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Патент USA US3029275

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p
IC€
r.
3,029,265
Patented Apr. 10, 1962
2
from 90 to 130° C. A temperature of 90° usually
insures a reasonable reaction speed. Above'about 130°,
decomposition and dehydration of hexitols often tends
3,929,265
POLYHYDROXY AMINO ETHERS AND AtCYLA
TION PRODUCTS THEREOF
to occur.
John D. Zech, Wilmington, DeL, assignor to Atlas (l'hemi
cal industries, Ind, Wilmington, Del, a corporation of
Delaware
'
'-
'
While the reaction is generally carried out in the
absence of solvent or diluent, such materials maybe used
-
if desired to lower the viscosity, as an aid in controlling
temperature, or to permit the use of lower temperatures
No Drawing. Filed Apr. 23, 1957, Ser. No. 654,442
16 Claims. (Cl. 260-'-4M.5)
where high melting polyhydric alcohols (such as hexitols)
This inventionvrelates to processes for the synthesis 10
are used.
’
of nitrogen compounds derived from polyhydric alcohols
having at least threehydroxyl groups per molecule and
to products which may be produced by such processes.
Particularly, it relates to acylation products of such
15
nitrogen compounds which are surface-active agents.
Suitable polyhydric alcohols or mixtures thereof for
use in this connection include, among others, triols (such
as glycerol), tetritols (such as erythritol), pentitols (such
as xylitol, arabitol, etc), the hexitols (such as sorbitol,
An object of this invention is to provide a new class
of polyhydroxy primary and secondary amino ethers
more than six hydroxy groups and polyhydric alcohols
such as for example gpentaerythritol, trimethylolethane,
which are useful intermediates for the chemical synthesis
and trimethylolpropane which are polymethylol alkanes.
mannitol, dulcitol, etc.), polyhydric alcohols containing
Suitable polyhydric alcohols also include anhydro
of amides, esters, ester amides, substituted polyhydroxy
amino ethers, and quaternary ammonium compounds. 20 derivatives of other polyhydric alcohols (having at least
three hydroxy groups per molecule) in which water vhas
An additional object of this invention is to provide a
new class of surfactants which are acylation products of
been removed from two hydroxyl groups to form a cyclic
fatty acids and polyhydroxy amino ethers.
ether, such as 1,4 sorbitan, and also external ethers of
A further object of this invention is to provide aclass
polyhydric alcohols, as, for example diglycerol.
Another group of suitable polyhydroxy alcohols :com
of surfactants which form stable emulsions over a wide 25
prises the .monosaccharides such as sorbose, mannose,
temperature range.
glucose, arabinose and xylose as well as methyl glucoside
It is also an object of this invention to provide a class
of compounds which, when used as additives in jet fuels,
impart anti-static properties thereto.
and similar compounds.
The polyhydric alcohols useful in this invention include
condensed with epichlorohydrin or a compound similar
to epichlorohydrin.
‘(2) The condensationproduct is in turn reacted with
group and the oxypropylene groups. For the purpose of
utilization in this invention the most suitable polyoxy
alkylene ethers of polyhydric alcohols are those formed
40 by reacting from one to six mols of alkylene oxide with
The above objects of this invention, as well as addi 30 those, of the type listed above, which have been modi?ed
by etheri?cation with alkylene oxides such as ethylene
tional objects, will be apparent to those skilled in the art
oxide, 1,2 propylene oxide and mixtures thereof. As
from a consideration of the following description.
is well known in the .art, such a reaction yields products
Brie?y summarized, methods of the present invention
containing polyoxyalkylene chains of varying length. If
‘involve the following steps:
(1) A polyhydric alcohol containing three or more 35 a mixture of alkylene oxides is employed, a given poly
oxyalkylene chain may contain both the oxyethylene
hydroxyl groups per molecule, preferably a hexitol, is
_ ammonia or an amine of the type described‘below.
(3) The product of step 2, which ;is in ‘the form of
each mol of polyhydric alcohol. The term polyhydric
a hydrohalide, is neutralized with an alkali .to liberate
a polyhydric amino ether.
alcohol when used hereafter is intended to include all of
the above exempli?ed compounds and mixturesthereof.
In lieu of epichlorohydrin other reactive epihalohydrins
(4) From these ethers, which are chemical intermedi
ates, amides and ester amides as well as other reaction 45 may be used such as epibromohydrin and epiiodohydrin.
Other compounds such as l-chloro-‘2,3 epoxybutane and
products can be derived. Surface-active agents can be
2-chloro-3,4 epoxybutane are also suitable for the
synthesized by reacting the ethers with an aliphatic mono
condensation.
carboxylic acid, in the manner described below.
The reaction products are for the most part very viscous
The initial step of the synthesis is the condensation
of a polyhydric alcohol having three or more hydroxyl 50 syrups. They are complex mixtures which may contain
residual free polyhydric alcohol in addition to various
groups per molecule with epichlorohydrin or its equivalent
in the presence of a catalyst.
The reaction can be exem
pli?ed by the following chemical equation:
(1)
on
[o-GEdonornOrh
isomeric epichlorohydrin-polyhydric alcohol condensates
(also referred to as chlorhydroxypropyl ethers).
The following are a few speci?c examples of the initial
55 reaction which are intended to illustrate the process but
not to limit it to the speci?c reactants involved.
EXAMPLE I.-1
613 grams of anhydrous sorbitol were heated to a
In the above equation x is a number of three or more 60 reaction temperature of between 97 and 107° C.; 1.5 cc.
and n is a number from one to x.
R is an hydroxyl-free
radical of a polyhydric alcohol. When the polyhydric
alcohol is a hexitol, from one to about three mols of
epichlorohydrin are usually preferred.
of BF, (45% BF3) etherate catalyst were then added.
Thereafter, 389 grams (molal ratio 1:1.25) of epichlo~
rohydrin were added dropwise, over a period " of 34
minutes with vigorous stirring and control of cooling,
Thereaction illustrated above may be performed in 65 so as to maintain the temperature within a speci?ed'limit.
the presence of an acidic catalyst as is well known in
the prior art.
Preferred catalysts are those of-the Lewis
acid type which include, for example, BF3, B133 etherate,
AlCl3, SnCl4, but H2504, p-toluene sulfonic acid and the
The temperature was maintained for one hour between
97 and 107° C. by the addition of heat to insure com
pletion of the reaction.
Additional examples are given in Table I. In each
like may also be used.
70 case, the procedure followed ‘was similar ‘to the procedure
The reaction may be carried out at any temperature
from about 75° to 175° C., the preferred range being
outlined above. However, the molal ratio of polyhydric
3,029,265
4
rohydrin addition time, the reaction temperature and the
120° C., with an optimum range from about 30° C. to
about 100° C. This reaction is exothermic and it may
amount of catalysts used.
be carried out in an inert solvent, such as water or a
alcohol to epichlorohydrin was varied, as was the epichlo
Table I
Grams
Example
Alcohol used
No.
Molal
Co. of
Reaction
Grams
epiehloro-
ratio
45% BF3
temp
Epichloro-hydrin
Total ‘reaction
alcohol
hydrin
alcohol:
etherate
° C.
addn. time
time
_
epl.
I-l ...... --
Sorbitol _____________ ._
1:1. 25
.
613
389
I-2__
_._-_do_-
1, 200
1, 220
1:2
3. 0
2 hrs. 20 mm
I—8-_
--___d0 ____ __
729
925
1:2. 5
2.0
1. 5
2 hrs. 10 min.
1 hr 34 mm
I—4__..
I-5I-6-
ErythritoLSorbitoL__.__do__
122
1, 459
651
92.5
925
578
1:1
1:1. 25
1:1. 75
0.5
3.0
1. 5
1 hr. 20 min.
3 hrs.
1 hr. 45 min.
I—7_
I—8..
_-_-d0-_
___do--
.... -_
.... __
1, 184
1, 200
602
1, 220
1:1
1:2
8.0
3.0
1 hr. 38 min.
2 hrs. 7 min.
I- _
--.-_do--
____ __
712
361
1:1
1. 5
2 hrs. 0 min.
600
1, 200
913
913
2,123
1, 184
460
610
1, 220
1,040
578
1, 345
3, 160
463
I-lOI-llI-12I-13I-14146.
146...
._do
__d0
do
-dO
.(10
._do_GlyceroL-
I-17---
. __-__d0-___-__
I-18 _ _ _ . __
__
Dl-glycerol .......... __
I-192 _____ _. Ttimethylol-ethane---
460
166. 5
170
698
1:2
1:2
1:2. 25
1:1. 25
1 :1. 25
1:5. 25
1:1
1:1. 5
92. 5
131
1. 5
3.0
2.0
2.0
5. 0
1 3. 4
1.0
D0.
3 hrs. 40 min.
2 hrs. 0 min.
1 hr. 30 min.
2 hrs. 0 min
5 hrs. 30 min.
1 hr. 40 min.
1. 25
1 hr. 53 min.
1:1
1. 0
1 hr. 37 min.
1:1
2.0
1 hr. 31 min.
1 Grams.
2 Prepared in 250 cc. dloxane. After reaction was complete, 14 g. trimethylolethane crystallized out and were ?ltered oil.
Considering now the production of surface-active com
positions which give stable emulsions over a wide range
lower alcohol. It is also possible to use an excess of
the primary amine as a solvent where the primary amine
of temperatures, their synthesis involves the reaction of 30 being used in a liquid. In the case of ammonia or a
volatile primary amine, such as methyl or ethyl amine, it
the condensation product of the initial step with arm
is desirable to carry out the reaction under pressure so
monia, a reactive primary amine or a polyamine. The
as to avoid the loss of the volatile reactant and thereby
reaction with ammonia or a reactive primary amine may
maintain it in excess of the theoretical molecular require
be illustrated by the equation set forth below.
35 ments.
By carrying out the reaction under super atmospheric
pressure, higher temperatures can be used and the re
action time correspondingly reduced.
Suitable primary mono-amines for use in this connec
40
tion are exempli?ed by methyl amine, ethyl amine, n-pro
pyl-amine, isopropyl amine, n-butyl amine, sec. butyl
amine, isobutyl amine, n-amyl amine, n-hexyl amine,
cyclo-hexyl amine, ethanol amine, propanol amine, and
1~amino~2, 3 dihydroxy propane (glycerol amine) or mix
tures thereof.
The reaction product, which is in the form of a hydro
Mixtures of primary amines, such as hexadecyl, octa
chloride, is neutralized in the next step with an alkali to 45
decyl, octadecenyl, and octadecadienyl may also be used.
liberate a polyhydric primary or secondary amino ether.
Such products are sold by Armour and Company under
This reaction may be illustrated as follows:
the generic trade name “Armeen.” These products are
(3)
OH
H01
more fully described on page 62 of the 1953 edition of
[00 zOHCHgNHR/ln
/
50 “Handbook of Material Trade Names” by Zimmerman
[OCH?‘JHOHzNHR’h
R/
+nNeCl+nHiO
\(OH) x-n
and Levine.
It is desirable, in many cases, to use the lower primary
amines, which are su?'iciently low-boiling, so that they
can be readily separated by distillation from the reaction
55 products which are non-volatile.
Suitable amines also include polyamines which con
tain not more than 3 amino nitrogen atoms. Such
amines are exempli?ed by the ethylene polyamines and
the propylene polyamines and include ethylene diamine,
The symbols in the equations above have the same
meaning as Equation 1. In addition, each R’ is inde
pendently selected from the group consisting of hydro
diethylene triarnine, propylene diamine, dipropylene tri
amine, triethylene triamine (N-aminoethyl piperazine),
gen, alkyl, hydroxy alkyl, cyclo alkyl, and polyhydroxy
alkyl.
7
The reaction takes place between ammonia or a re
active primary aliphatic amine (primary amines having
65
hydroxyethyl diethylene triamine (and other reaction
products of lower alkylene oxides such as ethylene oxide,
propylene oxide or mixtures thereof with polyamines,
provided however, that the resulting oxyalkylated amine
the amino group attached to tertiary carbon atoms, be
contains at least two amino hydrogens), 3, 3' iminobis
cause of steric hindrance effects, will not react with the
propylamine and mixtures of the above.
,
products of step 1 to give products which are suitable for
The neutralized reaction product of the polyamine de
the subsequent reaction and the term reactive amine, when
used henceforth, is intended to exclude such amines) and 70 rivative which corresponds to the monoamine product of
Equation 3 may be represented by the following formula
the product of the ?rst step synthesis. It is carried out
in the presence of an excess of ammonia or reactive pri
mary amine. The presence of the excess reactant serves
to suppress polycondensation.
Preferred reaction temperatures range from 20 to about 75
wherein all symbols have their previous meaning:
(ii-A)
R
3,029,265
and wherein each
‘is independently selected from the
group of monovalent radicals consisting of:
_
2;;
__
clave.
__NE__CN§_
_NE
Y 2y
(c)
Y 23’
2
5
held at 120° C. for 1.5 hours while the pressure devel
oped was 80—85 p.s.i.g.
The autoclave’s contents were discharged, the auto
clave rinsed with 700 g. of water and the combined
solution was heated to 100° C. to ‘boil off much of the
__N/
\
OYHZYNEQ
/C2H4
_N
The temperature of the autoclave’s' contents was
raised to 120° C. during a 1/2 hour period, and thereafter
QyH?NEZ
(d)
6
an autoclave, the ?ask was rinsed with 110 grams of
water, and the rinse water Was also added to the auto
10 excess NH3.
NAJZHPNE,
02114
(2)
02H‘
—-NE—~O2H4—N
Thereafter, 840 g. of 50% NaOH solu
tion (5% excess) were added and the reaction mixture
was heated to 110° C. to distill olf additional ammonia
and water. The resulting syrup amounted to 4,230‘ grams
and contained 10 moles of combined epichlorohydrin
15 residues. The amino-ether syrup which was thus pre
NE
CIH’
wherein further, in each radical, y is either 2 or 3; and
pared contained approximately 0.7 equiv. of nitrogen
per equlv. of eplchlorohydrm'
each E is independently selected from the group consisting of hydrogen and hydro!!!’ lower alkyl, PTOVidsd'hOW- 20
EXAMPLE II-Z
308 grams of the condensation product‘ of Example
ever that at least one E is hydrogen.
I-l were combined with 1160 cc. of a 40% solution of
The reaction with ammonia or primary amine produces
a hydrochloride of an amino ether. The amino other is
liberated by the addition of an amount of alkali equiva-
methyl amine at room temperature and the mixture
was allowed to stand over night. The temperature gradu
ally rose for several hours to about 35 to 40° C. and
lent to the chlorine content of the epichlorohydrin con- 25 then gradually decreased.
densate used.
The excess ammonia or primary amine,
After standing overv night,
the reaction mixture was heated on a steam bath for
as the case may be, is then Stripped oif and can be reseveral hours to insure completion of the reaction. Since
cycled to, the next batch.
methyl amine is a relatively volatile amine, some of the
The alkali used must be strong enough to liberate the
excess boiled oif during this heating.
amino ether from the amino hydrochloride and suit- 30
The reaction mixture was then treated with an amount
able alkalis are exempli?ed by the hydroxides of the
of aqueous NaOH equivalent to the chlorine content of
alkali metals.
the epichlorohydrin condensate used. The excess amine
The amino ethers can be separated from the by-prodand solvent were stripped off, using vacuum at the end
uct alkali metal chloride by known methods, such as
of the stripping operation. Thereupon, the product was
dilution with a non-solvent for the chloride followed by 35 taken up in su?icient methanol to obtain a suitable ?lter
?ltration and ion exchange- In some cases, the presing viscosity and the crystalline NaCl was ?ltered on.
ence of the chloride is not objectionable and the prodThe methanol was then stripped o?", leaving the poly
not can be used without separating it.
hydroxy amino ether as a residue which still contained
The following are a few speci?c examples of the for-
some Sodium chloride.
mation of polyhydroxy amino ethers and are to be con- 40
sidefed illustrative OIIIY- ‘It is t0 be noted that every
nitrogen compound used meets the fundamental require-
_
The reaction yielded 325 grams of polyhydric amino
ether which contained 4.86% nitrogen by weight. Addi
tional Examples II-3 to -IiI—-23 follow in Table II.
Table II
Example No.
Condensate
of Example
No.
Grams
condensate
Amount
of
amine
Amine used
Product
yield,
g.
Butyl amine--.“
1,100 cc--__
539. 5
Ethanolamine_...
2,000 cc.___
863
40% methyl amine-
1,000 co____
213. 5
Percent
N
NH4OH (28% N113)“
40% methyl amine" _.
Glyceryl amine: _ _ .
Butyl amine- ____
Gyclohexyl amine
“Armeen SD” l _______ __
6 46
____.
_
1,000 00....
1,000 e0___.
-._ 700 00-.....
Diethylene triamine _____________ __
900 cc- ____
Hydroxy ethyl ethylene diamine.. 105 g ____ ._
7 56
260. 5
345
373
365 -
357
4. 92
5. 9
8. 71
12. 45
7. 8v
1 A soft fatty amine sold by Armour dz 00. under this designation.
ment of containing at least two hydrogen atoms bonded
to basic nitrogen.
-
EXAMPLE II-l
To a ?ask containing 2,645 grams of a condensate
The polyhydroxy amino ethers are useful chemical
intermediates. From these ethers——amides‘, ester amides,
substituted polyhydroxy amino ethers, and quaternary
ammonium compounds can be readily and easily pre
prepared by a procedure similar to that of Example I-5, 70 pared.
Formation of the emulsi?er is completed by amida
which contained 10 moles of combined epichlorohydrin,
tion
of the polyhydroxy amino ether with an aliphatic
was added 2,430 grams of 28% aqueous ammonia (40
mono-carboxylic acid. Despite the selection of reac
moles, 300% excess). The addition of the ammonia
tion conditions which favor the formation
~took.place at temperatures from 15 to 26° C. and ex_ of amides,
tended over a half hour. The solution was charged to 75 some esteri?cation results.
Since-the ammo ethercon- \
3,029,265
8
selected from the group of monovalent radicals consist
ing of:
tains free hydroxyl groups in the portion of the mole
cule derived from alcohol, and since further, it may
contain additional free hydroxy groups if the primary
amine used in the second step was an alkanol amine
(such as, for instance, ethanol amine or propanol amine),
there is always ester formation. Thus, the ?nal reaction
product is a combined amide and ester. The relative
extent of amidation and esteri?cation may be varied by
varying the amount of fatty acid reacted with the poly
hydroxy amino ether.
10
Amidation of the polyhydroxy amino ethers may be
either total or partial. If only one amino nitrogen atom
capable of amidation is present in the ether molecule,
such as would be the case when the ether is formed by
the seriatim reaction of one molecule of polyol, one 15
molecule of epichlorohydn'n and one molecule of a re
active primary monoamine, then the surface-active com
positions of this invention are total amidation products.
wherein, further, y is an integer from 2 to 3, and eachY
is independently selected from the group consisting of
However, when more than one molecule of epichloro
hydrin attaches to a given polyol molecule and/or when
hydrogen, acyl radicals of aliphatic monocarboxylic acids,
a polyamine is used to form the amino ether then a
hydroxy lower alkyl and acylated hydroxy lower alkyl,
molecule of the ether may contain a plurality of amino
provided however that at least one Y is the acyl radical
nitrogen atoms which are capable of amidation. In the
of an aliphatic monocarboxylic acid.
case of such poly-amino ethers it is essential that at least
The amidation reaction, in which at least one mol of
one amino nitrogen be amidated. How many more will 25
H20 is evolved per mol of acid reacted, is carried out at
be amidated is a function of the carboxyhamino nitro
an elevated temperature, within the range of about 170
gen ratio of reactants. While some esteri?cation always
and about 220° C.
occurs, lower ratios favor products which are predomi
If none, or only part of the salt, was removed prior to
nantly amides whereas ratios above 1:1 tend to favor
this reaction, it can be ?ltered off from the amide either
increased ester formation. Generally any ratio of car
with or without dilution with a non-solvent for the salt.
boxylztotal nitrogen from 0.75 to 6 may be used, those
For some applications, the salt may be allowed to remain
compounds prepared using ratios of from 3 to 6 having
in the ?nal product.
higher ester content. However, the range from 0.75 to
As has been stated, it is also possible to only partially
2.0 is generally preferred.
Total amidation of an ether derived from a primary 35 amidate an amino ether which has been made from a poly
olepihalohydrin derivative wherein the ratio of epihalo
mono-amine can be illustrated by the following equation:
OH
hydrin to polyol was greater than 1:1. Thus, the amida
tion products formed by reacting a monocarboxylic acid
with the ether made from a polyol-epihalohydrin deriva
40 tive and ammonia or a reactive primary mono-amine may
be generally represented by the following formula:
(5)
(1?
CR”
O-CHz-OHO R”’—-OH¢—N
45
A
n
R£[O—CH:—CHO R’”-CH:——-NHA]m
(O R’”) X-(mn)
wherein x is a number of at least 3; n is a number from
1 to x;
And m is a number from zero to the quantity x--n; and
x is a number of at least 3 and n is a number from 1
to x.
wherein further,
_ "——C—-is the acyl radical of an aliphatic monocar
0
boxylic acid.
II
R is an hydroxyl-free radical of a polyhydric alcohol. 55
R’ is hydrogen, alkyl, cyclo alkyl, hydroxy alkyl or
is the acyl radical of an aliphatic monocarboxylic acid;
R is an hydroxyl-free radical of a polyhydric alcohol;
polyhydroxy alkyl.
Each R’” is independently selected from the group con
sisting of hydrogen atoms and acyl radicals of aliphatic
monocarboxylic acid.
RIIC~
Each A is independently selected from the group con
60
Each A is independently selected from the group con
sisting of hydrogen, alkyl, cyclo alkyl, hydroxy lower
alkyl, polyhydroxy lower alkyl, acylated hydroxy lower
alkyl and acylated polyhydroxy lower alkyl; and
sisting of hydrogen, alkyl, cyclo alkyl, hydroxy alkyl, poly
hydroxy alkyl, acylated hydroxy alkyl, and acylated poly
hydroxy alkyl.
Each R’” is independently selected from the group con
sisting of hydrogen atoms and acyl radicals of aliphatic
monocarboxylic acids.
In the case of the polyamines which have previously 65
The corresponding generalized formula for products
been described, the corresponding amidation products may
formed from polyamine derivatives is as follows:
be represented as having the formula:
(Ev-A)
[0 --c Hz-CHO R'”-—CH-a—-X]n
R—-[O—CH2—CHOR"'-—CHg-Z]m
70
R
(O R'”) x-(mi-n)
wherein Z has the meaning assigned in Formula 3-A,
X has the meaning assigned in Formula 4-A and x, m, n,,
R and R'" have the same meaning as in Formula 5.
In the case where total amidation does not occur and
Equation 4 above ‘and, wherein each X is independently 75
wherein common symbols have the same meaning as in
8,029,265
10
.
consequently only part of the amino ‘groups are reacted,
the resulting amides will contain free amino groups and
can, therefore, be used as cationic surfactants, whereas
the fully amidated products are non-ionic surfactants.
contained 1.046 equivalents of combined epichlorohy
drin residues) was added 925 grams (3.19 moles) of
clude the higher fatty acids such ‘as lauric, myristic, pa'lmitic, stearic, oleic, linoleic, linolenic, ricinoleic, 12-hydroxy
after which time the Acid Number of the amide product
was 29; and thereafter for an additional hour ‘at 230° C.,
oleic acid derived from tall oil. The reactant molal ratio
of fatty acid to nitrogen was approximately 4.421. ‘The
Suitable mono-carboxylic acids for the amidation in- 5 reaction was allowed to proceed for 4 hours at 200° C.,
stearic acid, erucic, as well as mixed acids such as the fatty
at which time the Acid Number of the amide product was
acids derived from animal and vegetable fats and oils,
17. ;To this product were added .346 equivalent of NaOH
tall oil, naphthenic acids ‘and acids obtained by the oxida- 10 and the reaction continued for another hour at 230° C.
tion of petroleum fractions. While fatty acids having
The ?nal product, which was calculated to contain 10.8%
12 to 18 carbon atoms are preferred for this reaction, it
soap, had an Acid Number of 11.
is also possible to use a short chain acid such as acetic
XQN
acid, provided that the amino other which is being amidated has a long alkyl chain which was derived from a 15
__
__
E_
PLE HI .3
_
A11 addlho?al POTUQH 0f the ammo-ether pregal'ed 111
fatty amine in the previous synthesis step.
Exalhple 11-? Was StI‘IPP‘Qd 10 180° C- ‘T0 this ether
AS is well known in the art, emulsions have both a
(which contained .848 equlvalent of combined epichloro
hydrophobe and a hydrophile function. .In the present
compounds, the hydrophobe function can be contributed
hyqfln heslduhs) Was added _995 grams (343 moles) 0f
oleic acid derived ‘from tall 011. The react-ant molal ratio
by either the carbon chains derived from the amine or 20 0f fafty acid t0 hltfogeh Was approximately 5-311- The
those derived from fatty acid, or both “ms, when ‘a
short chain acid as, for example, acetic is employed, a
reaction was allowed to proceed for 4 hours at 200° C.,
after Whlch tlme the Acld Nlllhbel: _of the amlde Product
long ‘chain amine Should be used_ In gengral, it is pre.
ferred that the combined carbon chain lengths of amine
WaS
and thereafter for an addltlonal hour at 230° 0.,
at which time the_ Acid Number of the amide Pfoduct
and fatty acid groups used in the preparation of the sur- 25 'Was 32-5factants ofthjsinventiontotalover12_
T0 thls prochlct Wei? added ‘68 equlvalent
of NaOH and the react1on continued for another hour
The following are examples of the amidation reaction:
at 239°
EXAMPLE 1H4
('yrhe ?hhllcl lgfodllfktagvllilfh ‘lavas éalclllated t0
.contaln 1 .1 0 soap,
A portion of the amino-ether prepared in Example 30
2
an
01
um er 0
1-8.
{EXAMPLE III-4
II-l was stripped to 183° C. To this ether (which con-
310 grams of 01616 301d W?fe added to_ 286 grams of
tained 1.44 equivalents of combined epichlorohydrin resi-
the product of. Example II-1 (molal ratio carboxylzN,
dues) was added 856 grams (2.95 moles) of oleic acid
1.1 :1). The mixlng took place at between 70 and.100° 0.
derived from tall oil (sold as the trademarked product
Thereafter, the reactants were heated to the reaction tem
Acintol FA-Z). The reactant molal ratio of fatty acid 35 perature of between 165 and 200°C» and held there for
to nitrogen was approximately 29:1. The reaction Was
a period of three hours. and 20 m1nutes.
_
_
allowed to proceed for 4 hours at 200° (3., after which
Imt1alv1scos1ty was high due to the formation of amine
time the Acid Number of the amide product was 11.5;
soaps. However, as the temperature was ralsed and the
and thereafter was allowed to proceed for an additional
amidat-lon proceeded, the v1scos1ty decreased.
hour at 230° 0., at which time the Acid Number of the 40
The resultant product has an acld number of 10-5. a
?nal amide product was 6.7.
saponi?cationpnumbervof 51 and an OH number of 40.
‘
Additional Examples LII-5 to III-33 are presented in
EXAMPLE 1H4
Another portion of the amino-ether prepared in 'Exam-
Table III. In each instance, the reaction procedures were
similar to those in Example III-4 which was described
ple 11-,1 was stripped to 180° C. To this ether (which 45 above in narrative form.
'
Table III
Example
No.
Grams
Acid used
acid
Amine ether
synthesized Grams
in Example
N0.
Characteristics
Mol ratio
ether carb0xyl:N
Reaction Product
Reaction time
tcmp.,° 0.
acid
number
Sap.
OH
number number
1:1
1 :1
111-18....
111-14....
I1I-15___.
111-15....
178-205
6.4
41
441
1 :1
175-211
179-210
5. 5
8. 2
44
41
875
429
1:1
1:1
1:1
1:1
1 :1
1 :1
1 :1
1:1
0.75:1
1 =1
1 :1
1:1
0. 97: 1
1:1
185-200
185-219
187-204
180-210
181-210
180-219
180-215
180-208
187-218
188-205
180-215
181-218
188-212
187-213
24
85
47
55
46
58
93
59
51
21
45
25
25
75
1:1
1 :1
187-218
172-213
5. 4
3. 7
8. 8
12.1
6.3
8. 1
8. 3
5. 9
22.8
4. 4
4. 0
5. 3
5. 8
8. 4.
3. 5
2. 6
38
40
550
858
257
324
818
895
275
858
277
425
881
488
555
545
38
458
180-200
188-225
2.0
5. 1
(1) 49
367
__________
1 : 1__
1:1
180-212
2. 2 .
99
294
1:1
180-199
8. 1
99
235
1:1
187-212
5. 2
0. 75: 1
0. 75:1
0. 9: 1
0.0: 1
0. 9: 1
175-208
180-188
177-218
175-211
175-210
0. 2
8. 5
4. 5
8.0
7.9
M
‘
WW.
280
23
27
63
37
30
485
885
807
258
899
3,029,265
12
11
such fuel in small quantities of about 0.2% and less.
Preferred compositions of the invention for this purpose
One use of the amides synthesized in the manner de
scribed is as the emulsi?er in a water-in-oil emulsion
drilling ?uid. Typical drilling ?uids employing the amide
as the emulsi?er also include a water phase (preferably
are those which are soluble in the fuel without haze at
concentrations up to 0.2% by weight at temperatures
containing salt), and an oil phase.
A water-in-oil emulsion drilling ?uid was prepared
as low as —60° F. The amount of composition of the
invention added for anti-static use should be su?icient
using the product of Example III-4. The drilling ?uid
had the following formulation:
to reduce the electrical resistivity of the fuel to a value
Grams
Saturated salt water _________________________ __ 252 10
amount will be between about 0.2% and 0.0025‘%.
A fuel which is particularly susceptible to this static
Fuel
electrical explosive hazard and in which the compositions
oil
_____ __ 117
325 mesh Bentonite _________________________ ....
20
Water-soluble emulsi?er ______________________ __
3
Product of Example III-4 ____________________ __
5
Total
below about 1><1010 ohm-centimeters. Usually that
_
of the present invention are particularly useful as anti
static additives is that used for jet engines and referred
to as JP-4 fuel. It is completely described in military
15 speci?cation MIL-F-S 624C.
In Table IV, are listed a number of examples of addi
397
The above formulation is representative of many which
can be prepared. All of them exhibit remarkable stabil
ity even under high temperature conditions.
20
Some of the products of the present invention are use
ful as corrosion inhibitors, particularly for brine solu
tions containing hydrogen sul?de which are commonly
encountered in the oil industry. For example, the prod
uct of Example III-16, when tested for corrosion inhib 25
iting properties in accordance with the procedure de
tive content of jet fuels containing compounds of the
invention. Each of these fuels was prepared by simply
adding the amount of additive listed in the table to JP-4
fuel. Each of the resulting fuels had a speci?c resistivity
below 1 X 101° ohm-centimeters and was useful as a fuel
in jet engines. Tests performed on each fuel indicated
that it could be handled without buildup of static elec
tricity and that no precipitate haze appeared in the fuel
when it was cooled to a temperature of —60° F.
Table IV
scribed in detail in “The Development of a Standard Lab
oratory Procedure for Screening Corrosion Inhibitors for
Use in Oil and Gas Wells” by E. C. Greco and J. C.
Spalding (paper prepared for National Association of 30
Corrosion Engineers, 1954), gives excellent corrosion pro
tection (95.4% protection) when used at a concentration
of 100 ppm. in a 5% brine solution containing 500 ppm.
The products of the invention are also useful for cre 35
ating water-in-oil emulsions for a number of other uses.
One applicaiton relates to marine diesel engines which em
ploy oil as a circulating lubricant. In order to maintain
lubricant in the form of a temperature-stable emulsion,
rather than being present as a separate phase. The fol
lowing formulation is illustrative of the wide range of
Concentration
(weight percent
of incl)
Product of Example
III-5
of hydrogen sul?de.
‘lubricating properties, it is desirable that any water which
may get into the lubricating system be incorporated in the
Additive
-_
III-R
III-22
III-9
III-l1
III-12
III—\ ‘1
III-29
III-30
. 05
0. l
0. l
0. l
0. 05
0. 05
0. 05
0. 05
0. 1
4.0
utility afforded by the instant emulsi?ers for such appli
Many changes in processing details may be made with
out departing ‘from the principles set forth herein and
the invention is to be broadly construed in accordance
with the following claims.
'
cations.
What is claimed is:
If the emulsi?er of Example III—6 is added to lubricat 45
1. A process comprising condensing sorbitol with epi
ing oil in the ratio of three parts by weight of emulsi?er
chlorohydrin in the molar ratio of 121.25, aminating the
to 70 parts by weight of lubricating oil, it will then be
product of the aforesaid reaction with ammonia at a
possible to incorporate amounts of water ranging from
temperature of about 20° to about 120° C. in the pres
0 to 150 parts. Throughout the entire range a homoge
neous water-in oil emulsion will exist. The emulsion can 50 ence of an excess of ammonia, liberating the ether con
densation product with an alkali, and thereafter amidat
be formed whether the water is salt water, such as is
ing and esterifying the resulting polyhydroxy amino ether
commonly found in marine service, or fresh water, which
by contacting it with oleic acid at a temperature within
might result from engine exhaust. These emulsions are
stable over a wide range of temperatures.
Compositions of this invention ?nd additional utility 55
as anti-static additives to hydrocarbon fuels of the low
vapor pressure wide cut gasoline type. Fuels of this
type may usually be characterized as having a Reid
vapor pressure within the range of about 2.0 to 3.0.
the range of about 170° to about 220° C.
2. A process comprising the steps of (1) aminating
the condensation product of a polyhydric alcohol, having
from 3 to 6 hydroxy groups per molecule, and an epi
halohydrin, with a basic nitrogen-containing compound
selected from the group consisting of ammonia, reactive
Handling them has, in the past, presented a considerable 60 primary alkyl monoamine, reactive primary hydroxy
lower alkyl monoamine, reactive primary cyclo alkyl
explosion hazard because their vapor pressure at ambient
monoamine, reactive primary polyhydroxy lower alkyl
temperatures is high enough that when a body of fuel is
monomanie, and alkylene polyamines containing from 2
maintained in an ordinary vented tank the amount of
to 3 amino nitrogen atoms and at least 2 amino hydro
vapor is suf?cient to provide an explosive mixture but
insu?icient to lower the proportion of air to such a de 65 gen atoms per molecule; (2) liberating polyhydroxy
amino ether condensation products by neutralizing the
gree that the mixture above the fuel is not explosive.
product of step 1 with an alkali; (3) and thereafter acylat
Consequently fuels of this sort have been susceptible to
ing the polyhydroxy amino ether condensation products
ignition by sparks such as can be generated by static elec
tricity build up in the fuel body.
70 of step 2 to form a fatty acid amide.
3. A process comprising the steps of (l) aminating
It has been found that compounds of this invention
the condensation products of sorbitol and epichlorohydrin
have the property of lowering the electrical resistivity of
with a ‘basic nitrogen-containing compound selected from
the fuels and/or inhibiting the buildup of static elec
the group consisting of ammonia, reactive primary alkyl
tricity in them. In this way the explosion hazard in
handling the fuel is greatly minimized when added to 75 monoamine, reactive primary hydroxy lower alkyl mono
3,029,265
13
14
11. The reaction product made 1by the process of
claim 5.
12. The reaction product made by the process of
claim 6.
13. The reaction product made by the process of
amine, reactive primary cyclo alkyl monoamine, reactive
primary polyhydroxy lower alkyl monoamine, and lower
alkylene polyamines containing from 2 to 3 ‘amino nitro
gen atoms and at least 2 amino hydrogen atoms per
molecule; (2) liberating polyhydroxy amino ether con
densation products by neutralizing the product of step 1
with an alkali; (3) and thereafter acylating the polyhy
droXy amino ether condensation products of step 2 to
claim 7.
14. The reaction product made by the process of
claim 8.
15. The reaction product made by the process of
4. The reaction product made by the process of claim 2. 10 claim 9.
16. The reaction product made by the process of
5. The process of claim 4 wherein the acylation is
claim 1.
carried out by contacting the polyhydroxy amino ether
condensation products with a higher fatty ‘acid which con
References Cited in the file of this patent
tains from 12 to 18 carbon atoms per molecule.
6. The process of claim 5 wherein said nitrogen 15
UNITED STATES PATENTS
form a fatty acid amide.
containing compound is ammonia.
,
7. The process of claim 5 wherein said nitrogen
containing compound is methylamine.
8. The process of claim 5 wherein said nitrogen
contaiuing compound is ethylene diamine.
9. The process of claim 5 wherein said nitrogen
containing compound is diethylene triamine.
10. The reaction product made by the process of
claim 3.
20
2,669,336
2,525,771
2,538,072
2,581,464
2,539,199
‘2,598,213
2,609,370
2,775,604
Schmidt et al ___________ __ Feb. 2,
Cook et a1. ___________ __ Oct. 17,
Zech ________________ -_ Jan. 16,
Zcch _________________ __ Jan. 8,
Morison _____________ __ Mar. 11,
Blair ________________ __ May 27,
Gaver et al ____________ __ ept. 2,
Zech ________________ __ Dec. 25,
1937
1950
1951
1952
1952
1952
1952
1956
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No, 3,02%265
April 10v 1962
John D. Zech
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Columns 9 and 101 Table IIIv under- the heading "Reaction
time", Example N0, III-~30q for "3 hrs‘, 50 min." read —— 3 hrs.
0 min. —-; column 1OF lines 9‘, l7 and 259 "equivalent"? each
occurrenceI read —— equivalents —~; column 120
"monomanie"
read
-‘~ monoamine
line‘ 639 for
»—.
Signed and sealed this 11th day of December 1962.
(SEAL)
Attest:
ERNEST w. SWIDER
Attesting Officer
DAVID L- LADD
Commissioner of Patents
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