CN103554189A - Schiff base nickel complex and application thereof as metal material pickling inhibitor - Google Patents
Schiff base nickel complex and application thereof as metal material pickling inhibitor Download PDFInfo
- Publication number
- CN103554189A CN103554189A CN201310557425.8A CN201310557425A CN103554189A CN 103554189 A CN103554189 A CN 103554189A CN 201310557425 A CN201310557425 A CN 201310557425A CN 103554189 A CN103554189 A CN 103554189A
- Authority
- CN
- China
- Prior art keywords
- schiff
- nickel complex
- base nickel
- distilled water
- methyl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 36
- 239000007769 metal material Substances 0.000 title claims abstract description 21
- 238000005554 pickling Methods 0.000 title abstract description 11
- 239000002262 Schiff base Substances 0.000 title abstract description 10
- 150000004753 Schiff bases Chemical class 0.000 title abstract description 8
- 239000003112 inhibitor Substances 0.000 title abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 claims abstract description 15
- FCHXJFJNDJXENQ-UHFFFAOYSA-N pyridoxal hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(C=O)=C1O FCHXJFJNDJXENQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229950000244 sulfanilic acid Drugs 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000002000 scavenging effect Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 230000003019 stabilising effect Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 14
- 230000005764 inhibitory process Effects 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 230000002459 sustained effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 27
- 238000012512 characterization method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- -1 schiff base metal complex Chemical class 0.000 description 4
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229960003581 pyridoxal Drugs 0.000 description 1
- 235000008164 pyridoxal Nutrition 0.000 description 1
- 239000011674 pyridoxal Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a Schiff base nickel complex and application thereof as a corrosion inhibitor in a metal material pickling process. The Schiff base nickel complex is prepared from pyridoxal hydrochloride, sulfanilic acid, potassium hydroxide and water-soluble nickel salt in a mixed solvent of methanol and water; the Schiff base nickel complex can prevent metal materials from being corroded by acid liquor in the acid pickling process and unnecessary consumption of the acid liquor. In the pickling solution with the hydrochloric acid concentration of 1.0mol/L, when the concentration of the Schiff base nickel complex in the pickling solution is 0.4-0.8 g/L, the corrosion inhibition effect on steel and copper materials is remarkable. The Schiff base nickel complex has the advantages of simple preparation, cheap and easily-obtained raw materials, simple use method, low consumption and strong corrosion inhibition sustained action capability when used as a corrosion inhibitor.
Description
Technical field
The present invention relates to a kind of Schiff's base nickel complex and in metallic substance acid cleaning process as the application of inhibiter.
Background technology
Schiff's base (Schiff base) refers to a class organic compound that contains imido grpup (-HC=N-) or azomethine base (RC=N-).N atom in the core position of Schiff's base has lone-pair electron, has very strong coordination ability.In Schiff's base, the both sides of the two keys of C=N all can be introduced types of functionality group and be made its derivatize, and it is synthetic relatively easy, can select neatly the various different aldehydes or ketones with carbonyl to react.Change the substituting group connecting, change atomic nature and the position thereof of electron donor, just can open many from chain to ring-type, from monodentate to multiple tooth, the schiff base ligand that performance is totally different, structure is changeable, and and then synthesize diversified title complex, thereby in application, show unique characteristics.Up to now, Schiff's base and title complex thereof are widely used in fields such as medicine, catalysis, analysis, photochromic, Materials science.In addition, Schiff's base can be similar to the chemical action of coordinate bond and be attracted to metal material surface with the atoms metal generation of metal material surface, thereby the inhibiter that can be used as metallic substance, and this corrosion inhibition shows particularly evidently in acid attack environment, the corrosion inhibition when the metallic substance pickling is studied to Schiff's base many investigators.Therefore, Schiff's base and title complex thereof are subject to the attention of researcher for a long time always.But schiff base metal complex is for the corrosion inhibition of metallic substance rarely seen report.Based on this, the present invention has announced a kind of pyridoxal contracting Sulphanilic Acid Schiff's base nickel complex.This title complex has good corrosion mitigating effect when metallic substance pickling.
Summary of the invention
The object of this invention is to provide a kind of simple in structure, raw material is cheap and easy to get, prepare simple Schiff's base nickel complex and preparation method thereof, and by this Schiff's base nickel complex the inhibiter when the metallic substance pickling.
For achieving the above object, the present invention adopts following technical scheme.
A nickel complex, its structural formula is as follows:
Described Schiff's base nickel complex has good corrosion mitigating effect when metallic substance pickling.
The preparation method of described Schiff's base nickel complex is as follows: by pyridoxal hydrochloride, Sulphanilic Acid and potassium hydroxide stirring and dissolving in the mixed solvent of methyl alcohol and distilled water, add again water-soluble divalent nickel salt and a certain amount of distilled water, after stirring reaction 2 ~ 10 h, stop stirring, liquid stabilising to be mixed is to greenhouse, by liquid filtering standing.After crystallization, filter, crystallization, with being dried to obtain the nearly black crystals of brown after methanol wash, is to product.
In the preparation method of described Schiff's base nickel complex, pyridoxal hydrochloride, Sulphanilic Acid, the ratio of the consumption of potassium hydroxide and water-soluble divalent nickel salt is 1 ﹕ 0.9 ~ 1.1 ﹕ 1.8 ~ 2.2 ﹕ 0.4 ~ 1.2(mol ratios); Pyridoxal hydrochloride is 1 ~ 3.38g pyridoxal hydrochloride/100mL methyl alcohol with the ratio of the consumption of methyl alcohol; In the mixed solvent of methyl alcohol and distilled water, the ratio of the consumption of methyl alcohol and distilled water is 2:1(volume ratio); The described amount of distilled water in the amount of a certain amount of distilled water and the mixed solvent of described methyl alcohol and distilled water that adds is again identical; The temperature of stirring reaction can be controlled at room temperature to the scope of 60oC.
In the preparation method of described Schiff's base nickel complex, water-soluble divalent nickel salt is a kind of of nickelous chloride, nickelous nitrate, single nickel salt or nickel acetate.
Described Schiff's base nickel complex is used as to inhibiter in metallic substance acid cleaning process, it is the metallic substance that need clean with the scavenging solution submergence that is added with Schiff's base nickel complex, in scavenging solution, the concentration of Schiff's base nickel complex is 0.4 ~ 0.8g/L, and submergence temperature is room temperature, and the time is 5 hours; Wherein scavenging solution is that concentration is the dilute hydrochloric acid of 1.0 mol/L.
Described metallic substance is steel or copper material.
Tool of the present invention has the following advantages.
Described Schiff's base nickel complex preparation is simple, and raw material is cheap and easy to get, and when using as inhibiter, using method is simple, consumption is low, inhibition efficiency is better, has expanded the range of application of schiff base metal complex.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure of the preparation-obtained Schiff's base nickel complex of the embodiment of the present invention 1, and wherein hydrogen atom does not show.
Fig. 2 is the infrared spectrogram of the preparation-obtained Schiff's base nickel complex of the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but these enforcements do not limit the scope of the invention as example.
The present invention carries out weight loss test according to GB10124-88 < < Uniform Corrosion Method of Laboratory Immersion Test method > >.
By 0.1g pyridoxal hydrochloride, the anhydrous Sulphanilic Acid of 0.087g and 0.056g potassium hydroxide stirring and dissolving in the mixed solvent of 10mL methyl alcohol and 5mL distilled water, add again 0.12g six water nickelous chlorides and 5mL distilled water, after 50oC condensing reflux stirring reaction 2 h, stop, after question response liquid cool to room temperature, by crystallization behind liquid filtering standing 2 days.Filter, crystallization, with being dried to obtain the nearly black crystals of brown after methanol wash, is to product.Product is through infrared spectrum characterization and its crystalline structure of Single Crystal X-ray diffraction.
Embodiment 2.
By 0.1g pyridoxal hydrochloride, the anhydrous Sulphanilic Acid of 0.078g and 0.05g potassium hydroxide stirring and dissolving in the mixed solvent of 10mL methyl alcohol and 5mL distilled water, add again 0.058g six water nickelous nitrates and 5mL distilled water, under room temperature, after stirring reaction 6h, stop stirring, by liquid filtering crystallization after standing three days.Filter, crystallization, with being dried to obtain the nearly black crystals of brown after methanol wash, is to product.Product proves that through infrared spectrum characterization itself and embodiment 1 are product of the same race.
Embodiment 3.
By 1.02g pyridoxal hydrochloride, the anhydrous Sulphanilic Acid of 0.95g and 0.63g potassium hydroxide stirring and dissolving in the mixed solvent of 50mL methyl alcohol and 25mL distilled water, add again 1.57g nickel sulfate hexahydrate and 25mL distilled water, under room temperature, after stirring reaction 10h, stop stirring, by liquid filtering crystallization after standing three days.Filter, crystallization, with being dried to obtain the nearly black crystals of brown after methanol wash, is to product.Product proves that through infrared spectrum characterization itself and embodiment 1 are product of the same race.
Embodiment 4.
By 2.03g pyridoxal hydrochloride, the anhydrous Sulphanilic Acid of 1.73g and 1.12g potassium hydroxide stirring and dissolving in the mixed solvent of 60mL methyl alcohol and 30mL distilled water, add again 1.25g tetra-water acetic acid nickel and 30mL distilled water, after 60oC condensing reflux stirring reaction 2h, stop, after reaction solution cool to room temperature, by crystallization behind liquid filtering standing 1 day.Filter, crystallization, with being dried to obtain the nearly black crystals of brown after methanol wash, is to product.Product proves that through infrared spectrum characterization itself and embodiment 1 are product of the same race.
Embodiment 5.
Acid washing rolled steel corrosion inhibition detects.Experiment is A3 steel with steel disc, is of a size of 2cm * 1cm * 0.2cm, the hydrochloric acid soln that etchant solution is 1mol/L, and etchant solution consumption is 100mL, adds Schiff's base nickel complex described in 0.04g.Steel disc is immersed in etchant solution, at room temperature without stirring, soaks 5h.Recording inhibition efficiency is 69.7%.
Embodiment 6.
Acid washing rolled steel corrosion inhibition detects.Experiment is A3 steel with steel disc, is of a size of 2cm * 1cm * 0.2cm, the hydrochloric acid soln that etchant solution is 1mol/L, and etchant solution consumption is 100mL, adds Schiff's base nickel complex described in 0.08g.Steel disc is immersed in etchant solution, at room temperature without stirring, soaks 5h.Recording inhibition efficiency is 80.3%.
Embodiment 7.
Copper material pickling corrosion inhibition detects.Experiment is brass with copper sheet, is of a size of 2cm * 1cm * 0.2cm, the hydrochloric acid soln that etchant solution is 1mol/L, and etchant solution consumption is 100mL, adds Schiff's base nickel complex described in 0.04g.Copper sheet is immersed in etchant solution, at room temperature without stirring, soaks 5h.Recording inhibition efficiency is 74.1%.
Embodiment 8.
Copper material pickling corrosion inhibition detects.Experiment is brass with copper sheet, is of a size of 2cm * 1cm * 0.2cm, the hydrochloric acid soln that etchant solution is 1mol/L, and etchant solution consumption is 100mL, adds Schiff's base nickel complex described in 0.08g.Copper sheet is immersed in etchant solution, at room temperature without stirring, soaks 5h.Recording inhibition efficiency is 86.4%.
Claims (7)
- A Schiff's base nickel complex and in metallic substance acid cleaning process as the application of inhibiter.
- 2. Schiff's base nickel complex as claimed in claim 1, is characterized in that its structural formula is as follows:。
- 3. Schiff's base nickel complex as claimed in claim 1, its preparation method is as follows: by pyridoxal hydrochloride, Sulphanilic Acid and potassium hydroxide stirring and dissolving in the mixed solvent of methyl alcohol and distilled water, add again water-soluble divalent nickel salt and a certain amount of distilled water, after stirring reaction 2 ~ 10h, stop stirring, liquid stabilising to be mixed, to greenhouse, by liquid filtering standing, filters after crystallization, crystallization, with being dried to obtain the nearly black crystals of brown after methanol wash, is to product.
- 4. the preparation method of Schiff's base nickel complex as claimed in claim 3, described pyridoxal hydrochloride, Sulphanilic Acid, the ratio of the consumption of potassium hydroxide and water-soluble divalent nickel salt is 1 ﹕ 0.9 ~ 1.1 ﹕ 1.8 ~ 2.2 ﹕ 0.4 ~ 1.2(mol ratios); Described pyridoxal hydrochloride is 1 ~ 3.38g pyridoxal hydrochloride/100mL methyl alcohol with the ratio of the consumption of methyl alcohol; In the mixed solvent of described methyl alcohol and distilled water, the ratio of the consumption of methyl alcohol and distilled water is 2:1(volume ratio); The described amount of distilled water in the amount of a certain amount of distilled water and the mixed solvent of described methyl alcohol and distilled water that adds is again identical; The temperature of described stirring reaction can be controlled at room temperature to the scope of 60oC.
- 5. the preparation method of Schiff's base nickel complex as claimed in claim 3, is characterized in that, described water-soluble divalent nickel salt is a kind of of nickelous chloride, nickelous nitrate, single nickel salt or nickel acetate.
- Schiff's base nickel complex as claimed in claim 1 in metallic substance acid cleaning process as the application of inhibiter, it is characterized in that: the metallic substance that need clean with the scavenging solution submergence that is added with Schiff's base nickel complex, in scavenging solution, the concentration of Schiff's base nickel complex is 0.4 ~ 0.8g/L, submergence temperature is room temperature, and the time is 5 hours; Wherein scavenging solution is that concentration is the dilute hydrochloric acid of 1.0mol/L.
- 7. Schiff's base nickel complex as claimed in claim 1, as the application of inhibiter in metallic substance acid cleaning process, is characterized in that described metallic substance is steel or copper material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310557425.8A CN103554189B (en) | 2013-11-12 | 2013-11-12 | Schiff base nickel complex and application thereof as metal material pickling inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310557425.8A CN103554189B (en) | 2013-11-12 | 2013-11-12 | Schiff base nickel complex and application thereof as metal material pickling inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554189A true CN103554189A (en) | 2014-02-05 |
| CN103554189B CN103554189B (en) | 2016-02-17 |
Family
ID=50008583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310557425.8A Expired - Fee Related CN103554189B (en) | 2013-11-12 | 2013-11-12 | Schiff base nickel complex and application thereof as metal material pickling inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554189B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796502A (en) * | 2019-03-18 | 2019-05-24 | 重庆大学 | The method and its application of nickel complex corrosion inhibiter are prepared using dibenzyl aminodithioformic acid potassium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870724A (en) * | 1968-03-12 | 1975-03-11 | Dainippon Pharmaceutical Co | Process for preparing pyridoxal-5{40 -monophosphate |
-
2013
- 2013-11-12 CN CN201310557425.8A patent/CN103554189B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870724A (en) * | 1968-03-12 | 1975-03-11 | Dainippon Pharmaceutical Co | Process for preparing pyridoxal-5{40 -monophosphate |
Non-Patent Citations (1)
| Title |
|---|
| VUKADIN M.LEOVAC等: "《Transition metal complexes with thiosemicarbazide-based ligands. Part LIV. Nikel(II) complexes with pyridoxal semi-(PLSC) and thiosemicarbazone (PLTSC).Crystal and molecular structure of [Ni(PLSC)(H2O)3](NO3)2 and [Ni(PLTSC-H)py]NO3》", 《POLYHEDRON》, vol. 26, 7 August 2006 (2006-08-07), pages 49 - 58 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796502A (en) * | 2019-03-18 | 2019-05-24 | 重庆大学 | The method and its application of nickel complex corrosion inhibiter are prepared using dibenzyl aminodithioformic acid potassium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103554189B (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105562122B (en) | A kind of metal oxide and its preparation method and application of Ca-Ti ore type core-shell structure | |
| CN107619929B (en) | Application of amide compounds, extraction composition containing amide compounds and extraction system | |
| JP5083762B2 (en) | Porous metal complex, method for producing the same, and gas storage material containing porous metal complex | |
| CN107447108B (en) | Extraction composition, extraction system, extraction method and back extraction method | |
| CN103012442B (en) | Copper (II) composition catalyst of selective catalytic oxidation thioether and preparation method thereof | |
| CN105013509A (en) | Catalyst for water phase hydrogenation preparation of cyclopentanone from furfural or furfural alcohol and preparation method and application method thereof | |
| CN103408056B (en) | A kind of liquid-phase precipitation method prepares the method for nano cupric oxide | |
| CN103554189B (en) | Schiff base nickel complex and application thereof as metal material pickling inhibitor | |
| CN103319506B (en) | A kind of [Cu 2(L 3) 2] in-situ synthetic method | |
| Yang et al. | Green separation of rare earth elements by valence-selective crystallization of MOFs | |
| CN106753300B (en) | A kind of double effect compound type hydrate inhibitor and preparation method thereof | |
| CN101709472A (en) | Preparation method of substituted pyridine carbonylhydrazone metal corrosion inhibitor | |
| CN104772153A (en) | Preparation method and applications of steel slag-based metal oxide solid base catalyst | |
| CN104163746B (en) | Application of nano-metal composite oxide bismuth tungstate and preparation method thereof | |
| Choudhury et al. | pH-triggered changes in the supramolecular self-assembly of Cu (II) malonate complexes | |
| CN103265565B (en) | The in-situ synthetic method of 3,5-dibromosalicylic acid azine bis-Schiff base copper complex | |
| CN104447806B (en) | A kind of cyano group copper fluorescence complex and synthetic method thereof | |
| CN103113417A (en) | Cobalt-amino acid complex catalyst, preparation method and application thereof | |
| CN103086920A (en) | Novel synthetic method of o-ethoxyl benzamidine hydrochloride | |
| CN102614737A (en) | Method for gas storage and release of metal organic framework material | |
| CN102433564A (en) | Preparation method of Schiff-base corrosion inhibitor by condensation of o-oxy-acetate-benzaldehyde and substituted aniline | |
| CN103965222A (en) | Trinuclear copper imidazole-4,5-dicarboxylic acid o-phenanthroline coordination compound, preparation method and application thereof | |
| CN103553949B (en) | The preparation method of a kind of alpha-amino group-p-hydroxyphenylaceticacid methyl esters or its vitriol | |
| CN102795603A (en) | Preparation method for simultaneously obtaining porous metal oxide nano material and high-purity perylene | |
| CN107619931B (en) | Application of amide compounds, extraction composition containing amide compounds and extraction system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160217 Termination date: 20161112 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |