Note: Descriptions are shown in the official language in which they were submitted.
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HOEC~ST AKTIENGESELLS~HAFT HOE 87/F 907 Dr.GL-ba
Werk Gendorf
Process for the preparation of quaternary ester amines,
and their use
Description
The invention relates to a process for the preparation of
quaternary ester amines, starting fro~ glycerides and
alkanolamines. The invention furthermore relates to the
use of the quaternary ester amines prepared.
Russian Patent Specification 925,978 (Derwent Reference
No. 26938 K/11) describes a process for the preparation
of ester am;nes in which glycerides are reacted with poly-
hydric alcohols such as ethylene glycol, glycerol, penta-
erythritol and sorbitol, or with amino alcohols such as
diethanolamine, triethanolamine, trimethylolmelamine and
oxamines. According to the abovementioned patent speci-
fication, the surfactant products obtained using thistransesterification reaction are suitable, in particular~
as emulsifiers for drilling and processing of mineral oil~
These known surfactant products leave something to be
desired with respect to their eff;cacy. It is further-
more disadvantageous that these ester amines, which are
advantageous per se, do not exhibit a strong surfactant
action in areas other than oil recovery. Ester amines
which can be employed in a wide variety of areas and in
each case have a strong surfactant action are thus desir-
able.
Surprisingly, it has now been found that this can be
achieved when glycerides are reacted with certain alkanol-
amines and when, in add;tion, the transesterification pro-
duct obtained is quaternized. The quaternary ester amines
thus obtained represent products which can be employed
in a wide variety of areas and in each case have a strong
action.
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Thus the pr2sent invention provides a process for -the
preparation of a quaternary ester amine by reacting a ~lyceride
with an alkanolamine, which comprises reacting a glyceride with an
alkanolamine of the formula I below
(R)3 X-N-[(cH2c~Rlo)n ]x
in which R is an alkyl group having 1 to 4 carbon atoms, x is 1, 2
or 3, n is an integer from 1 to 8, and R1 is H or CH3, it also
being possible for the (CH2CHR1O)n group to contain ethylene oxide
and propylene oxide units, and quaternizing the reaction product
obtained, wherein
a) the reaction of alkanolamine and glyceride is carried
out at a temperature of 120 to 200C,
b) the alkanolamine and the glyceride are employed in the
molar ratio 3 : 1 in order to produce a transes-terlfication
product essen-tially comprising monoesters, and in the molar ratio
1.5 : 1 in oxder to procluce a transesteri~ication product
essentially comprising diesters,
c) the transesterification product made from alkanolamine
~0 and glyceride is qua~ernized using an alkylating qua~ernizing
agent or using ethylene oxide, propylene oxide or mixtures of
these two alkylene oxides, and an amount of a carboxylic acid or
mlneral acid which is equimolar for salt formation, at a
temperature of 60 to 100C to a degree of quaternization of 70 to
100%.
Alkanolamines which are preferably employed are those
which arise from -the formula I when the (CH2CHR1O)n group
comprises exclusively ethylene oxide units or exclusively
. .~ ~, ~
13 L2~9
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propylene oxicle units and n i5 simultaneously an integer from 1 -to
4, or when i~ comprises an ethylene oxide block containing 1 LO 4
ethylene oxide units and a propylene oxide block containing l -to 4
propylene oxide units.
With respect to R in the formula I, it may be stated
that, in the case of several alkyl groups, these may be identical
or different. The alkanolamines below are partieularly preferably
employed:
monomethylamine or monopropylamine, ethoxylated using 2 to 4
moles of ethylene oxide (per mole of amine), dimethylamine or
dipropylamine, ethoxylated using 1 to 2 moles of e-thylene oxide,
triethanolamine or tripropanolamine and triethanolamine or
tripropanolamine, ethoxylated using 1 to 3 moles of ethylene
oxide.
The alkanolamines to be employed accordincJ to the
inven~ion are well known compounds. The ethoxylates and/or
propoxylates are generally mi.xtures of homolo~ous alkanolamines.
It is obvious that, in the case of dialkanolamines and
trialkanolamines, the 2 or 3 ethoxylate and/or propoxylate
radicals are generally not identical (in length).
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The ~lycerides to be employe~ according to the invention,
i.e. fatty acid glycerol esters, correspond to the formula
II below
~H20--COR
THO--COR3
CH O-COR
in which R2, R~ and R4 may be identical or different,
straight-chain or branched and saturated or unsaturated.
They are preferably straight-chain alkyl or alk~yl
groups having 5 to 23 carbon atoms, preferably 11 to 17
carbon atoms, the alkenyl groups preferably having 1 to
3 double bonds. The acyl groups R2C0, R3C0 and R4C0 are
thus preferably derived from the following carboxylic
acids (fatty acids):
alkanoic acids having 6 to ~4, preferably 12 to 18, carbon
atoms, such as caproic acid, caprylic acid, pelargonic
acid, capric acid, undecanoic acid, lauric acid, myristic
acid, pentadecanoic acid, palmitic acid, stearic acid~
arachidic acid (eicosanoic acid) and behenic acid;
alkenoic acids, alkadienoic acids and alkatr;enoic acids,
such as lauroleic acid, myristoleic acid, palmitoleic
acid, oleic ac;d, erucic acid, linoleic ac;d, eicosadi-
enoic acid and linolenic acid. Preferred glycerides for
the process according to the invention are, above all,
natural (vegetable) or animal fats and oils, which rep-
resent mixtures of, predominantly, triglycerides. Ex-
amples of vegetable fats and oils which may be mentionedare: olive oil, coconut fat, palm kernel oil, palm oil,
groundnut oil, rape seed oil, castor oil, sesame oil,
sunflower oil, soya oil, hempseed ilr coco butter and
vegetable tallows; examples of animal fats and oils
which may be mentioned are: beef tallow, pork fat, bone
fat, mutton tallow, Japan tallow, whale oil and other
fish oils. Single triglycerides or mixtures thereof can
likewise be employed if isolated from natural fats or
obtained by synthetic means. Examples which may be
mentioned here are: trilaurin, trimyristin, tripalmitin,
tristearin, triolein, trilinc,lein and trilinolenin, or
mixed glycerides, for example palmitodistearin, distearo-
olein, dipalmitoolein and myristopalmitostearin. of the
glycerides mentioned, the commercially available indus-
trial products, such as refined tallow, hardened tallowand coconut fat, are particularly preferred.
The reaction (transesterification reaction) according to
the invention of an alkanolamine with a glyceride is
carried out at a temperature of 120 to 200C, preferably
130 to 170C. It is possible to carry out the reaction
in the presence of acid catalysts. Suitable aci~ cata-
lysts are: hydrohalic acids, such as hydrochloric acid;
phosphoric acids, such as hypophosphorous acid or ortho-
phosphoric acid; sulfuric acid and sulfonic acids, suchas methanesulfonic acid, para-toluenesulfonic acid or
dodecylbenzenesulfonic acid. Phosphoric acids and suLfo-
nic acids are preferred~ ~esides these acidic compounds,
monomeric or polymeric titanium or zirconium compounds are
also suitable as catalysts, the titanium compounds being
preferred for reasons of expediency. Preferred titanium
compounds are those from the group comprising the alkyl-
titanates ~monomeric alkyltitanates or titanic acid esters)
and alkylpolytitanates ~polymeric alkyltitanates or poly-
meric titanic acid esters~. Alkyltitanates of the formulaTi(OR)4 in which R is an alkyl rad;cal having 1 to 18
carbon atoms, preferably having 1 to 6 carbon atoms, and
alkylpolytitanates of the formula RO-~Ti(OR)zO]n-R in
which R has the abovementioned meaning and n is a (whole)
number from 1 to 10, preferably from 4 to 7, are particu-
larly preferred titanium catalysts; alkyl radicals are
preferably identical both in the first and in the second
formula. The amount of acid catalyst or titanium or zir-
conium compound as catalyst is generally 0.05 to 1 ~ by
weight, preferably 0.1 to 0.5 ~ by weight, relative to
the weight of the glyceride employed. Depending on the
reaction temperature and the type of reaction components,
the reaction proceeds without pressure or under the
autogenous (in particular due to the alkanolamine employed)
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pressure. The react;on is pre-ferably carr;ed out without
using a solvent, i.e. in the solid state. The molar ratio
of the two reaction components alkanolamine and glyceride
depends on the intended transesterification product, i.e.
whe~her the transesterification product is to contain
mainly monoesters, diesters or triesters. It is preferred
according to the invention to direct the transesterifi-
cation reaction towards monoester and/or diester formation,
preferably towards diester formation. If a transesterifi-
cation product comprising mainly monoesters is desired, amolar ratio of about 1 mole of glyceride to about 3 moles
of alkanolamine is advantageous; if the transesterifi-
cation product is to comprise mainly diesters, a molar
ratio of about 1 mole of glyceride to about 1.5 moles of
alkanolamine is advantageous.
The transesterification reaction is expedien~ly followed
by gas-chromatographic analysis. Since this reaction is
an equilibrium reaction~ the reaction is terminated (for
example by cooling the contents of the reaction vessel)
when the maximum of the intended ester is reached. The
reaction ti~e is generally in the range S to 20 hours.
The transesterification product obtained, which is washed
with water, if desired, generally contains varying amounts
of unreacted starting compounds and glycerol formed, in
addition to the ester compounds formed~ This product is
a colorless to pale yellow product which is sol;d at room
temperature~
According to the invention, the transesterification pro-
duct obtained is subjected to a quaternization reaction.
The quaternization can be carried out by reacting the
transesterification product a) with alkylating quaterniz-
ing agents such as methyl chloride, dimethyl sulfate, di-
ethyl sulfate and benzyl chloride, or b) with ethyleneoxide, propylene oxide or a mixture thereof, preferably
with ethylene oxide, in the presence of an amount of
carboxylic acid or mineral acid which is equimolar for
salt formation (corresponding to the moles of nitrogen
lL3 ~ 2~
-- 6 -
atoms). ~oth types of quaternization are carried out at
a temperature of 60 to l00C, preferably 75 to ~5C, it
being advant3geous for the reaction pressure not to exceed
6 bar. They are carried out in the solid state, but pre-
ferably using a solvent; suitable solvents are loweralkanols having a boiling point which is above the quater
nization temperature. Su;table mineral ac;ds for the
quaternization using ethylene oxide and/or propylene oxide,
preferably ethylene oxide, are phosphoric acids, prefer-
ably phosphoric acid (H3P04). Suitable carbo~ylic acidsare aliphatic carboxylic acids having 1 to 6 carbon atoms,
such as formic acid, acetic acid, propionic acid and buty-
ric acid, aliphatic hydroxycarboxylic acids having 1 to
6 carbon atoms and having 1 to 3 hydroxyl groups, such as
glycolic acid and lactic acid, and aromatic carboxylic
acids, such as benzoic acid and salicylic acid. The car-
boxylic acid may alternatively be an optionally OH-sub-
stituted dicarboxylic acid or tricarboxylic acid, such as
succinic acid, malonic acid, maleic acid, fumaric acid,
malic acid, tartaric acid and citric acid. Preferred acids
are acetic acid, propionic acid, lactic acid and phosphoric
acid. The alkylene oxides mentioned are expediently em-
ployed in an amount of 3 to 5 moles per mole of nitrogen in
the product to be quaternized. The quaternizing agents
mentioned under a) are employed in an amount of 1 to 1.5
moles per mole of nitrogen. The reaction time in both types
of quaternization is in the range 5 to 25 hours. The degree
of quaternization o~ the quaternary reaction product ob-
tained can be determined by two-phase titration using sodium
dodecyl sulfate at pH 1 to 2, al~d at pH 10.
The quaternary ester amines obtained by the process accord-
ing to the invention are colorless to pale yellow products
which are pasty to solid at room temperature. Their degree
of quaternization is preferably in the range 70 to 100 ~.
They have a strong surfactant action and can be employed
in a wide variety of areas. They represent, in particular,
surprisingly active fabric conditioners, cosmetic bases,
preferably for the preparation of hair rinses, and softeners
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for textiles made from synthetic and/or natural fibers.
They are furthermore dist;nguished by an unexpectedly good
emulsi-f;ability, due to which they become, inter alia, sig-
ni-ficantly easier and faster to incorporate during prepara-
tion of formulations. For use as fabr;c conditioners andso~teners, those quaternization products have proven part-
icularly suitable which essentially comprise diesters,
whereas the products containing essentially monoesters are
particularly suitable for use in cosmetics.
The invention is now described in greater detail with refe-
rence to examples.
Example 1
a) Preparation of a transester;fication product made from
glycerol tristearate and N-methyldiethanolamine:
220 3 9 (0 25 mol) of glycerol tristearate and 44.0 9
(0.375 mol) of methyldiethanolamine are introduced into a
1 l stirred flask fitted with condenser, gas inlet and
heater. The mixture is he3ted to 160C under a protective-
gas atmosphere (nitrogen), and kept at this temperature,
at wh;ch the condensation reaction (transesterif;cation
reaction) proceeds, with stirring. After a react;on time
of 8.5 hours, the product mixture is analyzed by gas chrom-
atography, a proportion of 40.7 % by weight of N-methyl-
diethanolamine monostearate and distearate being deter-
mined.
b) ~uaternization using methyl chloride of the condensation
product (transester;fication product) obtained under a):
181.2 9 of the condensation product (0.25 mol, relative to
the amine number determined) are mixed with 34.Z g of iso-
propanol ~solvent). The mixture is heated to 75C while
flushing with protective gas, and 12.6 9 (0.~5 mol) o~
methyl chloride are added with stirring. The quatern;z-
ation reaction is complete after 7 hours at a temperature
of about 75C and a max;mum pressure o-f 6 bar. The degree
of quaternization of the product ~the quaternary ester
amines), which is calculated from the analytical
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determination of residual -free amine and amine salt, is
98 ~.
Example Z
a) Preparation of a transesterificat;on product made from
glycerol tristearate and N-butyldiethanolamine:
528.7 9 (0.6 mol) of glycerol tristearate and 148.8 9 (0 9
mol) of butyldiethanolamine are introduced into the stirred
flask of Example 1. The m;xture is heated to 160C under
a protective-gas atmosphere, and kept at this temperature,
at wh;ch the condensation reaction proceeds, with stirring.
After a react;on time of 15 hours, the product mixture is
analyzed by gas chromatography, a proportion of 37.6 % by
weight of N-butyldiethanolamine monostearate and d;stearate
being determined.
b) Quaternization using methyl chloride of the condensation
product obtained under a):
200.0 g of condensation product (0.25 mol, relative to the
amine number determ;ned) are m;xed w;th 37.5 g of isopro-
panol. The mixture is heated to 75C while flush;ng w;thprotect;ve gas, and 12.6 9 (0.25 mol) of methyl chlor;de
are added with stirring. The quaternization reaction is
complete after 7 hours at a temperature of 7~ to 80C and
a maximum pressure of 6 bar. The degree of quatern;zation
of the product, determined as in Example 1, is 80 %.
Example 3
a) Preparation of a transesterificat;on product made from
glycerol tr;stearate and triethanolamine:
282.0 g (0.32 mol) of glycerol tristearate and 76.1 g
(0.51 mol) of triethanolamine are ;ntroduced ;nto the
st;rred flask of Example 1. The mixture ;s heated to 160C
under a protective gas atmosphere, and kept at th;s tempera-
ture, at which the condensation reaction proceeds, with stir-
ring. After a react;on t;me of 15 hours, the product mixtureis analyzed by gas chromatography, a proportion of 52.2 % by
weight of tr;ethanolamine monostearate and triethanolamine
distearate along w;th a little tr;ethanolam;ne tr;stearate
be;ng determ;ned.
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b) Quaternization using ~ethyl chloride of the condensation
product obtained under a):
178.6 9 of condensation product (0.35 mol, relative to the
amine number de~ermined) are mixed with 34.3 9 of isopro-
panol. The mixture is heated to 75C while flushing withprotective gas, and 17.7 9 tO.35 mol) of methyl chloride
are added with stirring. The quaternization reaction is
complete after 20 hours at a temperature of 75 to 80C and
a maximum pressure of 6 bar. The degree of quaternization
of the product, determined as in Example 1, is 95 %.
Example ~
a) Preparation of a transesterification product made from
glycerol tristearate and N-dimethylethanolamine:
308.4 9 (0.35 mol) of glycerol tristearate and 93.6 9
(1.05 mol) of dimethylethanolamine are introduced into the
stirred flask of Example 1. The mixture is heated to 130C
under a protective gas atmosphere, and kept at ~his tempera-
ture, at which the condensation reaction proceeds, with
stirring. After a reaction time of ZO hours~ the product
m;xture is analyzed by gas chromatography, a proportion of
35.7 % by weight o-f N-dimethylethanolamine monostearate
being determined.
b) Quaternization using methyl chloride of the condensation
product obtained under a):
274.0 9 of the condensation product (0.6 mol, relative to
the amine number determined) are mixed with 53.7 9 of iso-
propanol. The mixture is heated to 80C while flushing
with protective gas, and 30.3 g (0.6 mol) of methyl chlor-
ide are added with stirring~ The quaternization reactionis complete after 12 hours at a temperature of about 80C
and a maximum pressure of 6 bar. The degree of quaterniz-
ation of the product, determined as in Example 1~ is 99 %.
Example 5
a) Preparation of a transesterification product made from
hardened coconut fat and N-dimethylethanolamine:
11~.1 9 (0~17 mol) of coconut fat and 45.5 9 tO.51 mol) of
dimethylethanolamine are introduced into the stirred flask
-~ 3 ~ c~
- 10 -
of Example 1. The mixture is heated to 135C under a pro-
tective-gas atmosphere, and kept at this temperature, at
which the condensation reaction proceeds, with stirring.
After a reaction time of 5 hours, the product mixture is
analyzed by gas chromatography, a proportion of 44.6 % by
weight of N-dimethylethanolamine monococoate being deter-
mined.
b) Quaternization using methyl chloride of the condensation
product obtained under a):
120.0 g of the condensation product (0.38 mol~ relative to
the amine number determined) are mixed with 25.6 9 of iso-
propanol. The mixture is heated to 80C while flushing
with protective gas, and 19.3 9 (0.38 mol) of methyl chlor-
ide are added with stirring. The quaternization reaction
is complete after 6 hours at a temperature of about 80C and
a maximum pressure of 6 bar. The degree of quaternization
of the product, determined as in Example 1, is 99 %.
