CN103772227A - Preparation method for grease-based amino acid salt-series surfactant - Google Patents
Preparation method for grease-based amino acid salt-series surfactant Download PDFInfo
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- CN103772227A CN103772227A CN201410012744.5A CN201410012744A CN103772227A CN 103772227 A CN103772227 A CN 103772227A CN 201410012744 A CN201410012744 A CN 201410012744A CN 103772227 A CN103772227 A CN 103772227A
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Abstract
The invention relates to a preparation method for a grease-based amino acid salt-series surfactant. The method comprises the steps of adding grease and amino acid salt, of which the molar ratio is 1:(1.5-5) or fatty acid and amino acid salt, of which the molar ratio is 1:(1.05-1.5), into a normal pressure reactor with heating, stirring and temperature regulation devices; adding a catalyst, raising the temperature after full stirring, and performing reaction for 2 to 8 hours by controlling the reaction temperature to be 130 to 190 DEG C, reducing the reaction temperature to 60 to 90 DEG C, adding a neutralizing agent, and adjusting the pH to be 7 to 8 to obtain a product. The method has the characteristics of environment friendliness and simplicity of a synthesis process, convenience in operation, high yield, high product purity, readily available raw materials, no environmental pollution and the like; the product has high surface activity, high biodegradability and stable performance; the method is a novel synthesis method with broad application prospect.
Description
Technical field
The invention belongs to organic compound synthesis technical field, be specifically related to a kind of preparation method of fat-based amino acid salts series of surfactants.
Technical background
Fat-based amino acid salts series of surfactants is the compounds being obtained by amino acid amide, owing to having increased amide group and amino acid moiety in molecular structure, there is good surfactivity, foam performance, emulsifying property, detergency ability, gentle performance, the low stimulation of low toxicity, erosion resistant rust-preventing characteristic, outstanding readily biodegradable performance and the safe affinity to human body etc.Be widely used as whipping agent, lubricant, emulsifying agent, dispersion agent, inhibiter etc., can be used for washing composition, medicine, antiseptic-germicide, wastewater treatment, makeup, metal processing and other fields.
At present; the preparation method of industrial common employing is chloride method; what adopt is Xiao Dun-Bao Man (Schotten-Banmann) condensation reaction method; it first carries out chloride by lipid acid; added after catalyzer, organic solvent by fatty acid chloride and amino acid again; under the protection of 170 ℃-190 ℃ and nitrogen, make N-fatty acyl group amino acid, then in mineral acid with separates, then add alkali and neutralize and form.The advantage of this method is that equipment is uncomplicated, and reaction process does not need high pressure, working condition convenient operation, but all not high (general productive rate is 75% left and right) of the productive rate of the method and product purity.In actual production process, first the preparation of acyl chlorides need to adopt PCL in addition
3or SOCL
2deng the larger material of environmental pollution, this product workshop appliance of will seeking survival has higher acid resistance, fat acyl chloride slowly need to be added in amino acid whose solution at the second step of reaction simultaneously, for guaranteeing that reaction can all be carried out smoothly and not producing more lipid acid because acyl chlorides is hydrolyzed, need in reaction system, add a small amount of organic solvent, under homogeneous reaction condition not, reduce the hydrolysis of acyl chlorides.Because second step reaction is thermopositive reaction, and temperature raises and has accelerated the hydrolysis of side reaction acyl chlorides, therefore needs to control temperature of reaction and also will control the rate of addition of acyl chlorides, avoids because adding the too fast increase side reaction that causes.And reaction solution PH in the process of carrying out has considerable change, the environment of crossing alkali or peracid is all unfavorable for the production of product therefore also will regulating pH value.Above condition has increased the difficulty that acyl chlorides method is prepared fat-based amino acid salts tensio-active agent.Although Schotten-Banmann reaction is applied widely industrial by the method for fat acyl chloride and amino acid condensation, and through constantly improving, single this technique is quite long with regard to flow process from the preparation of acyl chlorides.
And adopt this technique, and in technique is synthetic, can use the raw material that has severe corrosive and strong and stimulating, producing a large amount of spent acid needs processing, operating procedure complexity, has environmental pollution.And very high to acyl chlorides specification of quality in the time of condensation, must store by isolated moisture, to reduce its hydrolysis, otherwise hydrolysate is introduced after product, remove very difficult, and by product is many, product color is poor and have the shortcomings such as peculiar smell, has limited the application of product in the fields such as food, medicine and makeup in addition.
Summary of the invention
The present invention
objectjust be to provide for the deficiencies in the prior art a kind of preparation method of fat-based amino acid salts, have that technique green is simple and direct, reaction conditions is gentle, synthesis under normal pressure is easy to operate, be easy to realize suitability for industrialized production, product purity is high, cost is low and eco-friendly, and good surface activity, synthetic raw materials used being easy to get, the advantages such as production process cleanliness without any pollution are a kind of very promising new synthetic methods.
Realize above-mentioned purpose of the present invention
technical schemefor:
A kind of fat-based amino acid salts of the present invention series of surfactants, be with grease or lipid acid and amino acid salts under the effect of catalyzer, make fat-based amino acid salts, wherein grease and amino acid salts mol ratio 1:1.5～5 through amidate action, separation, post-treating and other steps; Lipid acid and amino acid salts mol ratio 1:1.05～1.5.
Synthetic fat-based amino acid salts of the present invention has following form:
R in formula
1for C
5～C
30alkyl or their mixture, preferably C
8～C
18alkyl or their mixture.
R
2for H or CH
3
R
3for H or C
1～C
6straight chain or the alkyl of straight chain, hydroxyl alkyl, COOH;
N is 1～5
M
+for metal ion or organic amino ion
the preparation method of a kind of fat-based amino acid salts of the present invention series of surfactants, its method steps is as follows:
First the grease that is 1:1.5～5 by mol ratio and amino acid salts, or lipid acid and amino acid salts that mol ratio is 1:1.05～1.5 join in the normal pressure reactor with heating, stirring and register; Next adds catalyzer to heat up temperature of reaction is controlled to 130 ℃～190 ℃ after fully stirring, and reaction is carried out 2～8 hours, finally temperature of reaction is cooled to 60～90 ℃, adds neutralizing agent, regulates pH value to 7～8, obtains product; Measure fat-based amino acid salts content, product yield.
Catalyzer of the present invention is the single or mixture of methylsulphonic acid, metilsulfate.The add-on of catalyzer is the 0.1wt%-0.5wt% of reactant; Described neutralizing agent is one or more mixtures in citric acid, ethylenediamine tetraacetic acid (EDTA), phosphoric acid.
Grease provided by the present invention can be Vegetable oil lipoprotein, has soya-bean oil, Semen Maydis oil, Oleum Gossypii semen, Oleum Cocois, plam oil, palm-kernel oil, Viscotrol C, Rice pollard oil, sweet oil or fruital wet goods; Also can be animal grease, have butter, sheep oil, lard, skin oil or animal oil etc.
Lipid acid provided by the invention can be lauric acid, cocinic acid, tetradecanoic acid, palmitinic acid, oleic acid, linolic acid, stearic acid etc.
Amino acid salts provided by the invention can be metal-salt or the organic amino salt of sarkosine, L-glutamic acid, L-Ala, leucine, Isoleucine, glycine, proline(Pro), Methionin, Serine, arginine etc., is preferably sodium salt or sylvite.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1:
0.1mol Oleum Cocois and 0.35mol Sodium Glutamate are added in the normal pressure reactor with heating, stirring and register, add again the novalgin (catalyzer) of the 0.3wt% of reactant, after fully stirring, be warming up to gradually 140 ℃, react 5 hours, be cooled to 80 ℃ of citric acids that are incorporated as reactant 0.08wt%, regulate pH value 7～8, reaction finishes to obtain product.Finally measure material Glutamic Acid sodium content 0.3%, product N-cocoyl Sodium Glutamate yield 98.7%.
Embodiment 2:
0.1mol lauric acid and 0.12mol Potassium glutamate are added in the normal pressure reactor with heating, stirring and register, add again the methylsulphonic acid potassium (catalyzer) of the 0.2wt% of reactant, after fully stirring, be warming up to gradually 150 ℃, react 5 hours, be cooled to 80 ℃ of citric acids that are incorporated as reactant 0.05wt%, regulate pH value 7～8, reaction finishes to obtain product.Measure material Glutamic Acid potassium content 0.2%, product lauroyl glutamate potassium yield 99.2%.
Embodiment 3:
0.1mol plam oil and 0.33mol sodium sarcosinate are added in the normal pressure reactor with heating, stirring and register, add again the methylsulphonic acid (catalyzer) of the 0.2wt% of reactant, after fully stirring, be warming up to gradually 150 ℃, react 6 hours, be cooled to 70 ℃ of ethylenediamine tetraacetic acid (EDTA)s that are incorporated as reactant weight 0.03wt%, regulate pH value 7～8, reaction finishes to obtain product.Measure sodium sarcosinate content 0.2% in material, product N-palm oil-base sodium sarcosinate yield 99.0%.
Be below chloride method preparation technology and preparation technology's contrast table of the present invention
As can be seen from the above table, the preparation method of industrial common employing is chloride method, and this technique is two-step approach reaction, quite long with regard to flow process from the preparation of acyl chlorides; Severe reaction conditions, needs nitrogen protection, complex process; Transformation efficiency only reaches 75%; Product yield is low; In reaction process, need raw material PCL
3(or SOCL
2) pungency is large; In production process, have HCl to produce, corrodibility is large, and producing a large amount of spent acid needs to process, and operating procedure complexity, has environmental pollution; And it is very high to acyl chlorides specification of quality in the time of condensation, must store by isolated moisture, to reduce its hydrolysis, otherwise hydrolysate is introduced after product, remove very difficult, and also have by product many, product color is poor and have the shortcomings such as peculiar smell, has limited the application of product in the fields such as food, medicine and makeup, can only be used for washing and metal processing industry, use range is restricted.
Preparation method of the present invention, compared with chloride method, has the following advantages: this technique is the direct amidation condensation reaction of single stage method, and technical process is short; Reaction conditions gentleness, does not need nitrogen protection, synthesis under normal pressure, and technique is simple; Transformation efficiency is up to 98%; Product yield is high; Synthetic raw materials used being easy to get, production process cleanliness without any pollution; Products obtained therefrom purity is high, product color is shallow, good surface activity, gentle safe, is widely used in makeup, washing composition, foodstuff additive, metal processing, oil production, biological products and medicine and the various fields such as prepares.
Claims (3)
1. a preparation method for fat-based amino acid salts series of surfactants, is characterized in that method steps is as follows:
First the grease that is 1:1.5～5 by mol ratio and amino acid salts, or lipid acid and amino acid salts that mol ratio is 1:1.05～1.5 join in the normal pressure reactor with heating, stirring and register; Next adds catalyzer to heat up temperature of reaction is controlled to 130 ℃～190 ℃ after fully stirring, and reaction is carried out 2～8 hours, finally temperature of reaction is cooled to 60～90 ℃, adds neutralizing agent, regulates pH value to 7～8, obtains product; Measure fat-based amino acid salts content, product yield;
Described catalyzer is the single or mixture of methylsulphonic acid, metilsulfate; The add-on of catalyzer is the 0.1wt%-0.5wt% of reactant; Described neutralizing agent is one or more mixtures in citric acid, ethylenediamine tetraacetic acid (EDTA), phosphoric acid.
2. the preparation method of a kind of fat-based amino acid salts series of surfactants according to claim 1, is characterized in that:
Described grease is Vegetable oil lipoprotein, or is animal grease; Vegetable oil lipoprotein has soya-bean oil, Semen Maydis oil, Oleum Gossypii semen, Oleum Cocois, plam oil, brown paulownia benevolence oil, Viscotrol C, Rice pollard oil, sweet oil or ethereal fruit oil; Animal grease has butter, sheep oil, lard, skin oil or animal oil;
Described lipid acid is lauric acid, cocinic acid, tetradecanoic acid, palmitinic acid, oleic acid, linolic acid, stearic acid;
Described amino acid salts can be sarkosine, L-glutamic acid, L-Ala, leucine, Isoleucine, glycine, proline(Pro), Methionin, Serine, arginic metal-salt or organic amino ion salt.
3. the preparation method of a kind of fat-based amino acid salts series of surfactants according to claim 2, is characterized in that: described fat-based amino acid salts is sodium salt, sylvite or organic amino salt.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607098A (en) * | 2015-01-30 | 2015-05-13 | 北京工商大学 | Method for preparing grease acyl sodium leucine and surface active agent composition containing grease acyl sodium leucine in phase-transfer catalysis way |
| CN104607095A (en) * | 2015-01-30 | 2015-05-13 | 北京工商大学 | Method for preparing sodium fatty-acyl threonine and composition containing surfactant |
| CN104741032A (en) * | 2015-01-30 | 2015-07-01 | 北京工商大学 | Method for preparing fatty acyl sodium methionine and composition comprising surfactant |
| CN108358802A (en) * | 2018-01-05 | 2018-08-03 | 石家庄菠莉亚日用化工有限公司 | A kind of preparation method of fat acidyl glycine salt surfactant |
| CN108837774A (en) * | 2018-07-25 | 2018-11-20 | 中国林业科学研究院林产化学工业研究所 | Lacquer tree fat acyl amino acid surfactant and preparation method thereof |
| CN109626510A (en) * | 2018-11-26 | 2019-04-16 | 中海油天津化工研究设计院有限公司 | A kind of electrochemistry circulating water treatment device water treatment agent and preparation method thereof |
| CN112871074A (en) * | 2021-01-19 | 2021-06-01 | 长江大学 | Synthetic method of castor oil acyl sulfamate amphoteric surfactant |
| CN114133344A (en) * | 2021-11-29 | 2022-03-04 | 江苏奥洁生物科技有限公司 | Method for preparing N-fatty acyl amino acid surfactant by high-temperature melting direct condensation |
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| CN1187184A (en) * | 1995-06-06 | 1998-07-08 | 汉普郡化学公司 | Preparation of alkali metal acyl amino acids |
| JP2006183030A (en) * | 2004-11-30 | 2006-07-13 | Lion Corp | Pasty cleanser composition |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607098A (en) * | 2015-01-30 | 2015-05-13 | 北京工商大学 | Method for preparing grease acyl sodium leucine and surface active agent composition containing grease acyl sodium leucine in phase-transfer catalysis way |
| CN104607095A (en) * | 2015-01-30 | 2015-05-13 | 北京工商大学 | Method for preparing sodium fatty-acyl threonine and composition containing surfactant |
| CN104741032A (en) * | 2015-01-30 | 2015-07-01 | 北京工商大学 | Method for preparing fatty acyl sodium methionine and composition comprising surfactant |
| CN108358802A (en) * | 2018-01-05 | 2018-08-03 | 石家庄菠莉亚日用化工有限公司 | A kind of preparation method of fat acidyl glycine salt surfactant |
| CN108837774A (en) * | 2018-07-25 | 2018-11-20 | 中国林业科学研究院林产化学工业研究所 | Lacquer tree fat acyl amino acid surfactant and preparation method thereof |
| CN109626510A (en) * | 2018-11-26 | 2019-04-16 | 中海油天津化工研究设计院有限公司 | A kind of electrochemistry circulating water treatment device water treatment agent and preparation method thereof |
| CN112871074A (en) * | 2021-01-19 | 2021-06-01 | 长江大学 | Synthetic method of castor oil acyl sulfamate amphoteric surfactant |
| CN114133344A (en) * | 2021-11-29 | 2022-03-04 | 江苏奥洁生物科技有限公司 | Method for preparing N-fatty acyl amino acid surfactant by high-temperature melting direct condensation |
| WO2023093560A1 (en) * | 2021-11-29 | 2023-06-01 | 江苏奥洁生物科技有限公司 | Method for preparing n-fatty acyl amino acid surfactant by means of high-temperature melting and direct condensation |
| CN114133344B (en) * | 2021-11-29 | 2024-03-22 | 江苏奥洁生物科技有限公司 | Method for preparing N-fatty acyl amino acid surfactant by high-temperature melting direct condensation |
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