CN101709472A - Preparation method of substituted pyridine carbonylhydrazone metal corrosion inhibitor - Google Patents
Preparation method of substituted pyridine carbonylhydrazone metal corrosion inhibitor Download PDFInfo
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- CN101709472A CN101709472A CN200910114543A CN200910114543A CN101709472A CN 101709472 A CN101709472 A CN 101709472A CN 200910114543 A CN200910114543 A CN 200910114543A CN 200910114543 A CN200910114543 A CN 200910114543A CN 101709472 A CN101709472 A CN 101709472A
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- pyridine
- corrosion inhibitor
- carboxylic acid
- absolute ethanol
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Abstract
The invention discloses a preparation method of substituted pyridine carbonylhydrazone metal corrosion inhibitor. The method comprises the following steps: using methylisonicotinate and hydrazine hydrate in a molar ratio of 1:1-1.2:1 and absolute ethanol or methanol used as solvent of which volume is 3-6 times of hydrazine hydrate to react for 6-8h in a three-neck flask under the condition of refluxing at 70-80 DEG C and magnetic stirring, obtaining a product to perform reduced pressure distillation, recrystallizing with absolute ethanol, drying to obtain pyridine formylhydrazine, then using the obtained pyridine formylhydrazine and o-vanillin in a molar ratio of 1:1-1:1.2 and absolute ethanol or methanol used as solvent of which volume is 2-5 times of pyridine formylhydrazine to react for 7-9h under the condition of refluxing at 70-90 DEG C and magnetic stirring, cooling, performing suction filtration, washing with absolute ethanol, and recrystallizing. The preparation method of the invention designs the corrosion inhibitor molecule with good oil solubility which meets the environmental protection requirements; and the corrosion inhibitor molecule is characterized by good biodegradability, low toxicity and corrosion resistance within the pH value range of 4-9, and has good corrosion resistance to A3 carbon steel and copper.
Description
Technical field
The present invention relates to the substituted pyridine carbonylhydrazone compounds of metallic substance protection, belong to green corrosion inhibitor molecular designing field, particularly a kind of preparation method of substituted pyridine carbonylhydrazone metal corrosion inhibitor.
Background technology
Compare with the most frequently used inorganic inhibitor (nitrite, phosphoric acid salt, poly-phosphate, carbonate, silicate, borate, chromic salt), the kind of the organic inhibitor of synthetic is more.But the Molecular Structure Design of present organic inhibitor, also there are a lot of weak points in synthetic route and technology, application performance, and its theoretical progress still far lags behind practice.Select design green corrosion inhibitor molecular structure not only will consider corrosion mitigating effect, also must take into account biological activity and versatility.In order to adapt to nontoxic, the nuisanceless neutralization technology target of human living space, application and development based on the environmental friendliness inhibiter of Green Chemical Technology, obtain many valuable achievements in recent decades, but in the research of green corrosion inhibitor, still be faced with many problem demanding prompt solutions., synthetic route unreasonable as inhibiter large usage quantity, cost price height, molecular designing and complex process, the industrial by-products that generation hazardness is big, productive rate is low, of poor quality etc.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of substituted pyridine carbonylhydrazone metal corrosion inhibitor, prepared corrosion inhibitor compound, contain the acylhydrazone group in the basic comprising, be different from conventional Schiff's base group, can there be and brings into play good corrosion inhibition in it in the peracidity corrosive medium.
Substituted pyridine carbonylhydrazone Schiff's base inhibiter structural formula involved in the present invention is as follows:
In the formula: R
1Be pyridyl, carbonyl is positioned at 2,3 or 4 of pyridine ring;
The above-claimed cpd building-up process:
With pyridine carboxylic acid methyl esters and hydrazine hydrate mole proportioning with 1: 1～1.2: 1,3～6 times of dehydrated alcohol or methyl alcohol to the hydrazine hydrate volume react in there-necked flask as solvent, 70～80 ℃ of backflows down, magnetic agitation were reacted 6～8 hours, the product underpressure distillation that obtains, usefulness dehydrated alcohol recrystallization, drying obtain the pyridine formyl hydrazine; Then with the pyridine formyl hydrazine that obtains and o-vanillin mole proportioning with 1: 1～1: 1.2,2～5 times of dehydrated alcohol or methyl alcohol to pyridine formyl hydrazine quality are solvent reaction, 70～90 ℃ of backflows down, magnetic agitation were reacted 7～9 hours, cooling, suction filtration, absolute ethanol washing, recrystallization, the dry target compound that gets.
Described pyridine carboxylic acid methyl esters is a kind of in 2-pyridine carboxylic acid methyl esters, 3-pyridine carboxylic acid methyl esters and the 4-pyridine carboxylic acid methyl esters.
The present invention has designed the good inhibiter molecule of oil soluble that satisfies environmental protection requirement, has simultaneously that biological degradability is good, low toxicity, all has the characteristic of inhibition in wider pH value scope (4～9), and A3 carbon steel and copper are all had good corrosion inhibition.。
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Mark among the figure: A-pyridine carboxylic acid methyl esters (R
1-COOCH
3), C-hydrazine hydrate, B-o-vanillin, D-solvent.
Embodiment:
Embodiment 1:
Synthesizing of o-vanillin-2-pyridine carbonylhydrazone Schiff's base:
With 2-pyridine carboxylic acid methyl esters and hydrazine hydrate mole proportioning with 1: 1,4 times of dehydrated alcohols to the hydrazine hydrate volume react in there-necked flask as solvent, 75 ℃ of backflows down, magnetic agitation were reacted 7 hours, obtain the product underpressure distillation, use dehydrated alcohol recrystallization, drying, obtain 2-pyridine formyl hydrazine.Then with 2-pyridine formyl hydrazine and o-vanillin mole proportioning with 1: 1,3 times of dehydrated alcohols to pyridine formyl hydrazine quality are solvent reaction, 80 ℃ of backflows down, magnetic agitation were reacted 8 hours, cooling, there are a large amount of light yellow crystal to separate out, suction filtration, absolute ethanol washing, recrystallization gets faint yellow solid.Infrared spectra shows that this moment is at 1681cm
-1There are the charateristic avsorption band of acylhydrazone group, 3000～3100cm in the place
-1C-H absorption peak on the phenyl ring is arranged, 817～857cm in the scope
-1Belong to C-H absorption peak on the pyridine ring.Product is a target product.
Final reacting product is formed corrosion inhibitor solution under the situation of organic solvent dissolution.Prescription is by weight percentage: 10% o-vanillin-2-pyridine carbonylhydrazone Schiff's base inhibiter, 20% dehydrated alcohol, 7O% distilled water.
1, neutral etchant solution evaluation
Appreciation condition: etchant solution is 3.5% sodium chloride solution, and under the normal temperature and pressure, 72h, density of corrosion inhibitor are 75mg/L, and the test material is A3 carbon steel and copper sheet.Test-results sees Table 1.
Table 1: the inhibiter normal temperature and pressure conditions to embodiment 1 is estimated down
| Blank | The A3 carbon steel | ??/ | ??0.2475 | ??/ | Uniform corrosion |
| Embodiment 1 | The A3 carbon steel | The oil soluble water-dispersion | ??0.0094 | ??96.21 | Evenly bright |
| Blank | Copper sheet | ??/ | ??0.2164 | ??/ | Uniform corrosion |
| Embodiment 1 | Copper sheet | The oil soluble water-dispersion | ??0.0051 | ??97.65 | Evenly bright |
2, acid attack solution is estimated
Appreciation condition: etchant solution is the hydrochloric acid soln of concentration 1mol/L, and under the normal temperature and pressure, 72h, density of corrosion inhibitor are 75mg/L, and the test material is A3 carbon steel and copper sheet.Test-results sees Table 2.
Table 2: the inhibiter normal temperature and pressure conditions to embodiment 1 is estimated down
| Inhibiter | The test material | Solvability | Erosion rate | Inhibition efficiency | The test piece table |
| Blank | The A3 carbon steel | ??/ | ??0.6475 | ??/ | Uniform corrosion |
| Embodiment 1 | The A3 carbon steel | The oil soluble water-dispersion | ??0.0140 | ??97.85 | Evenly bright |
| Blank | Copper sheet | ??/ | ??0.4464 | ??/ | Uniform corrosion |
| Embodiment 1 | Copper sheet | The oil soluble water-dispersion | ??0.0051 | ??98.86 | Evenly bright |
Embodiment 2:
Synthesizing of o-vanillin-3-pyridine carbonylhydrazone Schiff's base
With 3-pyridine carboxylic acid methyl esters and hydrazine hydrate mole proportioning with 1: 1,4 times of dehydrated alcohols to the hydrazine hydrate volume react in there-necked flask or chemical reactor (as Lab Max reactor) as solvent, 75 ℃ of backflows down, magnetic agitation were reacted 7 hours, obtain the product underpressure distillation, use dehydrated alcohol recrystallization, drying, obtain 3-pyridine formyl hydrazine.Then with 3-pyridine formyl hydrazine and o-vanillin mole proportioning with 1: 1,3 times of dehydrated alcohols to pyridine formyl hydrazine quality are solvent reaction, 80 ℃ of backflows down, magnetic agitation were reacted 8 hours, cooling, there are a large amount of light yellow crystal to separate out, suction filtration, absolute ethanol washing, recrystallization gets faint yellow solid.Infrared spectra shows that this moment is at 1659cm
-1There are the charateristic avsorption band of acylhydrazone group, 3000～3100cm in the place
-1C-H absorption peak on the phenyl ring is arranged, 817～857cm in the scope
-1Belong to C-H absorption peak on the pyridine ring.Product is a target product.
Final reacting product is formed corrosion inhibitor solution under the situation of organic solvent dissolution.Prescription is by weight percentage: 10% o-vanillin-3-pyridine carbonylhydrazone Schiff's base inhibiter, 20% dehydrated alcohol, 70% distilled water.
1, neutral etchant solution evaluation
Appreciation condition: etchant solution is 3.5% sodium chloride solution, and under the normal temperature and pressure, 72h, density of corrosion inhibitor are 75mg/L, and the test material is A3 carbon steel and copper sheet.Test-results sees Table 3.
Table 3: the inhibiter normal temperature and pressure conditions to embodiment 2 is estimated down
| Blank | The A3 carbon steel | ??/ | ??0.2475 | ??/ | Uniform corrosion |
| Embodiment 2 | The A3 carbon steel | The oil soluble water-dispersion | ??0.0195 | ??92.14 | Evenly bright |
| Blank | Copper sheet | ??/ | ??0.2164 | ??/ | Uniform corrosion |
| Embodiment 2 | Copper sheet | The oil soluble water-dispersion | ??0.0146 | ??93.25 | Evenly bright |
2, acid attack solution is estimated
Appreciation condition: etchant solution is the hydrochloric acid soln of concentration 1mol/L, and under the normal temperature and pressure, 72h, density of corrosion inhibitor are 75mg/L, and the test material is A3 carbon steel and copper sheet.Test-results sees Table 4.
Table 4: the inhibiter normal temperature and pressure conditions to embodiment 2 is estimated down
| The inhibiter code name | The test material | Solvability | Erosion rate mm/a | Inhibition efficiency % | The test piece surface condition |
| Blank | The A3 carbon steel | ??/ | ??0.6475 | ??/ | Uniform corrosion |
| Embodiment 2 | The A3 carbon steel | The oil soluble water-dispersion | ??0.0461 | ??92.89 | Evenly bright |
| The inhibiter code name | The test material | Solvability | Erosion rate mm/a | Inhibition efficiency % | The test piece surface condition |
| Blank | Copper sheet | ??/ | ??0.4464 | ??/ | Uniform corrosion |
| Embodiment 2 | Copper sheet | The oil soluble water-dispersion | ??0.0144 | ??96.78 | Evenly bright |
Embodiment 3:
Synthesizing of o-vanillin-4-pyridine carbonylhydrazone Schiff's base
With 4-pyridine carboxylic acid methyl esters and hydrazine hydrate mole proportioning with 1: 1,4 times of dehydrated alcohols to the hydrazine hydrate volume react in there-necked flask or chemical reactor (as Lab Max reactor) as solvent, 75 ℃ of backflows down, magnetic agitation were reacted 7 hours, obtain the product underpressure distillation, use dehydrated alcohol recrystallization, drying, obtain 4-pyridine formyl hydrazine.Then with 4-pyridine formyl hydrazine and o-vanillin mole proportioning with 1: 1,3 times of dehydrated alcohols to pyridine formyl hydrazine quality are solvent reaction, 80 ℃ of backflows down, magnetic agitation were reacted 8 hours, cooling, there are a large amount of light yellow crystal to separate out, suction filtration, absolute ethanol washing, recrystallization gets faint yellow solid.Infrared spectra shows that this moment is at 1676cm
-1There are the charateristic avsorption band of acylhydrazone group, 3000～3100cm in the place
-1C-H absorption peak on the phenyl ring is arranged, 817～857cm in the scope
-1Belong to C-H absorption peak on the pyridine ring.Product is a target product.
Final reacting product is formed corrosion inhibitor solution under the situation of organic solvent dissolution.Prescription is by weight percentage: 10% o-vanillin-4-pyridine carbonylhydrazone Schiff's base inhibiter, and 20% dehydrated alcohol, 70% is distilled water.
1, neutral etchant solution evaluation:
Appreciation condition: etchant solution is 3.5% sodium chloride solution, and under the normal temperature and pressure, 72h, density of corrosion inhibitor are 75mg/L, and the test material is A3 carbon steel and copper sheet.Test-results sees Table 5.
Table 5: the inhibiter normal temperature and pressure conditions to embodiment 3 is estimated down
| The inhibiter code name | The test material | Solvability | Erosion rate mm/a | Inhibition efficiency % | The test piece surface condition |
| The inhibiter code name | The test material | Solvability | Erosion rate mm/a | Inhibition efficiency % | The test piece surface condition |
| Blank | The A3 carbon steel | ??/ | ??0.2475 | ??/ | Uniform corrosion |
| Embodiment 3 | The A3 carbon steel | The oil soluble water-dispersion | ??0.0173 | ??93.01 | Evenly bright |
| Blank | Copper sheet | ??/ | ??0.2164 | ??/ | Uniform corrosion |
| Embodiment 3 | Copper sheet | The oil soluble water-dispersion | ??0.0143 | ??93.35 | Evenly bright |
2, acid attack solution is estimated
Appreciation condition: etchant solution is the hydrochloric acid soln of concentration 1mol/L, and under the normal temperature and pressure, 72h, density of corrosion inhibitor are 75mg/L, and the test material is A3 carbon steel and copper sheet.Test-results sees Table 6.
Table 6: the inhibiter normal temperature and pressure conditions to embodiment 3 is estimated down
| Code name | ? | ? | ??mm/a | ??％ | The face situation |
| The inhibiter code name | The test material | Solvability | Erosion rate mm/a | Inhibition efficiency % | The test piece surface condition |
| Blank | The A3 carbon steel | ??/ | ??0.6475 | ??/ | Uniform corrosion |
| Embodiment 3 | The A3 carbon steel | The oil soluble water-dispersion | ??0.0413 | ??93.62 | Evenly bright |
| Blank | Copper sheet | ??/ | ??0.4464 | ??/ | Uniform corrosion |
| Embodiment 3 | Copper sheet | The oil soluble water-dispersion | ??0.0193 | ??95.67 | Evenly bright |
Claims (1)
1. the preparation method of a substituted pyridine carbonylhydrazone metal corrosion inhibitor, it is characterized in that concrete steps are: with pyridine carboxylic acid methyl esters and hydrazine hydrate mole proportioning with 1: 1～1.2: 1,3～6 times of dehydrated alcohol or methyl alcohol to the hydrazine hydrate volume react in there-necked flask as solvent, 70～80 ℃ of backflows down, magnetic agitation were reacted 6～8 hours, the product underpressure distillation that obtains, usefulness dehydrated alcohol recrystallization, drying obtain the pyridine formyl hydrazine; With the pyridine formyl hydrazine that obtains and the o-vanillin mole proportioning with 1: 1～1: 1.2,2～5 times of dehydrated alcohol or methyl alcohol to pyridine formyl hydrazine quality are solvent reaction then, 70～90 ℃ reflux down, magnetic agitation reaction 7～9 hours, cooling, suction filtration, absolute ethanol washing, recrystallization, drying;
Described pyridine carboxylic acid methyl esters is a kind of in 2-pyridine carboxylic acid methyl esters, 3-pyridine carboxylic acid methyl esters and the 4-pyridine carboxylic acid methyl esters.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711579A (en) * | 2014-11-28 | 2015-06-17 | 武汉工程大学 | Pyridine derivative corrosion inhibitor for metals and preparation method thereof |
| TWI586641B (en) * | 2016-04-13 | 2017-06-11 | 國立中興大學 | Bimetallic lanthanide complex, fabricating method and use thereof, polycarbonate and method of manufacturing polycarbonate |
| CN109293636A (en) * | 2018-10-22 | 2019-02-01 | 山东师范大学 | " one kettle way " synthesizes capsule shape complex and preparation method and application containing schiff base structure unit |
| CN110143677A (en) * | 2019-05-21 | 2019-08-20 | 南京工业大学 | A kind of antiscaling dispersion corrosion inhibiter and preparation method and application |
| CN112795928A (en) * | 2020-12-10 | 2021-05-14 | 上海应用技术大学 | Efficient environment-friendly rust remover and preparation method and application thereof |
-
2009
- 2009-11-10 CN CN200910114543A patent/CN101709472A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711579A (en) * | 2014-11-28 | 2015-06-17 | 武汉工程大学 | Pyridine derivative corrosion inhibitor for metals and preparation method thereof |
| TWI586641B (en) * | 2016-04-13 | 2017-06-11 | 國立中興大學 | Bimetallic lanthanide complex, fabricating method and use thereof, polycarbonate and method of manufacturing polycarbonate |
| CN109293636A (en) * | 2018-10-22 | 2019-02-01 | 山东师范大学 | " one kettle way " synthesizes capsule shape complex and preparation method and application containing schiff base structure unit |
| CN110143677A (en) * | 2019-05-21 | 2019-08-20 | 南京工业大学 | A kind of antiscaling dispersion corrosion inhibiter and preparation method and application |
| CN112795928A (en) * | 2020-12-10 | 2021-05-14 | 上海应用技术大学 | Efficient environment-friendly rust remover and preparation method and application thereof |
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Open date: 20100519 |