CN106496582A - 3 formic acid copper polymer of pyrazoles and preparation method thereof - Google Patents
3 formic acid copper polymer of pyrazoles and preparation method thereof Download PDFInfo
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- CN106496582A CN106496582A CN201610869708.XA CN201610869708A CN106496582A CN 106496582 A CN106496582 A CN 106496582A CN 201610869708 A CN201610869708 A CN 201610869708A CN 106496582 A CN106496582 A CN 106496582A
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses 3 formic acid polymer of a kind of pyrazoles and preparation method thereof.(1) weigh 0.5 ~ 1 mM of Gerhardite to be dissolved in 4 ~ 8 milliliters of distilled water, copper nitrate solution is obtained.(2) weigh 0.5 ~ 1 mM of 3 formic acid of pyrazoles to be dissolved in 3 ~ 6 milliliters of dehydrated alcohol, 3 formic acid solution of pyrazoles is obtained.(3) weigh 0.5 ~ 1 mM of imidazoles to be dissolved in 2 ~ 4 milliliters of dehydrated alcohol, imidazole solution is obtained.(4) weigh 0.5 ~ 1 mM of sodium hydroxide to be dissolved in 1 ~ 2 milliliter of distilled water, sodium hydroxide solution is obtained.(5) step (1), (2), (3) and solution obtained in (4) are added in ptfe autoclave inner bag, put stainless steel cauldron overcoat and be put in 80 degrees Celsius of baking ovens and react 48 ~ 72 hours, room temperature is down to 10 degrees Celsius of gradients per hour after the completion of reaction, kettle is driven after standing 12 hours and obtains blue solution, filtering, blue bulk crystals, as 3 formic acid polymer of pyrazoles are obtained on filter paper.Present invention process is simple, with low cost, reproducible.
Description
Technical field
The invention belongs to technical field of polymer preparation, more particularly to a kind of pyrazoles -3- formic acid polymer and its preparation side
Method.
Background technology
In recent years, the species of transition metal polymerization thing and number rapidly increase, and people are using with special construction and performance
Organic micromolecule ligand and metal ion coordination supramolecule, the polymerization of formation are synthesized by coordinate bond or other weak interactions
Thing is unique in structure and performance.But, for pyrazoles -3- formic acid polymer report still few.Due to pyrazoles -3- first
Sour coordination site is less, and coordination mode is simple, and most of coordination compounds of report belong to small molecule partner, for polymer this
Research report is still few, and therefore we, using this small molecule organic ligand synthetic polymer of pyrazoles -3- formic acid, are that such part exists
Certain foundation is provided in the research of polymer.
Content of the invention
It is an object of the invention to provide a kind of pyrazoles -3- formic acid copper polymers and preparation method thereof.
The thinking of the present invention：Using pyrazoles -3- formic acid, imidazoles and copper nitrate, copper polymer is obtained by solvent-thermal method.
Pyrazoles -3- formic acid polymer belongs to monoclinic system, and space group isP21/c, central metallic ions are Cu (II) ion.
The polymer each primitive includes Cu (II) ion, a pyrazoles -3- formic acid anion and an imidazole molecule.Pyrazoles-
N1 atoms on 3- formic acid on the O1 atoms and pyrazole ring of carboxyl are coordinated with copper ion in the form of chelating, and the N2 on pyrazole ring is former
Son and another copper ion coordination.On imidazoles, nitrogen-atoms are coordinated with copper ion.Central metallic ions Cu (II) respectively with come
Two oxygen atoms (O1, O2B) from two pyrazoles -3- formic acid, two nitrogen-atoms（N1、N2A）And the nitrogen on an imidazoles
Atom（N3）Coordination.Five coordination atoms form the tetragonal pyramid configuration of distortion around Cu (II) ion.Cd-O bond distance between
Between 2.0058-2.3858, Cd-N bond distance is between 1.9687-1.9928.
The preparation method of pyrazoles -3- formic acid polymer is concretely comprised the following steps：
(1) weigh 0.5 ~ 1 mM of Gerhardite to be dissolved in 4 ~ 8 milliliters of distilled water, copper nitrate solution is obtained.
(2) weigh 0.5 ~ 1 mM of pyrazoles -3- formic acid to be dissolved in 3 ~ 6 milliliters of dehydrated alcohol, pyrazoles -3- formic acid is obtained
Solution.
(3) weigh 0.5 ~ 1 mM of imidazoles to be dissolved in 2 ~ 4 milliliters of dehydrated alcohol, imidazole solution is obtained.
(4) weigh 0.5 ~ 1 mM of sodium hydroxide to be dissolved in 1 ~ 2 milliliter of distilled water, sodium hydroxide solution is obtained.
(5) step (1), (2), (3) and solution obtained in (4) are added in ptfe autoclave inner bag, are put
Stainless steel cauldron overcoat is put in 80 degrees Celsius of baking ovens and reacts 48 ~ 72 hours, with 10 degrees Celsius of ladders per hour after the completion of reaction
Degree is down to room temperature, drives kettle and obtains blue solution, filter and obtain blue bulk crystals on filter paper after standing 12 hours, as pyrazoles-
3- formic acid polymer.
The present invention has process is simple, with low cost, reproducible, has successfully synthesized double-core copper polymer,
Certain foundation is provided for synthesizing the polymer of the smaller ligand of transition metal.
Description of the drawings
Fig. 1 is the molecular structure of pyrazoles -3- formic acid polymer of the present invention.
Specific embodiment
Embodiment：
(1) 0.5 mM is weighed（0.1208 gram）Gerhardite is dissolved in 4 milliliters of distilled water, and copper nitrate solution is obtained.
(2) 0.5 mM is weighed（0.0556 gram）Pyrazoles -3- formic acid is dissolved in 3 milliliters of dehydrated alcohol, and prepared pyrazoles -
3- formic acid solutions.
(3) 0.5 mM is weighed（0.0343 gram）Imidazoles is dissolved in 2 milliliters of dehydrated alcohol, and imidazole solution is obtained.
(4) 0.5 mM is weighed（0.0200 gram）Sodium hydroxide is dissolved in 1 milliliter of distilled water, sodium hydroxide is obtained molten
Liquid.
(5) step (1), (2), (3) and solution obtained in (4) are added in ptfe autoclave inner bag, are put
Stainless steel cauldron overcoat is put in 80 degrees Celsius of baking ovens and reacts 50 hours, with 10 degrees Celsius of gradient drops per hour after the completion of reaction
To room temperature, kettle is driven after standing 12 hours and obtains blue solution, filtered and obtain blue bulk crystals, as pyrazoles -3- first on filter paper
Acid polymer.
Pyrazoles -3- formic acid polymer molecular structures are shown in that Fig. 1, crystallographic structural analysis show, the polymer belongs to monoclinic system,
Space group isP21/c, central metallic ions are Cu (II) ion.The polymer each primitive comprising Cu (II) ion, one
Individual pyrazoles -3- formic acid anion and an imidazole molecule.N1 atoms on pyrazoles -3- formic acid on the O1 atoms and pyrazole ring of carboxyl
It is coordinated with copper ion in the form of chelating, the N2 atoms on pyrazole ring are coordinated with another copper ion.Nitrogen-atoms on imidazoles
It is coordinated with copper ion.Central metallic ions Cu (II) respectively with two pyrazoles -3- formic acid two oxygen atoms (O1,
O2B), two nitrogen-atoms（N1、N2A）And the nitrogen-atoms on an imidazoles（N3）Coordination.Five coordination atoms Cu (II) from
The tetragonal pyramid configuration of distortion is formed around sub.Between 2.0058-2.3858, Cd-N bond distance's Cd-O bond distance exists
1.9687 between -1.9928.
Claims (2)
1. a kind of pyrazoles -3- formic acid copper polymers, it is characterised in that the molecular structural formula of pyrazoles -3- formic acid copper polymers is：
Pyrazoles -3- formic acid polymer belongs to monoclinic system, and space group is P21/ c, central metallic ions are Cu (II) ion；This gathers
Compound each primitive includes Cu (II) ion, a pyrazoles -3- formic acid anion and an imidazole molecule；Pyrazoles -3- first
N1 atoms in acid on the O1 atoms and pyrazole ring of carboxyl in the form of chelating with copper ion be coordinated, the N2 atoms on pyrazole ring with
Another copper ion coordination；On imidazoles, nitrogen-atoms are coordinated with copper ion；Central metallic ions Cu (II) respectively with from two
Two oxygen atoms on individual pyrazoles -3- formic acid are O1 and O2B, and two nitrogen-atoms are that the nitrogen on N1 and N2A and imidazoles is former
Son is N3 coordinations；Five coordination atoms form the tetragonal pyramid configuration of distortion around Cu (II) ion；Cd-O bond distance betweenBetween, Cd-N bond distance existsBetween.
2. the preparation method of pyrazoles -3- formic acid polymer according to claim 1, it is characterised in that concretely comprise the following steps：
(1) weigh 0.5～1 mM of Gerhardite to be dissolved in 4～8 milliliters of distilled water, copper nitrate solution is obtained；
(2) weigh 0.5～1 mM of pyrazoles -3- formic acid to be dissolved in 3～6 milliliters of dehydrated alcohol, pyrazoles -3- formic acid is obtained molten
Liquid；
(3) weigh 0.5～1 mM of imidazoles to be dissolved in 2～4 milliliters of dehydrated alcohol, imidazole solution is obtained；
(4) weigh 0.5～1 mM of sodium hydroxide to be dissolved in 1～2 milliliter of distilled water, sodium hydroxide solution is obtained；
(5) step (1), (2), (3) and solution obtained in (4) are added in ptfe autoclave inner bag, are put stainless
Steel reactor overcoat is put in 80 degrees Celsius of baking ovens and reacts 48～72 hours, with 10 degrees Celsius of gradient drops per hour after the completion of reaction
To room temperature, kettle is driven after standing 12 hours and obtains blue solution, filtered and obtain blue bulk crystals, as pyrazoles -3- first on filter paper
Acid polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610869708.XA CN106496582A (en) | 2016-10-01 | 2016-10-01 | 3 formic acid copper polymer of pyrazoles and preparation method thereof |
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| CN201610869708.XA CN106496582A (en) | 2016-10-01 | 2016-10-01 | 3 formic acid copper polymer of pyrazoles and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995456A (en) * | 2017-04-24 | 2017-08-01 | 桂林理工大学 | Preparation, structure and its application of the copper formate complexes of pyrazoles 3 |
| CN109456494A (en) * | 2018-11-23 | 2019-03-12 | 西安工业大学 | A method of acid amide type octahedron MOFs is quickly prepared by raw material room temperature of copper formate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028305A (en) * | 2014-06-19 | 2014-09-10 | 渤海大学 | Keggin-type crystalline material modified based on butyl parazole copper complexes, preparation method of Keggin-type crystalline material, and application of Keggin-type crystalline material to photo-catalytic material |
| CN104497015A (en) * | 2014-12-08 | 2015-04-08 | 天津师范大学 | Copper coordination polymer having ion exchange and solvent exchange functions and application of copper coordination polymer |
| CN104892643A (en) * | 2015-04-01 | 2015-09-09 | 广州科技贸易职业学院 | Tetranuclear copper cluster compound synthesized through in-situ ligand reaction, and synthetic method and application thereof |
-
2016
- 2016-10-01 CN CN201610869708.XA patent/CN106496582A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028305A (en) * | 2014-06-19 | 2014-09-10 | 渤海大学 | Keggin-type crystalline material modified based on butyl parazole copper complexes, preparation method of Keggin-type crystalline material, and application of Keggin-type crystalline material to photo-catalytic material |
| CN104497015A (en) * | 2014-12-08 | 2015-04-08 | 天津师范大学 | Copper coordination polymer having ion exchange and solvent exchange functions and application of copper coordination polymer |
| CN104892643A (en) * | 2015-04-01 | 2015-09-09 | 广州科技贸易职业学院 | Tetranuclear copper cluster compound synthesized through in-situ ligand reaction, and synthetic method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995456A (en) * | 2017-04-24 | 2017-08-01 | 桂林理工大学 | Preparation, structure and its application of the copper formate complexes of pyrazoles 3 |
| CN109456494A (en) * | 2018-11-23 | 2019-03-12 | 西安工业大学 | A method of acid amide type octahedron MOFs is quickly prepared by raw material room temperature of copper formate |
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