Homoserine-N, N-diacetate, preparation method and application thereof
Through the reaction of homoserine with chloroacetic acid and alkali solution, the preparation process of homoserine-N,N-diacetate is simplified, the problem of using highly toxic raw materials and complex processes in the prior art is solved, and high-purity products are achieved The preparation and good biodegradability can replace EDTA as a chelating agent.
Patent Information
- Application Number
- CN202410474937.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-19
- Publication Date
- 2024-12-13
AI Technical Summary
The existing industrial synthesis route of homoserine-N,N-diacetate is complex, and uses highly toxic hydrogen cyanate, which is difficult to control the process, and it is difficult to handle by-products, which affects the environment.
Homoserine or its metal salt is used to react with chloroacetic acid and alkali liquid, and filter it after hydrolysis to obtain high-purity homoserine-N,N-diacetate, avoid the use of highly toxic raw materials such as hydrocyanic acid, and simplify the process route.
It has achieved safe and reliable preparation of homoserine-N,N-diacetate, high product purity, improved process greening, and good biodegradability and chelation ability. It can replace EDTA as a chelating agent.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of compound preparation, and in particular, relates to homoserine-N,N-diacetic acid (or salt), a preparation method and application thereof. Background Art
[0002] Chelating agents form two or more coordinated covalent bonds with metal ions to form water-soluble metal complexes, so they are widely used in various industries and commerce, including metal processing, water treatment, textiles, cleaning, detergent formulations, and cosmetics. Chelating agents can chelate metal ions to form stable soluble complexes. In daily chemicals, they can be used as detergent auxiliaries and detergent auxiliaries; in industry, they can be used as descaling agents and scale inhibitors, and can also decompose metal salts and hydroxides to clean insoluble salt scales in various industries. At present, most traditional chelating agents on the market are aminocarboxylates, such as NTA, EDTA, citrate and other chelating agents. The main disadvantage of this type of chelating agent is that it cannot be biodegraded and has a great impact on the environment. Therefore, research on alternatives has emerged to address environmental issues.
[0003] Homoserine-N,N-diacetate is a small molecule amino acid chelating agent, which is easily biodegradable, non-toxic, and has high chelating ability. It can quickly act on inorganic and organic dirt. It is used in fabric detergents, automatic dishwashing detergents, and cleaning of inorganic precipitates. It is a biodegradable product that the chelating agent industry attaches great importance to. At the same time, homoserine-N,N-diacetate is a metal ion chelating agent that can chelate metal ions to form stable soluble complexes. It can be used as a descaling agent and scale inhibitor to increase the cleaning ability of washing powder, washing liquid and soap detergent.
[0004] Homoserine-N,N-diacetate salts have excellent biodegradability and can be used as a substitute for the chelating agent EDTA.
[0005] At present, the industrialized synthesis route of homoserine-N,N-diacetate is mainly through the Strecher reaction, but the reaction raw materials can be different and can be divided into two categories. One is the Strecher reaction of alanine with hydrocyanic acid and formaldehyde, followed by hydrolysis and saponification to obtain the product; the other is the Strecher reaction of iminodiacetonitrile with hydrocyanic acid and acetaldehyde, followed by hydrolysis and saponification to obtain the product. From the perspective of the reaction medium, it can be carried out in an alkaline medium or in an acidic medium.
[0006] These two processes require high production equipment and are difficult to control. They use highly toxic hydrocyanic acid, are difficult to treat cyanide-containing wastewater, and have residual aldehydes in the product. Therefore, the key to synthetic process innovation is to develop new non-toxic raw material alternatives, realize the recycling of by-products, and improve the greenness of the production process. Summary of the invention
[0007] The purpose of the present invention is to overcome the problems existing in the prior art and provide a homoserine-N,N-diacetate, a preparation method and an application thereof. The raw materials used in the preparation process of the homoserine-N,N-diacetate of the present invention are safe and reliable, the process route is simple, and the obtained product has high purity.
[0008] The purpose of the present invention and its solution are achieved through the following scheme:
[0009] The first aspect of the present invention provides a homoserine-N,N-diacetate having a structure as shown in formula (1):
[0010]
[0011] In the formula, X1 to X3 are hydrogen or metal atoms.
[0012] The second aspect of the present invention provides a method for preparing homoserine-N,N-diacetate, the method comprising the following steps:
[0013] Adding chloroacetic acid and alkali solution to homoserine or its metal salt to react, and hydrolyzing excess chloroacetic acid after the reaction is completed to obtain a crude product of homoserine-N,N-diacetate;
[0014] The obtained crude homoserine-N,N-diacetate is filtered through a nanofiltration membrane to obtain high-purity homoserine-N,N-diacetate.
[0015] Preferably, the molar ratio of homoserine or its metal salt to chloroacetic acid is 1:1 to 1:2, preferably 1:1.2 to 1:1.6.
[0016] Preferably, the mass percentage concentration of the alkali solution is 10-50%.
[0017] Preferably, the base comprises sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
[0018] Preferably, the reaction conditions are: temperature of 50-100° C., preferably 60-90° C.; time of 1-8 h; pH of 7-12.
[0019] Preferably, an alkali solution is used to hydrolyze excess chloroacetic acid.
[0020] Preferably, the mass percentage concentration of the alkali solution is 10-50%.
[0021] Preferably, the base comprises sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
[0022] Preferably, the conditions for hydrolyzing the excess chloroacetic acid are: temperature 50-100° C., preferably 80-100° C.; time 1-8 hours; pH 9-12.
[0023] Finally, the present invention also provides a use of homoserine-N,N-diacetate prepared according to the aforementioned homoserine-N,N-diacetate or its preparation method in the preparation of daily chemical products or industrial products.
[0024] By means of the above technical scheme, the present invention has at least the following advantages: the present invention uses homoserine as a raw material for the first time to prepare homoserine-N,N-diacetate, and the homoserine-N,N-diacetate is used as a chelating agent as a new compound for the first time, and the chelating ability is equivalent to that of EDTA, and it has good biodegradability. The raw materials used in the present invention do not involve raw materials such as hydrocyanic acid, sodium cyanate, formaldehyde or acetaldehyde, the raw materials are safe and reliable, and the process route is simple.
[0025] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the preferred embodiments of the present invention are described in detail as follows. DETAILED DESCRIPTION
[0026] In order to make the technical means, creative features, objectives and effects of the present invention easy to understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0027] According to a method for preparing homoserine-N,N-diacetate of the present invention, the method comprises the following steps:
[0028] Adding chloroacetic acid and alkali solution to homoserine or its metal salt to react, and after the reaction is completed, hydrolyzing excess chloroacetic acid to obtain a crude homoserine-N,N-diacetate;
[0029] The obtained crude homoserine-N,N-diacetate is filtered through a nanofiltration membrane to obtain high-purity homoserine-N,N-diacetate.
[0030] In some preferred embodiments, homoserine-N,N-diacetate has a structure as shown in formula (1):
[0031]
[0032] In the formula, X1 to X3 are hydrogen or metal atoms.
[0033] In some preferred embodiments, homoserine or its metal salt has a structure as shown in formula (2):
[0034]
[0035] In the formula, X1 is hydrogen or a metal atom.
[0036] In some preferred embodiments, the molar ratio of homoserine or its metal salt to chloroacetic acid is 1:1 to 1:2, preferably 1:1.2 to 1:1.6, for example, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or 1:1.6.
[0037] In some preferred embodiments, the mass percentage concentration of the alkali solution is 10-50%, for example, it can be 10%, 20%, 30%, 40% or 50%.
[0038] In some preferred embodiments, the base can be any suitable base in the art, including but not limited to sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
[0039] In some preferred embodiments, the reaction conditions are: temperature of 50-100°C, preferably 60-90°C, for example, 60°C, 70°C, 80°C or 90°C; time of 1-8h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h; pH of 7-12, for example, 7, 8, 9, 10, 11 or 12.
[0040] In some preferred embodiments, an alkaline solution is used to hydrolyze excess chloroacetic acid.
[0041] In some preferred embodiments, the mass percentage concentration of the alkali solution is 10-50%, for example, it can be 10%, 20%, 30%, 40% or 50%.
[0042] In some preferred embodiments, the base can be any suitable base in the art, including but not limited to sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
[0043] In some preferred embodiments, the conditions for hydrolyzing excess chloroacetic acid are: temperature 50-100°C, preferably 80-100°C, for example 80°C, 90°C or 100°C; time 1-8h, for example 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h; pH 9-12, for example 9, 10, 11 or 12.
[0044] According to another aspect of the present invention, there is provided a use of homoserine-N,N-diacetate prepared according to the aforementioned homoserine-N,N-diacetate or its preparation method in the preparation of daily chemical products or industrial products, wherein the homoserine-N,N-diacetate is used as a chelating agent.
[0045] In some preferred embodiments, the homoserine-N,N-diacetate is used as a chelating agent in daily chemical products or industrial products.
[0046] In some preferred embodiments, the effective content of homoserine-N,N-diacetate in daily chemical products or industrial products is 0.1-1.5 wt%, for example, 0.1 wt%, 0.5 wt%, 1.0 wt% or 1.5 wt%.
[0047] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.
[0048] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.
[0049] Embodiment 1:
[0050] Add 47.6g (0.4mol) of homoserine to a reaction flask, add 77g of deionized water. Heat to 80°C with mechanical stirring, dropwise add 99.2g (0.84mol) of 80% chloroacetic acid solution. Simultaneously add 166.4g (2.08mol) of 50% sodium hydroxide. Keep pH 8-10 and react for 5 hours.
[0051] 10 g of 50% sodium hydroxide was added, and the reaction solution was heated to 95° C. and stirred for 5 hours to hydrolyze the excess chloroacetic acid. The reaction solution was filtered through a 150-200 Da nanofiltration membrane to obtain a homoserine-N,N-diacetate sodium solution with an active ingredient content of 28.03%, MS (M+): 301.1.
[0052] Embodiment 2:
[0053] Add 47.6g (0.4mol) of homoserine to a reaction bottle, add 35g of deionized water. Heat to 80°C with mechanical stirring, dropwise add 118.2g (1mol) of 80% chloroacetic acid solution. At the same time, add 192g (2.4mol) of 50% sodium hydroxide. Keep the pH at 8-10 and react for 5 hours.
[0054] 10 g of 50% sodium hydroxide was added, and the reaction solution was heated to 90° C. and stirred for 5 hours to hydrolyze the excess chloroacetic acid. The reaction solution was filtered through a 150-200 Da nanofiltration membrane to obtain a homoserine-N,N-diacetate sodium solution with an active ingredient content of 29.83%, MS (M+): 301.1.
[0055] Embodiment 3:
[0056] Add 47.6g (0.4mol) of homoserine to a reaction flask, add 75g of deionized water. Heat to 60°C with mechanical stirring, dropwise add 99.2g (0.84mol) of 80% chloroacetic acid solution. Simultaneously add 233g (2.08mol) of 50% potassium hydroxide. Keep pH 8-10 and react for 5 hours.
[0057] 10 g of 50% potassium hydroxide was added, and the reaction solution was heated to 95° C. and stirred for 5 hours to hydrolyze the excess chloroacetic acid. The reaction solution was filtered through a 150-200 Da nanofiltration membrane to obtain a homoserine-N,N-diacetate potassium solution with an active ingredient content of 28.49%, MS (M+): 301.1.
[0058] Embodiment 4:
[0059] Add 47.6g (0.4mol) of homoserine to a reaction flask, add 53g of deionized water. Heat to 80°C with mechanical stirring, dropwise add 109.6g (0.92mol) of 80% chloroacetic acid solution. Simultaneously add 179.2g (2.24mol) of 50% sodium hydroxide. Keep pH 8-10 and react for 5 hours.
[0060] 10 g of 50% potassium hydroxide was added, and the reaction solution was heated to 95° C. and stirred for 4 hours to hydrolyze the excess chloroacetic acid. The reaction solution was filtered through a 150-200 Da nanofiltration membrane to obtain a homoserine-N,N-diacetate potassium solution with an active ingredient content of 29.14%, MS (M+): 301.1.
[0061] Embodiment 5:
[0062] Add 47.6g (0.4mol) of homoserine to a reaction flask, add 55g of deionized water. Heat to 80°C with mechanical stirring, dropwise add 109.6g (0.88mol) of 80% chloroacetic acid solution. Simultaneously add 241.92g (2.16mol) of 50% potassium hydroxide. Keep pH 8-10 and react for 4 hours.
[0063] 10 g of 50% potassium hydroxide was added, and the reaction solution was heated to 95° C. and stirred for 5 hours to hydrolyze the excess chloroacetic acid. The reaction solution was filtered through a 150-200 Da nanofiltration membrane to obtain a homoserine-N,N-diacetate potassium solution with an active ingredient content of 29.30%, MS (M+): 301.1.
[0064] Test example: Degreasing rate evaluation of detergent containing homoserine-N,N-diacetate
[0065] 1. Preparation of detergent formula
[0066] The formula of the homoserine-N,N-diacetate detergent in this test example is shown in Table 1 below, wherein the chelating agent is the homoserine-N,N-diacetate sodium obtained according to Example 4, and the active matter content is 29.14%.
[0067] Table 1 Formula of detergent containing homoserine-N,N-diacetate
[0068]
[0069]
[0070] Note: Total active matter refers to the content of effective ingredients.
[0071] 2. The preparation method of the above-mentioned detergent is:
[0072] Add a certain amount of deionized water into the bottle, heat it in a water bath to 40 degrees Celsius, slowly add sodium laureth sulfate while stirring, and stir until it is completely dissolved.
[0073] Keep the material temperature at 40 degrees Celsius, add cocamidopropyl betaine and disodium oleoyl glutamate in sequence while stirring, and stir to mix evenly.
[0074] The material temperature is lowered to below 40 degrees Celsius, flavors and preservatives are added, and then any one of homoserine-N,N-diacetate or methylglycine diacetate trisodium or glutamate diacetate tetrasodium is added according to the formula.
[0075] While stirring, add citric acid.
[0076] Finally, add sodium chloride and stir well to obtain the desired detergent.
[0077] 3. The degreasing rate of the homoserine-N,N-diacetate detergent was evaluated. The specific evaluation method was based on the degreasing rate method in GB / T 9985-2000 "Detergents for Hand-washing Dishware": the glass slide was smeared with artificial dirt in advance. The degreasing rate was measured by washing for 3 minutes at 30°C and 160 r / min using a vertical degreasing measuring machine.
[0078] 4. The results are shown in Table 2 below:
[0079] Oil removal rate = (m1-m2) / (m1-m0)*100%,
[0080] Among them, m0 is the mass of the slide before smearing (g); m1 is the mass of the slide after smearing (g); m2 is the mass of the stained slide after washing (g).
[0081] Table 2 Test results of oil removal filter with different detergents
[0082]
[0083] From the evaluation results of the oil removal rate of homoserine-N,N-diacetate dishwashing liquid in Table 2, it can be seen that the oil removal rate of the dishwashing liquid containing the homoserine-N,N-diacetate of the present invention is significantly better than the oil removal rate of the dishwashing liquid containing trisodium methylglycine diacetate or tetrasodium glutamate diacetate, which shows that the homoserine-N,N-diacetate of the present invention can completely replace the existing chelating agent products, and the effect is even better than the existing chelating agents.
[0084] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes by using the methods and technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.
Claims
1. A homoserine-N,N-diacetate having a structure as shown in formula (1): In the formula, X1 to X3 are hydrogen or metal atoms.
2. A method for preparing homoserine-N,N-diacetate, characterized in that: The method comprises the following steps: Adding chloroacetic acid and alkali solution to homoserine or its metal salt to react, and after the reaction is completed, hydrolyzing excess chloroacetic acid to obtain a crude homoserine-N,N-diacetate; The obtained crude homoserine-N,N-diacetate is filtered through a nanofiltration membrane to obtain high-purity homoserine-N,N-diacetate.
3. The preparation method according to claim 2, characterized in that: The molar ratio of homoserine or its metal salt to chloroacetic acid is 1:1 to 1:2, preferably 1:1.2 to 1:1.
6.
4. The preparation method according to claim 2, characterized in that: The mass percentage concentration of the alkali solution is 10-50%.
5. The preparation method according to claim 2 or 4, characterized in that: The alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
6. The preparation method according to claim 2, characterized in that: The reaction conditions are: temperature of 50-100° C., preferably 60-90° C.; time of 1-8 hours; pH of 7-12.
7. The preparation method according to claim 2, characterized in that: The excess chloroacetic acid is hydrolyzed by using an alkali solution with a mass percentage concentration of 10 to 50%.
8. The preparation method according to claim 7, characterized in that: The alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
9. The preparation method according to claim 2, characterized in that: The conditions for hydrolyzing the excess chloroacetic acid are: temperature 50-100° C., preferably 80-100° C.; time 1-8 hours; pH 9-12.
10. Use of the homoserine-N,N-diacetate according to claim 1 or the homoserine-N,N-diacetate prepared by the preparation method of the homoserine-N,N-diacetate according to any one of claims 2 to 9 in the preparation of daily chemical products or industrial products.