CN114369036B - Method for reducing amine byproducts in glycine surfactant - Google Patents
Method for reducing amine byproducts in glycine surfactant Download PDFInfo
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000004471 Glycine Substances 0.000 title claims abstract description 46
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000006227 byproduct Substances 0.000 title claims abstract description 25
- 150000001412 amines Chemical class 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 108
- 230000001105 regulatory effect Effects 0.000 claims description 26
- 150000001263 acyl chlorides Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 40
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 38
- 239000000047 product Substances 0.000 abstract description 27
- IKGKWKGYFJBGQJ-UHFFFAOYSA-M sodium;2-(dodecanoylamino)acetate Chemical compound [Na+].CCCCCCCCCCCC(=O)NCC([O-])=O IKGKWKGYFJBGQJ-UHFFFAOYSA-M 0.000 abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 abstract description 14
- 229940065859 sodium cocoyl glycinate Drugs 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 4
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 4
- 239000004247 glycine and its sodium salt Substances 0.000 description 4
- 229940029258 sodium glycinate Drugs 0.000 description 4
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 108700003601 dimethylglycine Proteins 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940078490 n,n-dimethylglycine Drugs 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 facial cleanser Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229940079988 potassium cocoyl glycinate Drugs 0.000 description 1
- WLPORNKIACJZBO-UHFFFAOYSA-M potassium;2-(dodecanoylamino)acetate Chemical compound [K+].CCCCCCCCCCCC(=O)NCC([O-])=O WLPORNKIACJZBO-UHFFFAOYSA-M 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for reducing amine byproducts in glycine surfactants, and relates to the technical field of fine chemical synthesis. The method for reducing amine byproducts in glycine surfactants is based on the traditional Shoton-Bowman condensation reaction principle adopted by the method for producing sodium cocoyl glycinate, and comprises the steps of firstly, utilizing acid-base to neutralize and heat, and discharging ammonia gas introduced from a reaction raw material (glycine) out of a solution system under a vacuum condition; next, chloroacetic acid is added to byproducts such as dimethylamine produced by the DMF catalyst to react with the byproducts. In the surfactant product prepared by the method, the content of ammonia and dimethylamine is greatly reduced, the residual amount of ammonia in the product can be controlled below 3ppm, and the residual amount of dimethylamine can be controlled below 2 ppm.
Description
Technical Field
The invention relates to the technical field of fine chemical synthesis, in particular to a method for reducing amine byproducts in glycine surfactants.
Background
In recent years, amino acid surfactants have been developed rapidly, mainly thanks to their advantages in terms of safety, mildness, functionality, environmental protection, etc. Currently, the most common amino acid surfactants are mainly classified into four types, namely sarcosines, glycine, alanine and glutamic acid. The most demanded amount is glycine and glutamic acid, and the two surfactants are mainly applied to products such as facial cleansing cream, facial cleanser, shampoo, bath foam and the like. The glycine surfactants in the current industry mainly comprise the following 4 types of sodium lauroyl glycinate, potassium lauroyl glycinate, sodium cocoyl glycinate and potassium cocoyl glycinate, wherein sodium cocoyl glycinate is the most common. The method for producing sodium cocoyl glycinate in the current industry basically adopts the Shoton-Bowman condensation reaction principle, uses water as a solvent, and reacts cocoyl chloride with glycine under alkaline conditions to produce sodium cocoyl glycinate, and the corresponding reaction equation is shown as formula (I). R in formula (I) is a fatty chain (C6-C18 single fatty acid or mixed fatty acid). The method utilizes strong alkali to carry out catalytic reaction in water phase, has simple process, is one-step reaction, does not need to carry out operations such as concentration, acidification, water washing and the like, and can obtain cocoyl sodium glycinate with the solid content of about 30 percent, wherein the sodium chloride content is about 4.5 percent, and is a conventional high-salt product in the market.
However, the amino acid surfactant prepared by the method has heavy ammonia smell, the smell source is mainly low molecular amine byproducts (such as ammonia gas, dimethylamine and the like) remained in the product, and researches show that the dimethylamine remains as long as more than 10ppm, namely has obvious ammonia smell, and the prior art does not carry out corresponding treatment on the dimethylamine.
The residue of the low molecular amine by-product has a direct relation with the reaction raw materials in the preparation process of the cocoyl sodium glycinate. Glycine is used as one of the reaction raw materials for synthesizing sodium cocoyl glycinate, and currently, the glycine is produced by a chloroacetic acid ammonolysis method basically on the market, and a specific reaction equation is shown as a formula (II). As can be seen from the formula (II), ammonia gas is used as a main raw material for synthesizing glycine, a little ammonia gas and ammonium chloride are inevitably remained in the glycine synthesis process, and the residual ammonium chloride in the glycine is separated into ammonia gas when being heated in the process of participating in the cocoyl sodium glycinate synthesis reaction, so that ammonia smell is formed.
Acyl chloride is used as one of reaction raw materials for synthesizing sodium cocoyl glycinate, DMF (N, N dimethylformamide) is generally used as a catalyst in the production of the acyl chloride, DMF generally remains in the acyl chloride and cannot be removed, and the residual DMF is converted into dimethylamine and formic acid under the action of acidity in the use process of the acyl chloride, and a specific reaction equation is shown in a formula (III). Dimethylamine has a heavy ammonia smell and a trace amount of dimethylamine can produce a remarkable ammonia smell, so that the dimethylamine is the most main source of ammonia smell.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for reducing amine byproducts in glycine surfactants.
To achieve the above object, in a first aspect, the present invention provides a method for reducing amine byproducts in glycine surfactants, comprising the steps of:
(1) Mixing glycine, sodium hydroxide and water at room temperature, stirring uniformly, carrying out acid-base neutralization reaction to obtain solution A with pH value of 12-13.5, regulating the temperature of the solution A to 40-60 ℃, and maintaining the temperature for 0.5-2h under the condition that the vacuum degree is not lower than-0.095 MPa;
(2) After the temperature of the solution A is regulated to 10-30 ℃, dropwise adding acyl chloride into the solution A, synchronously starting dropwise adding sodium hydroxide solution to obtain solution B when the pH value is 8-11, and regulating the pH value of the solution B to be 8-11;
(3) After the dripping is completed, chloroacetic acid is added into the solution B to obtain a solution C;
(4) And adding sodium hydroxide into the solution C until the pH value is 9-12, and ending the reaction.
In the technical scheme of the invention, based on the Shoton-Bowman condensation reaction principle adopted by the traditional method for producing sodium cocoyl glycinate, firstly, in the step (1), acid-base is utilized to neutralize and heat, and ammonia gas introduced from a reaction raw material (glycine) is discharged out of a solution system under a vacuum condition; secondly, in the step (3), aiming at byproducts such as dimethylamine generated by the DMF catalyst, chloroacetic acid is added to react with the byproducts to form N, N-dimethylglycine, and a corresponding reaction equation of the reaction is shown as a formula (IV);
In addition, because chloroacetic acid is a raw material for synthesizing glycine, ammonia gas remained in the step (1) can also form glycine with chloroacetic acid, finally, the residual chloroacetic acid is hydrolyzed to glycolic acid by adding liquid alkali, the corresponding hydrolysis reaction equation is shown in a formula (V), and the hydrolysis product glycolic acid has no influence on safety.
The surfactant prepared by the preparation method can greatly reduce the contents of ammonia and dimethylamine in the prepared surfactant product and has no pungent odor by strictly controlling the pH value of the acid-base neutralization reaction stage in the step (1) and the addition amount of chloroacetic acid in the step (3).
As a preferred embodiment of the method for reducing amine byproducts in glycine surfactant according to the present invention, the chloroacetic acid in the step (3) is added in an amount of 2-6wt% of glycine in the step (1).
The inventor has found through a plurality of experiments that when the chloroacetic acid in the step (3) is added in an amount of 2-6% of the mass of glycine in the step (1), the dimethylamine content in the prepared surfactant product can be further reduced.
As a preferred embodiment of the method for reducing amine byproducts in glycine surfactant according to the present invention, the pH value of the solution C in the step (3) is 7-9.
The pH of the solution C in step (3) is the result of adding chloroacetic acid, and in the actual preparation process, the chloroacetic acid in step (3) needs to be weighed in advance in proportion before adding, in which case, after the chloroacetic acid is added into the reaction system, the pH of the reaction system (i.e., the solution C) is measured and is typically in the range of 7-9. Conversely, the experimenter can monitor the pH value change condition of the solution C while adding chloroacetic acid in the experimental process, and adjust the addition amount of chloroacetic acid according to the monitored pH value. There is no contradiction between these two methods.
The inventor finds that the pH value of the solution C in the step (3) has a great influence on the dimethylamine residual quantity in the product through a large number of experiments, and when the pH value of the solution C in the step (3) is controlled to be 7-9, the dimethylamine content in the prepared surfactant product can be maintained at an extremely low level.
As a preferred embodiment of the method for reducing amine byproducts in glycine surfactants, the temperature of the solution C in the step (3) is 50-80 ℃ and the heat preservation time is 2-5h.
As a preferred embodiment of the method for reducing amine byproducts in glycine surfactant according to the present invention, the sodium hydroxide in the step (1) is sodium hydroxide solution, and the solute mass fraction of the sodium hydroxide solution is 32%.
As a preferred embodiment of the method for reducing amine byproducts in glycine surfactants, the solute mass fraction of the sodium hydroxide solution in the step (2) is 32%, and the dripping time of the sodium hydroxide solution is 1-5h.
As a preferred embodiment of the method for reducing amine byproducts in glycine surfactant, the temperature of the solution C in the step (4) is 90-95 ℃ and the reaction time is 2-5h.
Compared with the prior art, the invention has the beneficial effects that:
The technical scheme of the invention is based on the traditional Shore-Bowman condensation reaction principle adopted by the method for producing sodium cocoyl glycinate, firstly, acid-base is utilized to neutralize heat in the step (1), and ammonia gas introduced from the reaction raw material (glycine) is discharged out of a solution system under the vacuum condition; secondly, in the step (3), aiming at byproducts such as dimethylamine generated by the DMF catalyst, and the like, chloroacetic acid is added to react with the byproducts to form N, N-dimethylglycine; and reacting chloroacetic acid with the ammonia gas remained in the step (1) to form glycine; finally, the residual chloroacetic acid is hydrolyzed by adding liquid alkali to obtain the glycolic acid which has no influence on safety. In the surfactant product prepared by the preparation method, the content of ammonia and dimethylamine is greatly reduced, the residual amount of ammonia in the product can be controlled below 3ppm, and the residual amount of dimethylamine can be controlled below 2 ppm.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described by means of specific examples.
Example 1
The glycine surfactant is prepared by the following method, and the specific preparation steps comprise the following steps:
(1) Adding 21g of glycine, 165g of deionized water and 33+/-3 g of sodium hydroxide solution with the solute mass fraction of 32% into a reaction kettle, mixing and stirring uniformly at room temperature, obtaining solution A with different pH values after acid-base neutralization reaction, regulating the temperature of the solution A to 52 ℃, vacuumizing to the vacuum degree of-0.095 MPa, and vacuumizing for 1h;
(2) After the temperature of the solution A is regulated to 20 ℃, 59g of cocoyl chloride is dripped into the solution A, when the pH value is reduced to 8-11, 43g of sodium hydroxide solution with the solute mass fraction of 32% is synchronously dripped to obtain a solution B, and the flow rates of the acyl chloride and the sodium hydroxide are properly regulated in the reaction process, so that the temperature of the solution B is kept between 10 ℃ and 30 ℃ and the pH value is 8-11;
(3) After the dripping is completed, continuing to react for 1h, adding 0.8g of chloroacetic acid into the solution B, controlling the pH value to be 7-9, adjusting the temperature to be 50-80 ℃, and keeping the temperature (reaction) for 3h to obtain a solution C;
(4) And adding sodium hydroxide into the solution C until the pH value is 9-12, regulating the temperature of the solution C to 90-95 ℃, reacting for 2 hours, and cooling to obtain the cocoyl sodium glycinate surfactant product.
The content of sodium cocoyl glycinate and the residual amount of ammonia in the corresponding surfactant products at different pH in step (1) of this example are shown in Table 1 below.
TABLE 1 test results for example 1
| Sequence number | PH value of | Content of sodium cocoyl glycinate | Residual amount of ammonia gas |
| 1 | 10.4 | 25.5％ | 21ppm |
| 2 | 11.2 | 25.4％ | 17ppm |
| 3 | 12.2 | 25.4％ | 3ppm |
| 4 | 13.4 | 25.2％ | 2ppm |
| 5 | 14.0 | 23.6％ | 2ppm |
As shown in table 1, as the pH of the solution a in step (1) gradually increases, the ammonia residual amount in the product gradually decreases, and when the pH reaches 12.2, the ammonia residual amount in the product significantly decreases; however, when the pH value is raised to 14.0, the ammonia gas content in the product is not further reduced, but the content of an active substance (sodium cocoyl glycinate) in the product is reduced. Therefore, the too high pH value of the solution A in the step (1) can lead to the reduction of the content of the effective substances, while the too low pH value of the solution A can lead to the higher ammonia residue in the product, so that the removal effect is not obvious.
Example 2
The glycine surfactant is prepared by the following method, and the specific preparation steps comprise the following steps:
(1) Adding 21g of glycine, 165g of deionized water and 33g of sodium hydroxide solution with the solute mass fraction of 32% into a reaction kettle, mixing and stirring uniformly at room temperature, obtaining solution A with the pH value of 12.2 after acid-base neutralization reaction, regulating the temperature of the solution A to 52 ℃, vacuumizing to the vacuum degree of-0.095 MPa, and vacuumizing for 1h;
(2) After the temperature of the solution A is regulated to 25 ℃, 59g of lauroyl chloride is dripped into the solution A, when the pH value is reduced to 8-11, 43g of sodium hydroxide solution with the solute mass fraction of 32% is synchronously dripped to obtain a solution B, and the flow rates of the acyl chloride and the sodium hydroxide are properly regulated in the reaction process, so that the temperature of the solution B is kept between 10 ℃ and 30 ℃ and the pH value is 8-11;
(3) After the dripping is completed, continuing to react for 3 hours, adding chloroacetic acid into the solution B, controlling the pH value to be 7-9, adjusting the temperature to 50 ℃, and keeping the temperature (reaction) for 4 hours to obtain a solution C;
(4) And adding sodium hydroxide into the solution C until the pH value is 9-12, regulating the temperature of the solution C to 90-95 ℃, reacting for 2 hours, and cooling to obtain the sodium lauroyl glycinate surfactant product.
The residual amounts of dimethylamine and glycolic acid corresponding to the surfactant product prepared in step (3) of this example under the different chloroacetic acid addition conditions are shown in table 2 below.
TABLE 2 test results for example 2
Example 3
The glycine surfactant is prepared by the following method, and the specific preparation steps comprise the following steps:
(1) Adding 21g of glycine, 165g of deionized water and 33g of sodium hydroxide solution with the solute mass fraction of 32% into a reaction kettle, mixing and stirring uniformly at room temperature, obtaining solution A with the pH value of 12.2 after acid-base neutralization reaction, regulating the temperature of the solution A to 52 ℃, vacuumizing to the vacuum degree of-0.095 MPa, and vacuumizing for 1h;
(2) After the temperature of the solution A is regulated to 25 ℃, 59g of lauroyl chloride is dripped into the solution A, when the pH value is reduced to 8-11, 43g of sodium hydroxide solution with the solute mass fraction of 32% is synchronously dripped to obtain a solution B, and the flow rates of the acyl chloride and the sodium hydroxide are properly regulated in the reaction process, so that the temperature of the solution B is kept between 10 ℃ and 30 ℃ and the pH value is 8-11;
(3) After the dripping is completed, continuing to react for 3 hours, adding chloroacetic acid into the solution B, controlling different pH values, adjusting the temperature to 50 ℃, and keeping the temperature (reaction) for 4 hours to obtain a solution C;
(4) And adding sodium hydroxide into the solution C until the pH value is 9-12, regulating the temperature of the solution C to 90-95 ℃, reacting for 2 hours, and cooling to obtain the sodium lauroyl glycinate surfactant product.
The corresponding dimethylamine residue in the surfactant product prepared in step (3) of this example at different pH values is shown in Table 3 below.
TABLE 3 test results for example 3
| Sequence number | PH value of | Dimethylamine residue |
| 1 | 6.0 | 5ppm |
| 2 | 7.1 | ≤1ppm |
| 3 | 8.2 | ≤1ppm |
| 4 | 9.1 | ≤1ppm |
| 5 | 10.3 | 7ppm |
Example 4
The glycine surfactant is prepared by the following method, and the specific preparation steps comprise the following steps:
(1) Adding 21g of glycine, 165g of deionized water and 33g of sodium hydroxide solution with the solute mass fraction of 32% into a reaction kettle, mixing and stirring uniformly at room temperature, obtaining solution A with the pH value of 12.2 after acid-base neutralization reaction, regulating the temperature of the solution A to 52 ℃, vacuumizing to the vacuum degree of-0.095 MPa, and vacuumizing for 1h;
(2) After the temperature of the solution A is regulated to 25 ℃, 59g of lauroyl chloride is dripped into the solution A, when the pH value is reduced to 8-11, 43g of sodium hydroxide solution with the solute mass fraction of 32% is synchronously dripped to obtain a solution B, and the flow rates of the acyl chloride and the sodium hydroxide are properly regulated in the reaction process, so that the temperature of the solution B is kept between 10 ℃ and 30 ℃ and the pH value is 8-11;
(3) After the completion of the dropwise addition, the reaction was continued for 3 hours, and then 0.8g of chloroacetic acid was added to the solution B, the pH value was controlled to 8, and the heat preservation (reaction) time was 4 hours at different temperatures in Table 4 to obtain a solution C;
(4) And adding sodium hydroxide into the solution C until the pH value is 9-12, regulating the temperature of the solution C to 90-95 ℃, reacting for 2 hours, and cooling to obtain the sodium lauroyl glycinate surfactant product.
The corresponding dimethylamine residue in the surfactant product prepared in step (3) of this example under different temperature conditions is shown in table 4 below.
TABLE 4 test results for example 4
| Sequence number | Reaction temperature | Dimethylamine residue |
| 1 | 40℃ | 14ppm |
| 2 | 50℃ | ≤1ppm |
| 3 | 60℃ | ≤1ppm |
| 4 | 70℃ | ≤1ppm |
| 5 | 80℃ | ≤1ppm |
| 6 | 90℃ | 9ppm |
Example 5
The glycine surfactant is prepared by the following method, and the specific preparation steps comprise the following steps:
(1) Adding 21g of glycine, 165g of deionized water and 33g of sodium hydroxide solution with the solute mass fraction of 32% into a reaction kettle, mixing and stirring uniformly at room temperature, obtaining solution A with the pH value of 12.2 after acid-base neutralization reaction, regulating the temperature of the solution A to 52 ℃, vacuumizing to the vacuum degree of-0.095 MPa, and vacuumizing for 1h;
(2) After the temperature of the solution A is regulated to 25 ℃, 59g of lauroyl chloride is dripped into the solution A, when the pH value is reduced to 8-11, 43g of sodium hydroxide solution with the solute mass fraction of 32% is synchronously dripped to obtain a solution B, and the flow rates of the acyl chloride and the sodium hydroxide are properly regulated in the reaction process, so that the temperature of the solution B is kept between 10 ℃ and 30 ℃ and the pH value is 8-11;
(3) After the completion of the dropwise addition, the reaction was continued for 3 hours, and then 0.8g of chloroacetic acid was added to the solution B, the pH was controlled to 8, the temperature was adjusted to 50℃and the heat preservation (reaction) time was as shown in Table 5 below, to obtain a solution C;
(4) And adding sodium hydroxide into the solution C until the pH value is 9-12, regulating the temperature of the solution C to 90-95 ℃, reacting for 2 hours, and cooling to obtain the sodium lauroyl glycinate surfactant product.
The corresponding dimethylamine residue in the surfactant product prepared in step (3) of this example under different reaction time conditions is shown in table 5 below.
TABLE 5 test results for example 5
| Sequence number | Reaction time | Dimethylamine residue |
| 1 | 1h | 11ppm |
| 2 | 2h | ≤1ppm |
| 3 | 3h | ≤1ppm |
| 4 | 4h | ≤1ppm |
| 5 | 5h | ≤1ppm |
| 6 | 6h | ≤1ppm |
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. A method for reducing amine byproducts in glycine surfactants, comprising the steps of:
(1) Mixing glycine, sodium hydroxide and water at room temperature, stirring uniformly, carrying out acid-base neutralization reaction to obtain solution A with pH value of 12-13.5, regulating the temperature of the solution A to 40-60 ℃, and maintaining the temperature for 0.5-2h under the condition that the vacuum degree is not lower than-0.095 MPa;
(2) After the temperature of the solution A is regulated to 10-30 ℃, dropwise adding acyl chloride into the solution A, synchronously starting dropwise adding sodium hydroxide solution to obtain solution B when the pH value is 8-11, and regulating the pH value of the solution B to be 8-11;
(3) After the dripping is completed, chloroacetic acid is added into the solution B to obtain a solution C;
(4) Adding sodium hydroxide into the solution C until the pH value is 9-12, and ending the reaction;
The addition amount of chloroacetic acid in the step (3) is 2-6wt% of glycine in the step (1), the pH value of the solution C is 7-9, the temperature of the solution C is 50-80 ℃, and the heat preservation time of the solution C is 2-5h.
2. The method for reducing amine byproducts in a glycine surfactant of claim 1, wherein sodium hydroxide in step (1) is sodium hydroxide solution, and the solute mass fraction of the sodium hydroxide solution is 32%.
3. The method for reducing amine byproducts in a glycine surfactant of claim 1, wherein the solute mass fraction of the sodium hydroxide solution in the step (2) is 32%, and the dropping time of the sodium hydroxide solution is 1 to 5 hours.
4. The method for reducing amine byproducts in a glycine surfactant of claim 1, wherein the temperature of the solution C in the step (4) is 90-95 ℃ and the reaction time is 2-5h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0761957A (en) * | 1993-08-25 | 1995-03-07 | Ajinomoto Co Inc | Production of n-mixed saturated fatty acid acyl neutral amino acid |
| CN103467324A (en) * | 2013-09-26 | 2013-12-25 | 潍坊祥维斯化学品有限公司 | Preparation method of N, N-dimethylglycine for industrial production |
| CN109627179A (en) * | 2018-12-26 | 2019-04-16 | 江南大学 | A kind of synthetic method of N- fatty acid acylamino acid salt |
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| DE102007055265A1 (en) * | 2007-11-20 | 2009-05-28 | Clariant International Ltd. | Process for the preparation of acylglycinates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0761957A (en) * | 1993-08-25 | 1995-03-07 | Ajinomoto Co Inc | Production of n-mixed saturated fatty acid acyl neutral amino acid |
| CN103467324A (en) * | 2013-09-26 | 2013-12-25 | 潍坊祥维斯化学品有限公司 | Preparation method of N, N-dimethylglycine for industrial production |
| CN109627179A (en) * | 2018-12-26 | 2019-04-16 | 江南大学 | A kind of synthetic method of N- fatty acid acylamino acid salt |
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