CN112871074A - Synthetic method of castor oil acyl sulfamate amphoteric surfactant - Google Patents
Synthetic method of castor oil acyl sulfamate amphoteric surfactant Download PDFInfo
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- CN112871074A CN112871074A CN202110068570.4A CN202110068570A CN112871074A CN 112871074 A CN112871074 A CN 112871074A CN 202110068570 A CN202110068570 A CN 202110068570A CN 112871074 A CN112871074 A CN 112871074A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/025—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by saponification and release of fatty acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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Abstract
A synthetic method of castor oil acyl sulfamate amphoteric surfactant comprises the following steps: 1. pretreating castor oil; 2. dropwise adding an alkaline water solution into the pretreated castor oil, after the reaction is finished at low temperature, washing and layering the obtained solution, and collecting an organic phase to obtain a product B; 3. dropwise adding the product B into diamine or polyamine, adding a water carrying agent or a molecular sieve, and removing the diamine or polyamine after the reaction is finished at high temperature to obtain a product C; 4. and reacting the product C with a sulfonating agent at a low temperature to obtain a final product D, and treating the final product D as required. The synthetic method can simplify or not process the purification treatment process of the synthetic intermediate product and the final product according to the actual needs, has the characteristics of simple synthetic method, low operation cost, wide raw material source and reproducibility, high surface/interface activity, strong water solubility, excellent compatibility with other active substances and the like of the synthetic product, and is suitable for different fields of daily chemicals, industry and agriculture and the like.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a synthetic method of a castor oil acyl sulfamate amphoteric surfactant.
Background
The amino acid type surfactant is a green and environment-friendly mild surfactant, and has the basic performance of a conventional surfactant, and more importantly, the amino acid type surfactant has good affinity, low irritation, low toxicity, good biodegradability, good compatibility and the like to a human body. It is widely used in daily chemical products, foods, pesticides and other industrial chemical agents.
Conventional amino acid-type surfactants are mostly: (1) a molecule containing a single amino or amide group, or (2) a single component; and the like. The possible problems are: water solubility is not good enough; the purification process cost is increased to obtain a single component compound; poor surface/interfacial activity; poor compatibility, etc.
Disclosure of Invention
The invention provides a synthesis method of a castor oil acyl sulfamate amphoteric surfactant based on the problems of the conventional amino acid surfactants. The sulfamate amphoteric surfactant has good water solubility, easy degradation, good skin affinity, good surface/interface activity and compatibility with other substances, the raw material is directly from natural reproducible castor oil, and certain reaction products (such as glycerol and the like) are reserved according to the requirements of application performance, so that the product has good hydrophilic performance, excessive purification treatment on intermediate products in the reaction process is not required, the production process is simplified, the production cost is reduced, and the sulfamate amphoteric surfactant is an environment-friendly surfactant.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthetic method of castor oil acyl sulfamate amphoteric surfactant is characterized by comprising the following synthetic steps:
(1) pretreating castor oil, including removing color and other non-greasy substances;
(2) dropwise adding 10-45% alkaline water solution with the saponification value of 0.7-1.5 times of that of the castor oil into a reaction bottle containing the pretreated castor oil, and reacting at 40-95 ℃ for 1-15 hours to obtain solution A; washing the solution A with water, and collecting an organic phase to obtain a product B after layering;
(3) dropwise adding the product B into diamine or polyamine with the stoichiometric ratio of 1: 2-1: 6, adding a water carrying agent or a molecular sieve with the volume of 5-40% of the solution, introducing nitrogen, reacting at 120-185 ℃, stopping the reaction after the acid value is not higher than 10g/g, and then decompressing and distilling off the diamine or polyamine to obtain a product C;
(4) and (3) reacting the product C with an aqueous solution of a sulfonating agent for 8-38 hours at the temperature of 40-95 ℃ in a stoichiometric ratio of 0.8: 1-1: 0.8, adjusting the pH value with a 10-45% alkaline aqueous solution in the reaction process, and reacting until the system is transparent to obtain the final product, namely the castor oil acyl sulfamate amphoteric surfactant.
Further, the alkali in the aqueous alkali solution in the synthesis step (2) and the synthesis step (4) is an oxide or hydroxide of an alkali metal or an alkaline earth metal, or a mixture of any two or more of the oxide or hydroxide.
Further, the water carrying agent in the synthesis step (3) is toluene, xylene, or a mixture of the toluene and the xylene.
Further, the molecular sieve in the synthesis step (3) is a 4A molecular sieve.
Further, the diamine or polyamine in the synthesis step (3) is all diamine or polyamine containing at least two substitutable hydrogens on the amine group at the molecular chain, preferably ethylenediamine, hydroxymethyl ethylenediamine, hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 2-hydroxy-1, 3-propylenediamine, di (2-hydroxypropylene) triamine, tri (2-hydroxypropylene) tetramine, diethylenetriamine, triethylenetetramine.
Further, the sulfonating agent in the synthesis step (4) is halogenated metal sulfonate, halogenated alkyl metal sulfonate, sultone, and alkylene sulfite, preferably sodium (potassium) chloroethyl sulfonate, sodium (potassium) bromoethyl sulfonate, sodium (potassium) 2-hydroxy-3-chloropropyl sulfonate, and sodium (potassium) 2-hydroxy-3-bromopropyl sulfonate.
In the invention, the intermediate product and the final product of the reaction are properly purified according to the needs, so that the treatment cost is low, and hydrophilic components such as glycerol are reserved, so that the product has good hydrophilic performance; although the hydrophobic chain in the product molecule is longer, the product contains hydroxyl and unsaturated bonds, has good hydrophilicity and good affinity to skin; the product is formed by coexistence of surfactant molecules with different hydrophobic chains and other untreated surface active substances, and can effectively exert the synergistic interaction between molecules, so that good interface activity is obtained.
The synthetic method can simplify or not process the purification treatment process of the synthetic intermediate product and the final product according to the actual needs, has the characteristics of simple synthetic method, low operation cost, wide raw material source and reproducibility, high surface/interface activity, strong water solubility, excellent compatibility with other active substances and the like of the synthetic product, and is suitable for different fields of daily chemicals, industry and agriculture and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the present invention, and the selection of the raw materials in the synthesis process may be made according to local conditions without substantially affecting the results.
Example 1
Washing castor oil with hot saturated saline water for 3 times, pouring 50g of the treated castor oil into a reaction bottle with a stirrer and a temperature sensor, dropwise adding 30g of 20% NaOH aqueous solution at room temperature, and heating to 65 ℃ for reaction for 3 hours to obtain a solution A; the solution a was washed 2 times with saturated brine to give product B.
And (3) filling 29mL of diethylenetriamine and 15mL of xylene in a reaction bottle with a stirrer, a temperature sensor and a water separator, adding 18.8g of the product B in batches at 80 ℃, introducing nitrogen, uniformly stirring, slowly heating to 172 ℃, reacting until the acid value is 8.62g/g, and then decompressing and distilling off the diethylenetriamine to obtain a product C.
At room temperature, 18.4g of the product C is added into a reaction bottle containing 42mL of 30% chloroethyl sodium sulfonate aqueous solution, the mixture is uniformly stirred, the temperature is raised to 80 ℃, the reaction is started, 20% NaOH aqueous solution is used for adjusting the pH value of the system to be about 9.5, and the reaction is carried out until the system is transparent, so that the final product of the castor oil acyl sodium sulfamate amphoteric surfactant is obtained.
Example 2
Washing castor oil with hot saturated saline water for 3 times, pouring 198g of the treated castor oil into a reaction bottle with a stirrer and a temperature sensor, dropwise adding 102g of 20% NaOH aqueous solution at room temperature, and heating to 72 ℃ for reaction for 3.2 hours to obtain a solution A; the solution a was washed 3 times with saturated brine to give product B.
116mL of diethylenetriamine and 52mL of mixed solution of toluene and xylene (the volume ratio is 2: 8) are contained in a reaction bottle with a stirrer, a temperature sensor and a water separator, 76.4g of the product B is added in batches at 85 ℃, nitrogen is introduced, the mixture is uniformly stirred, the temperature is slowly raised to 166 ℃, the reaction is carried out until the acid value is 9.74g/g, and then the diethylenetriamine is evaporated under reduced pressure to obtain a product C.
Adding 71.6g of the product C into a reaction bottle containing 162mL of 32% 2-hydroxy-3-chloropropyl sodium sulfonate aqueous solution at room temperature, uniformly stirring, heating to 78 ℃, starting to react, adjusting the pH of the system to be about 9.0 by using 25% NaOH aqueous solution, and reacting until the system is transparent to obtain the final product of the castor oil acyl sodium sulfamate amphoteric surfactant.
Example 3
The products synthesized in examples 1 and 2 were investigated for their surface/interfacial activity, water solubility and compatibility with other surfactants, as shown in tables 1 and 2 below.
TABLE 1 Critical micelle concentration (cmc)
Wherein: the critical micelle concentration of the products of the embodiment 1 and the embodiment 2 is estimated by a tension method and a conductivity method, and the average value of the two is taken; reference is made to the critical micelle concentration values of octadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and octyl phenol polyoxyethylene ether (10): rosen M.J. surfactants and Interfacial Phenomena (3th edition) [ M ]. John Wiley & sons. Inc., 2004.
TABLE 2 Water solubility and compatibility
Wherein: water solubility was evaluated as the appearance of a 1 wt% aqueous solution (22 ℃ C.).
From the data in table 1, it can be seen that the synthesized product of the present invention shows better table/interfacial activity.
As can be seen from Table 2, the product synthesized by the method has good water solubility, and the water solubility of the mixed system is improved after the product is mixed with other surfactants; the mixed system has synergistic performance, and shows that the product synthesized by the invention has good compatibility.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
Claims (6)
1. A synthetic method of castor oil acyl sulfamate amphoteric surfactant is characterized by comprising the following synthetic steps:
(1) pretreating castor oil, including removing color and other non-greasy substances;
(2) dropwise adding 10-45% alkaline water solution with the saponification value of 0.7-1.5 times of that of the castor oil into a reaction bottle containing the pretreated castor oil, and reacting at 40-95 ℃ for 1-15 hours to obtain solution A; washing the solution A with water, and collecting an organic phase to obtain a product B after layering;
(3) dropwise adding the product B into diamine or polyamine with the stoichiometric ratio of 1: 2-1: 6, adding a water carrying agent or a molecular sieve with the volume of 5-40% of the solution, introducing nitrogen, reacting at 120-185 ℃, stopping the reaction after the acid value is not higher than 10g/g, and then decompressing and distilling off the diamine or polyamine to obtain a product C;
(4) and (3) reacting the product C with an aqueous solution of a sulfonating agent for 8-38 hours at the temperature of 40-95 ℃ in a stoichiometric ratio of 0.8: 1-1: 0.8, adjusting the pH value with a 10-45% alkaline aqueous solution in the reaction process, and reacting until the system is transparent to obtain the final product, namely the castor oil acyl sulfamate amphoteric surfactant.
2. The method for synthesizing the castor oil acyl sulfamate amphoteric surfactant according to claim 1, wherein the base in the aqueous base solution in the synthesis steps (2) and (4) is an oxide or hydroxide of an alkali metal or an alkaline earth metal, or a mixture of any two or more of the oxides or hydroxides.
3. The method for synthesizing the castor oil acyl sulfamate amphoteric surfactant according to claim 1, wherein the water carrying agent in the synthesis step (3) is toluene, xylene, or a mixture of the toluene and the xylene.
4. The method for synthesizing the castor oil acyl sulfamate amphoteric surfactant according to claim 1, wherein the molecular sieve in the synthesis step (3) is a 4A molecular sieve.
5. The method for synthesizing ricinoleic acyl sulfamate amphoteric surfactant according to claim 1, wherein the diamine or polyamine in the synthesis step (3) is all diamine or polyamine containing at least two substitutable hydrogens in amine groups on molecular chain, preferably ethylenediamine, hydroxymethyl ethylenediamine, hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 2-hydroxy-1, 3-propylenediamine, bis (2-hydroxypropylene) triamine, tris (2-hydroxypropylene) tetramine, diethylenetriamine, triethylenetetramine.
6. The method for synthesizing the castor oil acyl sulfamate amphoteric surfactant according to claim 1, wherein the sulfonating agent in the synthesis step (4) is metal halosulfonate, metal halohydrocarbyl sulfonate, sultone, and alkylene sulfite, preferably sodium (potassium) chloroethyl sulfonate, sodium (potassium) bromoethyl sulfonate, sodium (potassium) 2-hydroxy-3-chloropropyl sulfonate, and sodium (potassium) 2-hydroxy-3-bromopropyl sulfonate.
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| CN202110068570.4A CN112871074A (en) | 2021-01-19 | 2021-01-19 | Synthetic method of castor oil acyl sulfamate amphoteric surfactant |
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| CN202110068570.4A CN112871074A (en) | 2021-01-19 | 2021-01-19 | Synthetic method of castor oil acyl sulfamate amphoteric surfactant |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2543852A (en) * | 1946-10-29 | 1951-03-06 | Sandoz Ltd | Surface active derivatives of nitrogen-containing sulfonic acids |
| CN101912745A (en) * | 2009-10-31 | 2010-12-15 | 任朝华 | Sulfamic acid amphoteric surfactant and synthesis method thereof |
| CN103772227A (en) * | 2014-01-13 | 2014-05-07 | 石家庄菠莉亚日用化工有限公司 | Preparation method for grease-based amino acid salt-series surfactant |
| US20150315142A1 (en) * | 2014-04-30 | 2015-11-05 | Corrosion Y Proteccion Sa De Cv | Process to obtain imidazoline mixtures from vegetable oils |
| CN106552549A (en) * | 2015-09-29 | 2017-04-05 | 中国科学院成都有机化学有限公司 | A kind of high degree of cyclization imidazoline amophoteric surface active agent and its synthetic method |
-
2021
- 2021-01-19 CN CN202110068570.4A patent/CN112871074A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2543852A (en) * | 1946-10-29 | 1951-03-06 | Sandoz Ltd | Surface active derivatives of nitrogen-containing sulfonic acids |
| CN101912745A (en) * | 2009-10-31 | 2010-12-15 | 任朝华 | Sulfamic acid amphoteric surfactant and synthesis method thereof |
| CN103772227A (en) * | 2014-01-13 | 2014-05-07 | 石家庄菠莉亚日用化工有限公司 | Preparation method for grease-based amino acid salt-series surfactant |
| US20150315142A1 (en) * | 2014-04-30 | 2015-11-05 | Corrosion Y Proteccion Sa De Cv | Process to obtain imidazoline mixtures from vegetable oils |
| CN106552549A (en) * | 2015-09-29 | 2017-04-05 | 中国科学院成都有机化学有限公司 | A kind of high degree of cyclization imidazoline amophoteric surface active agent and its synthetic method |
Non-Patent Citations (3)
| Title |
|---|
| SHI-FA WANG ET AL.: ""Synthesis of 1-hydroxyethyl-2-alkyl-2-imidazoline and its derivative sulfonate amphoteric surfactant from tall oil fatty acid", 《JOURNAL OF WOOD SCIENCE》 * |
| 任朝华等: "Amino sulfonate amphoteric surfacatants synthesized by grease from natural products", 《中国化学会 第十六届全国有机合成化学学术研讨会》 * |
| 谢文磊等: "由蓖麻油合成C_(21)二元酸的研究", 《精细石油化工》 * |
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