Preparation method of alkanolamide

CN113773218A
China
Abstract
The application provides a preparation method of alkanolamide, which comprises
the following steps: (1) adding excessive alkyl alcohol amine and organic tertiary
amine catalyst into a rectification reaction kettle, heating to reaction temperature,
dropwise adding fatty acid ester, and reacting under set reaction pressure; the
rectification reaction kettle is a reaction kettle with a rectification tower; (2) after
the reaction is finished, standing and layering the materials in the reaction kettle,
and separating the lower layer liquid out of the rectification reaction kettle; (3)
distilling the lower layer liquid, and separating the organic tertiary amine catalyst
and unreacted alkyl alcohol amine to obtain an alkyl alcohol amine product; the
upper layer liquid is used as a reaction raw material and continuously reacts in the
reaction kettle. By using the invention, the color of the alkanolamide product
prepared by using the fatty acid monoester is lower than 303HAPA, and the amine
value is kept below 20 mgKOH/g. The color of the alkanolamide product prepared
by the diester lipoid fatty acid ester is lower than 103HAPA, and the product purity
is kept above 95.5 percent.
Description
Preparation method of alkanolamide
Technical Field
The invention relates to a preparation method of alkanolamide.
Background
The alkanolamide is a kind of fine chemical products widely applied, is widely
used in the fields of metal cleaning and metal processing formulas, personal care,
secondary oil displacement of oil fields, fuel additives, solid powder coatings and
the like, is commonly used as a foaming agent and a tackifier in washing products,
is commonly used as a curing agent in powder coatings, is a low-toxicity powder
coating curing agent, and has wide application prospect.
At present, alkali metal hydroxide is mostly used as a reaction catalyst for
preparing alkanolamide products, the alkali metal hydroxide is a strong-base
catalyst, the catalyst has high catalytic activity and high catalytic efficiency, but the
catalyst can generate saponification reaction with fatty acid ester raw materials and
is often quenched by the raw materials, so that a large amount of catalyst is needed
to play an expected catalytic effect, the catalyst is difficult to separate from the
products after the reaction is finished, the residual catalyst can also influence the
application performance of the products, and in addition, due to the high catalytic
activity of the catalyst, more esterification side reactions can be brought in the
reaction of catalytic alkylol amine and fatty acid ester; in terms of color effect, the
strongly basic alkali metal hydroxide catalyst also has a large effect on the color of
the product, and particularly under the condition of higher reaction temperature,
the effect on the color is more obvious.

Disclosure of Invention
In order to improve the product performance of alkanolamide, the application
provides a preparation method of alkanolamide,
in the preparation method, organic tertiary amine base is used as a catalyst, fatty
acid alkyl ester or dialkyl ester and excessive alkyl alcohol amine are used as raw
materials, a low-carbon alcohol byproduct is separated through rectification to
prepare a crude product, and the crude product is distilled to separate out residual
organic tertiary amine catalyst to obtain an alkanolamide product. The preparation
method specifically comprises the following steps:
(1) adding excessive alkyl alcohol amine and organic tertiary amine catalyst into a
rectification reaction kettle, heating to reaction temperature, dropwise adding fatty
acid ester, and reacting under set reaction pressure; the rectification reaction kettle
is a reaction kettle with a rectification tower;
(2) after the reaction is finished, standing and layering the materials in the reaction
kettle, and separating the lower layer liquid out of the rectification reaction kettle;
(3) distilling the lower layer liquid, and separating the organic tertiary amine
catalyst and unreacted alkyl alcohol amine to obtain an alkyl alcohol amine
product;
the upper layer liquid is used as a reaction raw material and continuously reacts in
the reaction kettle.
Preferably, in step (3), the distillation apparatus is a membrane evaporator or a
supergravity rectifier.
By using the invention, the color of the alkanolamide product prepared by using
the fatty acid monoester is lower than 303HAPA, and the amine value is kept
below 20 mgKOH/g. The color of the alkanolamide product prepared by the diester
lipoid fatty acid ester is lower than 103HAPA, and the product purity is kept above
95.5 percent.
Specifically, in the step (1), the alkyl alcohol amine is ethanolamine,
diethanolamine, N-methylethanolamine, N-methylisopropanolamine,
monoisopropanolamine or diisopropanolamine; the fatty acid ester can be at least
one of fatty acid methyl ester, fatty acid ethyl ester, adipic acid dimethyl ester,
phthalic acid dimethyl ester, benzoic acid methyl ester and succinic acid dimethyl
ester, namely the alkyl alcohol amine can be any one or a mixture of more than two
of the materials.
Specifically, in the step (1), the organic tertiary amine catalyst is any one of
triethylamine, tripropylamine, triisopropylamine, N-dimethylisopropylamine, N-
diethylisopropylamine, N-methyldiethylamine, N-ethyldiisopropylamine, and N-
methyldiisopropylamine.
In the present application, no alkali metal catalyst is used.
In the invention, a large amount of organic tertiary amine is used as a catalyst, low-
carbon alcohol generated by a rectification separation reaction is discharged from a
distillation tower of a reaction kettle in the reaction process, the characteristic that
the solubility of an alkanolamide product in the organic tertiary amine is low is
utilized, the synthesis reaction is favorably promoted, after standing and layering
are carried out, the generated alkanolamide enters lower-layer liquid, the lower-
layer liquid is distilled to separate out residual catalyst and a small amount of alkyl
alcohol amine raw material to obtain a high-purity alkanolamide product, and the
residual upper-layer liquid containing the tertiary amine catalyst can be added with
the alkyl alcohol amine raw material to continue the reaction to prepare the
alkanolamide product, so that the excessive raw material can be recycled. In the
preparation method, the conventional alkali metal hydroxide catalysts in the prior
art, such as sodium hydroxide, potassium hydroxide and the like, are omitted, and
the tertiary amine catalyst is adopted, so that the alkali metal is prevented from
remaining in the product, namely, no catalyst remains, the improvement of
chromaticity caused by the alkali metal is avoided, the prepared product has lower
chromaticity and higher purity, and simultaneously, the raw materials and the
catalyst can be recycled, so that the preparation method has higher comprehensive
yield.
Further, in the step (1), the mass ratio of the organic tertiary amine catalyst to the
raw material is 0.5-5.0: 1, and the raw material is the total amount of the alkyl
alcohol amine and the fatty acid ester. Within the above mass ratio range, the
catalyst function of the organic tertiary amine can be fully exerted, the catalytic
effect is affected when the amount of the organic tertiary amine is too low, and the
excessive organic tertiary amine does not play a role in catalyzing when the
amount of the organic tertiary amine is too large, and only the total amount of the
reaction materials is increased.
Preferably, in the step (1), the fatty acid ester is a mono-lipid fatty acid ester or a
diester-lipid fatty acid ester; when the fatty acid ester is a monoester fatty acid
ester, the feeding molar ratio of the alkyl alcohol amine to the fatty acid ester is
1.1-2.0: 1.0; when the fatty acid ester is a diester fatty acid ester, the feeding molar
ratio of the alkyl alcohol amine to the fatty acid ester is 2.1-6.0: 1.0. According to
the types of different fatty acid esters, different molar ratios are selected so that the
reaction groups of the fatty acid esters can be matched, and the upper limit ratio of
the alkyl alcohol amine is properly increased when the diester fatty acid esters are
adopted, so that the effective contact rate of the diester fatty acid esters is reduced
due to the mutual influence of two fatty acid branched chains when the alkyl
alcohol amine is contacted with the fatty acid esters, and the reaction speed is
ensured.
Further, in order to ensure the smooth reaction, in the step (1), the reaction
temperature is 80-150 ℃, and the reaction pressure is set to be-0.03 MPa-0.2 MPa.
Further, in the step (2), the temperature in the standing process is 10-150 ℃, and
the standing time is 1-4 h. Under the above conditions, the material after the
reaction can be smoothly layered.
Detailed Description
Comparative example 1
Adding 75g of isopropanolamine and 2.0g of potassium hydroxide into a reaction
kettle with a rectifying tower, starting a stirring device, heating to 100 ℃ under the
pressure of-0.03 MPa, adding 209.5g of coconut oil methyl ester through a
metering pump to start reaction, and after feeding of the coconut oil methyl ester is
finished, continuing stirring to react for 2 hours to obtain the coconut oil acid-
isopropanolamide. The product has an amine value of 20.3mgKOH/g and a color
of 783 HAPA.
Comparative example 2
Adding 133g of diisopropanolamine and 2.5g of sodium hydroxide into a reaction
kettle, starting a stirring device, heating to 100 ℃ under the pressure of-0.02 MPa,
adding 200g of cocoate methyl through a metering pump to start reaction, and after
the feeding of the cocoate methyl is finished, continuously stirring for reaction for
2 hours to obtain a cocoate diisopropanolamide product, wherein the amine value
of the product is 48mgKOH/g, and the chroma is 473 HAPA.
Comparative example 3
Adding 399g of diisopropanolamine and 4.0g of potassium hydroxide into a
reaction kettle with a rectifying tower, starting a stirring device, heating to 100 ℃
under the pressure of-0.03 MPa, adding 174.1g of dimethyl adipate through a
metering pump to start reaction, continuing stirring for reaction for 2 hours after
the dimethyl adipate is fed, and treating a crude product through a membrane
distiller to obtain a tetra (2-hydroxypropyl) adipamide product with the purity of
94.3 percent and the chroma of 194 HAPA.
Example 1
Adding 75g of isopropanolamine and 142.3g of tripropylamine into a reaction
kettle with a rectifying tower, starting a stirring device, heating to 80 ℃ under the
pressure of-0.03 MPa, adding 209.5g of cocoate methyl through a metering pump
to start reaction, continuously stirring for reacting for 2 hours after the cocoate
methyl is fed, separating and collecting a byproduct methanol through the
rectifying tower in the reaction process, cooling the reaction material to 60 ℃ after
the reaction is finished, standing for 1 hour, separating lower-layer liquid, and
distilling the lower-layer liquid through a membrane evaporator to obtain 200.1g of
cocoate isopropanolamide product with the amine value of 10.0mgKOH/g and the
chroma of 251 HAPA.
Example 2
Adding 75g of isopropanolamine and 925g of N, N-dimethyl isopropylamine into a
reaction kettle with a rectifying tower, starting a stirring device, heating to 100 ℃
under the pressure of-0.03 MPa, adding 110g of cocoanut oil methyl ester by a
metering pump to start reaction, continuously stirring for reaction for 2 hours after
the cocoanut oil methyl ester is fed, separating and collecting a byproduct
methanol by the rectifying tower in the reaction process, cooling the reaction
material to 60 ℃ after the reaction is finished, standing for 1 hour, separating
lower-layer liquid, and distilling the lower-layer liquid by a membrane evaporator
to obtain 117.3g of cocoanut oil acid isopropanolamide product with the amine
value of 9.3mgKOH/g and the chroma of 232 HAPA.
Example 3
Adding 75g of isopropanolamine and 275g of triethylamine into a reaction kettle
with a rectifying tower, starting a stirring device, heating to 100 ℃ under the
pressure of 0.1MPa, adding 200g of cocoanut oil methyl ester through a metering
pump to start reaction, continuing stirring to react for 2 hours after the cocoanut oil
methyl ester is fed, separating and collecting a byproduct methanol through the
rectifying tower in the reaction process, cooling the reaction material to 60 ℃ after
the reaction is finished, standing for 4 hours, separating lower-layer liquid, and
distilling the lower-layer liquid through a membrane evaporator to obtain 103.3g of
cocoanut oil acid isopropanolamide product, wherein the amine value of the
product is 11.4mgKOH/g, and the chroma is 297 HAPA.
Example 4
Adding 61g of ethanolamine and 783g of triethylamine into a reaction kettle with a
rectifying tower, starting a stirring device, heating to 100 ℃ under the pressure of
0.1MPa, adding 200g of cocoanut oil methyl ester through a metering pump to start
reaction, continuing stirring for reaction for 2 hours after the cocoanut oil methyl
ester is fed, separating and collecting a byproduct methanol through the rectifying
tower in the reaction process, cooling the reaction material to 60 ℃ after the
reaction is finished, standing for 4 hours, separating lower-layer liquid, and
distilling the lower-layer liquid through a membrane evaporator to obtain 103.3g of
cocoanut oil acid isopropanolamide product with the amine value of
10.7mgKOH/g and the chroma of 303 HAPA.
Example 5
133g of diisopropanolamine and 333g of triethylamine are added into a reaction
kettle with a rectifying tower, a stirring device is started, the temperature is raised
to 100 ℃ under the pressure of-0.02 MPa, 200g of cocoanut oil methyl ester is
added through a metering pump to start reaction, after the feeding of the cocoanut
oil methyl ester is finished, the stirring reaction is continued for 2 hours, a
byproduct methanol is separated and collected through the rectifying tower in the
reaction process, after the reaction is finished, the reaction material is cooled to 10
℃, after standing for 4 hours, the lower layer liquid is separated, and after the
lower layer liquid is distilled through a membrane evaporator, 253.4g of cocoanut
oil acid diisopropanolamide product is obtained, the amine value of the product is
19.4mgKOH/g, and the chroma is 285 HAPA.
Example 6
133g of diisopropanolamine and 1215g of triethylamine are added into a reaction
kettle with a rectifying tower, a stirring device is started, the temperature is raised
to 100 ℃ under the pressure of 0.1MPa, 110g of cocoanut oil methyl ester is added
through a metering pump to start reaction, the stirring reaction is continued for 2
hours after the feeding of the cocoanut oil methyl ester is finished, a byproduct
methanol is separated and collected through the rectifying tower in the reaction
process, after the reaction is finished, the reaction material is cooled to 25 ℃, the
reaction material is kept stand for 1 hour, lower layer liquid is separated, the lower
layer liquid is distilled through a membrane evaporator to obtain 247.9g of
cocoanut oil acid diisopropanolamine, the amine value of the product is
19.5mgKOH/g, and the chroma is 237 HAPA.
Example 7
Adding 140.0g of diisopropanolamine and 138.1g of tripropylamine into a reaction
kettle with a rectifying tower, starting a stirring device, heating to 150 ℃ under the
pressure of-0.03 MPa, adding 136.2g of methyl benzoate by a metering pump to
start reaction, continuing stirring for reaction for 2 hours after the methyl benzoate
is fed, separating and collecting a byproduct methanol by the rectifying tower in
the reaction process, cooling the reaction material to 120 ℃ after the reaction is
finished, standing for 1 hour, separating a lower layer liquid, and distilling the
lower layer liquid by a membrane evaporator to obtain 200.3g of
diisopropanolamine benzoate product with the purity of 95.7 percent and the
chroma of 103 HAPA.
Example 8
266g of diisopropanolamine and 2010.8g of tripropylamine are added into a
reaction kettle with a rectifying tower, a stirring device is started, the temperature
is raised to 150 ℃ under the pressure of-0.03 MPa, 136.2g of methyl benzoate is
added through a metering pump to start reaction, the stirring reaction is continued
for 2 hours after the methyl benzoate is fed, a byproduct methanol is separated and
collected through the rectifying tower in the reaction process, after the reaction is
finished, the reaction material is kept stand at 150 ℃ for 1 hour, the lower layer
liquid is separated, and 191.7g of diisopropanolamine benzoate product with the
purity of 97.7 percent and the chroma of 53HAPA is obtained after the lower layer
liquid is distilled through a membrane evaporator.
Example 9
199.5g of diisopropanolamine and 598.5g of tripropylamine are added into a
reaction kettle with a rectifying tower, a stirring device is started, the temperature
is raised to 150 ℃ under the pressure of-0.03 MPa, 136.2g of methyl benzoate is
added through a metering pump to start reaction, the stirring reaction is continued
for 2 hours after the methyl benzoate is fed, a by-product methanol is separated and
collected through the rectifying tower in the reaction process, after the reaction is
finished, the reaction material is cooled to 120 ℃, the lower layer liquid is
separated after standing for 4 hours, and after the lower layer liquid is distilled
through a membrane evaporator, 213.5g of diisopropanolamine benzoate product
with the purity of 97.1 percent and the chroma of 64HAPA is obtained.
Example 10
199.5g of diisopropanolamine and 335.7g of triethylamine are added into a
reaction kettle with a rectifying tower, a stirring device is started, the temperature
is raised to 110 ℃ under the pressure of 0.13MPa, 136.2g of methyl benzoate is
added through a metering pump to start reaction, the stirring reaction is continued
for 2 hours after the methyl benzoate is fed, a by-product methanol is separated and
collected through the rectifying tower in the reaction process, after the reaction is
finished, the reaction material is heated to 120 ℃, the reaction material is kept
stand for 1 hour, the lower layer liquid is separated, and 209.5g of
diisopropanolamine benzoate product with the product purity of 96.8 percent and
the chroma of 71HAPA is obtained after the lower layer liquid is distilled through a
membrane evaporator.
Example 11
266g of diisopropanolamine and 771.5g of triethylamine are added into a reaction
kettle with a rectifying tower, a stirring device is started, the temperature is raised
to 100 ℃ under the pressure of 0.13MPa, 136.2g of methyl benzoate is added
through a metering pump to start reaction, the stirring reaction is continued for 2
hours after the methyl benzoate is fed, a byproduct methanol is separated and
collected through the rectifying tower in the reaction process, after the reaction is
finished, the reaction material is heated to 120 ℃, the reaction material is kept
stand for 2 hours, the lower layer liquid is separated, and after the lower layer
liquid is distilled through a membrane evaporator, 193.4g of diisopropanolamine
benzoate product with the purity of 97.8 percent and the chroma of 56HAPA is
obtained.
Example 12
199.5g of diisopropanolamine and 335.7g of N, N-dimethyl isopropylamine are
added into a reaction kettle with a rectifying tower, a stirring device is started, the
temperature is raised to 100 ℃ under the pressure of 0.2MPa, 136.2g of methyl
benzoate is added through a metering pump to start reaction, the stirring reaction is
continued for 2 hours after the feeding of the methyl benzoate is finished, a by-
product methanol is separated and collected through the rectifying tower in the
reaction process, after the reaction is finished, the reaction material is kept stand
for 2 hours at 100 ℃, the lower layer liquid is separated, and the lower layer liquid
is distilled through a membrane evaporator to obtain 205.1g of diisopropanolamine
benzoate product with the purity of 96.1 percent and the chroma of 63 HAPA.
Example 13
399g of diisopropanolamine and 1150g of tripropylamine are added into a reaction
kettle with a rectifying tower, a stirring device is started, the temperature is raised
to 100 ℃ under the pressure of-0.03 MPa, 174.1g of dimethyl adipate is added
through a metering pump to start reaction, the stirring reaction is continued for 2
hours after the dimethyl adipate is fed, a by-product methanol is separated and
collected through the rectifying tower in the reaction process, after the reaction is
finished, the reaction material is kept stand for 1 hour at 100 ℃, the lower layer
liquid is separated, and after the lower layer liquid is distilled through a membrane
evaporator, 302.7g of tetra (2-hydroxypropyl) adipamide product with the purity of
97.3 percent and the chroma of 97HAPA is obtained.
Example 14
292.6g of diisopropanolamine and 933.4g of triethylamine are added into a
reaction kettle with a rectifying tower, a stirring device is started, the temperature
is raised to 100 ℃ under the pressure of 0.1MPa, 174.1g of dimethyl adipate is
added through a metering pump to start reaction, the stirring reaction is continued
for 2 hours after the feeding of the dimethyl adipate is finished, a by-product
methanol is separated and collected through the rectifying tower in the reaction
process, after the reaction is finished, the reaction material is kept stand at 100 ℃
for 1 hour, the lower layer liquid is separated, and after the lower layer liquid is
distilled through a membrane evaporator, 278.7g of tetra (2-hydroxypropyl)
adipamide product with the purity of 95.5 percent and the chroma of 46HAPA is
obtained.
Example 15
Adding 532g of diisopropanolamine and 2118g of triethylamine into a reaction
kettle with a rectifying tower, starting a stirring device, heating to 100 ℃ under the
pressure of 0.1MPa, adding 174.1g of dimethyl adipate through a metering pump
to start reaction, continuing stirring for reaction for 2 hours after the dimethyl
adipate is fed, separating and collecting a byproduct methanol through the
rectifying tower in the reaction process, standing the reaction material at 100 ℃ for
1 hour after the reaction is finished, separating lower-layer liquid, and distilling the
lower-layer liquid through a membrane evaporator to obtain 253.4g of tetra (2-
hydroxypropyl) adipamide product with the purity of 98.4 percent and the chroma
of 43 HAPA.
Example 16
Adding 105g of diethanolamine and 305g of triethylamine into a reaction kettle
with a rectifying tower, starting a stirring device, heating to 100 ℃ under the
pressure of-0.02 MPa, adding 200g of cocoanut oil methyl ester through a metering
pump to start reaction, continuing stirring to react for 2 hours after the feeding of
the cocoanut oil methyl ester is finished, separating and collecting a byproduct
methanol through the rectifying tower in the reaction process, cooling the reaction
material to 20 ℃ after the reaction is finished, standing for 4 hours, separating
lower-layer liquid, and distilling the lower-layer liquid through a membrane
evaporator to obtain 253.4g of cocoanut oil diethanolamide product with the amine
value of 15.7mgKOH/g and the chroma of 261 HAPA.

Example 17
Adding 78.8g of N-methylethanolamine and 600g of triethylamine into a reaction
kettle with a rectifying tower, starting a stirring device, heating to 100 ℃ under the
pressure of-0.01 MPa, adding 220g of cocoanut oil methyl ester through a metering
pump to start reaction, continuing stirring to react for 2 hours after the cocoanut oil
methyl ester is fed, separating and collecting a byproduct methanol through the
rectifying tower in the reaction process, cooling the reaction material to 20 ℃ after
the reaction is finished, standing for 4 hours, separating lower-layer liquid, and
distilling the lower-layer liquid through a membrane evaporator to obtain 192.1g of
N-methyl cocoanut oil acid ethanolamide product with the amine value of
18.9mgKOH/g and the chroma of 277 HAPA.
Of these, comparative example 1 corresponds to example 1, comparative example
2 corresponds to example 5, and comparative example 3 corresponds to example
13. It can be seen from the above comparative examples that the products produced
by the preparation process according to the invention have low amine numbers and
color or have a higher purity and a lower color.
Claims (8)
1. A method for preparing alkanolamide, which is characterized by comprising the
following steps:
(1) adding excessive alkyl alcohol amine and organic tertiary amine catalyst into a
rectification reaction kettle, heating to reaction temperature, dropwise adding fatty
acid ester, and reacting under set reaction pressure; the rectification reaction kettle
is a reaction kettle with a rectification tower;
(2) after the reaction is finished, standing and layering the materials in the reaction
kettle, and separating the lower layer liquid out of the rectification reaction kettle;
(3) distilling the lower layer liquid, and separating the organic tertiary amine
catalyst and unreacted alkyl alcohol amine to obtain an alkyl alcohol amine
product;
the upper layer liquid is used as a reaction raw material and continuously reacts in
the reaction kettle.
2. The process according to claim 1, wherein in the step (1), the organic tertiary
amine catalyst is any one of triethylamine, tripropylamine, triisopropylamine, N-
dimethylisopropylamine, N-diethylisopropylamine, N-methyldiethylamine, N-
ethyldiisopropylamine and N-methyldiisopropylamine.
3. The method according to claim 1, wherein in the step (1), the mass ratio of the
organic tertiary amine catalyst to the raw material is 0.5 to 5.0:1, and the raw
material is the total amount of the alkyl alcohol amine and the fatty acid ester.
4. The method according to claim 1, wherein in the step (1), the alkyl alcohol
amine is ethanolamine, diethanolamine, N-methylethanolamine, N-
methylisopropanolamine, monoisopropanolamine, diisopropanolamine; the fatty
acid ester can be at least one of fatty acid methyl ester, fatty acid ethyl ester, adipic
acid dimethyl ester, phthalic acid dimethyl ester, benzoic acid methyl ester, and
succinic acid dimethyl ester.
5. The method according to claim 1, wherein in the step (1), the fatty acid ester is a
mono-or di-aliphatic fatty acid ester;
when the fatty acid ester is a monoester fatty acid ester, the feeding molar ratio of
the alkyl alcohol amine to the fatty acid ester is 1.1-2.0: 1.0;
when the fatty acid ester is a diester fatty acid ester, the feeding molar ratio of the
alkyl alcohol amine to the fatty acid ester is 2.1-6.0: 1.0.
6. The production method according to claim 1, wherein in the step (1), the
reaction temperature is 80 ℃ to 150 ℃ and the reaction pressure is set to-0.03
MPa to 0.2 MPa.
7. The preparation method according to claim 1, wherein in the step (2), the
temperature during the standing is 10 ℃ to 150 ℃ and the standing time is 1h to 4
h.
8. The production method according to claim 1, wherein in the step (3), the
distillation apparatus is a membrane evaporator or a super-gravity rectifier.