CN1042427C - Synthetic method for 2-hydroxy-2-phosphono-acetic acid - Google Patents
Synthetic method for 2-hydroxy-2-phosphono-acetic acid Download PDFInfo
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- CN1042427C CN1042427C CN94110195A CN94110195A CN1042427C CN 1042427 C CN1042427 C CN 1042427C CN 94110195 A CN94110195 A CN 94110195A CN 94110195 A CN94110195 A CN 94110195A CN 1042427 C CN1042427 C CN 1042427C
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- hydroxy
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- phosphorus compound
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- UTCHNZLBVKHYKC-UHFFFAOYSA-N 2-hydroxy-2-phosphonoacetic acid Chemical compound OC(=O)C(O)P(O)(O)=O UTCHNZLBVKHYKC-UHFFFAOYSA-N 0.000 title claims description 11
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- -1 radical acetate Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000003112 inhibitor Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YXNNSWYDFRWCBQ-UHFFFAOYSA-N C(C)(=O)O.P(O)(O)=O Chemical compound C(C)(=O)O.P(O)(O)=O YXNNSWYDFRWCBQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 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 description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 2
- DEBRGDVXKPMWQZ-UHFFFAOYSA-N Formylphosphonate Chemical class OP(O)(=O)C=O DEBRGDVXKPMWQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical compound OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- IZQZNLBFNMTRMF-UHFFFAOYSA-N acetic acid;phosphoric acid Chemical compound CC(O)=O.OP(O)(O)=O IZQZNLBFNMTRMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- VWCFCFOIUSKKSC-UHFFFAOYSA-N ethane-1,2-diamine;2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound NCCN.OP1(=O)OCCCCO1 VWCFCFOIUSKKSC-UHFFFAOYSA-N 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention discloses a synthetic method of 2-hydroxy-2-phosphonic acid radical acetate. In the method, condensation reaction is carried out to glyoxylic acid and compounds comprising phosphorus; the reaction time is 1 to 30 hours, and the temperature is from 25 DEG C to 150 DEG C; products of HPA high efficiency corrosion inhibitors can be obtained by removing unwanted alcohol and water. The synthesis reaction has the advantages of easily controlled technological condition, simple synthetic route, no three waste and no pollution; products can be widely applied to the industrial cycle water systems of chemical industry, electric power industry, metallurgy industry, etc. The reaction formula is HCOCOOH+(RO)<x>P(OH)3-x+nH2O-(HO)2POCHOHCOOH+nROH.
Description
the invention belongs to a synthesis method of a scale and corrosion inhibitor 2-hydroxy-2 phosphonic acid acetic acid for industrial circulating water.
At present, industrial circulating water systems are widely applied in chemical, electric and metallurgical departments in China, and main equipment of the circulating water systems, such as water storage tanks, boilers, heat exchangers and the like, have serious corrosion and scale inhibition problems. To solve this problem, it is common practice to use corrosion inhibitors. The imported corrosion inhibitor has good effect, but the price is high,the synthetic process route is complex; the corrosion inhibitor in China has few varieties and can not meet the application requirements. 2-hydroxy-2 phosphonic acid acetic acid, also called HPA corrosion inhibitor, is a novel corrosion inhibitor. The structural formula is as follows:
it has the following characteristics: (1) the corrosion inhibition performance is good, and is 5-8 times higher than that of domestic common hydroxyethylidene diphosphonic acid (HEDP) and ethylenediamine tetramethylene phosphate (EDTMP); (2) low concentration and high efficiency, and is often used in PPM level; (3) the chemical stability is good, the hydrolysis is not easy, and the acid or alkali is not easy to damage; (4) the use is safe and reliable, nontoxic and pollution-free; (5) the water solubility is good. The HPA novel corrosion inhibitor is an ideal corrosion inhibitor and can be widely applied to corrosion prevention and scale inhibition of water storage tanks, boilers, heat exchangers and circulating water equipment of copper, steel, aluminum, tin and alloy products thereof. At present, no manufacturer for producing the HPA novel corrosion inhibitor exists at home, similar products are produced at abroad, and the typical representative of the similar products is a commercial product Belcor-575 of Ciba-Geigy company. The route for synthesizing the hydroxyphosphonoacetic acid which is the effective component of the HPA novel corrosion inhibitor has two routes: (1) the synthesis route reported in patent document eur.pat.appl.ep.50792 is that dialkyl phosphite ester is firstly reacted with orthoformate, then hydrolyzed to obtain phosphono formaldehyde salt, the phosphono formaldehyde salt is reacted with hydrocyanic acid to obtain hydroxyphosphonoacetonitrile, and nitrile is subjected to acidic hydrolysis to obtain the product; (2) the synthesis route reported in Ger. Offen.2941384(1979) is a reaction of dialkyl phosphite with glyoxylic acid ester to produce hydroxyphosphonate acetate, which is then hydrolyzed appropriately to give the product. The two methods need to complete multi-step reaction, toxic cyanide is used in the method (1) and is easy to cause harm, certain complex technology is needed for separating products, and the compounds involved in the method (2) are basically non-toxic but have great technical difficulty and mainly need to be distilled under higher vacuum to obtain the hydroxyl phosphonic acid ethyl ester.
The invention aims to find a new synthetic route, has simple synthetic method, high yield and no pollution, does not relate to a virulent substance, and overcomes the defects in the prior art.
The technical scheme of the invention is as follows: the invention relates to a method for synthesizing 2-hydroxy-2 phosphonic acid acetic acid by reacting a compound containing ROOCCHO structure with a phosphorus compound, which is characterized in that glyoxylic acid and the phosphorus compound (RO)nP(OH)3-nReacting at the molar ratio of 1.0: 0.5-2 at 25-150 deg.c for 1-30 hr to obtain product, and distilling the product to obtain 2-hydroxy-2-phosphonoacetic acid.
The glyoxylic acid is a pure solid or an aqueous solution with a concentration of 5 to 50%.
Phosphorus compound (RO)nP(OH)3-nWherein n may be 0,2 or 3, and R may be an alkyl group or an aralkyl group having a carbon number of 1 to 10.
The distillation product is carried out at 25 ℃ to 100 ℃ under normal pressure or at a pressure of 133-95000 Pa.
The reaction formula is as follows:
r of the phosphorus compound in the reaction formula represents an alkyl group or an aralkyl group having a carbon number of 1 to 10, particularly a C1 to C4 alkyl group, such as methyl phosphite, butyl phosphite, etc. Wherein n can be 0,2 or 3, and when n is 0, the compound is phosphorous acid; when n is 2, the compound is dialkyl phosphite or diaryl alkyl phosphite; when n is 3, the product is trialkyl phosphite or triarylalkyl phosphite. The reaction time is 1 to 30 hours depending on the concentration of the reactant glyoxylic acid and the concentration of the phosphorus compound and the reaction temperature.
The product obtained by the invention is proved to be the same compound 2-hydroxy-2-phosphonoacetic acid as foreign products by infrared spectrum, nuclear magnetic resonance, liquid chromatography analysis and the like. The 2-hydroxy-2-phosphonoacetic acid can be directly synthesized by dimethyl phosphite, glyoxylic acid and phosphorous acid, and the two new reactions are not reported in documents at home and abroad. The invention has high reaction yield which can reach more than 80 percent usually, no generation of hypertoxic substances, no pollution, no three wastes, easily controlled process conditions, simple synthesis method and lower cost.
The present invention will be further illustrated with reference to the following examples.
Example 1. Adding 16.4 g of phosphorous acid and 29.6 g of 50% glyoxylic acid solution into a reactor, installing a reflux condensing device, heating by using a boiling water bath, when the temperature of reactants is close to 100 ℃, the reaction heat release is obvious, the temperature of the reactants can automatically rise to about 104 ℃, after about half an hour, the temperature of the reactants falls back to about 100 ℃, and after the heating is maintained by using the boiling water bath for 5-6 hours, stopping heating to obtain the aqueous solution of the 2-hydroxy-2-phosphonoacetic acid. Distilling the aqueous solution at 25-100 deg.C under normal pressure to remove alcohol and part of water to obtain 2-hydroxy-2-phosphonoacetic acid.
Example 2. Adding 25 g of dimethyl phosphite and 29 g of 50% glyoxylic acid solution into a reactor, mixing, then emulsifying the reaction solution, firstly reacting for 2 hours at 25 ℃, and then slowly heating to boil in a water bath and keeping for 2-4 hours. Then distilling the reaction solution at 25-100 ℃ under reduced pressure of 133-95000Pa, and evaporating water and methanol to obtain the 2-hydroxy-2-phosphonoacetic acid.
Claims (3)
1. A process for synthesizing 2-hydroxy-2-phosphonoacetic acid by reaction between ROOCCHO compound and phosphorus compound features that the glyoxylic acid and phosphorus compound (RO)nP(OH)3-nReacting at a molar ratio of 1.0: 0.5-2 at 25-150 deg.C for 1-30 hr to obtain product, and distilling to obtain 2-hydroxy-2-phosphonoacetic acid and phosphorus compound (RO)nP(OH)3-nWherein n may be 0,2 or 3, and R may be an alkyl group or an aralkyl group having a carbon number of 1 to 10.
2. The process for the synthesis of 2-hydroxy-2-phosphonoacetic acid according to claim 1, wherein the glyoxylic acid is pure solid or an aqueous solution having a concentration of 5 to 50%.
3. The method as set forth in claim 2, wherein the distillation of the product is carried out at 25-100 ℃ under normal pressure or under pressure of 133-95000 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110195A CN1042427C (en) | 1994-04-15 | 1994-04-15 | Synthetic method for 2-hydroxy-2-phosphono-acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110195A CN1042427C (en) | 1994-04-15 | 1994-04-15 | Synthetic method for 2-hydroxy-2-phosphono-acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110277A CN1110277A (en) | 1995-10-18 |
| CN1042427C true CN1042427C (en) | 1999-03-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110195A Expired - Fee Related CN1042427C (en) | 1994-04-15 | 1994-04-15 | Synthetic method for 2-hydroxy-2-phosphono-acetic acid |
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| Country | Link |
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| CN (1) | CN1042427C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102363538B (en) * | 2010-12-07 | 2013-04-03 | 新疆德蓝股份有限公司 | Preparation of composite corrosion and scale inhibitor for low-hardness circulating cooling water |
| CN103087099B (en) * | 2013-01-15 | 2015-11-18 | 湖北兴发化工集团股份有限公司 | A kind of preparation method of 2-HPAA |
| CN103435644B (en) * | 2013-09-09 | 2015-07-08 | 山东省泰和水处理有限公司 | Preparation method of low chloride 2-hydroxyphosphonoacetic acid |
| CN104528962A (en) * | 2014-10-24 | 2015-04-22 | 中国海洋石油总公司 | Preparation method of novel furnace shutdown protecting liquid for heating system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2941384A1 (en) * | 1979-10-12 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | PHOSPHONO-HYDROXY-ACETIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS MEDICINAL PRODUCTS |
| EP0050792A1 (en) * | 1980-10-23 | 1982-05-05 | Bayer Ag | Process for the preparation of phospho-hydroxy-acetonitrile |
-
1994
- 1994-04-15 CN CN94110195A patent/CN1042427C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2941384A1 (en) * | 1979-10-12 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | PHOSPHONO-HYDROXY-ACETIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS MEDICINAL PRODUCTS |
| EP0050792A1 (en) * | 1980-10-23 | 1982-05-05 | Bayer Ag | Process for the preparation of phospho-hydroxy-acetonitrile |
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| Publication number | Publication date |
|---|---|
| CN1110277A (en) | 1995-10-18 |
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