CN103539817B - The synthetic method of PMIDA - Google Patents
The synthetic method of PMIDA Download PDFInfo
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- CN103539817B CN103539817B CN201310437827.4A CN201310437827A CN103539817B CN 103539817 B CN103539817 B CN 103539817B CN 201310437827 A CN201310437827 A CN 201310437827A CN 103539817 B CN103539817 B CN 103539817B
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- pmida
- acid
- hydrochloric acid
- suspension
- formaldehyde
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 title claims abstract 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 100
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 81
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000725 suspension Substances 0.000 claims abstract description 26
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 6
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 2
- 235000006408 oxalic acid Nutrition 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 4
- 239000012267 brine Substances 0.000 abstract description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- FUXALCGRSSRCQE-UHFFFAOYSA-N 2-(2,3-dihydro-1-benzofuran-7-yl)ethanamine Chemical compound NCCC1=CC=CC2=C1OCC2 FUXALCGRSSRCQE-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KKHJQZVEUKJURX-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid;hydrochloride Chemical compound Cl.OC(=O)CNCC(O)=O KKHJQZVEUKJURX-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention discloses the synthetic method of a kind of PMIDA, comprise the steps: 1) phosphorous acid, formaldehyde and hydrochloric acid are quantitatively mixed, and it is warming up to design temperature；2) to the suspension of the mixed solution and dripping iminodiacetic acid of phosphorous acid, formaldehyde and hydrochloric acid, it is incubated at a set temperature to reaction end, obtains PMIDA suspension；And the mol ratio of described hydrochloric acid and iminodiacetic acid is less than 0.1；3) by cooled for PMIDA suspension, crystallization, solid-liquid separation and dried, PMIDA is prepared.The synthetic method of the PMIDA of the present invention, it is iminodiacetic acid to be added drop-wise in the mixed solution of phosphorous acid, formaldehyde and hydrochloric acid, make in reaction system hydrogen chloride be in excess state all the time relative to iminodiacetic acid by this feed way, thus reach to reduce hydrochloric acid usage amount, reduce brine waste amount and improve the purpose of PMIDA yield.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the synthetic method of a kind of PMIDA.
Background technology
N-phosphonomethyl glycine (glyphosate) is a kind of important broad-spectrum herbicide, and a kind of common precursor synthesizing it is
N-phosphoryl methyl iminodiacetic acid (PMIDA).The synthetic reaction equation of PMIDA is as follows:
The conventional synthesis process of PMIDA is: first by phosphorous acid, hydrochloric acid, iminodiacetic acid mixing, and be heated to one
Fixed temperature；Next drips formaldehyde, and formaldehyde continues reaction to terminal after adding under uniform temperature；Finally add alkali liquor (ammonia or
Person's sodium hydroxide solution) it is neutralized to certain pH value, crystallisation by cooling separating solid substances, washing is dried to obtain qualified product.Its
The hydrochloric acid of middle use is excessive (in terms of iminodiacetic acid), it is ensured that iminodiacetic acid is all transformed into iminodiacetic acid
Hydrochlorate.
Summary of the invention
If it is demonstrated experimentally that use insufficient amount of hydrochloric acid, the yield of PMIDA can be substantially reduced.But from the synthesis of PMIDA
Reaction equation it can be seen that hydrochloric acid play in course of reaction function as catalyst, iminodiacetic acid hydrochlorid
Discharge hydrogen chloride after reacting generation PMIDA with phosphorous acid and formaldehyde, owing to reaction does not consume hydrogen chloride, therefore reacted
Alkali must be added after one-tenth neutralize, not only consume raw material, also generate by-product salt, need to add more water washing and desalting, cause wastewater flow rate
Greatly, product loss is many, defect that yield is low, and whole building-up process is the most uneconomical.
In view of this, in order to solve the problems referred to above, it is an object of the invention to provide the synthetic method of a kind of PMIDA.
For reaching above-mentioned purpose, the present invention provides following technical scheme:
The synthetic method of a kind of PMIDA, comprises the steps:
1) phosphorous acid, formaldehyde and hydrochloric acid are quantitatively mixed, and be warming up to design temperature；
2) to the suspension of the mixed solution and dripping iminodiacetic acid of phosphorous acid, formaldehyde and hydrochloric acid, at design temperature
Lower insulation, to reaction end, obtains PMIDA suspension；And the mol ratio of described hydrochloric acid and iminodiacetic acid is less than 0.1；
3) by cooled for PMIDA suspension, crystallization, solid-liquid separation and dried, PMIDA is prepared.
Further, the preparation method of described iminodiacetic acid is as follows: adding concentration to alkaline hydrolysis still is the hydrogen-oxygen of 10%-40%
Change sodium solution, under conditions of temperature control 45-50 DEG C, be dividedly in some parts Iminodiacetonitrile 1,1'-Imidodiacetonitrile, be incubated 1-3h after adding, then heat to
After 60-90 DEG C of steaming water is except ammonia, cooling reactant liquor, to 50-60 DEG C, adds hydrochloric acid and is acidified to pH=2.0-2.3, obtain iminodiacetic acid
Solution.
Further, the mol ratio between described iminodiacetic acid, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1.0-1.5:
1.0-1.4:0.01-0.1.
Further, in described step 1), the mixed liquor of phosphorous acid, formaldehyde and hydrochloric acid is warming up to 50-95 DEG C.
Further, described step 2) in, after adding iminodiacetic acid suspension, it is warming up to 100-120 DEG C, and is incubated anti-
Answer 2-4h.
Further, described step 2) in, stir mixed solution during dropping iminodiacetic acid suspension.
Further, in described step 3), after PMIDA suspension is cooled to 10-15 DEG C, crystallize 1-2h, through filtering, washing
Wash and obtain PMIDA after drying.
The beneficial effects of the present invention is:
The synthetic method of the PMIDA of the present invention, is that iminodiacetic acid is added drop-wise to mixing of phosphorous acid, formaldehyde and hydrochloric acid
Close in solution, make in reaction system hydrogen chloride be in excess shape all the time relative to iminodiacetic acid by this feed way
State, thus reach to reduce hydrochloric acid usage amount, reduce brine waste amount and improve the purpose of PMIDA yield；
Compared with prior art, hydrochloric acid consumption, by changing the feed postition of material, is successfully down to catalysis by the present invention
Amount, greatly reduces the consumption of material, and reaction need not after terminating add in substantial amounts of alkali and the hydrochloric acid of excess, brine waste amount
Greatly reduce, decrease washings consumption simultaneously and improve yield.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below to carry out
Illustrate:
Fig. 1 is the flow chart of the synthetic method of PMIDA of the present invention.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearer, below will be to the preferred embodiments of the present invention
It is described in detail.Should be appreciated that preferred embodiment is only for the explanation present invention rather than in order to limit the protection of the present invention
Scope.
Embodiment 1
One equipped with reflux condenser, thermometer, agitator, constant pressure funnel four-hole bottle in, add 101.5g sub-
Phosphoric acid (content 97%, 1.2mol), 113.5g formaldehyde (content 37%, 1.4mol) and 5.9g hydrochloric acid (content 31%, 0.05mol), mixed
After conjunction, temperature control is to 80 DEG C, and stirring phosphorous acid, formaldehyde and the mixed solution of hydrochloric acid also drip iminodiacetic acid suspension 365.0g
(content 36.4%, 1mol), is incubated 1h after adding, then heat to 120 DEG C of reaction 2h, reach reaction end, obtain PMIDA and hang
Supernatant liquid, by PMIDA suspension cooling down to 10 DEG C, and be incubated crystallization 2h after, filter, filter cake with 20mL water wash, be dried
White solid 216.5g, content 98.4%, yield 93.9%.
Wherein, the mol ratio between the iminodiacetic acid of the present embodiment, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1.2:
1.4:0.05.
The preparation method of the iminodiacetic acid of the present embodiment is as follows: adding concentration to alkaline hydrolysis still is the sodium hydroxide of 40%
Solution, is dividedly in some parts Iminodiacetonitrile 1,1'-Imidodiacetonitrile under conditions of temperature control 45 DEG C, is incubated 1h after adding, and then heats to 90 DEG C of steaming water and removes
After ammonia, cooling reactant liquor, to 60 DEG C, adds hydrochloric acid and is acidified to pH=2.0, obtain iminodiacetic acid (salt) acid solution.
Certainly, iminodiacetic acid also can use diethanolamine oxidizing process to prepare: is the most first aoxidized by diethanolamine
The iminodiacetic acid disodium salt arrived, then adds hydrochloric acid acidifying and obtains iminodiacetic acid, be not repeated.
Embodiment 2
One equipped with reflux condenser, thermometer, agitator, constant pressure funnel four-hole bottle in, add 84.5g phosphorous
Acid (content 97%, 1mol), 97.3g formaldehyde (content 37%, 1.2mol) and 11.8g hydrochloric acid (content 31%, 0.1mol), after mixing
Temperature control is to 95 DEG C, and stirring phosphorous acid, formaldehyde and the mixed solution of hydrochloric acid also drip iminodiacetic acid suspension 365.0g(content
36.4%, 1mol), it is incubated 1h after adding, then heats to 110 DEG C of reaction 4h, reach reaction end, obtain PMIDA suspension,
By PMIDA suspension cooling down to 15 DEG C, and be incubated crystallization 1h after, filter, filter cake with 20mL water wash, be dried white
Solid 216.9g, content 98.6%, yield 94.2%.
Wherein, the mol ratio between the iminodiacetic acid of the present embodiment, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1:1.2:
0.1。
The preparation method of the iminodiacetic acid of the present embodiment is as follows: adding concentration to alkaline hydrolysis still is the sodium hydroxide of 10%
Solution, is dividedly in some parts Iminodiacetonitrile 1,1'-Imidodiacetonitrile under conditions of temperature control 50 DEG C, is incubated 2h after adding, and then heats to 80 DEG C of steaming water and removes
After ammonia, cooling reactant liquor, to 50 DEG C, adds hydrochloric acid and is acidified to pH=2.3, obtain iminodiacetic acid (salt) acid solution.
Certainly, iminodiacetic acid also can use diethanolamine oxidizing process to prepare: is the most first aoxidized by diethanolamine
The iminodiacetic acid disodium salt arrived, then adds hydrochloric acid acidifying and obtains iminodiacetic acid, be not repeated.
Embodiment 3
One equipped with reflux condenser, thermometer, agitator, constant pressure funnel four-hole bottle in, add 126.8g sub-
Phosphoric acid (content 97%, 1.5mol), 81.1g formaldehyde (content 37%, 1mol) and 7.1g hydrochloric acid (content 31%, 0.06mol), mixing
Rear temperature control is to 50 DEG C, and stirring phosphorous acid, formaldehyde and the mixed solution of hydrochloric acid also drip iminodiacetic acid suspension 365.0g(and contain
Amount 36.4%, 1mol), it is incubated 1h after adding, then heats to 100 DEG C of reaction 4h, reach reaction end, obtain PMIDA and suspend
Liquid, by PMIDA suspension cooling down to 12 DEG C, and be incubated crystallization 1.5h after, filter, filter cake with 20mL water wash, be dried
White solid 216.1g, content 98.2%, yield 93.5%.
Wherein, the mol ratio between the iminodiacetic acid of the present embodiment, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1.5:1:
0.06。
The preparation method of the iminodiacetic acid of the present embodiment is as follows: adding concentration to alkaline hydrolysis still is the sodium hydroxide of 20%
Solution, is dividedly in some parts Iminodiacetonitrile 1,1'-Imidodiacetonitrile under conditions of temperature control 48 DEG C, is incubated 3h after adding, and then heats to 70 DEG C of steaming water and removes
After ammonia, cooling reactant liquor, to 55 DEG C, adds hydrochloric acid and is acidified to pH=2.1, obtain iminodiacetic acid (salt) acid solution.
Certainly, iminodiacetic acid also can use diethanolamine oxidizing process to prepare: is the most first aoxidized by diethanolamine
The iminodiacetic acid disodium salt arrived, then adds hydrochloric acid acidifying and obtains iminodiacetic acid, be not repeated.
Embodiment 4
One equipped with reflux condenser, thermometer, agitator, constant pressure funnel four-hole bottle in, add 93.0g phosphorous
Acid (content 97%, 1.1mol), 105.4g formaldehyde (content 37%, 1.3mol) and 1.2g hydrochloric acid (content 31%, 0.01mol), mixing
Rear temperature control is to 60 DEG C, and stirring phosphorous acid, formaldehyde and the mixed solution of hydrochloric acid also drip iminodiacetic acid suspension 365.0g(and contain
Amount 36.4%, 1mol), it is incubated 1h after adding, then heats to 105 DEG C of reaction 3h, reach reaction end, obtain PMIDA and suspend
Liquid, by PMIDA suspension cooling down to 13 DEG C, and be incubated crystallization 1.2h after, filter, filter cake with 20mL water wash, be dried
White solid 207.5g, content 98.8%, yield 90.3%.
Wherein, the mol ratio between the iminodiacetic acid of the present embodiment, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1.1:
1.3:0.01.
The preparation method of the iminodiacetic acid of the present embodiment is as follows: adding concentration to alkaline hydrolysis still is the sodium hydroxide of 30%
Solution, is dividedly in some parts Iminodiacetonitrile 1,1'-Imidodiacetonitrile under conditions of temperature control 46 DEG C, is incubated 2h after adding, and then heats to 60 DEG C of steaming water and removes
After ammonia, cooling reactant liquor, to 52 DEG C, adds hydrochloric acid and is acidified to pH=2.2, obtain iminodiacetic acid (salt) acid solution.
Certainly, iminodiacetic acid also can use diethanolamine oxidizing process to prepare: is the most first aoxidized by diethanolamine
The iminodiacetic acid disodium salt arrived, then adds hydrochloric acid acidifying and obtains iminodiacetic acid, be not repeated.
Embodiment 5
One equipped with reflux condenser, thermometer, agitator, constant pressure funnel four-hole bottle in, add 109.9g sub-
Phosphoric acid (content 97%, 1.3mol), 89.2g formaldehyde (content 37%, 1.1mol) and 9.4g hydrochloric acid (content 31%, 0.08mol), mixed
After conjunction, temperature control is to 70 DEG C, and stirring phosphorous acid, formaldehyde and the mixed solution of hydrochloric acid also drip iminodiacetic acid suspension 365.0g
(content 36.4%, 1mol), is incubated 0.5h after adding, then heat to 115 DEG C of reaction 2.5h, reach reaction end, obtains double sweet
Phosphine suspension, by PMIDA suspension cooling down to 14 DEG C, and be incubated crystallization 1.8h after, filter, filter cake with 20mL water wash,
It is dried to obtain white solid 216.6g, content 98.5%, yield 94%.
Wherein, the mol ratio between the iminodiacetic acid of the present embodiment, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1.3:
1.1:0.08.
The preparation method of the iminodiacetic acid of the present embodiment is as follows: adding concentration to alkaline hydrolysis still is the sodium hydroxide of 25%
Solution, is dividedly in some parts Iminodiacetonitrile 1,1'-Imidodiacetonitrile under conditions of temperature control 50 DEG C, is incubated 1h after adding, and then heats to 75 DEG C of steaming water and removes
After ammonia, cooling reactant liquor, to 58 DEG C, adds hydrochloric acid and is acidified to pH=2.3, obtain iminodiacetic acid (salt) acid solution.
Finally illustrate, preferred embodiment above only in order to technical scheme to be described and unrestricted, although logical
Cross above preferred embodiment the present invention to be described in detail, it is to be understood by those skilled in the art that can be
In form and it is made various change, without departing from claims of the present invention limited range in details.
Claims (5)
1. the synthetic method of a PMIDA, it is characterised in that: comprise the steps:
1) phosphorous acid, formaldehyde and hydrochloric acid are quantitatively mixed, and be warming up to design temperature；
2) to the suspension of the mixed solution and dripping iminodiacetic acid of phosphorous acid, formaldehyde and hydrochloric acid, protect at a set temperature
Temperature, to reaction end, obtains PMIDA suspension；And described hydrochloric acid is less than 0.1 and described with the mol ratio of iminodiacetic acid
Mol ratio between iminodiacetic acid, phosphorous acid, formaldehyde and hydrochloric acid is: 1:1.0-1.5:1.0-1.4:0.01-0.1；
3) by cooled for PMIDA suspension, crystallization, solid-liquid separation and dried, PMIDA is prepared.
The synthetic method of PMIDA the most according to claim 1, it is characterised in that: in described step 1), by phosphorous acid, first
The mixed liquor of aldehyde and hydrochloric acid is warming up to 50-95 DEG C.
The synthetic method of PMIDA the most according to claim 2, it is characterised in that: described step 2) in, add imino group
After oxalic acid suspension, it is warming up to 100-120 DEG C, and insulation reaction 2-4h.
The synthetic method of PMIDA the most according to claim 3, it is characterised in that: described step 2) in, drip imino group
Mixed solution is stirred during oxalic acid suspension.
The synthetic method of PMIDA the most according to claim 3, it is characterised in that: in described step 3), PMIDA is hanged
After supernatant liquid is cooled to 10-15 DEG C, crystallize 1-2h, through filtering, washing and obtain PMIDA after drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310437827.4A CN103539817B (en) | 2013-09-24 | The synthetic method of PMIDA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310437827.4A CN103539817B (en) | 2013-09-24 | The synthetic method of PMIDA |
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| Publication Number | Publication Date |
|---|---|
| CN103539817A CN103539817A (en) | 2014-01-29 |
| CN103539817B true CN103539817B (en) | 2016-11-30 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638419A (en) * | 2009-09-03 | 2010-02-03 | 上海力智生化科技有限公司 | Synthetic method of herbicide intermediate (PMIDA) |
| CN101648969A (en) * | 2009-09-14 | 2010-02-17 | 南京第一农药集团有限公司 | Preparation method of N-phosphonomethyliminodiacetic acid |
| CN101759718A (en) * | 2008-11-24 | 2010-06-30 | 陶伟平 | Method for producing N-(Phosphonomethyl)iminodiacetic acid |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759718A (en) * | 2008-11-24 | 2010-06-30 | 陶伟平 | Method for producing N-(Phosphonomethyl)iminodiacetic acid |
| CN101638419A (en) * | 2009-09-03 | 2010-02-03 | 上海力智生化科技有限公司 | Synthetic method of herbicide intermediate (PMIDA) |
| CN101648969A (en) * | 2009-09-14 | 2010-02-17 | 南京第一农药集团有限公司 | Preparation method of N-phosphonomethyliminodiacetic acid |
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