CN111718274A - Process for preparing fatty acid amido-acid salt - Google Patents
Process for preparing fatty acid amido-acid salt Download PDFInfo
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- CN111718274A CN111718274A CN202010561007.6A CN202010561007A CN111718274A CN 111718274 A CN111718274 A CN 111718274A CN 202010561007 A CN202010561007 A CN 202010561007A CN 111718274 A CN111718274 A CN 111718274A
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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Abstract
The invention relates to a preparation method of grease acylamino acid salt. The method comprises the following steps: mixing glycerol and an alkali catalyst, and reacting to prepare a mixture A; adding monolaurate, grease and amino acid salt into the mixture A, and heating to 90-138 ℃ for urethane exchange reaction. The glycerol can play a role of a dispersing agent, and the problems of uneven stirring and difficult stirring in the reaction process are solved; can also react with alkali catalyst to dehydrate between molecules, and the product can promote the subsequent urethane exchange reaction. The monolaurate not only can perform urethane reaction with grease and amino acid salt, but also can play a role of a penetration enhancer, reduce the difficulty of urethane exchange between the grease and the amino acid salt, accelerate the reaction process and improve the conversion rate; under a lower temperature, a heterogeneous system can be converted into a homogeneous system, the problems of uneven stirring and difficult stirring in the reaction process are solved, and the system is slowly changed into a paste in the later stage of the reaction, so that the reaction endpoint can be conveniently judged.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a preparation method of grease acylamino acid salt.
Background
At present, the synthesis methods for synthesizing fatty acyl amino acid series surfactants mainly comprise an acyl chloride method, a fatty acid anhydride method, a fatty cyanogen hydrolysis method, an enzyme method and the like, but the industrial application mainly comprises the acyl chloride method, and other factors such as low yield and complex process cause the industrial application to be hindered. The acyl chloride method is also named as Schotten-Baumann method, namely that fatty acyl chloride and amino acid salt solution are subjected to condensation reaction in an organic solvent/water mixed phase under the action of an alkaline catalyst and an acid-binding agent. The method has relatively simple production process requirements and relatively stable raw material sources, but still has a plurality of disadvantages, such as: the process from fatty acid synthesis of fatty acyl chloride to acylation is not environment-friendly; the presence of water in the solvent phase leads to an increase in the sodium fatty acid content of the product; the solvent adopts acetone or tetrahydrofuran to obtain a product with higher conversion rate, but the organic solvent can pollute the environment; the product contains equimolar sodium chloride by-product, and the post-treatment needs to adopt an acidification method and remove a low-boiling organic solvent, so that the industrial three wastes and the like are generated.
In recent years, some scientists at home and abroad try to synthesize fatty acylamino acid salt by adopting a non-acyl chloride method, such as fatty acid methyl ester, fatty acid glyceride, fatty acid triglyceride, natural oil and fat and the like, and the fatty acylamino acid salt is directly obtained under the catalysis of alkali metal oxide and alkoxide thereof.
The prior art discloses a technical scheme for producing N-fatty acid sodium amide by using fatty acid methyl ester and sodium amino acid to react under the condition of a catalyst, but in the reaction process, the viscosity of a system at the middle and later stages is very high due to no addition of a solvent, the fluidity of the system can be maintained only at a higher temperature, and the color of the obtained product is poor.
Or the fatty acid methyl ester and the sodium amino acid react under the catalysis condition to produce the N-fatty acid sodium amide, and the potassium oxide and the magnesium oxide are used as catalysts, so that the catalysts have low activity and low yield when catalyzing the reaction of the fatty acid methyl ester and the sodium amino acid at low temperature.
Or the fatty acid ester and the amino acid compound are utilized to synthesize the N-fatty acylamino acid salt in the polyhydric alcohol, wherein the N-fatty acylamino acid salt comprises fatty acid monoester or glycerate, the viscosity of the system is increased in the later reaction period of the reaction between glycerol and catalyst calcium oxide and buffer salt, the hardening temperature of the product is higher, the reaction is not uniform, and the color of the obtained product is poorer.
Or various grease and amino acid salts are utilized, a catalyst is formed by taking basic metal oxide and 4A zeolite as carriers, the reaction is carried out under the high-temperature condition, the temperature requirement is higher than 160 ℃, the stirring later period is extremely difficult, the color of the obtained product is higher, and the byproducts are more.
Disclosure of Invention
Therefore, in order to solve the problems, a preparation method of the grease acylamino acid salt is needed, wherein the preparation method is mild in reaction conditions, simple in process, good in system fluidity, less in by-products, suitable in product color and luster and easy to realize large-scale production.
The technical scheme is as follows:
a method for preparing grease amido acid salt comprises the following steps:
mixing glycerol and an alkali catalyst, and reacting to prepare a mixture A;
and adding monolaurate, grease and amino acid salt into the mixture A, and heating to 90-138 ℃ to perform urethane exchange reaction.
In one embodiment, the step of preparing mixture a further comprises a water removal process.
In one embodiment, the water removal method is as follows: introducing inert gas and controlling the temperature to be 50-80 ℃.
In one embodiment, the temperature of the urethane exchange reaction is 100 ℃ to 130 ℃ and the time is 3h to 10 h.
In one preferable embodiment, the temperature of the urethane exchange reaction is 105-110 ℃, and the reaction time is 6-8 h.
In one embodiment, the base catalyst is selected from at least one of potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.
In one embodiment, the molar ratio of the base catalyst to the glycerol is 1:20 to 1: 60.
In one embodiment, the molar total amount of ester groups in the monolaurate and the oil and fat is equal to-NH in the amino acid salt2The molar ratio of (A) to (B) is 1:1 to 1: 1.5.
In one embodiment, the monolaurate is selected from at least one of propylene glycol monolaurate, methyl laurate, ethyl laurate, and isopropyl laurate.
In one embodiment, the oil is at least one selected from coconut oil, palm oil, camellia seed oil, rapeseed oil, olive oil, and soybean oil.
In one embodiment, the amino acid salt is selected from at least one of sodium glycinate, sodium alanine, sodium sarcosinate and sodium taurate.
In one embodiment, the molar ratio of the monolaurate to the grease is 1: 1-1: 2.5.
In one embodiment, the urethane exchange reaction is followed by a dilution, acidification, and neutralization purification step.
In one embodiment, in the step of acidifying, the acidifying agent used is selected from hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid or citric acid.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the grease acylamino acid salt comprises the steps of mixing glycerol and an alkali catalyst to obtain a mixture, adding monolaurate, grease and an amino acid salt into the mixture, and heating for reaction.
The glycerol is added into the formula, so that the function of the dispersing agent can be exerted, and the problems of uneven stirring and difficult stirring in the reaction process are solved; or with alkali catalyst to dehydrate between molecules, and the product can promote the follow-up urethane exchange reaction. The monolaurate and the grease are added into the formula to react with the amino acid salt, the monolaurate can play a role of a penetration enhancer besides participating in the reaction, the difficulty of urethane exchange between the grease and the amino acid salt is reduced, the reaction process is accelerated, and the monolaurate and the amino acid salt are matched with each other to improve the conversion rate of the reaction; and at a lower temperature, the reaction system can be gradually converted from a heterogeneous system into a homogeneous system, so that the problems of uneven stirring and difficult stirring in the reaction process are greatly improved, and the system is converted into a paste in the later stage of the reaction, so that the reaction endpoint can be conveniently judged.
Furthermore, the hydroxide of alkali metal is used as a catalyst, so that dangerous metal oxide is avoided, the operation is safer, and the problem of complex post-treatment can be avoided. The post-treatment step is simple to operate, green and environment-friendly, is convenient to realize industrialization, and accords with the environment-friendly production concept.
The grease acylamino acid salt prepared by the method retains various unsaturated carbon chain components in grease, and greatly improves the foaming performance of the product. Meanwhile, the chroma of the obtained product is lighter due to lower reaction temperature.
Drawings
FIG. 1 is a liquid chromatogram of a potassium cocoyl glycinate control;
FIG. 2 is a liquid chromatogram of potassium cocoyl glycinate from example 1;
FIG. 3 is a mass spectrum of potassium cocoyl glycinate in example 1;
FIG. 4 is a mass spectrum of potassium octanoyl glycinate in example 1;
FIG. 5 is a mass spectrum of potassium decanoyl glycinate in example 1;
FIG. 6 is a mass spectrum of potassium lauroyl glycinate in example 1;
FIG. 7 is a mass spectrum of potassium myristoyl glycinate in example 1;
FIG. 8 is a mass spectrum of potassium palmitoyl glycinate in example 1;
FIG. 9 is a mass spectrum of potassium stearoyl glycinate in example 1;
FIG. 10 is a liquid chromatogram of Camellia oleifera seed oil potassium glycinate in example 3;
FIG. 11 is a liquid chromatogram of potassium cocoyl glycinate of example 6;
FIG. 12 is a liquid chromatogram of potassium cocoyl glycinate of example 7;
FIG. 13 is a liquid chromatogram of potassium cocoyl glycinate in comparative example 1;
fig. 14 is a liquid chromatogram of potassium cocoyl glycinate in comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the existing preparation method for preparing the grease acylamino acid salt by utilizing the fatty acid ester and the amino acid compound, the problems of high reaction temperature, nonuniform system stirring, difficulty in thickening and stirring in the later reaction period, very deep product color, difficulty in post-treatment and the like exist, and the product industrialization difficulty is high.
In order to solve the problems, the invention provides a preparation method of grease acylamino acid salt, which has low reaction temperature, good system fluidity, less byproducts, proper product color and luster and can realize industrial production.
The technical scheme is as follows:
a method for preparing grease amido acid salt comprises the following steps:
mixing glycerol and an alkali catalyst, and reacting to prepare a mixture A;
and adding monolaurate, grease and amino acid salt into the mixture A, and heating to 90-138 ℃ to perform urethane exchange reaction.
The glycerol is added into the formula, so that the function of the dispersing agent can be exerted, and the problems of uneven stirring and difficult stirring in the reaction process are solved; or with alkali catalyst to dehydrate between molecules, and the product can promote the follow-up urethane exchange reaction. The monolaurate and the grease are added into the formula to react with the amino acid salt, the monolaurate can play a role of a penetration enhancer besides participating in the reaction, the difficulty of urethane exchange between the grease and the amino acid salt is reduced, the reaction process is accelerated, and the monolaurate and the amino acid salt are matched with each other to improve the conversion rate of the reaction; and at a relatively low temperature (90-138 ℃), the reaction system can be gradually converted from a heterogeneous system into a homogeneous system, the problems of uneven stirring and difficult stirring in the reaction process are greatly improved, and the system is slowly converted into a paste in the later stage of the reaction, so that the reaction endpoint can be conveniently judged.
In addition, TLC thin-layer chromatography can be used for assisting in tracking the reaction condition of the grease and the monolaurate so as to quickly, effectively and conveniently determine the reaction progress condition.
In one embodiment, the urethane exchange reaction is followed by a dilution, acidification, and neutralization purification step.
Preferably, after the reaction is finished, water is directly added to dissolve until the mixture is clear, acidification is carried out by using an acidifying agent, separation is carried out, byproducts in the system, such as glycerin, alcohol and natural oil non-fatty acid ester substances, can be removed, drying is carried out, and then alkali solution is added to dissolve and neutralize, so that the oil acylates with higher purity can be obtained. The post-treatment step is simple to operate, green and environment-friendly, and accords with the environment-friendly production concept.
The reaction principle is as follows:
1)
2)
3)
(1) for the urethane exchange step, and (2) (3) for the purification step.
(2) Wherein R is1Is carboxylic acid alkyl part in grease or laurate; r2Is grease or alkyl part of lauric ester polyol; r3Are different amino acid groups; m1，M2Respectively, an alkali metal.
In one preferred embodiment, in the step of acidifying, the acidifying agent is selected from hydrochloric acid, phosphoric acid, sulfuric acid, oxalic acid or citric acid; hydrochloric acid is preferred.
In one preferred embodiment, the step of preparing mixture a further comprises a water removal process. The water generated by the reaction of the glycerin and the alkali catalyst is removed, which is beneficial to improving the conversion rate of the subsequent urethane exchange reaction.
Preferably, the water removal mode is as follows: introducing inert gas and controlling the temperature to be 50-80 ℃.
More preferably, the water removal mode is as follows: introducing nitrogen and controlling the temperature to be 50-80 ℃.
The temperature of the urethane exchange reaction is 90-138 ℃, the reaction system can be gradually converted into a homogeneous system from a heterogeneous system at a lower temperature, the problems of uneven stirring and difficult stirring in the reaction process are greatly improved, and the system is slowly converted into a paste in the later stage of the reaction, so that the reaction endpoint can be conveniently judged.
It is understood that the temperature of the urethane exchange reaction in the present invention can be set to, but not limited to, 90 ℃, 95 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃, 130 ℃, 132 ℃, 134 ℃, 135 ℃ and 138 ℃.
In one preferred embodiment, the temperature of the urethane exchange reaction is 100 ℃ to 130 ℃, and the reaction time is 3h to 10 h.
In a more preferred embodiment, the temperature of the urethane exchange reaction is 105 ℃ to 110 ℃ and the time is 6h to 8 h.
In one embodiment, the base catalyst is selected from at least one of potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide. More preferably, the base catalyst is potassium hydroxide.
In one embodiment, the molar ratio of the base catalyst to the glycerol is 1:20 to 1: 60. It is understood that, in the present invention, the molar ratio of the base catalyst to glycerol may be set to, but not limited to, 1:20, 1:30, 1:22, 1:25, 1:28, 1:30, 1:30.5, 1:31, 1:33, 1:35, 1:36, 1:38, 1:40, 1:42, 1:45, 1:50, 1:55, and 1: 60.
In one embodiment, the molar total amount of ester groups in the monolaurate and the oil and fat is equal to-NH in the amino acid salt2The molar ratio of (A) to (B) is 1:1 to 1: 1.5. Adding ester substances of monolaurate and grease and amino acid salt into the formulaIn the reaction, the monolaurate can play the role of a penetration enhancer besides participating in the reaction, so that the difficulty of urethane exchange between grease and amino acid salt is reduced, the reaction process is accelerated, and the reaction conversion rate is improved; and at a lower temperature, the reaction system can be gradually converted from a heterogeneous system into a homogeneous system, the problems of uneven stirring and difficult stirring in the reaction process are greatly improved, and the system is slowly converted into a paste in the later stage of the reaction, so that the reaction endpoint can be conveniently judged.
It is understood that in the present invention, the total molar amount of ester groups in the monolaurate and the oil and fat is related to-NH in the amino acid salt2The molar ratio of (A) to (B) can be set to, but is not limited to, 1:1, 1:1.02, 1:1.05, 1:1.15, 1:1.18, 1:1.2, 1:1.25, 1:1.3, 1:1.33, 1:1.35, 1:1.38, 1:14, 1:1.45 and 1: 1.5.
In one embodiment, the molar ratio of the monolaurate to the grease is 1: 1-1: 2.5. It is understood that the molar ratio of monolaurate to oil may be set to, but not limited to, 1:1, 1:1.5, 1:1.8, 1:2, 1:2.05, 1:2.15, 1:2.3, 1:2.35, 1:2.4, 1:2.45, and 1:2.5 in the present invention.
In one embodiment, the oil is selected from at least one of coconut oil, palm oil, camellia seed oil, rapeseed oil, olive oil, and soybean oil; coconut oil is preferred.
Generally, if only the oil-tea camellia seed oil and the amino acid salt are used for reaction, the reaction activity is low, and the reaction is difficult to carry out. According to the preparation method disclosed by the invention, the monolaurate is also added into the formula, and the monolaurate can play a role of a penetration enhancer, so that the difficulty of urethane exchange between the camellia oleosa seed oil and the amino acid salt is reduced, and the conversion rate of the reaction is improved.
In one embodiment, the monolaurate is selected from at least one of propylene glycol monolaurate, methyl laurate, ethyl laurate, and isopropyl laurate; propylene glycol monolaurate is preferred.
In one embodiment, the amino acid salt is selected from at least one of sodium glycinate, sodium alanine, sodium sarcosinate and sodium taurate; preferably sodium glycinate.
In one preferred embodiment, the preparation method of the grease amino acid salt comprises the following steps:
mixing a certain amount of glycerol and an alkali catalyst (preferably potassium hydroxide) under the conditions of introducing nitrogen and 50-80 ℃ to prepare a mixture A;
adding a certain amount of monolaurate, grease and amino acid salt into the mixture A, heating to 90-138 ℃, and reacting for 3-10 h;
after the reaction is finished, adding water to dissolve until the mixture is clear, then acidifying with an acidifying agent, filtering to remove byproducts in the system, drying, and then adding an alkali solution to dissolve and neutralize to obtain the oleoyl acylates with higher purity.
The invention is further illustrated by the following specific examples, all of which are commercially available, unless otherwise specified.
In the following examples and comparative examples, the color of the stock solution was measured by the method of GBT3143-1982 measurement of platinum-cobalt color.
The concentration algorithms in the following examples and comparative examples are both a siemer fly moisture meter MA35 infrared drying method.
The control in example 1 was derived from gustatory hormone GCK-12H and contained potassium cocoyl glycinate.
Example 1
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
then, 30.0g of propylene glycol monolaurate, 150.0g of coconut oil and 79.24g of sodium glycinate are sequentially added into the mixture A, the mixture is heated to 100 ℃ and reacted for 4 hours, TLC is used for monitoring the reaction process, deionized water is added into the mixture to dissolve the mixture when the conversion of the propylene glycol monolaurate and the coconut oil is finished to obtain clear and transparent sodium cocoyl glycinate solution, hydrochloric acid is added into the mixture to adjust the pH value to be about 3, the mixture is filtered and dried in vacuum at 50 ℃, 198.53g of white solid cocoyl glycinate is obtained, the conversion rate is 95.42 percent, the mixture is dissolved by potassium hydroxide solution to obtain 36.04 percent potassium cocoyl glycinate solution, the chroma of the stock solution is measured according to the method of GBT3143-1982 platinum-cobalt chroma measurement, and the result of the stock solution is 70 Hazen.
The potassium cocoyl glycinate obtained in this example was analyzed.
(1) The sample information is as follows:
(2) the instrument comprises the following steps: the liquid phase tandem mass spectrometer comprises a Sammer fly moisture determinator MA35, an Agilent HPLC-ELSD and a Sammer fly TSQ.
(3) Volatile component test results:
two parallel tests were carried out directly on a 1g sample and on a Saimer fly moisture tester MA35, with the following results:
(4) results of liquid phase analysis
Pretreatment: about 0.1g of sample was taken and tested at first order water volume. The liquid phase test results are shown in fig. 1 and 2:
fig. 1 is a liquid chromatogram of sample 1, and fig. 2 is a liquid chromatogram of sample 2.
(5) Analysis of qualitative results
The sample is tested by LC-MSMS, and the spectrogram is respectively shown in figures 3-9:
through a liquid phase tandem mass spectrum spectrogram, the octanoyl potassium glycinate M/z [ M-H ] can be extracted from the sample 1 and the sample 2+]200 (retention time 1.1min), potassium decanoyl glycinate M/z [ M-H ]+]228 (retention time 4.4min), potassium lauroyl glycinate M/z [ M-H [)+]256 (retention time 5.5min), potassium myristoyl glycinate M/z [ M-H ]+]284 (retention time 7)00min), potassium palmitoyl glycinate M/z [ M-H ]+]312 (retention time 10.0min), potassium stearoyl glycinate M/z [ M-H [)+]340 (retention time 16.36min)
The combination of the liquid phase spectrum and the mass spectrum shows that as the carbon chain length increases (C8< C10< C12< C14< C16< C18), the longer the interaction time with the chromatographic packing, the longer the retention time on the C18 column. Thus, the order of the appearance peaks in the liquid phase is capryl acyl potassium glycinate, capric acid acyl potassium glycinate, lauroyl potassium glycinate, myristoyl potassium glycinate, palmitoyl potassium glycinate and stearoyl potassium glycinate.
Example 2
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then, adding 30.0g of propylene glycol monolaurate, 150.0g of palm oil and 63.52g of sodium glycinate into the mixture A in sequence, heating to 100 ℃, reacting for 4 hours, monitoring the reaction process by TLC, adding deionized water to dissolve when the conversion of the propylene glycol monolaurate and the palm oil is finished to obtain a clear and transparent palmitoyl sodium glycinate solution, adding hydrochloric acid to adjust the pH value to be about 4, filtering, and drying at 50 ℃ in vacuum to obtain 210.90g of light yellow solid palmitoyl glycine with the yield of 94.79 percent, and dissolving with a potassium hydroxide solution to obtain 35.87 percent concentration of potassium palmitoyl glycinate, wherein the chroma of the stock solution is 120 Hazen.
Example 3
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.5g of potassium hydroxide and 75g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then, sequentially adding 30.0g of propylene glycol monolaurate, 120.0g of camellia seed oil and 51.92g of sodium glycinate into the mixture A, heating to 100 ℃, reacting for 6 hours, monitoring the reaction process by TLC, adding deionized water to dissolve when the conversion of the propylene glycol monolaurate and the camellia seed oil is finished to obtain a clear and transparent sodium cocoyl glycinate solution, adding hydrochloric acid to adjust the pH value to be about 4, filtering, and performing vacuum drying at 50 ℃ to obtain 160.86g of pale yellow solid camellia seed oleoyl glycinate, wherein the yield is 86.38%, dissolving with a potassium hydroxide solution to obtain 29.54% concentration potassium camellia seed oleoyl glycinate, wherein the stock solution is in a viscous clear state and the chroma is 130 Hazen.
FIG. 10 is a liquid chromatogram of camellia oleosa seed oil potassium acylglycinate of example 3;
example 4
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then adding 30g of propylene glycol monolaurate, 150g of coconut oil and 93.34g of sodium sarcosinate into the mixture A in sequence, heating to 100 ℃, reacting for 5 hours, monitoring the reaction process by TLC, adding deionized water to dissolve when the conversion of the propylene glycol monolaurate and the coconut oil is finished to obtain a clear and transparent sodium cocoyl glycinate solution, adding hydrochloric acid to adjust the pH value to be about 4, filtering, drying to obtain white solid cocoyl sarcosine 210.35, wherein the yield is 94.97%, dissolving by using a potassium hydroxide solution to obtain a 33.42% concentration potassium cocoyl sarcosinate solution, and the chroma of a stock solution is 100 Hazen.
Example 5
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then, adding 30g of propylene glycol monolaurate, 150g of coconut oil and 135.45g of sodium taurate into the mixture A in sequence, heating to 120 ℃, reacting for 5 hours, monitoring the reaction process by TLC, and adding deionized water to dissolve when the conversion of the propylene glycol monolaurate and the coconut oil is finished to obtain clear and transparent sodium cocoyl taurate with the concentration of 40.43% (because the water solubility of the cocoyl taurine is good, the adjusted acid cannot be separated out, so that the exact conversion rate cannot be obtained), wherein the chroma of the stock solution is 150 Hazen.
Example 6
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, and clarifying to obtain a mixture A;
and then, adding 30g of propylene glycol monolaurate, 150g of coconut oil and 79.24g of sodium glycinate into the mixture A in sequence, heating to 100 ℃, reacting for 4 hours, monitoring the reaction process by TLC, increasing the heating temperature to 120 ℃, reacting for 2 hours, after the conversion of the propylene glycol monolaurate and the coconut oil is finished, adding deionized water to dissolve the mixture to obtain a clear and transparent sodium cocoyl glycinate solution, adding hydrochloric acid to adjust the pH value to be about 3, filtering, and drying in vacuum at 50 ℃ to obtain 145.67g of white solid cocoyl glycinate, wherein the yield is 70.01%, and dissolving the white solid cocoyl glycinate with potassium hydroxide solution to obtain a 34.35% concentration potassium cocoyl glycinate solution, and the chroma of a stock solution is 120 Hazen.
Fig. 11 is a liquid chromatogram of potassium cocoyl glycinate from example 6.
Example 7
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.6g of potassium hydroxide and 77.5g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then adding 55g of propylene glycol monolaurate, 100g of coconut oil and 66.76g of sodium glycinate into the mixture A in sequence, heating to 110 ℃, reacting for 5 hours, monitoring the reaction process by TLC, adding deionized water to dissolve when the conversion of the propylene glycol monolaurate is finished to obtain a clear and transparent sodium lauroyl glycinate solution, adding hydrochloric acid to adjust the pH value to be about 3, filtering, and drying in vacuum at 50 ℃ to obtain 147.3g of white solid cocoyl glycinate, wherein the yield is 84.87%, dissolving by using a potassium hydroxide solution to obtain a 31.84% concentration potassium cocoyl glycinate solution, and the chroma of a stock solution is 100 Hazen.
Fig. 12 is a liquid chromatogram of potassium cocoyl glycinate from example 7.
Example 8
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then, adding 25g of methyl laurate, 150g of coconut oil and 79.29g of sodium glycinate into the mixture A in sequence, heating to 100 ℃, reacting for 4 hours, monitoring the reaction process by TLC (thin layer chromatography), wherein the methyl laurate and the coconut oil still have residues, heating to 120 ℃ in an improved mode, reacting for 2 hours for conversion, stopping the reaction, adding deionized water for dissolving to obtain a turbid cocoyl sodium glycinate solution, adding hydrochloric acid for adjusting the pH value to be about 3, filtering, and drying at 50 ℃ in vacuum to obtain 184.67g of white solid cocoyl glycine, wherein the yield is 88.70%, and dissolving by using a potassium hydroxide solution to obtain a cocoyl potassium glycinate solution with the concentration of 34.48%, and the chroma of a stock solution is 120 Hazen.
Example 9
This example provides a method for preparing an oleamidoate salt and the oleamidoate salt prepared by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then adding 28g of isopropyl laurate, 150g of coconut oil and 79.18g of sodium glycinate into the mixture A in sequence, heating to 120 ℃, reacting for 5 hours for conversion, monitoring the reaction process by TLC (thin layer chromatography), stopping the reaction when the coconut oil is slightly remained, adding deionized water for dissolution to obtain a slightly turbid sodium cocoyl glycinate solution, adding hydrochloric acid for adjusting the pH value to be about 3, filtering, and performing vacuum drying at 50 ℃ to obtain 179.32g of white solid cocoyl glycinate, wherein the yield is 86.25%, dissolving by using a potassium hydroxide solution to obtain a 31.41% concentration potassium cocoyl glycinate solution, and the chroma of the stock solution is 140 Hazen.
Comparative example 1
This comparative example provides a method of making an oleoyl amido acid salt and an oleoyl amido acid salt made by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of glycerol into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
then 175.15g of coconut oil and 79.24g of sodium glycinate are added into the mixture A in sequence, the mixture is heated to 100 ℃ and reacted for 5 hours, the TLC monitors the reaction process, the coconut oil still remains, the mixture is continuously heated to 130 ℃, the reaction is carried out for 3 hours, the TLC monitors the reaction process, and the coconut oil is reacted completely. Adding deionized water for dissolving to obtain a clear and transparent sodium cocoyl glycinate solution, adding hydrochloric acid for adjusting the pH value to be about 3, filtering, and carrying out vacuum drying at 50 ℃ to obtain 124.64g of light brown solid cocoyl glycinate with the yield of 59.91%, and dissolving with a potassium hydroxide solution to obtain a 32.06% potassium cocoyl glycinate solution with the chroma of 150 Hazen.
Fig. 13 is a liquid chromatogram of potassium cocoyl glycinate in comparative example 1.
Comparative example 2
This comparative example provides a method of making an oleoyl amido acid salt and an oleoyl amido acid salt made by the method.
Respectively adding 1.8g of potassium hydroxide and 90g of PEG-40090 g into a 1000mL four-mouth glass bottle, heating to 80 ℃ for dissolution, clarifying, and removing water by nitrogen for half an hour in the heating process to obtain a mixture A;
and then, adding 30g of propylene glycol monolaurate, 150g of coconut oil and 79.24g of sodium glycinate into the mixture A in sequence, heating to 100 ℃, reacting for 3 hours, making the system turbid, monitoring the reaction process by TLC (thin layer chromatography), and when more propylene glycol monolaurate and coconut oil are not reacted, raising the temperature to 130 ℃, reacting for 4 hours, wherein the system is dark brown, and when a little propylene glycol monolaurate and coconut oil remain, adding deionized water to dissolve the mixture to obtain a brown sodium cocoyl glycinate solution, adding hydrochloric acid to adjust the pH value to be about 3, filtering, and drying to obtain 133.37g of yellow brown solid cocoyl glycinate, wherein the yield is 64.10%, and then dissolving the yellow brown solid cocoyl glycinate with potassium hydroxide solution to obtain 32.15% potassium cocoyl glycinate solution, and the chroma of the stock solution is 180 Hazen.
Fig. 14 is a liquid chromatogram of potassium cocoyl glycinate in comparative example 2.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of grease acylamino acid salt is characterized by comprising the following steps:
mixing glycerol and an alkali catalyst, and reacting to prepare a mixture A;
and adding monolaurate, grease and amino acid salt into the mixture A, and heating to 90-138 ℃ to perform urethane exchange reaction.
2. The method of claim 1, further comprising a water removal step in the step of preparing mixture a.
3. The method for preparing the grease amino acid salt according to claim 2, wherein the water removal mode is as follows: introducing inert gas and controlling the temperature to be 50-80 ℃.
4. The method for preparing the grease amino acid salt according to claim 1, wherein the temperature of the urethane exchange reaction is 100 ℃ to 130 ℃ and the time is 3h to 10 h.
5. The method for producing an oil or fat acylamino acid salt according to any of claims 1 to 4, wherein the total molar amount of the monolaurate and the ester group in the oil or fat and the-NH in the amino acid salt2The molar ratio of (A) to (B) is 1:1 to 1: 1.5.
6. The method for producing an oil and fat acylamino acid salt according to claim 5, wherein the monolaurate is at least one selected from the group consisting of propylene glycol monolaurate, methyl laurate, ethyl laurate and isopropyl laurate.
7. The method for producing an oil and fat acylamino acid salt according to claim 5, wherein the molar ratio of the monolaurate to the oil and fat is 1:1 to 1: 2.5.
8. The method for producing an oil and fat acylamino acid salt according to claim 5 wherein the oil and fat is at least one selected from the group consisting of coconut oil, palm oil, camellia seed oil, rapeseed oil, olive oil and soybean oil; and/or the presence of a catalyst in the reaction mixture,
the amino acid salt is selected from at least one of sodium glycinate, sodium alanine, sodium sarcosinate and sodium taurate.
9. The method for producing an oil and fat acylamino acid salt according to any one of claims 1 to 4, wherein the alkali catalyst is at least one selected from the group consisting of potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide; and/or the presence of a catalyst in the reaction mixture,
the molar ratio of the alkali catalyst to the glycerol is 1: 20-1: 60.
10. The method for producing an oleoyl amido acid salt according to any of claims 1 to 4, characterized in that it further comprises a purification step of dilution, acidification, and further neutralization after the urethane exchange reaction.
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| CN114181118A (en) * | 2021-11-25 | 2022-03-15 | 张家港格瑞特化学有限公司 | Synthesis process of fatty acyl taurate |
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| CN114181118A (en) * | 2021-11-25 | 2022-03-15 | 张家港格瑞特化学有限公司 | Synthesis process of fatty acyl taurate |
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