CN101293846B - Method for preparing ethylene diamine triacetate - Google Patents
Method for preparing ethylene diamine triacetate Download PDFInfo
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- CN101293846B CN101293846B CN2008100712284A CN200810071228A CN101293846B CN 101293846 B CN101293846 B CN 101293846B CN 2008100712284 A CN2008100712284 A CN 2008100712284A CN 200810071228 A CN200810071228 A CN 200810071228A CN 101293846 B CN101293846 B CN 101293846B
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- tetraacetic acid
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Abstract
The invention provides a method for preparing ethylene diamine triacetic acid salt from low-price and easily-accessible raw materials such as titanium tetrachloride, ethylenediamine tetraacetic acid and oxidizer. The method has simple process, environment friendliness and mass production. The preparation method comprises allowing the titanium tetrachloride and the ethylene diamine tetraacetic acid to react at a molar ratio of 1:(1-2) under stirring to obtain ethylene diamine tetraacetic acid titanium hydrate 1; adding oxidizer at a molar ratio between the titanium tetrachloride and the oxidizer of 1:(1-10), and reacting at 0-90 DEC C for 1-24h to obtain peroxy ethylene diamine tetraacetic acid titanium 2; and adjusting the pH value to 4-10 with mineral alkali, reacting at 0-90 DEC C for 24-96h to separate out peroxy ethylenediamine triacetic acid titanium chelate 4, performing alkaline hydrolysis in water bath at 0-90 DEC C and with the pH value of 8-14 for 1-48h, and separating out final product ethylene diamine triacetic acid salt 5. The product is separated in solid phase, which can be separated and purified easily.
Description
Technical field
The present invention relates to a kind of preparation method of compound, especially the preparation method of ethylene diamine triacetate.
Background technology
Chelate surfactant is the tensio-active agent of developing recently.It also has the ability of chelated metal ions except all characteristics with tensio-active agent.Sequestrant be used for metal ion in the hierarchy of control concentration and form mixture with it, make it to have and be different from the performance of original molecule separately fully.Sequestrant has purposes in a lot of fields, for example: be used for industry such as printing and dyeing, paper pulp, ore dressing, cleaning as water-softening chemicals; Be used for industry such as pharmacy, sensitization, rare metal smelting as complexing agent.More typical sequestrant has edetate (EDTA), poly-phosphate such as tri-polyphosphate (STPP) etc.The EDTA molecule is a sexadentate, and metal ion is had very strong sequestering power, is a kind of good sequestrant.And surfactant molecule is made up of tool polar " head base " and nonpolar " last-of-chain " two portions.Polar " head base " has very strong avidity to water, is also referred to as hydrophilic group (hydrophilic group), and nonpolar " last-of-chain " has very strong avidity to oil, is also referred to as oleophilic group (lipophilicgroup).So this compounds molecule has not only oleophylic but also hydrophilic amphiphilic (amphiphile), in system, be tending towards and be enriched in water/air interface or oil/water termination, reduce surface or interfacial tension, thereby have " surfactivity ".Because this functional performance, tensio-active agent extensively is used as washing composition, emulsifying agent, wetting agent, permeate agent, whipping agent etc. as main component.
At detergent applications, tensio-active agent and sequestrant (as tri-polyphosphate-STPP and EDTA etc.) obtain using the most widely.In recent years, because the problem of " eutrophication " of natural stream networks, STPP has been subjected to blame.Detergent manufacturers and scientists are racked one's brains and are sought the STPP surrogate, it is reported the surrogate of having developed tens of kinds of STPP so far.But the chelating ability that can really the reach STPP substitute of environmental sound again is also few in number.Therefore, if can develop and a kind ofly have good soil release characteristics simultaneously and the environmentally safe again novel surfactant of chelating is that people expect.The common sequestrant that generally is used for chelated metal ions, particularly hardness ions is edetate (EDTA).And ethylene diamine triacetate-ED3A also is a kind of sequestrant of excellent property.Find in the research, during the EDTA chelated metal ions, because steric effect, four aceticoceptors often have only three in action, another free group is inoperative, has formed unnecessary thing, and this unnecessary position provides a good opportunity that forms new derivative exactly.If on the ED3A molecule, introduce a fatty acyl group, just can form a tensio-active agent, Here it is N-acyl group ED3A with chelating ability.This class tensio-active agent has good chelating ability and surfactivity, and gentle, nontoxic, non-stimulated, biology is easily degraded, thereby can be widely used in Industrial products such as personal care, household supplies, is with a wide range of applications.
The nineties in 20th century, it is raw material with the ethylenediamine-N,N'-diacetic acid(EDDA) disodium salt that people such as Parker have developed one, by five steps reaction such as formaldehyde condensation, prussic acid addition, hydrolysis, cyclisation and open loop, and the technology of commercialization ground preparation ethylene diamine triacetate.Present global bar one company size is produced ethylenediamine triacetic acid.But this complex process, equipment requirements is higher, and relates to the prussiate that human body and environment is had great murder by poisoning.Therefore, development method succinct, gentle, eco-friendly scale preparation ethylene diamine triacetate the particularly important that seems.
Present ethylenediamine triacetic acid trisodium salt (Na
3ED3A) synthetic method has following 5 kinds:
1, quadrol and Mono Chloro Acetic Acid are added the mineral acid acidifying in basic solution reaction back; Mixing solutions DMF recrystallization obtains 2-oxygen-1 subsequently, 4-piperazine oxalic acid (3-KP); With 3-KP and sodium hydroxide hydrolysis open loop, obtain Na again
3ED3A.This method by product is more, needs to adopt the organic solvent recrystallization.
2, with after the mixing solutions reaction of the nitrate of disodium EDTA and palladium 2-oxygen-1,4-piperazine palladium diacetate complex compound ([Pd (3-KP)
2]).Though this method adopts Pd (II) catalyzed oxidation to obtain 2-oxygen-1, the palladium complex of 4-piperazine oxalic acid, its transformation efficiency is lower, but also relates to the problem of using and reclaiming of noble metal palladium.
3, utilize N, N '-ethylenediamine-N,N'-diacetic acid(EDDA) (S-EDDA) cyclic condensation under hcl acidifying, DMF recrystallization obtain 2-oxygen-1-piperazine acetate (S-KP); By S-KP and bromoacetic acid substitution reaction, the DMF recrystallization obtains 2-oxygen-1 again, 4-piperazine oxalic acid (3-KP); With 3-KP alkaline hydrolysis open loop, obtain Na
3ED3A.This method steps is more, adopt organic solvent and bromoacetic acid.
4, utilize N, N '-ethylenediamine-N,N'-diacetic acid(EDDA) (S-EDDA) sodium salt solution and formaldehyde condensation generate 1, the pyridine of 3-dicarboxyl Methylimidazole quinoline; Add prussic acid nucleophilic addition(Adn) open loop, generate N-cyanogen methyl-ethylenediamine-N,N'-diacetic acid(EDDA) sodium; Under weakly alkaline, be hydrolyzed into N-amide group-ethylenediamine-N,N'-diacetic acid(EDDA) sodium; N-amide group-ethylenediamine-N,N'-diacetic acid(EDDA) sodium generation intramolecularly amine exchange reaction Cheng Huan obtains 3-KP; With 3-KP alkaline hydrolysis open loop, obtain Na again
3ED3A.This method productive rate is higher, has certain value, but adopts the big prussic acid of toxicity, to environment and human body harmful.
5, utilize N, N '-ethylenediamine-N,N'-diacetic acid(EDDA) sodium (S-EDDA) acidifying generates S-KP; With S-KP and formaldehyde condensation, generate 1-carboxymethyl-4-methylol-2-oxygen piperazine again; Add prussic acid and generate 1-carboxymethyl-4-cyanogen methyl-2-oxygen piperazine; Add the appropriate bases hydrolysis again, obtain 3-KP; With 3-KP alkaline hydrolysis open loop, obtain Na at last
3ED3A.This method can obtain Na
3Purity and the productive rate of ED3A are higher, but the big raw materials of toxicity such as employing prussic acid.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with titanium tetrachloride, ethylenediamine tetraacetic acid (EDTA) and oxygenant cheap, that be easy to get, and the preparation method is succinct, the preparation method of environmental friendliness, the ethylene diamine triacetate that is produced on a large scale.
Concrete synthetic route of the present invention is as follows:
Its concrete steps are as follows:
1) mol ratio by titanium tetrachloride and ethylenediamine tetraacetic acid (EDTA) is 1: (1～2), get in the aqueous solution that titanium tetrachloride joins ethylenediamine tetraacetic acid (EDTA), obtain ethylenediamine tetraacetic acid (EDTA) titanyl hydrate 1 after the reaction;
2) mol ratio by titanium tetrachloride and oxygenant is 1: (1～10), be preferably 1: (2～6), in the mixed solution of titanium tetrachloride and ethylenediamine tetraacetic acid (EDTA) or in the ethylenediamine tetraacetic acid (EDTA) titanyl hydrate 1, add oxygenant,, obtain peroxide ethylenediamine tetraacetic acid (EDTA) titanium 2 at 0～90 ℃ of reaction 1～24h;
3) aqueous solution of peroxide ethylenediamine tetraacetic acid (EDTA) titanium 2 is 4～10 with mineral alkali adjusting pH value, obtains the peroxide thing 3 of deprotonation;
4) peroxide thing 3 is kept above-mentioned pH value under 0～90 ℃, reaction 24～96h, and best 48～72h separates out peroxide ethylenediamine triacetic acid titanium chelate 4;
5) inner complex 4 is in pH value 8～14, and 0～90 ℃ of following alkaline hydrolysis 1～48h of water-bath isolates the finished product ethylene diamine triacetate 5.
Described ethylenediamine tetraacetic acid (EDTA) is selected from homologues such as ethylenediamine tetraacetic acid (EDTA) or disodium EDTA.Described oxygenant is selected from 5%～30% hydrogen peroxide or 5%～30% Peracetic Acid etc. by mass percentage.Described mineral alkali is selected from ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus etc.
The present invention compares with the synthetic method of existing ethylenediamine triacetic acid trisodium salt, and its raw material is cheap, and synthesis technique is simple, and after reaction finished, raw material and by product were at water, and product 4 is separated out for solid phase, separates and purifies easily; Solid product 4 is as the raw material hydrolysis, and the by product titania powder is a solid phase, and the product ethylenediamine triacetic acid is beneficial to separation at water, and by product titanium dioxide also can be used as a kind of product and sells.In addition, choose metal ion discharges ethylenediamine tetraacetic acid (EDTA) as sequestrant an acetate dentate, with after utilize the oxygenant oxidation to eliminate the novel process of this group, avoided adopting the organic synthesis process of the big raw material of toxicity such as prussiate, more production of by-products in the S-KP technology of having avoided simultaneously adopting halogenated acetic acids to replace cyclisation.
Embodiment
Further the present invention is elaborated with embodiment below.
Embodiment 1
1, compound [Ti (edta) (H
2O)] compound experiment of (1): toward filling 20ml distilled water and ethylenediamine tetraacetic acid (EDTA) (5.85g, dripping strong aqua in beaker 20mmol) is neutral to pH, drip titanium tetrachloride solution (2.2ml again, 20mmol), with strong aqua regulator solution pH value to 3.0, room temperature reaction 0.5h has many fine crystals to generate in the solution subsequently, the compound 1 that obtains after suction filtration, washing and the drying (3.0g, 43%).Ultimate analysis: calculated value (%): C, 33.8; H, 4.0; N, 7.9.Experimental value (%): C, 33.6; H, 3.9; N, 7.8.IR(KBr，cm
-1)：
as(CO
2)1701
vs，1700
vs，1613
m；
s(CO
2)1463
m，1349
s，1329
m；(Ti-O)667
m，554
m。
2, compound (NH
4) [Ti (O
2) (Hedta)] 2H
2O's (2a) is synthetic: toward contain compound 1 (3.55g, 10mmol) and in the stirred solution of 10ml distilled water, drip 30% hydrogen peroxide (10ml, 100mmol).The pH value of regulating mixed solution with strong aqua is 2.0, reacts 24h down at 25 ℃, and solution at room temperature rotary evaporation concentrates, and collects and separates out yellow solid, obtains compound 2a (2.0g, 47%) after the washing drying.Solution UV-Vis spectrum:
365=812Lmol
-1Cm
-1Ultimate analysis: calculated value (%): C, 28.4; H, 5.0; N, 9.9.Experimental value (%): C, 28.1; H, 5.0; N, 9.9.IR(KBr，cm
-1)：(CO
2H)1721
m，
as(CO
2)1684
vs，1650
vs，1594
vs，
s(CO
2)1385
s，1368
s，1324.1
m，(O-O)890
s；[Ti-(O
2)]629
m。Raman：(O-O)890
m，[Ti-(O
2)]628
vs。Nucleus magnetic resonance:
1H NMR (500MHz),
H(ppm, D
2O), 4.112 (b, 8H, CH
2CO
2 -), 3.344 (b, 4H, N-CH
2);
13C NMR (125MHz), C (ppm, D
2O), 179.9 (CO
2), 66.1 (CH
2CO
2), 59.7 (N-CH
2).
3, compound (NH
4)
2[Ti (O
2) (edta)] 2H
2O's (3a) is synthetic: (4.23g 10mmol) is dissolved in the beaker that fills 5ml distilled water compound 2a, and the pH value of regulating mixed solution with weak ammonia is 5.0, solution at room temperature rotary evaporation concentrates, yellow solid is separated out in collection, obtains compound 3a (1.7g, 39%) after the washing drying.Solution UV-Vis spectrum:
365=899Lmol
-1Cm
-1Ultimate analysis: calculated value (%): C, 27.3; H, 5.5; N, 12.7.Experimental value (%): C, 27.0; H, 5.4; N, 12.6.IR(KBr，cm
-1)：
as(CO
2)1655
vs，1604
m；
s(CO
2)1399
s，1347
m；(O-O)888
m；[Ti-(O
2)]627
m。Raman：(O-O)887
m，[Ti-(O
2)]626
vscm
-1。
1H?NMR(500MHz)，.(ppm，D
2O)，4.101(d，J?17.0Hz，4H，CH
2)，4.023(d，J?16.0Hz，4H，CH
2)，3.333(b，4H，N-CH
2)；
13CNMR(125MHz)，C(ppm，D
2O)，180.4(CO
2)66.7(-CH
2CO
2)，60.3(N-CH
2)。
4, compound N H
4[Ti (O
2) (ed3a)] (4a) synthetic: (4.4g 10mmol) is dissolved in the beaker that fills 5ml distilled water compound 3a, and the pH value of regulating mixed solution with weak ammonia is 5.0, react 96h down at 25 ℃, the yellow solid that collection is separated out obtains compound 4a (1.5g, 46%) after the washing drying.Solution UV-Vis spectrum:
363=1383Lmol
-1Cm
-1Ultimate analysis: calculated value (%): C, 29.2; H, 4.6; N, 12.8.Experimental value (%): C, 28.8; H, 4.6; N, 12.7.IR(KBr，cm
-1)：
as(CO
2)1640
vs，1613
vs，
s(CO
2)1432
m，1395
m，1319
s，(O-O)884
s，867
s，[Ti-(O
2)]629
m。Raman：(O-O)885
m，[Ti-(O
2)]627
vs。
1H?NMR(500MHz)，
H(ppm，D
2O)，4.604(d，J?18.0Hz，1H，CH
2)，4.023(d，J?18.5Hz，1H，CH
2)；3.849(d，J?7.5Hz，1H，CH
2)，3.814(d，J?7.5Hz，1H，CH
2)；3.679(d，J?17.0Hz，1H，CH
2)，3.632(d，J?18.0Hz，1H，CH
2)，3.111-3.357(m，4H，N-CH
2)；
13C?NMR(125MHz)，C(ppm，D
2O)，183.1，182.8(＝NCH
2CO
2)，181.8[-HNCH
2(CO
2)]，67.2，66.8(-CH
2CO
2)，61.0，60.3(＝NCH
2)，54.4(-HNCH
2)。
5, compound (NH
4)
3ED3A's (5a) is synthetic: (10.0g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4a, and the pH value of regulating mixed solution with 25% strong aqua is 13.0, about 70 ℃ of following hydrolysis 10h, leach and wash titanium dioxide precipitation, isolate product 5a (1.0g, 14%).IR(KBr，cm
-1)：
as(CO
2)1627.8
m，1441
vs，
s(CO
2)1194
s?cm
-1。
1H?NMR(400MHz)，
H(ppm，D
2O)，3.930(s，2H，CH
2)，3.450(t，J?5.6Hz，2H，CH
2)；3.294(s，2H，CH
2)，3.138(s，2H，CH
2)；2.882(t，J?5.6Hz，2H，CH
2)。
Embodiment 2
1, compound [Ti (edta) (H
2O)] synthesizing of (1): toward filling 20ml distilled water and ethylenediamine-N,N'-diacetic acid(EDDA) disodium (6.7g, Dropwise 5 molL in beaker 20mmol)
-1NaOH to pH be neutral, drip again titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h, suction filtration, washing after drying obtain the compound 1 (4.0g, 57%) of white powder
2, compound N a[Ti (O
2) (Hedta)] 2H
2O's (2b) is synthetic: compound 1 (3.55g 10mmol) adds 10ml distilled water, and dropping 30% hydrogen peroxide under constantly stirring (10ml, 100mmol).Use 5molL
-1The pH value that NaOH regulates mixed solution is 1.0, reacts 10h down at 60 ℃, and solution at room temperature rotary evaporation concentrates, and collects and separates out yellow solid, obtains compound 2b (1.9g, 45%) after the washing drying.Ultimate analysis: calculated value (%): C, 28.1; H, 4.0; N, 6.5.Experimental value (%): C, 28.0; H, 4.0; N, 6.4.IR(KBr，cm
-1)：(CO
2H)1717
m，
as(CO
2)1647
vs，1614
vs，1543
vs，
s(CO
2)1443
s，1412
vs，1401
vs，1346
m，(O-O)887
s；[Ti-(O
2)]626
s。Raman：(O-O)888
m，[Ti-(O
2)]626
vscm
-1。
3, compound N a[Ti (O
2) (ed3a)] H
2O's (4b) is synthetic: (4.28g 10mmol) is dissolved in the beaker that fills 5ml distilled water compound 2b, uses 5molL
-1The NaOH pH value to 7.0 of regulating mixed solution, at 60 ℃ of reaction 48h down, collect and separate out yellow solid, obtain compound 4b (1.0g, 28%) after the washing drying.Solution UV-Vis spectrum:
364=1420Lmol
-1Cm
-1Ultimate analysis: calculated value (%): C, 27.3; H, 3.7; N, 8.0.Experimental value (%): C, 27.0; H, 3.6; N, 7.6.IR(KBr，cm
-1)：
as(CO
2)1678
vs，1639
vs，
s(CO
2)1363
s，1306
s，(O-O)884
s，868
s，[Ti-(O
2)]633
m。Raman：(O-O)885
m，[Ti-(O
2)]626
vscm
-1。
1H?NMR(400MHz)，
H(ppm，D
2O)，4.639(d，J?18.0Hz，1H，CH
2)，4.055(d，J?18.4Hz，1H，CH
2)；3.891(d，J?3.6Hz，1H，CH
2)，3.847(d，J?6.0Hz，1H，CH
2)；3.711(d，J?16.0Hz，1H，CH
2)，3.689(d，J?18.0Hz，1H，CH
2)，3.148-3.413(m，4H，N-CH
2)；
13C?NMR(100MHz)，C(ppm，D
2O)，183.1，182.7(＝NCH
2CO
2)，181.7[-HNCH
2CO
2]，67.2，66.8(-CH
2CO
2)，60.9，60.3(＝NCH
2)，54.4(-HNCH
2)。
4, compound N a
3ED3A's (5b) is synthetic: (10.6g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4b, uses 5molL
-1The pH value that NaOH regulates mixed solution is 13.0, at 25 ℃ of hydrolysis 48h, leaches and wash titanium dioxide precipitation, isolates product 5b (1.5g, 17%).
1H?NMR(400MHz)，
H(ppm，D
2O)，3.930(s，2H，CH
2)，3.450(t，J?5.6Hz，2H，CH
2)；3.294(s，2H，CH
2)，3.138(s，2H，CH
2)；2.882(t，J?5.6Hz，2H，CH
2)。
Embodiment 3
1, compound (NH
4)
2[Ti (O
2) (edta)] 2H
2O's (3a) is synthetic: toward fill 20ml distilled water and ethylenediamine tetraacetic acid (EDTA) (11.7g, 40mmol) drip in the beaker of suspension liquid titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h.(12ml, 120mmol), regulating the pH value with strong aqua is 6.0, reacts 10h down at 70 ℃, obtains the mixing solutions of compound 3a then to drip 30% hydrogen peroxide.
2, compound N H
4[Ti (O
2) (ed3a)] (4a) synthetic: the mixing solutions of compound 3a, the pH value of regulating mixed solution with strong aqua is 8.0, at 80 ℃ down behind the reaction 24h, collects and separates out yellow solid, obtains compound 4a (3.5g, 53%) after washing drying.
3, compound 5b's is synthetic: (10.0g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4a, uses 5molL
-1The pH value that NaOH regulates mixed solution is 12.0, behind 90 ℃ of following hydrolysis 5h, leaches and wash titanium dioxide precipitation, isolates product 5b (1.6g, 18%).
Embodiment 4
1, compound (NH
4)
2[Ti (O
2) (edta)] 2H
2O's (3a) is synthetic: toward fill 20ml distilled water and ethylenediamine tetraacetic acid (EDTA) (8.77g, 30mmol) drip in the beaker of suspension liquid titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h.(5ml, 50mmol), regulating the pH value with strong aqua is 4.5, reacts 24h down at 25 ℃, obtains the mixing solutions of compound 3a then to drip 30% hydrogen peroxide.
2, compound N H
4[Ti (O
2) (ed3a)] (4a) synthetic: the mixing solutions of compound 3a, keep above-mentioned pH value, at 25 ℃ down behind the reaction 96h, collect and separate out yellow solid, obtain compound 4a (2.8g, 52%) after washing drying.
3, compound 5b's is synthetic: (10.0g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4a, slowly adds Na
2CO
3Or NaHCO
3Powder, the pH value of stirring and adjusting mixed solution is 10.0, behind hydrolysis 10h under 90 ℃ of water-baths, leaches and wash titanium dioxide precipitation, isolates product 5b (1.0g, 11%).
Embodiment 5
1, compound (NH
4)
2[Ti (O
2) (edta)] 2H
2O's (3a) is synthetic: toward fill 20ml distilled water and ethylenediamine tetraacetic acid (EDTA) (7.0g, 24mmol) drip in the beaker of suspension liquid titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h.(5ml, 50mmol), regulating the pH value with strong aqua is 5.0, reacts 10h down at 60 ℃, obtains the mixing solutions of compound 3a then to drip 30% hydrogen peroxide.
2, compound N H
4[Ti (O
2) (ed3a)] (4a) synthetic: the mixing solutions of compound 3a, the pH value of regulating mixed solution with weak ammonia is 7.0, at 60 ℃ down behind the reaction 48h, collects and separates out yellow solid, obtains compound 4a (2.5g, 37%) after washing drying.
3, compound K
3ED3A's (5c) is synthetic: (10.0g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4a, uses 5molL
-1The pH value that KOH regulates mixed solution is 12, and hydrolysis 48h under 25 ℃ of water-baths leaches and wash titanium dioxide precipitation, isolates product 5c (1.5g, 14%).
Embodiment 6
1, compound (NH
4)
2[Ti (O
2) (edta)] 2H
2O's (3a) is synthetic: toward fill 20ml distilled water and ethylenediamine tetraacetic acid (EDTA) (5.85g, 20mmol) drip in the beaker of suspension liquid titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h.(2ml, 20mmol), regulating the pH value with strong aqua is 6.0, reacts 10h down at 25 ℃, obtains the mixing solutions of compound 3a then to drip 30% hydrogen peroxide.
2, compound N H
4[Ti (O
2) (ed3a)] (4a) synthetic: the mixing solutions of compound 3a, the pH value of regulating mixed solution with weak ammonia is 8.0, at 25 ℃ down behind the reaction 96h, collects and separates out yellow crystals, obtains compound 4a (2.0g, 30%) after washing drying.
3, compound 5c's is synthetic: (10.0g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4a, slowly adds K
2CO
3Or KHCO
3Powder to the pH value of regulating mixed solution is 10.0, at 80 ℃ of following hydrolysis 12h, leaches and wash titanium dioxide precipitation, isolates product 5c (1.2g, 11%).
Embodiment 7
1, compound [Ti (edta) (H
2O)] synthesizing of (1): (6.7g slowly adds Na in beaker 20mmol) toward filling 20ml distilled water and ethylenediamine-N,N'-diacetic acid(EDDA) disodium
2CO
3Or NaHCO
3Powder, stirring reaction are neutral to pH, drip again titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h, suction filtration, washing after drying obtain the compound 1 (3.8g, 54%) of white powder
2, compound N a[Ti (O
2) (Hedta)] 2H
2O's (2b) is synthetic: compound 1 (3.55g 10mmol) adds 10ml distilled water, and dropping 30% hydrogen peroxide under constantly stirring (10ml, 100mmol).Use Na
2CO
3Or NaHCO
3The pH value that powder is regulated mixed solution is 3.0, reacts 2h down at 60 ℃, and solution at room temperature rotary evaporation concentrates, and collects and separates out yellow solid, obtains compound 2b (1.4g, 33%) after the washing drying.
3, compound N a[Ti (O
2) (ed3a)] H
2O's (4b) is synthetic: (4.28g 10mmol) is dissolved in the beaker that fills 5ml distilled water compound 2b, uses Na
2CO
3Or NaHCO
3Powder is regulated the pH value to 7.0 of mixed solution, reacts 96h down at 25 ℃, collects and separates out yellow solid, obtains compound 4b (1.2g, 39%) after the washing drying.
Embodiment 8
1, compound [Ti (edta) (H
2O)] synthesizing of (1): toward filling 20ml distilled water and ethylenediamine-N,N'-diacetic acid(EDDA) disodium (6.7g, Dropwise 5 molL in beaker 20mmol)
-1KOH to pH be neutral, drip again titanium tetrachloride solution (2.2ml, 20mmol), stirring reaction 0.5h, suction filtration, washing after drying obtain the compound 1 (3.2g, 46%) of white powder
2, compound K [Ti (O
2) (Hedta)] 2H
2O's (2c) is synthetic: compound 1 (3.55g 10mmol) adds 10ml distilled water, and dropping 30% hydrogen peroxide under constantly stirring (10ml, 100mmol).Use 5molL
-1The pH value that KOH regulates mixed solution is 1.0, reacts 12h down at 40 ℃, and solution at room temperature rotary evaporation concentrates, and collects and separates out yellow solid, obtains compound 2b (2.3g, 52%) after the washing drying.
3, compound K [Ti (O
2) (ed3a)] H
2O's (4c) is synthetic: (4.28g 10mmol) is dissolved in the beaker that fills 5ml distilled water compound 2b, uses 5molL
-1The KOH pH value to 5.0 of regulating mixed solution, at 60 ℃ of reaction 24h down, collect and separate out yellow solid, obtain compound 4c (1.0g, 28%) after the washing drying.
4, compound 5c's is synthetic: (11g 30mmol) is dissolved in the beaker that fills 300ml distilled water compound 4b, uses 5molL
-1The KOH pH value of regulating mixed solution be 13, at 50 ℃ of hydrolysis 10h, leach and wash titanium dioxide precipitation, isolate product 5c (1.5g, 14%).
Claims (4)
1. the preparation method of ethylene diamine triacetate is characterized in that synthetic route is as follows:
Its concrete steps are as follows:
1) mol ratio by titanium tetrachloride and ethylenediamine tetraacetic acid (EDTA) is 1: 1～2, gets in the aqueous solution that titanium tetrachloride joins ethylenediamine tetraacetic acid (EDTA), obtains ethylenediamine tetraacetic acid (EDTA) titanyl hydrate 1 after the reaction;
2) mol ratio by titanium tetrachloride and oxygenant is 1: 1～10, adds oxygenant in the mixed solution of titanium tetrachloride and ethylenediamine tetraacetic acid (EDTA) or in the ethylenediamine tetraacetic acid (EDTA) titanyl hydrate 1, at 0～90 ℃ of reaction 1～24h, obtains peroxide ethylenediamine tetraacetic acid (EDTA) titanium 2;
3) aqueous solution of peroxide ethylenediamine tetraacetic acid (EDTA) titanium 2 is 4～10 with mineral alkali adjusting pH value, obtains the peroxide thing 3 of deprotonation;
4) peroxide thing 3 is kept above-mentioned pH value under 0～90 ℃, and reaction 24～96h separates out peroxide ethylenediamine triacetic acid titanium chelate 4;
5) inner complex 4 is in pH value 8～14, and 0～90 ℃ of following alkaline hydrolysis 1～48h of water-bath isolates finished product ethylene diamine triacetate 5;
Described oxygenant is selected from 5%～30% hydrogen peroxide or 5%～30% Peracetic Acid by mass percentage.
2. the preparation method of ethylene diamine triacetate as claimed in claim 1, the mol ratio that it is characterized in that titanium tetrachloride and oxygenant is 1: 2～6.
3. the preparation method of ethylene diamine triacetate as claimed in claim 1 is characterized in that the reaction times is 48～72h in the step 4.
4. the preparation method of ethylene diamine triacetate as claimed in claim 1 is characterized in that described mineral alkali is selected from ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010007042A1 (en) * | 2000-01-05 | 2001-07-05 | Van Doorn Marcellinus Alexander | Process for preparing alkylene diamine triacetic acid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010007042A1 (en) * | 2000-01-05 | 2001-07-05 | Van Doorn Marcellinus Alexander | Process for preparing alkylene diamine triacetic acid |
Non-Patent Citations (2)
| Title |
|---|
| Bose, Rathindra N..Oxidation of ethylenediaminetetraacetic acid by permanganate ion: a kinetic study.Inorganic Chemistry.1991,30(12),2638-42. * |
| 周朝晖.过氧氨三乙酸钛配合物分子前体热分解制备纯钛基复氧化物.化学学报.2004,62(24),2379-2385. * |
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