April 17, 1958, and a con
segments can be used to control the ?nal properties of
tinuation-in-part of my co-pending application Serial No.
the cogeneric mixtures so that new, novel, and eminently
677,907, ?led August 13, 1957. This latter application
useful materials are produced. It is one purpose of this
is in turn a continuation-impart of my co-pending applica 15 invention to set forth means whereby a class of new and
tions Serial No. 425,944, ?led April 27, 1954 (now aban
novel cogeneric mixtures may be obtained with speci?
doned), Serial No. 475,727, ?led December 16, 1954,
vcally controlled and predetermined properties so as to
and Serial No. 475,728, ?led December 16, 1954.
make them of greatly enhanced usefulness for a wide
The present invention relates to the monomeric and
range of purposes.
polymeric solvent-soluble esters of polycarboxy acids 20
The products of this invention have been de?ned sta
ware
with a polyoxyalkylene glycol mixture consisting of a
product which statistically represented has a plurality of
alternating hydrophobic and hydrophilic polyoxyalkylene
chains or segments, the hydrophilic chains (segments)
tistically and are often referred to as cogeneric mixtures.
This is for the reason that if one selects any hydroxylated
compound and subjects it to oxyalkylation, particularly
where the amount of oxide added is comparatively large,
consisting of oxyethylene radicals linked one to the other 25 for example 30' units of ethylene oxide, it is well known
and the hydrophobic chains (segments) consisting of
radicals selected from the group consisting of oxypropyl
RO(C2H4O)3OH. Instead, one obtains a cogeneric mix
ene and oxybutylene radicals linked one to the other, each
such chain (segment) containing at least 2 and not more
the formula may be shown as the following:
that one does not obtain a single constituent such as
ture of closely related homologous compounds in which
than 110 oxyalkylene radicals, said statistically repre 30
sented product having an odd number of such chains
(segments) linked together so that it consists of a series
of alternating hydrophile and hydrophobe chains (seg
wherein x, asv far as the statistical average goes, is 30,
but the individual members present in signi?cant amount
may vary from compounds Where x has a value of 25
ments) with the proviso that it contain a total of at least
three hydrophobe chains (segments) and at least two 35 and perhaps less, to a point where x may represent 35
or more. Such mixture is, as stated, a cogeneric closely
hydrophile chains (segments), with the further proviso
related series of touching homologous compounds. Con
that there be not more than ?fteen such chains (seg
siderable investigation has been made in regard to the
ments), and with the ?nal proviso that at least one inter
distribution curves for linear polymers. Attention is
nal hydrophile chain (segment) contain at least 5 oxy
ethylene radicals and that the molecular weight of the 40 directed to the article entitled “Fundamental Principles»
polyoxyalkylene glycol mixture be at least 1000.
The above described polyoxyalkylene glycol mixtures,
of Condensation Polymerization,” by Paul J. Flory, which
appeared in Chemical Reviews, volume 39, No. 1,
which are the subject matter of my copending applica
page 137.
What has been said in regard to a monohydric com
tion Serial No. 677,907, ?led August 13, 1957, are built
up from either a hydrophilic or a hydrophobic glycol 45 pound is of course multiplied many times in the case of
a glycol. Accordingly, in the above statistical representa
nucleus by successive oxyalkylation with the appropriate
tion the number of oxyalkylene radicals in each chain or
alkylene oxide. Thus they are obtained, when the nu
segment other than the nucleus, as far as the statistical
cleus is hydrophilic, by the oxypropylation or oxybutyl-a
average goes, corresponds to one-half the number of
tion or both of a polyethylene glycol, which introduces
two hydrophobic segments, followed by oxyethylation, 50 alkylene oxide units, i.e., the number of units of ethylene,
propylene and/or butylene oxide, introduced during the
which introduces two hydrophilic segments, and further
particular oxyalkylation step when that particular chain
oxypropylation, oxybutylation or both, which introduces
two more hydrophobic segments.
When the nucleus is
or segment was formed.
hydrophobic, the mixtures are obtained by the oxyethyla
For purpose of convenience, what is said hereinafter
tion of a polypropylene glycol or a polybutylene glycol 55 Will be divided into six parts.
Part 1 is concerned with polyoxyalkylene glycols
or a mixed polypropylene-polybutylene glycol, which in
suitable for use as initial reactants.
troduces two hydrophilic segments, followed by oxypro
pylation or oxybutylation or both, which introduces two
Part 2 has three subdivisions.
Subdivision A describes the oxyethylation of polypro
hydrophobic segments. Additional pairs of alternate hy
drophilic and/or hydrophobic segments can be added by 60 pylene glycols and polybutylene glycols and the oxybu
tylation and oxypropylation of the respective intermedi—
further oxyalkylation with the appropriate alkylene oxide.
ates to provide ?nal products having three hydrophobic
The initial glycol representing the nucleus is the addition
segments and two hydrophilic segments and having a
nucleus composed of hydrophobic radicals different from
alkylation step, moreover, must be carried out with at 65 those of the terminal hydrophobic segments.
Subdivision B describes the stepwise successive reaction
least 4 and not more than 220- molar proportions of the
of polypropylene glycols with ethylene oxide, propylene
appropriate alkylene oxide, in terms of the initial mole
oxide and ethylene oxide to provide ?nal products having
of water or glycol, in order to introduce at least 2 and
three hydrophobic segments and four hydrophilic seg
not more than 110 oxyalkylene radicals in each chain or
segment. Further, there must be present at least one 70 ments.
Subdivision C describes the preparation of more highly
internal, i.e., other than terminal, hydrophile chain or
product of one mole of water and at least 2 and not over
110 moles of the appropriate alkylene oxide. Each oxy
segment containing at least ?ve oxyethylene radicals.
segmented products having alternating hydrophilic and
3,057,892
3
hydrophobic segments in which the hydrophobic segments
consist of oxypropylene radicals, oxybutylene radicals and
mixed oxypropylene-oxybutylene radicals.
Part 3 is concerned with a description of suitable poly
carboxy acids, particularly dicarboxy acids, employed as
reactants.
Part 4 is concerned with the reaction involving the gly
cols and the polycarboxy acids, particularly the dicarboxy
acids.
Part 5 is concerned with the use of the ?nal products 10
4
.
length is not available, one may select an available poly
ethylene glycol of lower chain length and treat it with
ethylene oxide in the presence of an alkaline or other suit
able catalyst to produce a material of the desired molec
ular weight. The process for the production of polyethyl
ene glycols by the addition of ethylene oxide to water or
a glycol are well known to the art.
Actually, as is well known, when one prepares even
lower molecular weight glycols, for instance, tetraethyl
eneglycol, pentaethyleneglycol, hexaethyleneglycol, hepta~
ethyleneglycol, decaethyleneglycol, etc., one obtains a
cogeneric mixture from which it is difficult or impossible
or expensive to separate the single glycol. Indeed, this
Part 6 is concerned with some of the other more im
is true of even the simplest oxyalkylation as, for example,
portant industrial applications wherein the ?nal products
can be most advantageously utilized.
15 the oxyalkylation of a monohydric alcohol. Reference is
made to US. Patent No. 2,679,513, dated May 25, 1954,
to De Groote, with particular reference to columns 19
PART 1
in the resolution of petroleum emulsions of the water-in
oil type.
As stated above, one class of products of this invention
is obtained from intermediates prepared by the oxypro
pylation or oxybutylation, or both, of an initial polyoxy
ethylene glycol, which glycol is the addition product of
one mole of water and at least 2, and not over 110 moles
of ethylene oxide. Thus, for all practical purposes, the
parent glycols represent not only ethylene glycol, diethyl
ene glycol, triethylene glycol, tetraethylene glycol, penta
ethylene glycol, hexaethylene glycol, and heptaethylene
glycol, but also the higher range of polyethylene glycols
up to the point where approximately 110 moles of ethyl
ene oxide have been combined with one mole of water.
In other words, the range up to approximately 4,800
molecular weight.
As is well known, ethylene glycol, diethylene glycol
and 20 thereof.
It is understood, of course, that polyethylene glycols
may be synthesized by other means than the reaction of
ethylene oxide. For example, ethylene carbonate, which
is available commercially, can be used in place of ethylene
oxide. For special purposes where particularly pure
materials are desired or where exact molecular con?gura
tions are wanted, any of a number of well known ether
i?cation reactions may be employed. However, for most
commercial processes where economy is of chief impor
tance treatment with ethylene oxide is employed. For
the purposes of this invention any polyethylene glycol of
the general formula:
and triethylene glycol are obtainable both in the labora
tory and commercially as materials of technical purity,
where x is at least 2 and not over 110 can be employed.
as differentiated from mixtures.
initial polyoxypropylene glycol, a polyoxybutylene glycol
Tetraethylene glycol can be obtained in technically
Another class of products of this invention is obtained
from intermediates prepared by the oxyethylation of an
or a mixed glycol containing both oxypropylene and oxy
ethylene radicals.
if separated from its cogeners. Actually the form of this
The manufacture of propyleneglycol and polypropylene
product most readily available on a commercial scale is
polyethylene glycol 200 which represents principally a 4.0 glycol is well known. One procedure, of course, is to sim
pure form, but this represents a more expensive reactant
mixture of glycols, to produce a mole of which a mole
of water and 4 moles or 5 moles of ethylene oxide have
been combined, i.e., it is a mixture of tetraethylene glycol
and pentaethylene glycol.
Another polyethylene glycol commercially available
represents a mixture having approximately 6 or 7 ethylene
oxide units in the molecule. This material is sold com
mercially as polyethylene glycol 300.
The average molecular weight of polyethylene glycol
200 runs from 190 to 210. The average molecular Weight
of polyethylene glycol 300 runs from 285 to 315.
Some manufacturers furnish, if speci?ed, a product
referred to as “polyethylene glycol 200 minus” or “poly
ethylene glycol 300 minus.” In both instances the molec
ular weights are about one-eighth less than the usual aver 55
age indicated above. Any such glycols can be readily
ply oxypropylate water so as to obtain the polypropylene
glycol of the desired molecular weight.
However, one
need not start with water and one can start with a low
molal Water-soluble glycol, for instance, propylene di
propylene or tripropyleneglycol.
If desired one can purchase the polypropylene glycol
in the open market.
For instance, one manufacturer
regularly manufactures polypropyleneglycol within the
following three molecular weight classes, to wit, 400
450; 975-1075; and 1950 to 2100. Higher molecular
weights are also available as, for example, at least one
product having a molecular weight of approximately
2750 or thereabouts. Thus, if desired one can purchase
a suitable polypropyleneglycol and not resort to oxy
propylation at all.
For reasons which have been stated previously, two or
three different manufacturers may furnish a polypropylene
glycol 1200 or 1500, or 2000, or the like, and although
There are available commercially a variety of poly
they are substantially the same there is a slight variation
ethylene glycols whose molecular Weights come within
the range herein speci?ed. The lower members of the 60 in composition. The reason is due to at least two factors.
As pointed out previously one does not get a single
series are liquids and the higher molecular weight mem
product but one obtains cogeneric mixtures whose average
bers are waxy solids. In general these materials are
composition corresponds to the molecular Weight indi
soluble in water, being less soluble in hot Water than in
cated. For instance, one manufacturer of a polypropyl
cold water. These include products such as polyethylene
eneglycol whose average molecular weight is 1025 states
glycol 400, polyethylene glycol 600, polyethylene glycol
the molecular Weight in fact varies from 975 to 1075
1000, polyethylene glycol 1500, etc.
and similarly in the case of a product whose average mo
The preferred initial starting materials for the manu
lecular weight is 2025 the variation runs from 1950 to
facture of the herein disclosed products are the lower
2100. Depending on the catalyst used, the rate of re
molecular range polyethyleneglycols or cogeneric mix
action and other factors the variation may be even some
tures of the same. This applies not only to the range of
what wider, for instance, 1025 to 1125 in one case, and
200, 300 and 400, but also up to the range to which
1900 and 2150 in another case. The other factor is one
approximately 14 up to 20, 22, or 23 moles of ethylene
that has been pointed out a number of times and par
oxide have been added to one mole of water. In other
ticularly in a series of articles dealing with derivatives
words, the range up to the molecular weight just short of
prepared if desired.
1000. If a polyethylene glycol of the appropriate chain 75 of propylene oxide. See “Les Dérives de l’Oxyde de
r5
3,057,892
6
and trans-form of straght chain isomers 2,3-epoxybutar'ie
Propylene,” Parts I, II and III, Industrie Chimique, vol
ume 40, 1953, pages 221-9, 249-58, and 281—6.
Since propyleneglycol has both a primary alcohol and
see page 341 of “A Manual of Organic Chemistry,” vol
ume 1, G. Malcom Dyson, Longmans, Green and Com
pany, New York, 1950.
a secondary alcohol radical and since one can look upon
polypropyleneglycols as polymeric linear condensation
Reference to butylene oxide herein of course is to the
derivatives of propylene oxide, it is obvious one could
compound or compounds having the oxirane ring and
thus excludes 1,4-butylene‘oxide (tetrahydrofurane) or a
obtain head-to-head polymerization, tail-to-tail polym
erization, and head-to-tail polymerization. This is il
trimethylene ring compound.
lustrated by the fact that there are three dipropylene
When reference is made to butylene oxide, one can
glycols. If one goes to tripropyleneglycol there are theo 10 use the corresponding carbonate. Butylene carbonate, or
retically at least eight possibilities. In the higher poly
the carbonate corresponding to a particular oxide, is not
propyleneglycols these possibilities increase enormously.
available commercially but can be prepared by the usual
methods in the laboratory.
Thus, the ?rst variation is in the breadth of the molecular
weight spectrum or range which determines the average
In the present invention I have found that outstanding
molecular weight and the second variation is concerned 15 products are obtained by the use of certain preferred
with the fact that dependent on the method of oxy
butylene oxides, i.e., those entirely free or substantially
propylation employed, and various factors such as cata
free from isobutylene oxide (usually 1% or less) and
composed of approximately 85% orlmore of the 1,2
lyst used, temperature, pressure, speed of reaction, etc.,
there may be variations in the actual structure. For this
isomer with the remainder, if any, being the 2,3-isomer.
In the preparation of the compounds of this invention
reason solubility in water must be interpreted in light
I have studiously avoided the presence of the isobutylene
of such fact and, thus, although polypropyleneglycol of
oxide as far as practical. When any signi?cant amount of
an average molecular weight of 1000 or thereabouts may
isobutylene oxide happens to be present, the results are
not as satisfactory regardless of the point when the butyl
Thus, it is customary to consider polypropyleneglycols 25 ene oxide is introduced. One explanation may be the
following. The initial oxybutylation which may be sim
having a molecular weight of 1,000 or more as being
pli?ed by reference to a monohydric alcohol, produces a
substantially water-insoluble. Such customary use is
tertiary alcohol. Thus the oxybutylation in the presence
herein included. Even if the molecular weight is double,
of an alkaline catalyst may be shown thus:
up to 2000 or thereabout, there may even be a trace of
the ‘glycol which is water soluble, for instance, some 30
where in the neighborhood of .015 %.
show solubility of about 1.5% in water actually this may
be the solubility of some of the low molal cogeners.
Similarly the manufacture of butylene glycol and poly
butylene glycol is well known. Again one can oxy
butylate water but it is my preference to oxybutylate a
butyleneglycol, particularly the 1,4-butyleneglycol.
In
35
all of the subsequent examples, where reference is made
to butylene glycol, 1,4-butyleneglycol was employed.
At the present time there is available butylene oxide
Further oxyalkylation becomes di?‘icult when a tertiary
which includes isomeric mixtures. For instance, one
alcohol is involved although the literature records suc
manufacturer has previously supplied a mixed butylene 4.0 cessful oxyalkylation of tertiary alcohols. This does not
oxide which is in essence a mixture of l-butene oxide,
necessarily apply when oxyalkylation takes place in the
2-butene oxide isomers and approximately 10% iso
presence of an acidic catalyst, for instance, a metallic
butylene oxide. Another manufacturer has supplied an
chloride such as ferric chloride, stannic chloride, alumi
oxide which is roughly a ?fty-?fty mixture of the-cis
num chloride, etc.
45
and trans-isomers of 2-butene oxide.
In regard to certain di?iculties involved in the oxybu
There is also axailable a butylene oxide which is char
tylation by means of isobutylene oxide one explanation is
acterized as straight chain isomers being a mixture of
that isobutylene oxide may show a tendency to revert back
the 1,2 and the 2,3 isomers and substantially free from
the isobutylene oxide.
to isobutylene and oxygen and this oxygen may tend to
oxidize the terminal hydroxyl radicals. This possibility
This latter product appears to consist of 80% of the 50 is purely a matter of speculation, but may account for
1,2 isomer and 15% of the mixed 2,3 cis- and 2,3 trans
the reason I obtain much better results using a butylene
isomer. I have obtained the best results by using an
oxide as speci?ed. In regard to this reaction, i.e., pos
oxide that is roughly 80% or more of the 1,2 isomer and
with either none, or just a few percent if any, of the iso
sible conversion of an alkylene oxide back to the ole?n
and nascent oxygen, see “Tall Oil Studies II. Decoloriza
butylene oxide, the difference being either form of the 55 tion of Polyethenoxy Tallates with Ozone and Hydrogen
2,3 or a mixture of the two forms.
Peroxide,” I . V. Karabinos et al., J. Am. Oil Chem. Soc.
My preference is to use an oxide substantially free
31, 71 (1954).
from the isobutylene oxide, or at least having minimum
Mixed glycols containing both oxypropylene radicals
amounts of isobutylene oxide present.
and oxybutylene radicals can be prepared by the suc
Since the varying solubility of different butanols is 60 cessive reaction of water with propylene and butylene
well known, it is unnecessary to comment on the effect
oxides in either order, by the oxybutylation of a propyl
that the varying structure has on solubility of derivatives
ene glycol or by the oxypropylation of a butylene glycol.
obtained by butylene oxide. Purely by way of example,
The following examples illustrate the preparation of
I have tested the solubility of the ?rst two available
such mixed glycols.
butylene oxides and noted in one instance that the butylene 65
Example A
oxide would dissolve to the extent of 23 grams in 100
grams of water, whereas the other butylene oxide would
6.57 pounds of butylene glycol (equivalent to 5.25
only dissolve to the extent of 6 grams in 100 grams of
pounds of butylene oxide) and .5 pound of powdered
water. These tests were made at 25° C.
caustic soda were placed in an autoclave of 25 gallons
As to further reference in regard to the isomeric 70 capacity. The autoclave was flushed with nitrogen, heated
butylene oxides see “Chemistry of Carbon Compounds,”
to 100° C., and then placed under vacuum to remove
volume I, Part A, “Aliphatic Compounds,” edited by
E. H. Rodd, Elsevier Publishing Company, New York,
any nitrogen and any moisture.
It was agitated at ap
proximately 350 r.p.m., with temperature raised to 125—
130° C. before starting to add the 94.7 pounds of propyl~
1951, page 671.
As to the difference in certain proportions of the cis 75 ene oxide. It was added over a period of 31/2 hours.
3,057,892
8
the product, it is immaterial because at a very early stage
the material becomes a liquid and becomes homogeneous
The reaction temperature was left Within the range of
l25-130° C. The pressure was kept at approximately
10 to 15 pounds per square inch. The time required for
by solution or dispersion. The following examples illus~
trate the preparation of the type of product of my in
vention described above. In the examples, the designa
complete oxyalkylation was one-half hour additional. At
the end of this period reaction was complete and vacuum
again noted on the reactor. The molecular weight of the
product was 1400.
tion “AA” means that the compounds were obtained by
initially reacting a polybutylene glycol with ethylene
oxide. The designation “BB” means that the compounds
Example B
were obtained by initially reacting a polypropyleneglycol
13.15 pounds of butyleneglycol (equivalent to 10.5
with ethylene oxide.
pounds of butylene oxide) were mixed with .5 pound 10
Example AA-]
caustic soda and then reacted with 10.5 pounds of butyl
ene oxide, followed by reaction with 79 pounds of butyl
10 pounds of butyleneglycol (equivalent to 8 pounds
ene oxide, followed by reaction with 79 pounds of propyl
of butylene oxide) and .5 pound caustic soda were placed
ene oxide, molecular weight was 1340.
15 in an autoclave of 25 gallons capacity. The autoclave
was flushed With nitrogen, heated to 100° C., and then
PART 2
placed under vacuum to remove any nitrogen and any
Subdivision A
moisture. It was agitated at approximately 350 r.p.m.,
with temperature raised to l25—l30° C. before starting
to add the 42 pounds of butylene oxide (straight chain
In this subdivision the preparation of products having
three hydrophobic polyoxyalkylene segments and two hy
drophilic polyoxyalkylene segments is described. The
products have a hydrophobic nucleus and terminal hy
isomer). It was added over a period of 31/2 hours. The
reaction temperature was left within the range of 125
130° C. The pressure was kept at approximately 10-15
drophobic radicals derived from a different alkylene oxide
pounds per square inch. The time required for com
than is the nucleus. They are prepared by the reaction
of a polypropylene or polybutylene glycol with at least ten 25 plete oxyalkylation was one-half hour additional. At the
end of this period reaction was complete and vacuum
molar proportions of ethylene oxide followed by oxy
again noted on the reactor.
propylation or oxybutylation, depending on the initial
The reaction was again started with 50 pounds of
polyglycol reactant, of the intermediate with at least four
ethylene oxide being used during a second oxyalkylation
molar proportions of propylene oxide or butylene oxide.
The oxyalkylation of various glycols with various oxides 30 step. The time period, operating conditions as far as
temperature and pressure were concerned, all were sub
and particularly alpha-beta ole?nic oxides having 4 car
stantially the same as in the preceding part.
bon atoms or less, has been described in the literature.
This applies particularly to oxyethylation, oxypropyla
tion and oxybutylation. Instead of using ethylene oxide
The mixed polyglycol ether so obtained was reserved
for further reaction.
one can, of course, use ethylene carbonate. Similarly, 35
one could use propylene carbonate or butylene carbonate.
As is well known the oxyalkylation derivatives of any
Molecular weight was 918.
Example AA-Z
10 pounds of butylene glycol and 0.5 pound of caustic
soda were employed as in Example AA-l, preceding but
oxyalkylation-susceptible compound are prepared by the
addition reaction between the alkylene oxide and such
reacted with only .7 pound of butylene oxide. The op
a compound. The addition reaction is advantageously 40 erating conditions in a general way were the same as in
the previous example, and this is true of all succeeding
carried out at an elevated temperature and pressure and
examples. After adding the .7 pound of butylene oxide
in the presence of a small amount of alkaline catalyst.
without interruption the butylene oxide line was shut off
Usually, the catalyst is sodium hydroxide or sodium
and ethylene oxide equivalent to 91.3 pounds was added.
methylate. Metallic sodium, with the prior elimination
'Ql‘he time required was 53/4 hours. Molecular weight was
of hydrogen (formation of an alkoxide) can be used.
18.
The reaction temperature is apt to be 150° C., or some
Example AA-3
what less, and the reaction pressure is not in excess of
30 to 60 pounds per square inch. The reaction proceeds
22.5 pounds of butylene glycol were employed as the
rapidly. Actually, there is little difference between the
raw material along with 1.0 pound of caustic soda. Op
use of propylene oxide and ethylene oxide or, for that 50 erating conditions were substantially the same as in pre
matter straight chain butylene oxide. See, for example,
vious examples. 12.8 pounds of butylene oxide were
U.S. Patent No. 2,636,038, dated April 21, 1953, to Brand
added and without interruption as soon as the butylene
ner, although another hydroxylated compound is there
oxide was in, 69.2 pounds of ethylene oxide were added.
employed.
Molecular weight is 418.
As to further information in regard to the mechanical 55
Example BB-Z
steps involved in oxyalkylation, see U.S. Patent No.
Using a 50 gallon autoclave, 38 pounds of propylene
2,499,365, dated March 7, 1950, to De Groote et a1.
glycol (equivalent to 29.3 pounds of propylene oxide)
Particular reference is made to columns 92 et seq. thereof.
mixed with 5.5 pounds of caustic soda, were reacted with
The oxyalkylation of a liquid or a product which is liq
uid at ordinary temperature and particularly at oxyalkyla
tion temperatures is comparatively simple and this is true
also where both hydroxyls are primary hydroxyls, as in the
60
225.7 pounds of propylene oxide followed by reaction
with 332.4 pounds of ethylene oxide. Molecular weight
was 1200.
case of the alkylene glycols. Thus one can do either one
Simply for convenience, Table I following gives the
of two things: mix the glycol or polyglycol with a suit
able solvent such as xylene or a high boiling aromatic
conversion factor for converting the more common gly'
solvent so as to produce a solution or suspension, or else
simply melt the product so that it is liquid prior to intro
duction of the oxide. My preference is simply to mix
cols into the equivalent amount of alkylene oxide. For
instance, if one starts with one pound of ethylene glycol,
it would be the equivalent of .71 pound of ethylene oxide.
Similarly, if one started with 10 pounds of dipropylene
glycol it would be the equivalent of 8.7 pounds of propyl
the product with a suitable amount of a selected catalyst,
such as powdered caustic soda or powdered sodium 70 ene oxide. If one started with 100 pounds of butylene
methylate. The amount of catalyst may vary from 1%
to 5%. The reaction vessel is ?ushed out, the tempera
ture raised to an appropriate point, and oxyalkylation
proceeds in the customary manner. In any event, whether
glycol it would be the equivalent of 80 pounds of butylene
oxide. Note the ratios in Table I give these conversion
factors. Thus in Example AA-l, 10 pounds of butylene
glycol were combined with 92 pounds of alkylene oxide.
one adds a solvent or suspending medium or merely melts 75 The total weight of the ?nal reaction product was 102
3,057,892
9
10
pounds. The ratio of 102/10 gives a factor of 10.2 which,
In the following Table III, therintermediates of Table
when multiplied by the molecular weight of 90 for butyl
II have been reacted with propylene oxide or butylene
oxide in the indicated proportions by weight to give the
eneglycol, gives the average molecular weight of the re
action product based on completeness of reaction, as 918.
?nal products having three hydrophobic segments and
two hydrophilic segments.
The same procedure as in Examples AA-l and BB-Z
was followed in making various combinations as indicated
TABLE III
in Table II. These two-component reaction products (in
reality a three-component reaction mass if one includes
water) were then subjected to reaction to give the three
component (or four-component) reaction products de
10
Intermediate
Parts by
weight
scribed subsequently and shown in Table III.
Whether to consider the reaction mass a three-compo
nent derivative or a four-component derivative depends
10
57. 5
65
25
15
30
entirely on the convenience of whether or not to include a
single molecule of Water per mole of polyglycol ether
which may vary from 1000 molecular weight to 4,150
component system, bearing in mind that water stays con
Factor to
convert to
Factor to
convert to
oxide
oxide
oxide
ethylene
propylene
butylene
EthyleneglycoL.
Triet-hyleneglycol:
95
80
95
80
95
80
5.0
20.0
5.0
20.0
5.0
20.0
38.0
84
16.0
48. O
44. 5
52.0
52. O
56. 0
92
82. 5
93. 5
86
88
8.0
17. 5
6. 5
14. 0
12.0
41. 5
43
38
34
33
32
27
22. 5
21
15
58. 5
57.0
62.0
66.0
67.0
68. 0
73. 0
77. 5
79.0
85. 0
92. 5
83
88
88
92. 5
82. 5
88
92. 5
86. 5
93
7. 5
17.0
12. 0
12.0
7. 5
17. 5
12.0
7. 5
13. 5
7. 0
ever, in calculating molecular weight, the one mole of
TABLE I
5.0
5. 0
20.0
20. 0
5.0
20. 0
62
water is not only important, but in fact, controlling.
Factor to
convert to
70. 0
75.0
60.0
65. 0
50.0
55.0
40.0
95
95
80
80
95
80
52
55. 5
48
48
44
stant as one molecule per molecule of glycol ether. How
Molccular
90. 0
42. 5
35.0
75. 0
85. 0
25
40
35
50
45
60
molecular weight or even higher.
For purpose of characterization in terms of the initial
oxides used as reactants, it is best to employ a three
Weight
Parts by
Parts by
weight
Parts by weight
added Intermediate weight
added
PrO
Bu 0
Further examples are shown in Table IV in which one
Pentaethylencglycol
Hexaethyleneglycol
Propyleneglycol..
Diproplyencglycol. . ___
Tripropyleneglyr'nl
'l‘etrapropyleneglycoL _
PentapropylencglycoL.
I-Ierapropyleneglycol...
Butyleneglycnl
Tributyleneglyonl
Pentabutyleneglycol___
Hexabutyleneglycol____
comszwl
Dibutylcneglycol ____ __
Tetrabu tyleneglycol _ _ _
pound mole of butylene glycol (equal to 18 pounds of
water and 72 pounds of butylene oxide) was successively
reacted with butylene, ethylene and propylene oxides in
UIQTPNO!
the amounts indicated.
The ?rst two of these products
‘have the proportions by weight of the ?nal product in
Table III made by oxypropylating intermediate AA-2.
The last three of these products have the proportions by
weight ofthe ?nal product in Table III made by oxy
propylating intermediate AA-14.
The intermediate reaction products of the two oxides
in terms of the weight percent of the respective oxides 45 Exam- Butylene
in the intermediates are tabulated in Table II, immediate
ple num- glycol]
ly following:
her
lbs.
TABLE IV
Butylene
oxide/
lbs.
Ethylene Propylene Molecular
oxide llbs. oxide/lbs. weight to
product
TABLE II
Oxyethylated
polybutylcneglycol
Example
number
Oxyethylated
polypropylene
glycol
Example
Weight
percent
Weight
percent
t0
number
AA—29_ _
AA-SO- _
90
90
78
12s
1, 575
2, 100
1, 275
1, 300
AA-Bl _ _
50 AA—32_
_
90
152
880
960
2, 018
90
90
232
312
1, 320
1, 760
1, 440
1, 920
3, 018
4, 018
AA-33- _
-
Weight
Weight
PrO
EtO
percent
3, 018
4, 01s
Further examples of glycols having three hydrophobic
polyoxyalkylene segments and two hydrophilic polyoxy
percent
55 ethylene segments are represented as points on the graphs
of FIGURES 1 through 4 of my co-pending application
Serial No. ‘677,907, ?led August 13, 1957. A represen
tative number of these glycols are set forth in tabular
form below:
60
TABLE V
PrO in
EtO
PrO
B110
weight of
glycol,
moles
added,
moles
added,
moles
added,
moles
product ex
eluding ml.
H2
AA—34_ _
15
AA-35 _ _
AA- _ _
15
15
3, 780
4, 650
AA-
18.7
3,025
18. 7
3, 605
65
__
70 AA~38_ _
AA-
wo
IQ
75
M01.
initial
Ex. No.
-_
18.7
3, 200
4, 765
AA-40_ _
28
8, 514
AA~41 _ _
.AA-42 _ _
28
428
8, 804
9, 964
Ali-43--
2s
11, 124
Ark-44 _ _
6
3, 108
3,057,392
12
"1
the examples of Table VII, can be re-subjected to oxy
propylation so as to give products comparable to those
described in Table VIII, immediately following. In
Table VIH, the initial reactants indicated as 1b, 211, etc.
are the products of the reactions described in Table VII.
TABLE VI
Ex. No.
BuO
in initial
EtO
PrO
BuO
glycol,
added,
added,
added,
moles
moles
rnoles
M01.
weight of
moles
product ex
eluding ml.
H20
TABLE VIII
AA-45. _
6
15
Ark-46 _ _
Ark-47 - _
AA-48 _ _
4
7
7
15
1O
10
5
__________ ._
1, 310
20 __________ __
__________ __
5
__________ __
10
2,108
l, 304
1, 664
Final oxypropylated
derivative
Oxyethylated
polypropyleneglyeol
10
In the above tables, the amounts employed were gram
moles.
Subdivision B
In this subdivision the preparation of products having
three hydrophobic polyoxyalkylene segments and four
hydrophilic polyoxyalkylene segments in which the hy
drophobic segments are all derived from propylene oxide
is described. The products have a hydrophobic nucleus
and are obtained by the successive reaction of a poly
propylene glycol with at least four molar proportions of
?rst ethylene oxide, then propylene oxide, and then eth
ylene oxide, provided that one oxyethylation step is car
ried out with at least ten molar proportions of ethylene
oxide.
The preparation of the polyalkyleneglycols described in
this subdivision can be a continuous process in which wa
ter, propylene glycol, or a low molal polypropyleneglycol
is oxypropylated by means of any suitable catalyst, either
acid or alkaline, and then subjected to oxyethylation,
followed by oxypropylation. Instead of being a single
step process one can employ a two step process in which
the oxyethylated intermediate is subsequently oxypro
pylated. For convenience the two step process will be
described but it is obvious the two step process may be
merged into a single step. One reason for doing so is
the fact that oxyethylated propyleneglycols are available
in the open market, or manufacturers can furnish such in
termediates which are particularly satisfactory for use as
a reactant.
In the examples set forth in Table V, immediately fol
lowing, the polypropyleneglycol employed had a molecu~
lar weight of about 2920. It was obtained as the equiv
alent of reacting one mole of water with 50 moles of
propylene oxide. It was then reacted with from 10 to
Ex.
N 0.
Moles
of PrO
added
Ignoring ini
by sec0nd oxy-
tial mole of
water
alkyla-
Ex.
No.
1e. -_
2e_-_
3c---
Melee. Pcr~
weight cent
PrO
3, 35s
3, 35s
3, 35s
3,402
3, 402
3, 402
3, 446
3,446
3, 446
3, 400
3, 400
3, 400
3, 534
3, 534
3, 534
3, 57s
3, 57s
3, 573
4e_ -_
5c. __
6e___
7c. __
3c. __
9c_ __
100.-
115.125..
13c__
145“
15c__
16c__
170..
18c..
80. 33
36. 33
s6. s3
85. 70
85. 70
35. 70
34. 60
84.00
84. 6o
33. 52
33. 52
33. 52
32. 47
82. 47
32. 47
81. 47
31. 47
81. 47
Percent
EtO
tion
step
13. 17
13. 17
13. 17
14.30
14. 30
14. 30
15. 40
15. 40
15. 46
16. 4s
16. 4s
16. 4s
17. 53
17.53
17. 53
1s. 53
13. 53
1s. 53
10
20
30
11
22
33
12
24
30
13
26
39
14
2s
42
15
30
45
Pcrcent
PrO
Percent
EtO
as. 79
00. 22
91. 34
37. 97
30. 61
90. so
37. 20
so. 05
90. 42
86. 46
33. 51
00. 62
35. 73
33. 02
30. 65
35. 10
37.
89.30
11.21
9. 7s
3. G6
12.03
10. 30
9. 14
12. so
10. 95
9. 5s
13. 54
11. 49
0. 9s
14.22
11. 0s
10. 35
14. 00
12. 45
10. 70
Molec.
weight
includ
ing 1
mo].
H1O
3, 933
4, 513
5, 09s
4, 040
4, 67%;
5, 316
4, 142
4, 338
5, 5:44
4, 2-44
4, 093
5, 752
4, 346
159
5, 070
4, 443
5, 318
6, 13s
The products obtained and described in preceding Table
VIII not only represent one type of the ultimate
glycols to be esteri?ed but also represent the oxypro
pylated intermediate which when subjected to oxyethyla
tion produces another type of ultimate glycol. Needless
to say, the oxyethylation is identical with the oxyethyla
tion where a polypropylcneglycol is subjected to oxyeth
ylation. Four of such ?nal oxyethylated products have
been prepared and are included in Table IX, following.
In each case the compounds are indicated by numbers
with a small “:2” thereafter, such as 1d, 2d, etc. In
each instance the oxypropylated intermediate was 16c
and was the product of reaction described in Table VIII.
TABLE IX
Final oxyethylated
derivative
15 moles of ethylene oxide. Table VII gives the data
in complete form covering these oxyethylated polypro
pyleneglycols which were obtained by conventional pro
cedures using an alkaline catalyst. The molecular weight,
including the initial mole of water, is shown. Also the
weight percentage of the two oxides in the reaction prod
uct ignoring the initial mole of water is shown.
Ignoring initial mole of
water
Oxypropy-
Ignoring ini-
Moles of
lated inter-
tial mole of
EtO
mediate
water
Ex.
No.
added by
Ignoring
second
oxyetliylation
initial mole
of water
step
Ex.
No.
Molec. Perweight cent
PrO
Percent
EtO
Percont
PrO
I’ercent
ELO
74.10
65.00
53. 30
44.90
25.00
34.40
‘i0. 70
55.10
Molecu
lar weight
including
1 mole
1110
TABLE VII
Ex
No
1b___
2b--3b__4b-__
5b--6b---
Molec.
Propy- Ethyl- weight
lene
ene
contriboxide oxide uted by
moles moles
PrO
50
50
50
50
50
50
10
11
12
13
14
15
2,900
2, 000
2,900
2,900
2,900
2, 900
Molec. Ignoring initial Inelud~
weight
mole of water mg 1111
contribtial
uted by
mole of
EtO
Percent Percent water
PrO
EtO
440
484
523
572
616
660
86.83
35. 70
84. 60
33. 52
32. 47
81. 47
13.17
14.30
15. 40
16. 4s
17.53
18.53
3,353
3,402
3,446
3, 490
3, 534
3,473
The oxyethylated polypropyleneglycols of the ‘kind ex
empli?ed in the examples of Table VII are next subject
ed to reaction with propylene oxide.
The use of propylene oxide has been widely described
in the literature particularly in the oxyalkylation of al
cohols, either monohydric or polyhydric, and informa 70
tion is furnished freely by the several manufacturers of
propylene oxide as to its use in oxyalkylation.
Either acid or alkaline catalysts can be used.
Brie?y
1d___
2d___
3d-.4d___
160...
16c__.
l6e___
l6e_.-
4,448
4,448
4,448
4,448
85.10
85.10
85.10
85.10
14.90
14.90
14.90
14. 90
15
30
60
90
5,108
5, 708
7, 988
8,408
Subdivision C
In this subdivision the preparation of products having
up to and including ?fteen alternating hydrophobic and
hydrophilic polyoxyalkylene chains is described. These
more highly segmented products are prepared generally
according to the procedures described in Subdivisions
A and B of this Part 2 and represent ultimate glycols hav
ing either a hydrophobic nucleus or a hydrophilic nucleus.
They also represent products in which a single hydro
phobic segment consists of both oxypropylene and oxy
butylene radicals.
The preparation of the more highly segmented prod
ucts is illustrated by the following examples and tables.
Example 1
The reaction vessel employed was a stainless steel auto
clave with the usual devices for heating, heat control,
purchased in the open market or prepared according to 75 stirrer, inlet, outlet, etc., which are conventional in this
stated, various oxyethylated polypropyleneglycols, either
8,057,892
‘
'
a’
13
type of apparatus. The stirrer operated at approximately
col reacant.
14
Also Table X sets forth more highly seg
250 r.p.m. There were charged into the autoclave 30
mented products obtained by further oxyalkylation of the
pounds of polyethylene glycol -—300. There was added
products of Examples laa, 2aa, 3aa, with the indicated
.06 pound of sodium methylate. ‘The autoclave was sealed
alkylene oxide in the order shown. These more highly
and swept with nitrogen gas. Heat was applied with 5 segmented products were prepared by oxyalkylating the
stirring so as to get an appropriate solution or suspension
appropriate intermediate with the indicated proportion of
of catalyst. The temperature was allowed to rise to
the appropriate alkylene oxide generally according to the
130° C. At this point addition of a mixture of butylene
procedure of Example 1.
oxide and proylene oxide, wherein the mole ratio was 1
TABLE X
[Molal proportion based on one mole of Water]
mole of butylene oxide to 2 moles of propylene oxide, 10'
was begun.
Addition of the butylene oxide-propylene
oxide mixture was continuous until 371/2 pounds of the
mixture had been added. This represents the addition of
approximately 2 moles of butylene oxide and 4 moles of
propylene oxide per mole of initial reactant.
7 Ex. No.
.
EtO
Added
in
BuO-
initial
PrO 1
glycol
Example 2
The same general procedure was followed as in Exam
ple 1 except that the addition of the ?nal butylene oxide
propylene oxide mixture was continued until the equiva
lent of 4 moles of butylene oxide and 8 moles of propyl
ene oxide had been added.
Example 3
The same procedure was followed as in Examples 1 and
2 preceding, except that the addition of the butylene oxide
propylene oxide mixture was continued until the equiva
lent of 6 moles of butylene oxide and 12 moles of propyl
ene oxide per mole of initial reactant had been added.
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
6.4
2.0
2.0
2.0
2.0
2.0
2.0
4.0
4.0
4.0
4.0
4.0
4.0
6.0
6.0
6.0
6.0
6.0
6.0
.
.
Added Added Added Added Added
EtO
BuO
EtO
PrO
EtO
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
1 The M. W. of the mixture was taken as 188, Le, 2 PrO: 1 BuO. Thus
a l-mole addition of the mixture would theoretically give 2 moles of PrO
Example 1a
The same apparatus and general procedure were used 30
as described in Example 1 except that as an initial re
actant the product of Example 1 was used and ethylene
oxide Was added until the equivalent of 5 moles of ethyl
and 1 mole BuO addition.
'
Tables XI and XII present additional examples of more
highly segmented products of my invention also in terms
of the molar proportions, based on one mole of water, of
the particular alkylene oxides added to the initial poly
ene oxide had been added per mole of intermediate re
35 alkylene glycol reactant. The examples of Table XI illus
actant.
trate products obtained by reacting a polypropylene glycol
Example 2a
alternately with ethylene and propylene oxides. The ex
The same general procedure was followed as in Exam
amples of Table XII illustrate products obtained by re
ple 1 except that as an initial reactant the product of Ex
acting a polyethylene glycol alternately with propylene
ample 2 Was used and ethylene oxide was added until the 40 and ethylene oxides. The products of these examples "were
equivalent of 5 moles of ethylene oxide had been added
similarly prepared by oxyalkylating the initial glycol or
per mole of intermediate reactant.
the appropriate intermediate with the indicated propor
Example 3a
tion of the appropriate alkylene oxide generally according
to the procedure described in Example 1.
The same general procedure was followed as in Exam
ple 1a except that as an initial reactant the product of 45
TABLE XI
[Molal proportion based on one mole of water]
Example 3 was used and ethylene oxide was added until
the equivalent of 5 moles of ethylene oxide had been
added per mole of intermediate reactant.
The same apparatus and general procedure was used
as described in Example 1 except that as an inital reactant
the product of Example 1a was used and butylene oxide
was added until the equivalent of 5 moles of butylene
oxide had been added per mole of intermediate reactant.
Example Zaa
The same general procedure was followed as in Exam
ple 1 except that as an initial reactant the product of Ex
ample 2a was used and butylene oxide was added until
the equivalent of 5 moles of butylene oxide had been added
per mole of intermediate reactant.
PrO in
Added
Added
Added
Added
Added
initial
EtO
PrO
EtO
PrO
EtO
glycol
Example Jaa
'
Example 3aa
The same general procedure was followed as in Exam
ple 1 except that as an initial reactant the product of Ex
ample 3a was used and butylene oxide was added until the
equivalent of 5 moles of butylene oxide had been added
per mole of intermediate reactant.
The products of Examples 1, 1a, 2, 2a, 3 and 3a repre
sent intermediate glycols and the products of Examples
laa, 2aa, 3aa, 4, 4a, 5, 5a, 6 and 6a represent ?nal glycols
to be esteri?ed.
The products obtained in the above examples are set
forth in the following Table X in terms of the molar
proporations, based on one mole of water, of the particu
lar alkylene oxides added to the initial polyalkylene gly
'
10.7
10. 7
10. 7
10.7
6.04
6.04
6.04
82.1
108
147
6.04
6.04
6.04
6.04
6.04
12.3
12.3
61.7
61.7
82.1
82. 1
82.1
71.4
94. 8
11.3
43.6
14.2
32.0
54.9
10. 7
12.3
71. 4
33. 6
10.7
10.7
10.7
10. 7
10. 7
10. 7
10.7
10.7
10.7
10.7
12.4
12.4
12.4
12.4
12.4
12. 4
12.4
12.4
12. 4
12.4
12.4
12.4
36.7
36. 7
36.7
36.7
12.3
12.3
12.3
12. 3
12.3
12. 3
12.3
12.3
12.3
12.3
30.5
30.5
30.5
30.5
30.5
30. 5
30.5
30.5
30. 5
30.5
30.5
30.5
30.5
30. 5
30.5
30.5
71.4
71.4
71.4
94.8
94. 8
94. 8
94.8
138
138
138
110
110
110
110
133
133
110
133
133
133
133
133
22.8
22. 8
22.8
22.8
13.4
51.7
80.3
16. 8
37. 8
64. 9
101
23.2
52.2
89.4
10.8
4.21
22.9
51.5
11.7
4. 55
15.5
24.6
16. 8
39.3
74.0
55.7
36. 7
30. 5
22. 8
35. 7
10.7
10.7
10. 7
10.7
10.7
10. 7
__________________ _
6. 22
15.7
21.4
__________________ _
3,057,892
[Molal proportion based on one mole of water]
E\'.N0
PrO in
initial
Added
EtO
Added
PrO
Added
EtO
Added
PrO
16
carboxyl groups. When using a dicarboxy acid or an
hydride that has only two carboxyl groups or the equiva
lent, one usually does not have dit?culty from the stand
TABLE XL-Continued
point of cross-linking or gelation. Therefore, the pref
Added
EtO
erence is to employ dicarboxy acids. Actually, as pre
‘glycol
viously noted, due to the long chain length between the
hydroxyl groups there is comparatively little danger of
22
cross-linking or gelation to the stage Where an insoluble
product is obtained even when tricarboxy and tetracar
22
22
boxy acid are employed. The dicarboxy acids may be
comparatively low molal acids or high molal acids.
Dicarboxy acids may have as many as 32 carbon atoms
and even more, particularly when derived by the oxida
tion of Wax or by other procedures as subsequently noted.
Common well known dicarboxy acids having 8 carbon
atoms or more (excluding carboxyl group carbon atoms)
are sebacic acid, methylene disalicylic acid, etc. Com
parable disalicylic acids have ‘been obtained by intro
ducing an alkyl substituent having not over 10 carbon
atoms into both phenolic nuclei.
Other Well known types of dibasic acids are those de
rived from maleic anhydride and are known as adduct
acids. Examples are the products obtained by reaction
between maleic anhydride and terpcnes to yield well
known adduct acids having the hydrophobe characteriza
tion above described. Monocarboxy acids, such as sorbic
acid, can be reacted in a comparable manner with an
unsaturated fatty acid such as linolenic acid to give a
suitable reactant. Other types can be obtained from
compounds comparable to Clocker adducts involving
addition next to an unsaturated bond but not involving
the bond as such, as for example, where oleic acid is
used as one of the initial reactants. Sometimes the pro
duction of the adduct acid yields as an initial stage the
110
133
157
136
71. 2
71. 2
71. 2
9. 1
3. 5
19. 0
71. 2
71. 2
71. 2
13. 0
47. 2
30. 5
119
anhydride. Obviously the anhydride can be reacted with
water to give the parent acid.
A variety of dimerized fatty acids have been obtained
_______ _.
....... -_
_______ __
4. 81
119
12. 5
119
12. 95
119
26. 2
_______ - .
and are described in the patent literature.
4.0 to De Groote, and more particularly to U.S. Patent No.
2,632,695, dated March 24, 1953, to Landis et al.
An analogous variety of dicarboxy acids are obtained
_______ _
-.-_
________ __
22. 8
22. 8
35. 6
35. 6
22. 8
35. 6
119
________ __
22.8
22.8
22. 8
22. 8
22. 8
22. 9
22. 9
22. 9
22. 9
22. 9
35. 6
35. 6
35. 6
35. 6
35. 6
35. 7
35. 7
35. 7
35. 7
35. 7
119
119
119
119
119
14. 8
30. 4
47. 0
62. 7
76. 5
from abietic acid or the like and generally referred to
as dimerized rosin acids. Dimerized acids have been ob
.
.
45 tained from ?sh oil fatty acids in which the total number
of carbon atoms may have varied from 20 to 24 and
thus the dimerized acids may have as many as 44, or
even more, carbon atoms.
The same applies to certain
dimerized acids obtained from the oxidation of wax. Fur
thermore, esters of dimerized acids have been reacted
with aromatic materials such as alkylated or polyalkylated
naphthalene in the presence of aluminum chloride, or
the like, to yield dicarboxy acids having as many as 50
TABLE XII
[Molal Proportion Based on One Mole of Water]
carbon atoms.
EtO in Added Added Added Added Added Added Added
ES. No. initial
Pl'O EtO PrO E’LO
PrO EtO PrO
55
Referring to a consideration of dimeric fatty acids one
may illustrate this structure by the following composi
glycol
tion:
16. 6
38. 8
34. 3
26. 0 ____________ __
16.6
16.6
1.6. 6
38. 8
38. 8
38. 8
38. 8
34. 3
34. 3
34. 3
34. 3
26.0
26. 0
26. 0
l6. 6
See, for ex
ample, U.S. Patent No. 2,417,739, dated March 18, 1947,
26. 0
6. 8
19. 0
27. 5
30. 2
(I)
(CHINE-OH
60
0
16.6
38. 8
34.3
26.0
34. 0
16. 6
38. 8
34. 3
26. 0
34. 0
2 .
16. 6
16. 6
16.6
16. 6
16. G
38. S
38.8
38.8
38. 8
38. 8
34. 3
34.3
34.3
34. 3
34. 3
26. 0
26.0
26. 0
26. 0
26. 0
34. 0
34.0
34. 0
34. 0
34. 0
_.. _.
38.
51.
64.
77.
104.
16. 6
l6. 6
16.6
16.6
16. 6
16. 6
3S. 8
38. S
38. 8
38. 8
38. 8
38. 8
34. 3
34. 3
34. 3
34. 3
34. 3
34. 3
26. O
26. 0
26. 0
26. 0
26. 0
26. 0
34. 0
34. 0
34. 0
34.0
34.0
34. O
129. 5
129. 5
129. 5
129. 5
129. 5
129. 5
_____ -_
16. 8
34. 1
67. 4
103. 6
109. 5
16. 6
16. 6
16. 6
38. 8
3S. 8
38. 8
34. 3
34. 3
34.3
26. 0
26. 0
26. 0
34. O
34. 0
34. 0
129. 5
129. 5
129. 5
109. 5
109. 5
109. 5
(?g Eo-wnmii-on
H
65
_____ __
_____ __
_____ _____ __
_____ ._
25. 1
39. 0
53. 1
PART 3
The polycarboxy acids used may have two or more 75
o
H n
3,057,892
18
The acids produced commercially run approximately
Also note U.S. Patent No. 2,182,178 describes iso
docylene succinic acid anhydride, isononylene succinic
acid anhydride, isotetradecylene succinic anhydride, etc.
85% or better dimer content with some trimer and some
monomer. As pointed out in aforementioned U.S. Patent
No. 2,632,695, a well-known source of these dimeric acids
As to a description of a number of other suitable di
carboxy acids derived from various raw materials refer
ence is made to the following patents: U.S. Patent Nos.
is the product sold by Emery Industries, Inc., and said
to be dilinoleic acid. In the literature published by the
Emery Industries, Inc., the properties of this product are
1,702,002; 1,721,560; 1,944,731; 1,993,025; 2,230,005;
2,232,435; 2,368,602; 2,402,825; 2,490,744; 2,514,533;
given as follows:
and 2,518,495.
Neutral equivalent ____________ __ 290-310.
Iodine Value _________________ __ 80-95.
10
‘Note that U.S. Patent No. 2,360,426 describes the pro
duction of a higher alkene-substituted dicarboxylic acid
of the general formula
Color __________ __. ___________ __ Gardner 12 (max).
Dimer content _______________ __ Approx. 85%.
Trimer and higher ____________ __ Approx. 12%.
Monomer ____________________ __ Approx. 3%.
It is known that mono-ole?nic hydrocarbons react by 15
What is termed the 1,2-addition reaction, with compounds
containing an ethylenic group linked directly and in con~
jugated relation to a carbonyl group such as maleic acid
in which R is selected from the group consisting of hydro
anhydride to give unsaturated compounds. The reac
gen and alkyl radicals, and alkene is an alkene group hav
tion is shown by Eichwald in U.S. Patent 2,055,456, as 20 ing not less than 5 and not more than 16 carbon atoms,
well as by Moser in U.S. Patents 2,124,628; 2,133,734;
which comprises heating an alkyl halide containing not
and 2,230,005.
The reaction is also disclosed in an ap
less than 5 and not more than 16 carbon atoms with
plication of Van Melsen, Serial No. 263,056, ?led March
20, 1939.
In each case, the condensation or addition
an unsaturated aliphatic dicarboxylic acid of the general
formula:
products obtained by the 1,2-addition reaction are un
saturated compounds. This disclosed reaction may be
illustrated, for example, by that which occurs in the re—
action of octadecylene With maleic anhydride. The re
25
action may be represented as follows:
30 in which R is selected from the group consisting of hydro
0
(DH-ll;
C1sHao+
gen and alkyl radicals, at a temperature at which hydro
gen halide is split out.
It particularly describes in detail the preparation of
0
\O -——> O?Hzp-OH-(‘il
\O
CHr-C/
(I )
decene-succinic acid, undecene-succinic acid, and dodec
35 ene~succinic acid, all of which are particularly desirable
for the present purpose.
The above speci?cally described dicarboxy acids are
characterized by the presence of at least one hydrocarbon
It is seen that the product is unsaturated, being an alkenyl
group containing at least 8 carbon atoms and are rela
succinic acid anhydride.
40 tively high molal acids. However, one can also produce
Alkenyl succinic acids are produced by various pro
excellent compounds by the use of low molal dicarboxy
cedures and particularly by condensing maleic acid an~
acids alone or in combination with high molal dicarboxy
hydride with C12 and higher mono-ole?nes, hydrolyzing
acids. Examples of such low molal dicarboxy acids are
the reaction product and hydrogenating the hydrolyzed
material to remove ole?nic double bonds.
Similarly, another class of analogous compounds are
substituted malonic acids such as cety’l malonic acid,
succinic acid, glutaric acid, adipic acid, pamelic acid,
45 suberic acid, and azelaic acid.
terephthalic acid.
stearyl malonic acid, oleyl malonic acid, octyl cetyl ma
lonic acid, etc.
Other suitable dicarboxy acids are illustrated by
CH3
One can also use tetrahydrophthalic
anhydride and hexahydrophthalic anhydride.
As is well known one can obtain low molal glycols
50
such as ethyleneglycol, diethyleneglycol, triethyleneglycol,
propyleneglycol, dipropyleneglycol, tripropyleneglycol,
CH3
—butyleneglycol, etc. Such products can be converted
into dicarboxy acids by either one of two well known
procedures. Reaction with acrylonitrile or with chloro
HOzC CHzéG-Qé CHzC 02H
CIlHa
Similarly, one may use
cyclic acids such as phthalic acid, isophthalic acid, and
03H;
See U.S. Patent No. 2,497,673, dated February 14, 1950, 55 acetic acid can be used. In the use of acrylonitrile the
to Kirk.
See also U.S. Patent No. 2,369,640, dated
terminal hydroxyl hydrogen atom is replaced by the
February 20, 1945, to Barnum. This particular patent il
radical
lustrates a dicarboxy acid of the ether type, such as the
following:
60
COOH
COOH
H H
—0 0-020 0 OH
H H
In the use of chloroacetic acid the terminal hydrogen
atom is replaced by
—O— H
XBHS3
65
Another variety is illustrated in U.S. Patent No. 2,459,
717, dated January 18, 1949, to Perry. An example of
this particular variety is the following:
HO 0 O
0 CH0 0 OH
isHaa
I have vfound that for many purposes including de
mulsi?cation the most effective compounds are obtained
from reactants characterized by freedom from any radical
having 8 carbon atoms or more. For this reason, it is
our preference to use low molal dicarboxy acids and
particularly glycolic acid, ethylene bis (glycolic acid) of
the formula HOOCCH2OCH2CH2OCH2COOH, oxalic
Note also the variety of polycarboxy acids, many of
acid, provided decomposition is avoided, and other low
which are dicarboxy acids, described in U.S. Patent No.
molal acids such as succinic acid or maleic acid. Previ
75 ous reference has been made to the use of the acids.
2,349,044, dated May 16, 1944, to Jahn.
20
1&9
A variety of tricarboxylic acids which are of particu
lar interest is obtained by reaction between maleic anhy
Needless to say, any one of a number of functional
equivalents such as the anhydride, an ester, an amide,
or the like, may be used to replace the acid. Indeed,
many of the acids are more readily available in the an
dride and a suitable unsaturated acid, such as linolenic
acid. There are two types, depending on the nature of
hydride form than the acid form.
What has been said in regard to the dicarboxy acids
applies of course to the polycarboxy acids although the
known type is the type commonly referred to as Clocker
adducts and described in considerable detail in US. Pat
the unsaturation of the fatty acid employed. One well
ents Nos. 2,188,883; 2,188,884; 2,188,885; 2,188,886;
2,188,887; 2,188,888; 2,188,889; and 2,188,890, all dated
January 30, 1940, to Clocker. An example of such well
known reaction is the following:
number available at comparatively low prices is some
what limited. Here, again, however, the variety used
may be large and thus particularly of interest are low
molal acids such as tricarballylic acid, aconitic acid, and
tetracarboxybutane. Other acids are obtainable such as
Diels-Alder adducts, Clocker adducts, and the like. They
include, among others, examples of tetracarboxy acids
Linolenic acid
described in US. Patent No. 2,329,432, dated September 15
14, 1943, to Bruson. As examples of the ketcnic tetra
carboxylic acids they are described as follows:
110:0];
0
% \ / §
O
Heat
O
Malelc anhydrides
20
25
Maleie condensation product of linolcnlc acid
As to similar products more akin to Diels-Alder de
rivatives see US. Patent No. 2,124,628, dated July 26,
1938, to Moser.
See, also, U.S. Patent No. 2,264,354, dated December
30
2, 1941, to Alder et al.
Another tricarboxylic acid is described in US. Patent
No. 2,517,563, dated August 8, 1950, to Harris.
CH3—
CHrCHs
Cés
Other suitable examples are described in US. Patents
CH~C
Nos. 2,390,024, dated November 27, 1945, to Bruson;
2,359,980, dated October 10, 1944, to Fleck; and 2,039,
243, dated April 28, 1936, to Krzikalla et al.
GET-Cg:
Various aryl tetracarboxylic acid anhydrides which
PART 4
can be readily converted into the corresponding acids
Part 4 is concerned with the esters, either monomeric
are described in U.S. Patent 2,625,555, dated January 13, 40 or polymeric, obtained from the glycols prepared in the
1953, to Miller.
manner described in Part 2, and the polycarboxy acids
Suitable tetracarboxy derivatives are described in U.S.
described in Part 3. One may use any obvious equivalent
Patent No. 2,450,627, dated October 5, 1948, to Bloch.
instead of a polycarboxy acid such as the anhydride, the
Such acids are obtained by a process which comprises
heating at a temperature of from about 100° C. to about
350° C. in the presence of an aqueous alkaline reagent
the adduct of a dienophilic dibasic acidic compound and
a cyclic polyole?nic hydrocarbon containing isolated un
saturation and at least some conjugated unsaturation, and
acidifying the polymer product formed in the said heat
ing step to form said tetrabasic acid.
Comparable to the ketonic carboxylic acids above de
scribed are the ketonic tricarboxylic acids. See US.
Patent No. 2,320,217, dated May 25, 1943, to Bruson.
Examples are as follows:
acyl chloride, or an ester. One may follow a procedure
so the one product is largely a monomer; for instance,
if one uses the ratio of two parts of polycarboxy acid
to one part of glycol the reaction yields a fractional ester
having free carboxyl radicals. Inversely, if one uses
two moles of the glycol and one mole of a dicarboxy
acid one obtains principally a monomer which is a frac
tional ester having free hydroxyl radicals.
If, on the
other hand, one selects a one-to-one ratio of a dicarboxy
acid and a glycol the tendency is to produce linear poly
mers, particularly if an effort is made to conduct the
reaction as far as it will go without decomposition. A
variety of intermediates can be obtained which vary in
molecular Weight. All of this is simple conventional
procedure and information concerning such procedure
60 has appeared repeatedly in numerous patents. See, for
example, the description in US. Patent No. 2,562,878,
dated August 7, 1951, to Blair. in the instant procedure
CHZCHZCOOH
one can ‘follow the same method outlined in the text
O < CHzCHsUOOH
beginning in column 4, line 62.
Similarly, US. Patent No. 2,679,516, dated May 25,
65
1954, to De Groote describes a procedure for making
Substituted pimelic acids having 3 carboxyl radicals
are described in US. Patent No. 2,339,218, dated Janu
ary 11, 1944, to Bruson. An example is the following
fractional esters but the obvious variation in molal ratio
of glycol to reactant corresponding, for example, to the
ratios in the aforementioned Blair patent, produce poly
70 mers. Particular attention is directed to Part 3 of said
patent. Note that a procedure is included for removing
the slight amount of alkali which may remain from the
oxyalkylation procedure. In the examples which are
summarized in Tables XIII and Xl’V the excess of alkali
HO O C CHzCHz
CHzCHzC O OH
75 was eliminated entirely, or for all practical purposes,
3,057,392
2.2
by using the procedure outlined in the aforementioned
De Groote patent in column 19, beginning at line 11.’
darker colored esters than some other acids. The esters
can be bleached by any conventional method, such as
In other examples particularly where the ?nal alkali
those for bleaching glycols, i.e., ?ltering clays, chars, and
content was low no e?ort was made to remove the
even organic bleaches such as peroxides or the like. For
alkali ‘but enough of the carboxy acid was added in ex- 5 most applications there is no need to bleach the prod
cess ‘over the amount employed for esteri?cat-ion pu-rnets and there is no need to remove the small amounts
poses to neutralize the alkali. This is particularly satisof salts if present due to neutralization of a catalyst.
factory when low molal polycarboxy acids are used and
After mixing with a suitable solvent the solution may be
especially dicarboxy acid.
allowed to stand in a quiescent state until any insolubles
‘
In practically all cases the esteri?cation took place 10 separate by settling.
readily by using the temperatures as indicated ‘in Table
XIII and the reaction times as indicated in the same
E
l 4
xamp e a
table. The particular equipment employed was a resin
The polyalkylene glycol employed was that of Ex
pot as described in aforementioned De Groote Patent
ample 4. The theoretical molecular weight of the glycol
2,679,516, in the second paragraph of Part 3. If the 15 was 5660. The acid used for esteri?ca-ti'on was digly
reaction does not proceed rapidly then sometimes a small
amount of sulfonic acid, either an alkane sulfonic acid
or an aromatic sulfonic acid, is employed. The amount
used varies from a few tenths percent up to one percent
colic acid. The ratio employed was 1.9:1. The amount
of glycol used was 200 grams. The amount of digly
colic acid employed was 9 grams. This was mixed with
100 grams of a mixed aromatic solvent. Esteri?cation
or even more. Such use is dependent in part on whether 20 was conducted by means of a glass resin pot using the
or not the residual vcatalyst would be objectionable.
When the carboxy acid reactants are fairly strong acids
conventional stirrer, inlet, outlet, and phase-separating
trap. The maximum temperature during the esten'fica
they, of course, serve vas their own catalyst. In other
tion was 204° C. The time of esteri?cation was 8 hours.
instances the reaction has been speeded up by passing
The amount of water out was 0.5 cc. In the ?nal solu
just a slow stream of dry hydrochloric acid gas through 25 tion the solvent represented approximately 32.4% of the
the mixture. Any suitable and conventional method of
mixture. Such solvent can be removed readily by dis
esteri?cation commonly employed in producing esters,
til-‘lation, particularly vacuum ‘distillation, if desired. In
both monomeric or linear, from polycarboxy acids and
some instances it is desirable to use a variant of this
glycols can be employed.
procedure employing both benzene, as a dehydrating
The esters may be water soluble but in most instances 30 agent and also as the solvent during the re?ux period,
they will be organic ‘solvent soluble or at ‘least soluble
in a mixture of the kind described in the text which ap-
in combination with a high boiling aromatic petroleum
solvent. This procedure is described in detail in columns
pears as the ?rst part of Part 5. rIlhe esters as produced
one and two of U.S. Patent No. 2,679,510, dated May 25,
will vary in color from almost water-white or pale straw,
1954, to De Groote.
to a darker color depending in part on the polycarboxy 35
Example 4a, with other examples, appears in- tabular
acid used. For instance, dimeri-c fatty acids tend to give
form in Tables XI and XII, following.
TABLE XIII
Mol.
Ex. No. Ex. No. weight
of ester otglycol of glycol
Acid or anhydride
used
5,660
Diglycollc .......... -_
Mel.
weight
of acid
Molal
ratio,
acid to
glycol
Glycol Poly
used, carboxy
gms. reactant,
gms.
134
1.90
200
9
7,130 _____do_--_
9,440 _-__.do-_
4,975 __.-.do--
134
134
134
2.41
3.17
1.67
200
200
200
9
9
9
6,400
2.15
1.08
0.48
200
200
9
9
200
6,400
Dodecenyl 3110011110--
134
266
6, 400
Dimeric fatty acid- __
600
6, 280
Diglycolic __________ __
_____do ......... -
7, 030
3, 040
d
9
134
2.11
200
9
134
134
2. 36
2. 70
'200
200
9
9
5,305 _
134
1.73
200
9
6, 675
6,675
6, 675
6, 760
5, 370
7, 560
134
93
133
134
134
134
2. 24
3. 06
1. 00
2. 27
1. 97
2. 54
200
200
200
150
150
150
9
9
9
6. 75
6. 75
6. 75
3,320
134
2.96
- 150
6.75
7, 390
7, 390
134
154
2. 43
2. 16
150
150
6. 75
6. 75
7, 39
143 ,
2. 24
150
6. 75
3, 310
9, 500
11,10
134
134
134
2. 79
3. 19
3. 73
150
150
150
6. 75
6. 75
6. 75
, 13
134
3. 42
150
11,460
134
3. 35
150
6. 75
11,460
93
5.26
150
> 6. 75
6. 75
11,460
13, 100
9, 570
133
134
134
2. 74
4. 40
3. 21
150
150
175
6. 75
6. 75
7. 33
9, 270
10, 100
134
134
3. 11
3. 39
175
175
7. 33
7. 33
11,350 __-__d0 .............. -_
134
3.31
175
7.33
11,350
11,350
Hexahydrophthalic_.
Dodecenyl succim'c___
154
266
3.32
1.92
175
175
7.33
7.88
10,300
Diglycolic __________ __
134
3.46
175
7.33
134
3.35
175
134
3. 27
> 175
7.33
134
134
3.66
3.54
175
175
7.33
7.33
7.33
d
7. 33
10,540
Dimeric fatty 301
600
174
2.72
175
11,520
Diglycolic .......... __
134
3.37
175
7.33
134
4.33
150
6.75
0
0.79
175
7.88
134
4.11
175
134
134
143
1. 61
1. 70
1. 54
250
250
‘250
'
11.25
11.25
11.25
7.33
93
2.32
250
11. 25
3,057,892
24
TABLE XIII—C0ntinued
Mel.
Ex. N0. Ex. No. weight
0f ester ofglycol of glycol
M01.
weight
of acid
Acid or anhydride
used
5, 510
5, 750
6, 380
7, 720
8, 400
134
134
134
134
134
1. 85
1. 93
2. 14
2. 59
2. 82
8,400
8, 400
9,120
9, 710
3, 250
3, 425
176
174
134
134
134
134
2.15
2.17
3.06
3. 26
1. 09
1.15
3,635
150
11.25
11.25
11. 25
11.25
6. 75
6.75
134
Tetracarboxybutane.
234
0. 70
150
6. 75
Azelaic _____________ __
188
0. 87
150
6. 75
6.75
134
134
134
134
134
835
1. 30
1.38
1. 23
1. 30
1. 38
0. 22
6. 75
11.25
6. 75
6. 75
6. 75
6. 75
6. 75
Dig1yco1ic_
___._do_._
_,__.do_
_____do.
_____do__
Trilinolelc-
.
.
.
_
4, 115
Phthalic. _
_
148
1. 25
150
250
150
150
150
150
150
4, 350
4, 650
5, 360
5, 630
6, 080
Diglycohm
_.___do.._
_____do_
__-__do_
_____do.__
_
_
.
134
134
134
134
134
1. 46
1.56
1. 80
1. 89
2.04
150
250
150
150
150
6. 75
11.25
6. 75
6.75
6. 75
6. 75
6, 080
Tricarballyllc ______ __
176
1. 55
150
6, 080
6, 350
Tetracarboxybutane.
Dig1yc01ic.__
234
134
1. 17
2. 13
150
150
6. 75
6. 75
_
_
.
_--
134
134
134
134
835
2. 27
1. 97
2.05
2.17
0. 35
250
150
160
150
150
11.25
6. 75
6. 75
6. 75
6. 75
6, 460
Dodecenyl succimc...
266
1.09
6, 880
Diglycolic __________ __
134
2. 31
150
6. 75
134
2. 46
250
11.25
134
134
2. 03
2. 14
150
150
6. 75
6.75
_____do.._
_____do-._
_____do.
_.___d0-__
'1‘r'11ino1e1c
-__
6,050
6, 380
6, 880 _____do ______________ __
134
Hexahydrophthalic- _
154
2. 01
150
6. 75
Phthalic ___________ _-
148
2.09
150
6. 75
134
134
134
98
148
134
98
148
134
98
148
134
2. 41
2. 57
4. 05
5. 54
3. 67
4. 53
6.20
4.10
5. 02
6. 87
4. 55
1. 71
150
150
200
200
200
300
300
300
300
300
300
200
6. 76
6. 75
10
10
10
15
15
15
15
15
15
9
7, 540 -
7, 680 _
8, 370
6.75
134
2. 53
200
9
134
134
134
266
600
134
134
134
134
134
98
188
134
134
134
3. 46
4.07
1.87
O. 94
0.42
4. 65
1. 36
2. 31
2. 84
3. 28
4. 48
2. 34
3. 76
4. 32
2.66
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
9
9
9
9
9
9
9
9
9
9
9
9
9
9
9
134
2. 58
200
9
-__
134
2.81
200
9
8, 370
8, 370
Hexahydrophthahc- _
Tetracarboxybutane _
154
234
2. 35
1. 61
200
200
9
9
8, 100
Diglycolic __________ _.
134
2. 72
200
9
134
134
134
134
835
174
134
134
134
134
134
134
98
134
134
134
134
148
134
600
266
3. 23
2. 98
3. 53
3. 65
0. 59
2. 81
3. 65
3. 85
3.35
3.80
4. 31
4. 51
6.17
4. 72
4. 96
5. 38
5. 92
5. 36
2. 23
0.52
1. 18
200
200
200
200
200
200
200
200
300
300
300
300
300
300
300
300
300
300
200
200
200
9
9
9
9
9
9
9
9
13
13
13
13
13
13
13
13. 5
13. 5
13. 5
10
1D
10
200
10
1489..-”
9, 620
8, 880
10, 510
10, 870
10, 870
10, 870
10, 890
11, 470
10, 360
11, 730
13,330
13, 930
13,930
14,610
15, 330
16,010
17, 620
17, 620
5, 980
6, 290
6, 290
149m..-
6, 290
1503-..-
6,830
15121....
15211.-“
, 330
, 480
15321----
9, 000
9, 720
9, 720
.___. 0 _________ _.
150
6.75
6, 880
10, 300
12, 130
5, 575
5, 575
5, 575
13, 850
4, 050
6, 880
8, 470
9, 770
9, 770
9, 770
11, 190
12, 870
7, 930
2. 31
150
6, 880
7, 180
7, 660
10, 850
10,850
10, 850
12, 150
12,150
12,150
13,470
13, 470
13, 470
5,100
15491..-15521..--
250
250
250
250
250
150
150
11. 25
11. 25
11. 25
11. 25
11. 25
__.__ 0 ______________ __
7, 330 _____do _________ -_
14621.-"
250
250
250
25
3,635
6, 760
5,870
6, 110
6,460
6, 460
14711----
1.22
Glycol Poly
used, carboxy
gms. reactant,
gms.
3, 635
3, 875
4, 115
3, 665
3, 875
4,115
4, 115
1448.--14521.---
Molal
ratio,
acid to
glycol
Dig1yc011c_____
Dimeric fatty acxd. ._
Dodecenyl succinic...
Diglycolic _____ _.
_
(1
11
Tetracarboxybutane _
134
2. 35
134
2. 55
200
10
134
134
2. 73
2. 79
200
200
10
10
134
3. 36
3. 2B
200
200
2. 07
200
148
234
10
10
10
3,057,892
25
26
TABLE XIII—Continued
M01.
Ex. No. Ex. N 0. weight
of ester of glycol of glycol
Acid or anhydride
used
15621...157a..__15821..-15921...16021...1612...“
116".-117_.._118-.-"
119..._.
120...-121“.-1622.-.- 121.___.
14, 970
1638..-16421.---
121..-__
122_-_--
14,970 Diglycolic _____ _.
15,
_--_.d0 _____ ._
1655-.-1660...16721.--.
16821....
16921...17051....
1715....
17221.-.-
123..-_.
124___-_
125..-“
127..-“
127.._-.
127_-._128__.__
129_..--
16, 450 --.__do.-.
17,
-..--do.
19, 570 ._..-(10.
21,250 AZe1aic._
21, 250 Tricarballyhc.
21, 250 Diglycolic.-22,100
d
22, 880
1732..." AA-34 _
Dimeric fatty acid-- -
M01.
Weight
of acid
M01211
ratio,
acid to
glycol
134
134
134
134
134
98
3. 62
3. 91
4.19
4. 47
5.02
7. 64
Glycol Poly
used, carboxy
gins. reactant,
gms.
200
200
200
200
200
200
10
10
10
10
10
10
600
1. 25
200
10
_
134
134
5. 58
5. 86
200
200
10
10
.
_
_
.
134
134
134
188
176
134
134
134
6.14
6. 70
7. 30
5. 65
6. 04
7. 93
8. 25
8. 53
200
200
200
200
200
200
200
200
10
10
10
10
10
10
10
10
.
3,200
_
174a._..- AA—35_
3, 780
_
134
1.26
100
4.5
17521.-.- AA-36 _
4, 650
_
134
l. 54
100
4. 5
176a..-“
1772...“
17851....
1795.--.
18021...-
.
.
134
134
1.01
1.19
100
4.5
_
98
1. 98
100
100
4.5
4. 5
98
2.85
100
AA-41 .
3, 025
3,605
4, 765
8, 514
8, 804
-
98
4. 39
100
4. 5
- AA-42 _
9, 964
.
148
3.04
100
4. 5
.
100
181a.
AA—37_
AA-38.
AA- .
A1140-
.
134
1.06
100
4. 5
4. 5
1825--.. AA-43 _
11, 124
148
3. 39
18321...- AA-44 .
3, 108
134
1.03
100
4. 5
18421...- AA-45.
1,310
134
.43
100
4.5
4. 5
1855---- AA~46 .
186a.-_. AA-47 .
2,108
1, 304
134
134
.70
.43
100
100
4. 5
4. 5
18721.... 111148 _
1, 664
134
. 55
100
4. 5
1885...- 15a“---
1, 238
134
.41
100
4. 5
18%.... 12121212....
190a.--“ laaaaa _
1, 748
1, 968
98
148
. 79
.60
100
100
4. 5
4. 5
1915.... 3215.....
1925...- 33am.--
1, 990
2, 500
134
98
.66
1. 24
100
100
4. 5
4. 5
1935....
2, 720
148
. 83
100
4. 5
321212521 .
Phthalic ........... ..
TABLE XIV
TABLE XIV——Con1:inued
35
Ex. N0.
of ester
Max. Time of
Percent
Amount esteri?- cstcri?- Water solvent
solvent, cation cation, out. in ?nal
Solvent used
grams teongx,
hrs.
0.0. product
Ex. No.
of ester
Solvent used
Max. Time of
Percent
Amount esteri?~ esteri?- Water solvent
solvent, cation cation, out. in ?nal
grams tengm,
0.0. product
45 .... __ Mixed aromatic..
100
204
8
0.5
32. 4
100
7
2. 3
55. _________ __do ______ ._
100
200
7. 5
1. 5
32.4
100
206
7
2. 1
27. 4.
100
203
7. 5
0.8
32. 4
100
210
7
2. 4
27 . 4
100
100
100
176
202
198
7. 5
10
10
1. 4
1. 4
0
32.4
32.0
32.0
100
100
75
204
204
212
7
7.
7
0.7
0. 3
1. 9 .
100
100
100
199
188
196
10
10
10
1. 4
0. 5
0. 3
32.0
32. 0
32.0
75
75
75
183
190
190
6
6
6
1.1
0. 6
1. 8
27. 4
27.4
31. 8
31.8
31.8
31.8
100
187
10
2.0
, 32.0
75
191
6
0.6
31.8
100
100
100
100
106
117
101
105
108. 5
105
105
105
101
97. 5
99
112
110
110
93
74
74
72
67
196
217
209
211
210
244
230
300
225
230
210
204
201
227
225
203
200
204
206
192
197
185
188
32.0
32. 0
32.0
32.0
29. 4
41. 7
38. 3
39. 3
40. 3
40. 1
39. 8
39. 6
38. 6
37. 8
38. 1
41. 0
40. 8
41.1
36. 8
28. 4
28. 2
27.6
26.3
75
100
75
75
75
75
75
75
100
75
75
75
75
75
75
100
75
75
75
75
75
75
100
192
199
192
196
189
190
189
189
199
196
199
192
196
192
197
196
197
195
196
195
196
196
175
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6. 75
6. 75
6. 75
6.75
6. 75
6.75
6. 75
6. 75
7
0. 5
1.9
1. 2
0.3
2.1
2.0
0
0.85
0.5
0.3
0. 6
2. 2
2. 1
0.8
0. 5
1. 1
0.4
0.3
2. 5
2. 4
0
1. 4
1.4
31.8
27. 4
31.8
31. 8
31.8
31.8
31.8
31.8
27. 4
31. 8
31.8
31.8
31.8
31.8
31.8
27. 4
31.8
31.8
31.8
31.8
31.8
31.8
27. 4
..
7. 75
7. 75
7. 75
7. 75
7. 75
7. 75
7. 75
7. 75
7. 5
7. 5
7. 5
7. 5
7. 5
7. 5
7. 5
7. 5
7. 5
7. 5
95
6. 25
6.25
6. 25
6. 25
2. 6
0.7
O
1.0
0.9
1.1
1. 55
0
2. 3
0
0
1. 45
1.0
0.9
1. 2
1. 1
0
1. 4
2. 2
1. 3
0.6
1. 15
1. 75
' 27. 0
75
211
hrs.
27.4
70
191
6. 25
0
189
7
1. 6
31.8
70
196
6. 25
0
27. 2
75
185
7
0.5
31.8
71
197
6. 25
1.1
27.5
. 75
190
7
1.1
31.8
69
71
69
66
195
188
195
195
6. 25
6
6
6
0. 1
1. 5
0
O. 55
27.0
27.6
26. 9
26. 2
75
75
75
75
199
200
250
195
7
7
7
7
0
0
0.2
2.05
31. 8
31. 8
31. 8
31. 8
66
66
66
58
62
195
195
195
195
196
6
6
6
6
6
1. 2
0.5
0. 9
1. 4
1.1
26. 1
26.0
26. 1
26.3
26
190
190
190
190
190
6
6
8
8
8
2. 0
0
0
3.0
0
...... _.
.
.
_
.
100
100
100
100
205
199
198
196
6. 5
6. 5
6. 5
6. 5
1. 2
1. 1
0
0
27.4
27. 6
27. 6
27. 4
190
190
190
190
8
6
7
6
0
2. 7
0
0
.
.
.
.
100
100
100
100
194
202
176
184
6.5
6. 5
7
7
0.3
1. 05
2. 1
0. 5
27. 4
27.4
27. 4
27.4
190
190
190
190
6
6
6
6
2. O
1.0
1. 0
l. 0
3,057,892
28
2"]a
nary 7, 1953, to De Groote, and particularly to Part 3.
TABLE XIV-Continued
Everything that appears therein applies with equal force
Ex. No.
of ester
Solvent used
grams teongx,
Mixed aromatic. _
do
and eifect to the instant process, noting only that where
reference is made to Example 13b in said text beginning
0.0. product U! in column 15 and ending in column 18, the products of
the present invention are employed instead.
In general, the products of this invention which have
1. 0
23. 5
been
found most effective in the resolution of petroleum
0
24. 2
Max. Time of
Percent
Amount esteri?- esteri?- Water solvent
solvent, cation cation, out. in ?nal
110
190
5
110
196
100
190
190
196
190
190
6
6
6
6
6
6
6
190
190
190
190
190
190
100
190
190
190
190
190
190
190
190
190
190
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
190
6
.
_
_
.
.
_
hrs.
6
.
_
_
_
_
.
.
_
.
_
_
_
..
_
_
-
1. 0
3. 2
3. 1
2. O
2. 2
3. 4
0
2. 0
2. 0
2. O
2. 0
2. 0
l. 0
0
2. O
2. 0
2. 5
3. 0
2. 0
2. 0
2. 6
2. 0
2. 5
2. 0
12. 5
dist.
147a_ _ __
148B. _ ..
190
190
190
190
190
190
190
6
6
6
6
6
6
6
100
6
25. 3
26. 6
28. 0
26. 4
25. 9
25. 7
25. 7
25. 9
25. 8
27. 6
26. 0
27. 0
28. 6
28. 2
28. 0
28. 6
25. 3
25. 6
24. 4
25. 7'
25. 3
25. 1
24. 3
21. 5
—25”
.
emulsions of the water-in-oil type are those having a mo
10 lecular weight greater than about 2,000 although some
of the products having a molecular weight as low as
1,500 have been found to be effective.
The following examples of Table XV show results ob
tained in the resolution of crude petroleum emulsions ob
tained from various sources. These crude petroleum emul
sions are described as Emulsi?ed Oils A through R and
their source and water content are set forth below.
For
Emulsi?ed Oils A through 0, the pipeline oil requirement
was 1/2 of 1% basic sediment and water content (B.S. & S.)
20 or less and for ‘Emulsi?ed Oils P, Q and R, the pipeline oil
requirement was 3% BS. & W. or less. 'In the examples,
the crude oils in all instances, after demulsi?cation, met
these standards and in many instances the amount of
foreign material remaining (B.S. & W.) was considerably
In some instances the
25 less than pipeline requirements.
ratios reported are comparatively low but the reason is
9. 5
8. O
7. 0
0
12. 0
5. 6
4. 0
that the oil treated was either a more difficult oil or that
tests were run against standards in a comparatively short
period of time, for instance two hours or maybe two
hours cold, Whereas actually, in the plant where com
mercial demulsi?cation occurs, the oils take a matter of
5. 5
190
6
0
190
6
2. O
21. 8
110
190
190
6
6
2. 0
0
23. 8
24. 6
110
110
110
190
100
190
6
6
6
2. 0
2. 5
3. O
23. 4
26. 0
25. 4
110
110
110
110
110
110
110
158
175. 8
110
110
110
110
110
110
110
110
110
110
110
110
190
190
190
190
190
190
190
190
190
190
190
190
190
190
190
190
160
190
190
190
190
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
3. 0
3. 0
0
3. 0
3. O
3. 5
2. 5
3. 5
3. 0
3. O
3. 0
3. 0
3. 0
2. 0
3. 0
3. 0
2. O
2. 0
2. 5
3. 0
3. 0
24. 6
20. 9
23. 6
24. 0
23. 5
24. 1
24. 3
26. 1
37. 7
24. 7
25. 1
24. 7
26. 1
22. 9
25. 7
26. 1
25. 2
24. 2
23. 5
22. 5
26. 2
PART 5
For the purpose of resolving petroleum emulsions of
the water-in-oil type, I prefer to employ products having
six or eight hours and the temperature instead of being
cold may have been 120 or 130° F.
The emulsi?ed oils employed in the examples were
35 as follows:
Emulsi?ed Oil A
This was obtained from Duval 49 Lease, Well No. 3,
of Magnolia Petroleum Company, Freer, Texas. The
40
amount of emulsi?ed water Was about 45%.
This was obtained from Cockrum Lease, Well No. 2,
of Magnolia Petroleum Company, Bolton, Mississippi,
and the amount of emulsi?ed water was 20%.
Emulsi?ed Oil C
This oil was from Shyrock Lease, Well No. 3, Stano
lind Oil and Gas Company, Hastings, Texas. The
50 amount of water was equivalent to 35%.
This was a sample from Taylor Lease, Well No. 7, of
Gulf Coast Leaseholders Oil Company, Bolling, Texas.
The amount of Water was 35% .
suf?cient hydrophile character to meet at least the test set
forth in US. Patent 2,499,368, dated March 7, 1950, to
De Groote and Keiser. In said patent such test for
‘Oil was obtained from Well No. D~3, O’Brien Lease,
emulsi?cation using a water insoluble solvent, generally
Blanco Oil Company, Greta, Texas, and amount of emul
xylene, is described as an index of surface activity.
The above mentioned test, Le, a conventional emulsi
si?ed water was 60%.
?cation test, simply means that the preferred product for
demulsi?cation is soluble in a solvent having hydrophobe
properties or in an oxygenated water-insoluble solvent,
This was from Chubbee Lease, Well No. 7, Texas Com
pany, Lone Grove, Oklahoma. Amount of emulsi?ed
or a mixture containing a fraction of such solvent with
water was 50%.
the proviso that when such solution in a hydrocarbon
Emulsi?ed Oil G
solvent is shaken with water the product may remain
This
was
obtained
from Dowlen Lease, Well No. 12,
in the nonaqueous solvent or, for that matter, it may
of Stanolind Oil and Gas Company, West Beaumont,
pass into the aqueous solvent. In other words, although
it is xylene soluble, for example, it may also be water 70 Texas, and the amount of emulsi?ed water was 40%.
soluble to an equal or greater degree. This test is per
formed with distilled water at ordinary room temperature,
This oil was from Well No. l, Pennock Lease, Stano
lind Oil and Gas Company, Hastings, Texas. Amount of
As to the use of conventional demulsifying agents, ref
erence is made to US. Patent No. 2,626,929, dated Jan 75 emulsi?ed water was 40%.
for instance, 22.5 ° C. or thereabouts.
3,057,892
29
30
ene oxide, and then in the ?nal stage with 4.7 pounds of
Em-ulsified Oil I
Oil obtained from Well No. 12, O’Brien Lease, Sunray
ethylene oxide.
7
'
10 pounds of the diol were reacted with 0.45 pound
Oil Company, Refugio, Texas. The emulsi?ed oil was in
the amount of 40%.
of diglycolic acid.
This oil was from the Alexander Lease, Pan American
Oil Company, Conroe, Texas, and was a composite, con
taining 35% emulsi?ed water.
pounds of ethylene oxide, then with 39.3 pounds of propyl
ene oxide, and then with 18.3 pounds of ethylene oxide.
Demulsi?er N0. 3
One pound of dipropyleneglycol was reacted with 2
10 pounds of the diol were reacted with 0.45 pound of
diglycolic acid.
Demulsi?er N0. 4
One pound of dipropyleneglycol was reacted with 4
This oil was from the Trosclair Lease, Well No. 3-1,
of Austral Exploration Company, Anse La Butte, Lou
pounds of propylene oxide, then with four pounds of
ethylene, oxide, and in the ?nal step with 30.7 pounds
of propylene oxide.
isiana, and emulsi?ed water was equivalent to 20% .
10 pounds of the diol were reacted with 0.45 pound of
Oil from Well No. 1, D. Case Lease, California Oil
diglycolic acid.
Company, Brookhaven, Mississippi, containing about
Demulsi?er No. 5
15% emulsi?ed water.
20
pounds of propylene oxide, then with 4 pounds of ethylene
oxide, followed by 31.5 pounds of propylene oxide, and
then with 4.4 pounds of ethylene oxide.
This was from Fuller Lease Well No. l, J. G. Beard
Oil Company, Seven Pines, Texas. It contained about
35% water, emulsi?ed.
10 pounds of the diol were reacted with 0.45 pound
25
emulsi?ed water.
'
'
Emulsi?ed Oil 0
'
of diglycolic acid.
Demulsi?er No. 6
One pound of dipropyleneglycol was reacted with 4
pounds of propylene oxide, followed by 4 pounds of
This oil was from Well No. 1, Cathey Lease, Frankfort
Oil Company, Ringling, Oklahoma, containing 45%
Y
One pound of dipropyleneglycol was reacted with 4
30
. This oil was from Well No. 7, Mann Lease, A. _J.
Atkinson Company, Comanche, Oklahoma, containing
ethylene oxide, followed by 30.7 pounds of propylene
oxide, followed by 45.7 pounds of ethylene oxide.
10 pounds of the diol were reacted with 0.45 pound
of diglycolic ' acid.
12% water in emulsi?ed form.
Demulsi?er N0. 7
35
This oil was obtained from Ten A, lst-low trap, North
. One pound of dipropyleneglycol was reacted with 4
pounds of propylene oxide, followed by 4 pounds of
ethylene oxide, and then with 59 pounds of propylene
Coles Levee, Rich?eld Oil Company, Los Angles, Cali
fornia, and contained 8.5% water, emulsi?ed.
oxide, and then in the ?nal stage with 7.7 pounds of ethyl;
ene oxide.
40
Oil from Tank Farm 1, Wash Tank 5 and 3, Southwest
'
10 pounds of the diol were reacted with 0.45-pound
of diglycolic acid.
Exploration Co., Huntington Beach, California, and
contained about 16% emulsi?ed water.
,
One pound of dipropyleneglycol was reacted with 5
45
This was from Taylor Lease, composite, Shell Oil Com
pany, Ventura, California, and contained 6% emulsi?ed
pounds of propylene oxide, followed by 10 pounds of
ethylene oxide, followed by ‘9.9 pounds of propylene
oxide, followed by 2 pounds of ethylene oxide, and in the
?nal stage with 4.2 pounds of propylene oxide.
10 pounds of the diol were reacted with 0.45 pound
The compounds of this invention employed as demulsi
of diglycolic acid.
50
?er in the examples were as follows:
Demulsi?er N0. 9
This demulsi?er was prepared in the same way as
Demulsi?er No. 1
Demulsi?er No. 8, preceding, except that in the ?nal
This demulsi?er was prepared by reacting one pound
oxypropylation
stage, instead of using 4.2 pounds of
of dipropyleneglycol with 2 pounds of ethylene oxide,
propylene oxide, 6.7 pounds of propylene oxide were em
then with 30.5 pounds of propylene oxide, and then with
ployed.
3.7 pounds of ethylene oxide.
10 pounds of the diol were reacted with 0.45 pound
The diol thus obtained, using an alkaline catalyst and
of diglycolic acid.
water.
an oxyalkylating temperature of not over 125 ° C., was
'
Demulsi?er N0. 10
neutralized with acetic acid.
60
One pound of dipropyleneglycol was reacted with 15
10 pounds of the diol were reacted with 0.45 pound
pounds of propylene oxide followed by reaction with 9
of diglycolic acid.
- The reaction took place in the presence of an equal
volume of xylene and a phase separating trap was em
ployed. The reaction was continued until there was no
further evolution of water.
The same procedure in regard to oxyalkylation, i.e.,
use of an alkaline catalyst at a temperature of not over
125° C., was employed in all subsequent examples. The
method of esteri?cation, which is conventional, was em
ployed in all subsequent examples.
Demulsi?er N0. 2
One pound of dipropyleneglycol was reacted with 2
pounds of ethylene oxide, then with 39.3 pounds of propyl 75
pounds of ethylene oxide, followed by reaction with 9.9
pounds of propylene oxide, followed by reaction with
11.7 pounds of ethylene oxide, followed by reaction
with 51.5 pounds of propylene oxide, and in the ?nal stage
with 4.87 pounds of ethylene oxide.
10 pounds of the diol were reacted with 0.455 pound
of diglycolic acid.
Demulsi?er N0. 11
The demulsi?er was prepared exactly in the same ‘way
as in the ‘case of Demulsi?er No. 9, above except that
in the ?nal stage instead of reacting with 4.87 pounds of
ethylene oxide, there was u-sed,25.1 pounds of ethylene
oxide.
'
'
3,057,892
32
31
10 pounds of the diol were reacted with .45 pound of
diglycolic acid.
Demulsi?er No. 12
One pound of dipropylene glycol was reacted with 15
pounds of propylene oxide followed by reaction with
10 pounds of ethylene oxide, followed by reaction with
9.9 pounds of propylene oxide and in the ?nal stage by
7.0 pounds of ethylene oxide.
10 pounds of the diol were reacted with 0.45 pound of
diglycolic acid.
hydrophile balance may be changed comparatively little
or not at all.
Such derivatives obtained in the manner
described may be used for breaking petroleum emulsions
of the water-in-oil type. They also can be converted into
derivatives of the kind subsequently described which also
may be used for this same purpose. Such derivatives are
useful for other purposes including the same purpose for
which the herein described products are effective. The
10 herein described products may be used for various pur
poses where detergents, common solvents, emulsi?ers,
Demulsi?er N0. 13
The diol employed was the same as the diol described
in the preceding demulsi?er through the second oxypro
pylation stage, i.e., where 9.9 pounds of propylene oxide
were added.
hydrophile direction. In some instances the hydrophobe
In the next stage, instead of adding 7
pounds, 11.7 pounds of ethylene oxide were added, and
then there was added in the ?nal stage 20.4 pounds of
propylene oxide.
10 pounds of the diol were reacted with 0.45 pound
of diglycolic acid.
Demulsi?er N0. 14
and the like are used. They may be used as lubricants
and as additives to ?uids used in hydraulic brake sys
terns; they may be used as emulsifying agents to emulsify
or remove greases or dirt; they may be used in the manu
facture of a variety of other materials such as soluble
oils, insecticide sprays, etc.
One may use a salt of the kind described as a fuel oil
additive in the manner described in U.S. Patent No.
2,553,183, dated May 15, 1951, to Caron et al. It can
be used in substantially the same proportions or lower
proportions and this is particularly true when used in
conjunction with a glyoxalidine, or amido glyoxaladine.
An analogous use in which these products are equally
The same procedure was followed as in the prepara
tion of the diol as in Demulsi?er No. 12, preceding, ex 25 satisfactory is that described in U.S. Patent No. 2,665,
978, dated January 12, 1954, to Stayner et al. The
cept that after the ?nal oxyethylation stage in which 7 .0
amount employed is in the same proportion or lesser
pounds of ethylene oxide were added, there was added
amounts than referred to in said aforementioned Caron
instead 4.7 pounds of propylene oxide.
et al. patent.
10 pounds of the product were reacted with 0.45
The second use is for the purpose of inhibiting fogs in
30
pound of diglycolic acid.
hydrocarbon products as described in U.S. Patents Nos.
TABLE XV
2,550,981 and 2,550,982, both dated May 1, 1951, and
both to Eberz. Here, again, it can be used in the same
DeTest No.
Per
Emulsi?ed
mul-
oil No.
sl?er
No.
A..-----_.
Ratio
° F.
Hours
cent
temp
time
water
separ
ated
proportions as herein indicated or even small propor
35 tions.
A third use is to replace oil soluble petroleum sul
fonates, so-called mahogany soaps, in the preparation of
certain emulsions or soluble oils or emulsi?able lubri
5
4
7
4
5
5
6
7
8
9
8
9
4
9
8
1:6, 250
1 :6, 250
1:6, 250
1 :12, 500
1 :12, 500
1 :8, 333
1:12, 500
1 :7, 143
1:10, 000
1 :12, 500
1:12, 500
1 :12, 500
1 :8, 333
1 :8, 333
1:6, 250
Cold
Cold
160
Cold
Cold
Cold
Cold
Cold
Cold
Cold
Cold
Cold
140
140
140
2
2
3
1
1‘ g
1%
2
2
1
1
3
2
2
3
1
45
45
20
35
35
35
60
50
40
40
40
40
35
35
20
8
9
8
9
1:4, 167
1:10, 000
1:8, 333
1:6, 250
1:20, 000
170
130
Cold
Cold
140
1%
21/5
1%
3
15
35
in the summary of this article, it states:
45
“The technical oil-in-water emulsion
12 50
1:20, 000
1:16, 000
1:16, 000
1:16, 000
140
140
10
11
12
13
14
140
140
11
11
24
24
24
14
14
26
26
26
cants where such mahogany soaps are employed. The
co-generic mixtures having this peculiar property serve
to replace all or a substantial part of the mahogany soap.
Another use is where the product does not serve as an
emulsifying agent alone but serves as an adjunct.
Brie?y stated, the fourth use is concerned with use as
45 a coupling agent to be employed with an emulsifying
agent. See “The Compositions and Structure of Techni
cal Emulsions,” I. H. Goodey, Roy. Australian Chem.
Inst. J. and Proc., vol. 16, 1949, pp. 47-75. As stated,
is regarded as a
system of four components: the dispersion medium, con
sisting of the highly polar substance water; the disperse
phase composed of hydrocarbons or other substances of
comparatively weak polarity; the coupling agent, being an
55 oil-soluble substance involving an hydroxyl, carboxyl or
similar polar group; and the emulsifying agent, which is
PART 6
a water-soluble substance involving a hydrocarbon radi
The esters herein described, whether monomeric or
cal attached to an ionizable group.”
polymeric and whether having a free hydroxyl group or
Fifth, these materials have particular utility in increas
free carboxyl group or both, may be used for a variety
of purposes. However, we have found it particularly 60 ing the yield of an oil well by various procedures which
in essence involve the use of fracturing of the strata by
desirable for many applications to obtain an acidic ester,
means of liquid pressure. A mixture of these products
whether monomeric or polymeric and neutralize with
with oil or oil in combination with a gel former alone, or
caustic soda, caustic potash, or ammonia. Likewise, we
a gel former and ?nely divided mineral particles. yields
can neutralize with a water-soluble amine, such as meth
ylamine, diethylamine, or trimethylamine or the compar 65 a product which, when it reaches crevices in the strata
which are yielding water, forms a gelatinous mass of
able ethyl or propyl derivatives. We can also neutralize
curdy precipitate or solid or semi-solid emulsion of a
with derivatives such as hydroxylated amines including
high viscosity. In any event it represents a rapid geling
ethanolamine, diethanolamine and triethanolamine. We
agent for the strata crevices and permits pressure to be
can also neutralize with high molal amines as, for exam
ple, amines obtained from higher fatty acids having 8 to 70 applied to fracture the strata without loss of ?uid through
crevices, openings or the like.
18 carbon atoms. We can also neutralize with poly
The herein described products and the derivatives
amines such as ethylene diamine, diethylene triamine, etc.
thereof are particularly valuable in ?ooding processes for
Thus, we have been able to obtain a variety of products
recovery of oil from subterranean oil-bearing strata when
in which we can shift the hydrophobe-hydrophile balance
to some degree, either in the hydrophobe direction or 75 employed in the manner described in U.S. Patent No.
3,057,892
33
34
2,233,381, dated February 25, 1941, to De Groote and
that it consists of a series of alternating hydrophile and
hydrophobe chains with the proviso that it contain a
total of at least three hydrophobe chains and at least two
Keiser.
I claim:
hydrophile chains, with the further proviso that there be
A member of the class consisting of monomeric and
polymeric solvent soluble esters of polycarboxy acids hav 5 not more than ?fteen such chains and with the ?nal
proviso that at least one internal hydrophile chain con
ing up to four carboxyl groups, having up to 50 carbon
tain at least ?ve oxyethylene radicals and that the molec
atoms, and in which the carboxy groups are the sole
ular weight of the polyoxyalkylene glycol mixture be at
reactive groups with a polyoxyalkylene glycol mixture
least 1000.
consisting of a product which statistically represented has
a plurality of alternating hydrophobic and hydrophilic 10
polyoxyalkylene chains the hydrophilic chains consisting
of oxyethylene radicals linked one to the other and the
hydrophobic chains consisting of radicals selected from
the group consisting of oxypropylene and straight chain
oxybutylene radicals linked one to the other, each such 15
chain containing at least 2 and not more than 110 oxy
alkylene radicals, said statistically represented product
having an odd number of such chains linked together so
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,295,165
De Groote et a1. ______ __ Sept. 8, 1942
2,562,878
2,695,914
2,911,434
Blair ________________ __ Aug. 7, 1951
De Groote __________ __ Nov. 30, 1954
Kocher ______________ __ Nov. 3, 1959
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