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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- amino acid
- acid type
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- type chelated
- chloride
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000003275 alpha amino acid group Chemical group 0.000 title 1
- 150000001413 amino acids Chemical class 0.000 claims abstract description 42
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 6
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 3
- 238000011938 amidation process Methods 0.000 claims abstract 2
- 235000001014 amino acid Nutrition 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 235000003704 aspartic acid Nutrition 0.000 claims description 6
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- -1 glutaryl chlorine Chemical compound 0.000 claims description 5
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- LVIMBOHJGMDKEJ-UHFFFAOYSA-N heptanedioyl dichloride Chemical compound ClC(=O)CCCCCC(Cl)=O LVIMBOHJGMDKEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000002738 chelating agent Substances 0.000 abstract description 24
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 11
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 229940024606 amino acid Drugs 0.000 description 27
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 17
- 229960001484 edetic acid Drugs 0.000 description 11
- 239000000344 soap Substances 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 235000013923 monosodium glutamate Nutrition 0.000 description 5
- 229940073490 sodium glutamate Drugs 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHECKPXUCKQCSH-UHFFFAOYSA-J calcium;disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Ca+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JHECKPXUCKQCSH-UHFFFAOYSA-J 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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