CN109942450A - It is amino acid type chelated dose a kind of and its preparation method and application - Google Patents
It is amino acid type chelated dose a kind of and its preparation method and application Download PDFInfo
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- CN109942450A CN109942450A CN201910238035.1A CN201910238035A CN109942450A CN 109942450 A CN109942450 A CN 109942450A CN 201910238035 A CN201910238035 A CN 201910238035A CN 109942450 A CN109942450 A CN 109942450A
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Abstract
The invention discloses amino acid type chelated dose of one kind, and general formula is as follows, and wherein R is CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2OCH2Or CH2CH2OCH2CH2；R1, R2For CH2CH2Or CH2CH2CH2.The amino acid type chelated dose of sequestering power with higher and preferable biological degradability are the preferable substitutes of EDTA in chelating agent application field.The invention also discloses amino acid type chelated dose of the preparation methods, synthesize to obtain by amidation process with bridging reagent for acidic amino acid.
Description
Technical field
The present invention relates to a kind of chelating agents, more particularly to a kind of amino acid type chelated dose and the system of the chelating agent
Preparation Method and its application.
Background technique
Metallic atom or ion are acted on the ligand containing two or more coordination atoms, and generating has cyclic annular knot
The chelate of structure.The ligand substance of chelate can be generated chelating agent.A small amount of chelating agent is added in the system of needs, it can be with
Metal ion in effective articulated system, reduces and negatively affects caused by metal ion, reaches application or technique requirement.Chela
Mixture has extensive demand in daily washing, water process, weaving, papermaking, agricultural, medicine and other fields.
Common chelating agent mainly has phosphate, carboxylic acid, amino carboxylic acid and polycarboxylic acid.Phosphate is mainly trimerization
Sodium phosphate (STPP), was once widely used in the daily necessities such as washing powder and industrial circle, but its there are high temperature easily to decompose, phosphorus
Discharge the disadvantages of water eutrophication is caused to environment, various countries put into effect the use that relevant laws and regulations limit phosphorous chemicals in succession,
Phosphonate chelating agent fades out market gradually.Carboxylic acid mainly has sodium gluconate, sodium citrate, sodium tartrate etc., general to chelate
Ability is poor, and price is higher, influences its use, only uses at present in some specific areas.Polycarboxylic acid chelating agent belongs to height
Molecule chelating agent has both peptizaiton, but sequestering power is poor in addition to sequestering power, usually as answering for other chelating agents
It is used with object.Amino carboxylic acid quasi-chelate compound chelate effect is preferable, and typical such as ethylenediamine tetra-acetic acid (EDTA) can be complexed a variety of
Metal ion forms 1:1 compound with various metals ion, and chelating ability is good, however EDTA biological degradability is poor, to environment
Less friendly, in Europe etc., country has limited use, disables in certain fields；The chelate that nitrilotriacetic acid (NTA) generates
Stablize, price is advantageous, but toxicity height has carcinogenic risk；Diethylene triamine pentacetic acid (DTPA) (DTPA) may have human body and fetus
Evil.
Novel biological degradability is good, sequestering power is strong, environmental type chelating agent is increasingly taken seriously, the market demand
Also increasing.
Summary of the invention
The purpose of the present invention is to provide amino acid type chelated dose of one kind and preparation method thereof, above-mentioned chelating agent is overcome to exist
Sequestering power is poor, the disadvantages of biological degradability is poor, the amino acid type chelated dose of sequestering power with higher and preferably
Biological degradability, be a kind of new environmental type chelating agent.
Another object of the present invention, which also resides in, provides amino acid type chelated dose of the application.
For achieving the above object, the present invention adopts the following technical scheme:
It is amino acid type chelated dose a kind of, general formula are as follows:
Or
Wherein R is CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2OCH2Or
CH2CH2OCH2CH2；R1, R2For CH2CH2Or CH2CH2CH2。
The invention further relates to amino acid type chelated dose of the preparation methods, pass through acyl for acidic amino acid and bridging reagent
Aminating reaction synthesizes to obtain.Used acidic amino acid is glutamic acid and/or aspartic acid or their salt；Bridging examination
Agent is selected from ethanedioly chloride, malonyl chloride, succinyl chloride, glutaryl chlorine, Adipoyl Chloride, pimeloyl chloride, the double methyl esters of ethanedioic acid, diethyl
Glycol bischloroformates or dipropylene glycol bischloroformates；
Acidic amino acid is dissolved in the mixed liquor of water or water and organic solvent, is stirred, dripped at 0-40 DEG C
Add bridging reagent, the pH of alkaline agent control reaction mixture is added dropwise, maintains 0-40 DEG C to complete to reaction, the amino acid pattern is made
Chelating agent.
Reaction product obtained by the above method is crude product, can directly be used, or further rotary evaporation in vacuo removes
After removing water or solvent, acidification, dehydrated alcohol is refining to obtain high-purity product.
In the above method, the molar ratio of the acidic amino acid and bridging reagent is preferably 1.8-2.7:1.
In the above method, the alkaline agent is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide or triethanolamine etc..
In the above method, the pH for controlling reaction mixture is preferably 8~11.
In the above method, the mixed liquor of the water and organic solvent, organic solvent is usually methylene chloride, acetone, four
The volume ratio of hydrogen furans, isopropanol or propylene glycol, water and organic solvent is 1:1-1:7.
Acidic amino acid such as glutamic acid, aspartic acid tool is there are two carboxyl, while active group amino again, using spreading out
Two amino acid are connected as polyaminocarboxylic acid's structure by raw reaction, but are different from EDTA, of the present invention amino acid type chelated
It is connected as amide groups rather than the alkylamine of EDTA for agent, and amide structure has better biological degradability.Four carboxyls simultaneously
Structure provide good sequestering power for it, can preferably bind metal ion, can in daily washing, water process, weave, make
Paper, agricultural, medicine and other fields have a wide range of applications.
The invention further relates to described amino acid type chelated dose to remove or trap the application in polyvalent metal ion.
Of the invention amino acid type chelated dose has preferable sequestering power, can be widely used for chelating agent, corrosion inhibiter, surface
Reinforcing agent etc. is cleaned, application field involves a need to stablize the purposes of polyvalent metal ion, such as daily chemicals field prevents hard water from depositing,
It can also be used in water treatment agent, washing additive, illumination chemicals, papermaking chemical product, oil field chemical, boilercompound and divide
Analyse the fields such as reagent.Usage amount is usually 0.1-5%, compound with other chelating agents in practical application and reaches better effect
Fruit such as compounds with polycarboxylic acid and can get more preferably chelating ability and dispersion effect.
The utility model has the advantages that of the invention amino acid type chelated dose is to be obtained by amino acid derived, and amino acid starting material is paddy
The fermented approach of object obtains, and meets the theory and trend of sustainable development, is environmental type chelating agent.Amino acid of the invention
Chelating agent contains 4 carboxylic groups, has good chemical stability, good water solubility, chelating ability is good, is better than
EDTA is the preferable substitute of EDTA in chelating agent application aspect, has practical reference value.Described by this method preparation
Amino acid type chelated dose of mild condition, subsequent purification separation process is simple, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is amino acid type chelated dose prepared by embodiment 2, raw material sodium glutamate, diethylene glycol bischloroformates
Infrared spectrogram.
Specific embodiment
Following embodiment in the range of the design of technical solution of the present invention and objective, give detailed embodiment and
Specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
Two aspartic acid of succinyl base and its preparation:
Aspartic acid is soluble in water, and it is 0 DEG C that ice-water bath, which keeps temperature,.Succinyl chloride is added dropwise dropwise
(ClCOCH2CH2COCl) into reaction solution, at the same the NaOH solution of dropwise addition 10%, the molar ratio of aspartic acid and succinyl chloride
For 2.3:1, control reaction pH is 8~10, maintains the temperature at 0~15 DEG C, time for adding 4 hours, then it is small in 25~35 DEG C of heat preservations 1
When, product is obtained, with titration measuring content, and calculating conversion ratio is 78%.
Embodiment 2
The preparation of two sodium glutamate of diethylene glycol diformyl:
Sodium glutamate is soluble in water, methylene chloride is added and is sufficiently stirred, the volume ratio of water and methylene chloride is 1:7, ice
It is 0 DEG C that water-bath, which keeps temperature,.Diethylene glycol bischloroformates are then added dropwise dropwise into reaction dissolvent, sodium glutamate and diethyl two
The molar ratio of alcohol bischloroformates is 1.8:1, while 10% KOH solution is added dropwise, and control reaction pH is 9~10, dropwise reaction 4
Hour, then 1 hour is kept the temperature at 30~40 DEG C.Liquid separation removes organic solvent after standing, and rotary evaporation in vacuo obtains after removing water
Crude product is washed 2 times with dehydrated alcohol after vacuum filtration and is obtained solid product with 10ml 1mol/L salt acid elution crude product, is dripped
Determining method measurement content is 97.0%.
Embodiment 3~8
Different aminoacids and bridging agent are selected according to the method for embodiment 1, using different proportions, solvent and neutralizer system
It is amino acid type chelated dose standby, and its conversion ratio is measured, as a result such as table 1.
Table 1
The test of embodiment nine amino acid type chelating agent dispersion of calcium soap
Soap and calcium, magnesium easily form indissoluble fatty acid calcium, fatty acid magnesium, and addition chelating agent is then able to maintain metallic soap and does not sink
It forms sediment muddy, usually with enuatrol, the mass fraction of required chelated dispersants indicates the dispersing agent in the hard water of 330mg/L concentration
Dispersion index (LSDP%), the value is lower, and chelating ability and dispersion force are stronger.
At room temperature, drawing 5mL concentration is that 5g/L sodium oleate solution has in plug graduated cylinder in 100mL, and appropriate 2.5g/L is added
Chelating agent solution (i.e. experimental liquid is advisable with 5ml) is added 10mL hard water, adds water to 30ml and jump a queue, and reverses 20 times, every time
The case where returning to initial position, standing 30s, observe calcium soap grain, if there is coagulative precipitation between clear solution, illustrates dispersing agent
Dosage is inadequate, and the dosage of Ying Zengjia dispersing agent disperses condensation product all in pipe, until be translucent in graduated cylinder, no bulk
It is terminal that condensation product, which exists,.The dosage for recording dispersing agent in corresponding colorimetric cylinder, calculates calcium soap dispersion index (LSDP).
Contrast test EDTA calcium soap dispersion index, result are the soap of 2 diethylene glycol diformyl of embodiment, two sodium glutamate
The calcium soap dispersion index that dispersion index is 18%, EDTA is 19%, shows that 2 product dispersion of calcium soap of embodiment is higher than EDTA.
Application in 10 laundry liquid formulation of embodiment
In the liquid detergent of product application prepared by embodiment 1, formula (wt%) is as shown in table 2 below:
Table 2
| Raw material | Formula 1 | Formula 2 | Formula 3 |
| AES-70 (70%) | 15 | 15 | 15 |
| AEO-9 | 5 | 5 | 5 |
| Amine-oxides OB-2 (30%) | 5 | 5 | 5 |
| Polyacrylic acid maleic anhydride | 1.5 | 1.5 | 1.5 |
| 1 product of embodiment | 0.5 | 1 | - |
| EDTA | - | - | 0.5 |
| Water | To 100 | To 100 | To 100 |
Chelating agent can prevent doped calcium for detergent, and the deposition of calcium will lead to the decline of detergent detergency, to preparation
Liquid detergent be respectively formulated and carry out detergency test, be control with standard stain release powder, as a result such as table 3.
Table 3
| Project | Formula 1 | Formula 2 | Formula 3 | Standard stain release powder |
| Carbon black detergency | 12.76 | 13.96 | 13.56 | 9.62 |
| Albumen detergency | 17.7 | 17.79 | 17.83 | 3.14 |
| Skin ester detergency | 11.1 | 12.14 | 11.65 | 8.49 |
The result shows that the liquid detergent detergency that addition embodiment 1 prepares product is suitable with the addition liquid detergent result of EDTA,
Increasing chelating agent usage amount can be improved detergency, and of the invention amino acid type chelated dose can effectively prevent soap scum suspended matter function
The formation of substance, using good in terms of washing assisant.
Claims (6)
1. amino acid type chelated dose a kind of, which is characterized in that general structure are as follows:
Wherein, R CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2OCH2Or
CH2CH2OCH2CH2；R1, R2For CH2CH2Or CH2CH2CH2。
2. amino acid type chelated dose of preparation method described in claim 1, which is characterized in that try acidic amino acid and bridging
Agent carries out amidation process, and the acidic amino acid is glutamic acid and/or aspartic acid or their salt；Bridging reagent
Selected from ethanedioly chloride, malonyl chloride, succinyl chloride, glutaryl chlorine, Adipoyl Chloride, pimeloyl chloride, the double methyl esters of ethanedioic acid, diethyl two
Alcohol bischloroformates or dipropylene glycol bischloroformates；
Acidic amino acid is dissolved in the mixed liquor of water or water and organic solvent, is stirred, bridge is added dropwise at 0-40 DEG C
The pH of alkaline agent control reaction mixture is added dropwise in even reagent, maintains 0-40 DEG C to complete to reaction, is made described amino acid type chelated
Agent.
3. amino acid type chelated dose of preparation method according to claim 2, which is characterized in that the acidic amino acid
Molar ratio with bridging reagent is 1.8-2.7:1.
4. amino acid type chelated dose of preparation method according to claim 2, which is characterized in that the alkaline agent is selected from hydrogen
Sodium oxide molybdena, potassium hydroxide, ammonium hydroxide or triethanolamine.
5. amino acid type chelated dose of preparation method according to claim 2, which is characterized in that in the above method, control
The pH of reaction mixture is 8~11.
6. amino acid type chelated dose of preparation method according to claim 2, which is characterized in that the water with it is organic molten
The mixed liquor of agent, organic solvent are selected from methylene chloride, acetone, tetrahydrofuran, isopropanol or propylene glycol, the body of water and organic solvent
Product ratio is 1:1-1:7.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391466A (en) * | 1992-11-25 | 1995-02-21 | Konica Corporation | Chemical compositions and a processing method using the same for processing silver halide photographic light-sensitive material |
| WO2002022627A2 (en) * | 2000-09-15 | 2002-03-21 | Georgetwon University | Ligands for metabotropic glutamate receptors |
| CN1405150A (en) * | 2001-09-17 | 2003-03-26 | 中国科学院过程工程研究所 | Protein modifier, preparation method and use thereof |
| US20090311338A1 (en) * | 2006-04-24 | 2009-12-17 | Incept Llc | Crosslinking methods and applications thereof |
| WO2013028664A1 (en) * | 2011-08-22 | 2013-02-28 | Siemens Medical Solutions Usa, Inc. | Psma imaging agents |
| CN104649927A (en) * | 2013-11-25 | 2015-05-27 | 刘现梅 | N-undecane diacyl diglutamic acid triethanolamine salt and preparation method thereof |
| CN104649926A (en) * | 2013-11-25 | 2015-05-27 | 刘现梅 | N,N'-sebacoyl biaspartic acid and preparation method thereof |
| EP2797900B1 (en) * | 2011-12-30 | 2016-09-28 | Stratoxer(S) Kft. | Complex-forming compounds |
| CN109400492A (en) * | 2018-12-26 | 2019-03-01 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of four sodium of aspartic acid oxalic acid |
-
2019
- 2019-03-27 CN CN201910238035.1A patent/CN109942450A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391466A (en) * | 1992-11-25 | 1995-02-21 | Konica Corporation | Chemical compositions and a processing method using the same for processing silver halide photographic light-sensitive material |
| WO2002022627A2 (en) * | 2000-09-15 | 2002-03-21 | Georgetwon University | Ligands for metabotropic glutamate receptors |
| CN1405150A (en) * | 2001-09-17 | 2003-03-26 | 中国科学院过程工程研究所 | Protein modifier, preparation method and use thereof |
| US20090311338A1 (en) * | 2006-04-24 | 2009-12-17 | Incept Llc | Crosslinking methods and applications thereof |
| WO2013028664A1 (en) * | 2011-08-22 | 2013-02-28 | Siemens Medical Solutions Usa, Inc. | Psma imaging agents |
| EP2797900B1 (en) * | 2011-12-30 | 2016-09-28 | Stratoxer(S) Kft. | Complex-forming compounds |
| CN104649927A (en) * | 2013-11-25 | 2015-05-27 | 刘现梅 | N-undecane diacyl diglutamic acid triethanolamine salt and preparation method thereof |
| CN104649926A (en) * | 2013-11-25 | 2015-05-27 | 刘现梅 | N,N'-sebacoyl biaspartic acid and preparation method thereof |
| CN109400492A (en) * | 2018-12-26 | 2019-03-01 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of four sodium of aspartic acid oxalic acid |
Non-Patent Citations (3)
| Title |
|---|
| MARGULIS, M. N.ETAL: "Effect of double derivatives of glutamic acid on mollusk neurons", 《NEIROFIZIOLOGIYA》 * |
| T. AHAMAD ETAL: "Synthesis, characterization and anti-microbial activity of poly(ethylene oxamide-N,N0-disuccinate) and its polymer metal complexes", 《JOURNAL OF COORDINATION CHEMISTRY》 * |
| 王军等: "N-十二酰基天冬氨酸及其钠盐的合成与性能", 《精细石油化工》 * |
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