CN101723962A - Simple pyridinedicarboxylic acid rare earth complex and preparation method thereof - Google Patents
Simple pyridinedicarboxylic acid rare earth complex and preparation method thereof Download PDFInfo
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- CN101723962A CN101723962A CN200810202107A CN200810202107A CN101723962A CN 101723962 A CN101723962 A CN 101723962A CN 200810202107 A CN200810202107 A CN 200810202107A CN 200810202107 A CN200810202107 A CN 200810202107A CN 101723962 A CN101723962 A CN 101723962A
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- rare earth
- solution
- pyridine
- acid
- dioctyl phthalate
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Abstract
The invention relates to a simple pyridinedicarboxylic acid rare earth complex as well as a preparation method and application thereof. The simple pyridinedicarboxylic acid rare earth complex is characterized by having the following chemical general formula: MxREy(pydcH)a(pydc)b.n H2O and being used as a rare earth antibacterial agent. The invention has moderate process conditions, simple needed equipment and convenient operation; in addition, the obtained simple pyridinedicarboxylic acid rare earth complex has high antibiosis efficiency, broad antibiosis spectrum, long antibiosis aging, and the like, has better antibiosis effect on colibacillus, staphylococcus aureus, and the like and can be widely used for various antibacterial materials.
Description
Technical field
The present invention relates to simple title complex of a class pyridine carboxylic acid rare earth and preparation method thereof, particularly a class is the simple rare earth compounding of part with dinicotinic acid and derivative.
Background technology
Rare earth element comprises scandium, yttrium and group of the lanthanides totally 16 elements, because their ionic charges are identical, radius is approaching, so character is closely similar.Materials such as that rare earth salts and title complex thereof can be used as is luminous, magnetic, catalysis, air-sensitive sensing, superconduction, be widely used in the various fields of industrial production and scientific research, and the application of rare earth compound at aspects such as medicine, agricultural, biological chemistry and environmental purification is a brand-new field, especially aspect anti-biotic material, rare earth salts and organic coordination compound thereof receive much concern because of having characteristics such as the strong and has a broad antifungal spectrum of germ resistance.
Rare earth ion has intensive and is penetrated into the plysiochemical character of biological intravital uniqueness, can disclose Na in the organism as probe
+, K
+, Ca
2+Function Deng metal ion.Utilize this biological nature, rare earth salts and rare earth organic complex thereof have advantages such as germ resistance is strong, has a broad antifungal spectrum, good heat resistance as antiseptic-germicide, therefore become the focus of domestic and international research.
Chinese invention patent CN101020820 and CN101020819 have introduced a kind of by two kinds of rare earth ions and two kinds of metal-rare-earth title complexs that organic ligand forms, and are mainly used in the plastics film of agriculture field as light-converting agent.The metal-rare-earth title complex that above-mentioned patent provides is not suitable as antiseptic-germicide and uses.
Chinese invention patent CN1803804 has introduced a kind of by two trivalent rare earth ionses and two rare earth metal complexs that part forms, can be used as photoelectric functional material and be applied to each field, but a kind of part 3 wherein, 5-two (4-carboxyl benzoic ether) the easy oxidation of methyl benzoate is restricted in application.
It is the rare earth metal complex of main part with the beta-diketon or derivatives thereof that Chinese invention patent CN1730522, CN1730454, CN101037390 and CN1687079 have introduced a kind of, this title complex is mainly used in the photoluminescence field of functional materials, have advantages such as good light stability, thermotolerance height, difficult generation bloom phenomenon as photostabilizer, but in title complex, contain more hydroxide ion or hydroxyl, under the irradiation of light, be easy to go bad.
Chinese invention patent CN101220060 relates to the novel single-indenyl rareearth complexes of a class, and this title complex is obtained by substituted indenyl part and the reaction of rare earth alkyl compound.This class title complex is mainly used in the polymerization of catalyzed ethylene, vinylbenzene, norbornylene and alhpa olefin, and is relatively poor as antiseptic-germicide Use Limitation fruit.
Chinese invention patent CN101019555 has introduced a kind of ternary RE-amino acid-vitamin complex as plant growth conditioning agent.It is the rare earth compounding of part with the kilnitamin that Chinese invention patent CN1044029 discloses a kind of, mainly as disinfectant use in agriculture and plant-growth regulator, but be kilnitamin just because of part, so its sterilization effect is not fine.
Chinese invention patent CN101235047 and CN101235048 disclose by sunaptic acid and 1, and the 10-phenanthroline is the rare earth compounding of part and the application aspect antimycotic thereof.Naphthoic acid is a monocarboxylic acid, be not very desirable aspect design molecular structure and the self-assembly formation super molecular complex.
Chinese invention patent CN101156589 discloses binary or the ternary complex that a kind of rare earth element and oxine and other organic ligands are formed, and this kind Caspase inhibitors is mainly used in the agricultural as agricultural bactericide control plant fungus damage.But the organic ligand thermostability that this patent provides is not high, easily decomposes.
Chinese invention patent CN101041666 has related to a kind of rare earth ternary complexes of being made up of Schiff's base and phenanthroline or pyridine, is applied to the environmental purification field as antibacterial agent.The performance of product was subjected to Effect of Environmental bigger when this rare earth ternary complexes was used as antiseptic-germicide.
Summary of the invention
The object of the present invention is to provide simple pyridinedicarboxylicacid acid rare earth complex and its production and application,, satisfy the needs of the parties concerned to overcome the above-mentioned defective that prior art exists.
Simple pyridinedicarboxylicacid acid rare earth complex provided by the invention, its chemical general formula is:
M
xRE
y(pydcH)
a(pydc)
b·nH
2O
Wherein:
RE is a kind of in scandium (Sc), yttrium (Y) or the lanthanon;
PydcH
2Expression contains two unionized dinicotinic acids of proton;
PydcH represents the single anion (pydcH of the dinicotinic acid of a carboxylic ionsization
-);
Pydc represents the dianion (pydc of two whole Ionized dinicotinic acids of carboxyl
2-);
Described dinicotinic acid is a pyridine-2,3-dioctyl phthalate, pyridine-2,4-dioctyl phthalate, pyridine-2,5-dioctyl phthalate, pyridine-2,6-dioctyl phthalate, pyridine-3,4-dioctyl phthalate or pyridine-3,5-dioctyl phthalate;
M is Na
+, K
+, NH
4 +Or pyridine (py);
X=0～3, y=1～2, a=0～6, b=0～6, a and b are not 0 simultaneously, n=1～15.
The preparation method of simple pyridinedicarboxylicacid acid rare earth complex of the present invention comprises the steps:
(1) rare-earth salts in the water-soluble or ethanol, is prepared the rare earth ion solution A;
Described rare-earth salts is rare earth chloride, rare-earth oxalate or rare earth nitrate, the preferred YCl of described rare-earth salts
3, Ce
2(C
2O
4)
3, Y (NO
3)
3Or La (NO
3)
3
The concentration of solution A is 0.01～0.20molL
-1
(2) the part dinicotinic acid is dissolved in the solvent, obtains solution B;
Described solvent is any one or two kinds in water, methyl-sulphoxide, acetone, butanone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol or the ethanol, is preferably water or ethanol;
The concentration of dinicotinic acid is 0.02～0.40molL in the solution B
-1
(3) solution A is mixed with solution B, behind 50～80 ℃ of stirring 10～30min, use pH value to 6～7 of alkaline solution regulator solution then, 50～80 ℃, react 2～6h under preferred 60～70 ℃ of temperature, preferred 3～4h collects described simple pyridinedicarboxylicacid acid rare earth complex then from reaction product.
The solute in the solution A and the mol ratio of the solute in the solution B are 1: 1～1: 3;
Described alkaline solution is a kind of in NaOH, KOH or the ammoniacal liquor, and the concentration of alkaline solution is 0.1～1.0molL
-1
Simple pyridinedicarboxylicacid acid rare earth complex provided by the invention can be used as the rare earth antiseptic-germicide and uses.
Simple pyridinedicarboxylicacid acid rare earth complex provided by the invention has the following advantages:
(1) this synthetic method craft mild condition, required equipment is simple, and is easy to operate.
(2) the gained simple pyridinedicarboxylicacid acid rare earth complex has advantages such as antimicrobial efficiency height, has a broad antifungal spectrum, antibiotic timeliness length, and intestinal bacteria, streptococcus aureus etc. are had anti-microbial effect preferably, can be widely used in the various anti-biotic materials.
Embodiment
Embodiment 1
Take by weighing Yttrium trichloride 0.1175g and be dissolved in and make solution (A1) in the 10mL water, with 0.3010g pyridine-2,6-dioctyl phthalate (pydcH
2) be dissolved in 60 ℃ the 30mL water and make solution (B1).
Solution (A1) is dropped to solution (B1), behind 60 ℃ of stirring 20min, have a large amount of white precipitates to occur; Use 1.0molL
-1The pH value of NaOH solution conditioned reaction system about 6.5.Behind 60 ℃ of continuation stirring reaction 4h, leave standstill 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain Na at last
3Y (pydc)
312H
2The simple rare earth metal organic coordination compound of O.
Embodiment 2
Take by weighing Yttrium trinitrate 0.1658g and be dissolved in and make solution (A2) in the 10mL ethanol, with 0.3010g pyridine-2,6-dioctyl phthalate (pydcH
2) be dissolved in 60 ℃ the 30mL ethanol and make solution (B2).
Solution (A2) is dropped to solution (B2), behind 60 ℃ of stirring 10min, have a large amount of white precipitates to occur; Behind 60 ℃ of continuation stirring reaction 3h, still aging 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain Y (pydcH) at last
32H
2The simple rare earth metal organic coordination compound of O.
Embodiment 3
Take by weighing Yttrium trinitrate 0.1658g and be dissolved in and make solution (A3) in the 10mL ethanol, with 0.3010g pyridine-2,6-dioctyl phthalate (pydcH
2) be dissolved in 60 ℃ 30mL pyridine (py) solution and make solution (B3).
Solution (A3) is dropped to solution (B3), behind 60 ℃ of stirring 15min, have a large amount of white precipitates to occur; Behind 60 ℃ of continuation stirring reaction 4h, still aging 24h under the room temperature.Filtering, is that 1: 1 aqueous ethanolic solution washs with volume ratio, and 60 ℃ of vacuum-dryings obtain Y (pyH) at last
3(pydc)
33H
2The simple rare earth metal organic coordination compound of O.
Embodiment 4
Take by weighing Yttrium trichloride 0.1175g and be dissolved in and make solution (A4) in the 10mL water, with 0.2006g pyridine-2,6-dioctyl phthalate (pydcH
2) be dissolved in 60 ℃ the 30mL water and make solution (B4).
Solution (A4) is dropped to solution (B4), and behind 60 ℃ of stirring 20min, it is muddy that liquid becomes; Use 1.0molL
-1The pH value of NaOH solution conditioned reaction system about 6.5.Behind 60 ℃ of continuation stirring reaction 4h, leave standstill 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain NaY (pydc) at last
25H
2The simple rare earth metal organic coordination compound of O.
Embodiment 5
Take by weighing Yttrium trinitrate 0.0826g and be dissolved in and make solution (A5) in the 5mL water, take by weighing lanthanum nitrate 0.0976g and be dissolved in and make solution (B5) in the 5mL water, with 0.3010g pyridine-2,6-dioctyl phthalate (pydcH
2) be dissolved in 60 ℃ the 30mL water and make solution (C5).
Drop in the solution (C5) after solution (A5) and solution (B5) at room temperature mixed, 60 ℃ stir 20min after, have a large amount of white precipitates to occur; Use 1.0molL
-1The pH value of NaOH solution conditioned reaction system about 6.5.Behind 60 ℃ of continuation stirring reaction 4h, leave standstill 24h under the room temperature.Filter, washing, 60 ℃ of vacuum-dryings obtain Na at last
3La
0.5Y
0.5(pydc)
312H
2The simple rare earth metal organic coordination compound of O.
Embodiment 6
Various title complexs prepared among the embodiment 1～5 are done minimal inhibitory concentration (MIC) test respectively, data are as follows: title complex to colibacillary MIC between 200～300mg/L, to the MIC (the more little expression antibacterial effect of MIC is good more) between 300～450mg/L of streptococcus aureus.The result shows that the MIC of gained title complex is far smaller than the regulation of the antiseptic-germicide MIC＜800mg/L of chemical industry standard code, and antibacterial effect is obvious.
The main range of application of the said goods is the aspects such as packaging material, building coating, sports goods, furniture material, rubber plastic, adhesive, toy, biological medicine, agricultural, have the advantages such as antimicrobial efficiency height, has a broad antifungal spectrum, antibiotic timeliness length, Escherichia coli, staphylococcus aureus etc. are had preferably antibiotic effect.
Claims (9)
1. a simple pyridinedicarboxylicacid acid rare earth complex is characterized in that, chemical general formula is:
M
xRE
y(pydcH)
a(pydc)
b·nH
2O
Wherein:
RE is a kind of in scandium (Sc), yttrium (Y) or the lanthanon;
PydcH
2Expression contains two unionized dinicotinic acids of proton;
PydcH represents the single anion (pydcH of the dinicotinic acid of a carboxylic ionsization
-);
Pydc represents the dianion (pydc of two whole Ionized dinicotinic acids of carboxyl
2-);
M is Na
+, K
+, NH
4 +Or pyridine (py);
X=0～3, y=1～2, a=0～6, b=0～6, a and b can not be 0 simultaneously, n=1～15.
2. simple pyridinedicarboxylicacid acid rare earth complex according to claim 1 is characterized in that, described dinicotinic acid is a pyridine-2,3-dioctyl phthalate, pyridine-2,4-dioctyl phthalate, pyridine-2,5-dioctyl phthalate, pyridine-2,6-dioctyl phthalate, pyridine-3,4-dioctyl phthalate or pyridine-3,5-dioctyl phthalate.
3. simple pyridinedicarboxylicacid acid rare earth complex according to claim 1 is characterized in that, preferred RE ion is Y
3+, Ce
3+Or La
3+
4. the preparation method of claim 1,2 or 3 described simple pyridinedicarboxylicacid acid rare earth complexes is characterized in that, comprises the steps:
(1) rare salt in the water-soluble or ethanol, is prepared the rare earth ion solution A;
(2) the part dinicotinic acid is dissolved in the solvent, obtains solution B;
(3) solution A is mixed with solution B, behind 50～80 ℃ of stirring 10～30min, with pH value to 6～7 of alkaline solution regulator solution, under 50～80 ℃ of temperature, react 2～6h then, from reaction product, collect described simple pyridinedicarboxylicacid acid rare earth complex then.
5. method according to claim 4 is characterized in that, described rare-earth salts is rare earth chloride, lanthanon acetate or rare earth nitrate; The concentration of solution A is 0.01～0.20molL
-1The solute in the solution A and the mol ratio of the solute in the solution B are 1: 1～1: 3.
6. method according to claim 5 is characterized in that, described rare-earth salts is YCl
3, Ce
2(C
2O
4)
3, Y (NO
3)
3Or La (NO
3)
3
7. method according to claim 4 is characterized in that, described solvent is any one or two kinds in water, methyl-sulphoxide, acetone, butanone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol or the ethanol; The concentration of dinicotinic acid is 0.02～0.20molL in the solution B
-1
8. method according to claim 4 is characterized in that, described alkaline solution is a kind of in NaOH, KOH or the ammoniacal liquor, and the concentration of alkaline solution is 0.1～1.0molL
-1
9. claim 1,2 or 3 described simple pyridinedicarboxylicacid acid rare earth complexes are used as antiseptic-germicide.
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|---|---|---|---|---|
| CN105037907A (en) * | 2015-06-18 | 2015-11-11 | 王宏城 | Novel EVA composition for packing material and preparation method of EVA composition |
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| JP2017043559A (en) * | 2015-08-27 | 2017-03-02 | 住化エンバイロメンタルサイエンス株式会社 | Antibacterial agent composition |
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| CN111205312A (en) * | 2020-03-31 | 2020-05-29 | 张治滔 | Antibacterial rare earth complex material and preparation method thereof |
| CN114736222A (en) * | 2022-03-30 | 2022-07-12 | 厦门稀土材料研究所 | Rare earth-based complex antibacterial agent and preparation method thereof |
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| CN117229755A (en) * | 2023-08-30 | 2023-12-15 | 中国科学院重庆绿色智能技术研究院 | Water-soluble supermolecule binder with rare earth catalytic function, preparation method thereof and application thereof in lithium-sulfur battery |
-
2008
- 2008-10-31 CN CN200810202107A patent/CN101723962A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037907A (en) * | 2015-06-18 | 2015-11-11 | 王宏城 | Novel EVA composition for packing material and preparation method of EVA composition |
| JP2017043559A (en) * | 2015-08-27 | 2017-03-02 | 住化エンバイロメンタルサイエンス株式会社 | Antibacterial agent composition |
| CN105567218A (en) * | 2015-12-25 | 2016-05-11 | 哈尔滨工业大学 | Red luminescent material europium coordination polymer and preparation method thereof and preparation method of complex light energy conversion film based on red luminescent material europium coordination polymer |
| CN107129728A (en) * | 2017-05-19 | 2017-09-05 | 浙江伟星新型建材股份有限公司 | A kind of antibiotic fungus-resisting paint and preparation method thereof |
| CN111205312A (en) * | 2020-03-31 | 2020-05-29 | 张治滔 | Antibacterial rare earth complex material and preparation method thereof |
| CN114736222A (en) * | 2022-03-30 | 2022-07-12 | 厦门稀土材料研究所 | Rare earth-based complex antibacterial agent and preparation method thereof |
| CN114806307A (en) * | 2022-03-30 | 2022-07-29 | 厦门稀土材料研究所 | Rare earth-based complex environment-friendly marine antifouling paint and preparation method thereof |
| CN114806307B (en) * | 2022-03-30 | 2023-08-29 | 厦门稀土材料研究所 | Rare earth-based complex environment-friendly marine antifouling paint and preparation method thereof |
| CN117229755A (en) * | 2023-08-30 | 2023-12-15 | 中国科学院重庆绿色智能技术研究院 | Water-soluble supermolecule binder with rare earth catalytic function, preparation method thereof and application thereof in lithium-sulfur battery |
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Application publication date: 20100609 |