CN103145978A - Pegylation polyoxometallate and preparation method thereof - Google Patents
Pegylation polyoxometallate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses pegylation polyoxometallate and preparation method thereof. According to the invention, polyethylene glycol and polyoxometallate are connected by utilizing a covalent bond mode, and a pegylated tungsten-containing polyoxometallate hybrid polymer is obtained. The method comprises the following synthesis steps: 1) reacting polyethylene glycol with succinic anhydride to obtain carboxyl polyethylene glycol; 2) carrying out an amidation reaction between the carboxyl polyethylene glycol and trihydroxymethyl aminomethane to obtain trihydroxymethyl polyethylene glycol; and 3) reacting the trihydroxymethyl polyethylene glycol and the tungsten-containing polyoxometallate to obtain the hybrid compound. The pegylated polyoxometallate hybrid compound is synthesized in the covalent bond mode. According to the synthetic method, a novel organic-inorganic hybrid compound can be obtained, the preparation method is easy and feasible, and the reaction process is easy to control, simple in purification and high in yield. According to the hybrid compound, the excellent performances of the inorganic polyoxometallate and organic polyethylene glycol are kept, so that the hybrid molecule has potential application values in the aspects of catalysis, materials, medicines and the like.
Description
Technical field
The present invention relates to the preparation of the polyoxometallate hybrid compounds of Pegylation, obtain novel hybrid inorganic-organic compound on the tungstenic polyoxometallate thereby utilize this method the polyoxyethylene glycol of different molecular weight can be connected to.
Background technology
Polyoxometallate claims again multi-metal oxygen cluster (Polyoxometalates, be abbreviated as POMs, be called for short polyacid), be to be had the negatively charged ion unit molecule duster compound of definite structure by the class that the early transition metal atom forms by oxygen coordination bridging, wherein take elements such as vanadium, molybdenum, tungsten as main representative.The transmission, the storage power that have good electronics and proton due to polyoxometallate, special redox potential and stronger proton are acid, it all demonstrates tempting application prospect in catalysis, photoelectricity, the energy, material, biology, medicine and other fields, therefore causes gradually in recent years various countries scientist's extensive concern.Yet polyoxometallate exists with the form of crystal or powder usually as a kind of inorganic materials, bad being dissolved in common solvent, be difficult to machine-shaping, and it has high lattice energy, the pH value stabilization is low, therefore poor with the consistency of other materials, it is a kind of material of difficult processing from the angle of material.These factors have limited it to a great extent as actual development and the application of material and device.Therefore, making great efforts molecule, device that the new method of exploitation prepares take polyoxometallate as main body is very important.The method of preparation is divided into two kinds of non covalent bond and covalent linkage.The hybrid compounds that non covalent bond obtains easily is separated when processing treatment, and is unstable in nature, therefore has been subject to certain restriction on using.We are devoted to obtain hybrid compounds with the mode that covalent linkage connects, and its stable in properties more can be widely used in practice.
Polymkeric substance is contemporary the most widely used organic synthesis material, has advantages of that easy processing, easily modification, resolvability, good stability etc. are numerous, and these advantages can make up polyoxometallate deficiency in actual applications.The polymkeric substance of selecting in the present invention is polyoxyethylene glycol, and it is suitability for industrialized production, and we can buy the product of different molecular weight in enormous quantities in market, and molecular weight distribution all very narrow (PDI＜1.1).Soluble in water and the multiple organic solvent of polyoxyethylene glycol simultaneously, and with many organic matter components, good intermiscibility is arranged, nontoxic, nonirritant has good stability, is present scientist's research one of polymkeric substance the most widely.Therefore, the method that we utilize covalent linkage to modify links together polyoxyethylene glycol and polyoxometallate, thereby obtains the novel hybrid inorganic-organic compound of a class.
Summary of the invention
The present invention be directed to above-mentioned technical Analysis, provide a kind of simple and practical, with low cost and be easy to realize the chemical synthesis process that utilizes of suitability for industrialized production, utilize this method to obtain to obtain the hybrid compounds of the Pegylation polyoxometallate of different molecular weight.
Technical scheme of the present invention:
Synthetic method is to utilize R-C (CH
2OH)
3(R=CH
3, NO
2, CH
2OH) with [P
2W
15V
3O
62l
9-esterification occurs, namely replace bridging at V with alkoxyl group
3Sauerstoffatom on bunch comes covalently bound polyoxometallate.Can obtain in this way an end connection polyoxometallate and be similar to A-B type hybrid compounds, its chemical formula is respectively:
TBA
6H
3[(P
2W
15V
3O
59)(OCH
2)
3CNHCOCH
2CH
2CO(OCH
2CH2)
nOCH
3]，TBA＝((C
4H
9)
4N)
+。
The molecular-weight average of described polyoxyethylene glycol is 1000,2000,5000.
The synthesis step of described preparation Pegylation polyoxometallate hybrid compounds is as follows:
1) carboxy polyethylene glycol is synthetic
Under argon shield, with polyoxyethylene glycol, succinyl oxide and DMAP are dissolved in dry toluene, stir and are warming up to 80 ℃, reaction 12h.Be spin-dried for after reaction, with the methylene dichloride dissolving, use successively the aqueous hydrochloric acid of PH=2, the saturated sodium-chloride water solution extraction.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid.
2) the trishydroxymethyl polyoxyethylene glycol is synthetic
Under argon shield, with carboxy polyethylene glycol, 2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline and Tutofusin tris are dissolved in anhydrous acetonitrile, stir and are warming up to 80 ℃, reaction 24h.Be spin-dried for after reaction, with the methylene dichloride dissolving, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid.
3) Pegylation polyoxometallate hybrid compounds is synthetic
Under argon shield, with trishydroxymethyl polyoxyethylene glycol and polyoxometallate TBA
6H
3P
2W
15V
3O
62Be dissolved in DMF, stir and be warming up to 80 ℃, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid.
The mol ratio of described polyoxyethylene glycol, succinyl oxide and DMAP is 1: 1.2-2: 1.0-1.3; Carboxy polyethylene glycol, 2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-dihydroquinoline and the mol ratio of Tutofusin tris be 1: 1.2-2: 1.2-2.The synthetic route of above-mentioned Pegylation polyoxometallate hybrid compounds is expressed as follows:
Advantage of the present invention is: first Application covalent linkage of the present invention links together polyoxyethylene glycol and polyoxometallate, and synthetic hydridization molecule can be dissolved in more organic solvent compared to simple polyoxometallate, has strengthened greatly its stability.The method synthesis technique is simple, mild condition, easy handling, reaction are easily controlled, product purity is high, be convenient to realize suitability for industrialized production and apply.
Description of drawings
Fig. 1 is for adopting the GPC spectrogram of molecule described in embodiment 1.
Fig. 2 adopts molecule described in embodiment 1
1H NMR spectrogram.
Fig. 3 is for adopting the GPC spectrogram of molecule described in embodiment 2.
Fig. 4 adopts molecule described in embodiment 2
1H NMR spectrogram.
Fig. 5 is for adopting the GPC spectrogram of molecule described in embodiment 3.
Fig. 6 adopts molecule described in embodiment 3
1H NMR spectrogram.
Fig. 7 adopts molecule described in embodiment 1, example 2 and example 3
31P NMR spectrogram.
Specific implementation method
Embodiment 1:
Using the molecular-weight average of polyoxyethylene glycol is that 1000, one ends are-OH, and an end is-OCH
3
1) carboxy polyethylene glycol is synthetic
Under argon shield, with the 8g cetomacrogol 1000,1.2g succinyl oxide, 0.98g4-Dimethylamino pyridine are dissolved in the 50mL dry toluene, stir and are warming up to 80 ℃, reaction 12h.Be spin-dried for after reaction, with the methylene dichloride dissolving, use successively the aqueous hydrochloric acid of PH=2, the saturated sodium-chloride water solution extraction.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid 5.0g, productive rate 56.8%.
2) the trishydroxymethyl polyoxyethylene glycol is synthetic
Under argon shield, with 0.5g carboxy polyethylene glycol 1000,0.15g2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-dihydroquinoline, the 0.08g Tutofusin tris is dissolved in the 30mL anhydrous acetonitrile, stirs and is warming up to 80 ℃, reaction 24h.Be spin-dried for after reaction, with the methylene dichloride dissolving, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid 0.21g, productive rate 38.9%.
3) Pegylation polyoxometallate hybrid compounds is synthetic
Under argon shield, with 0.14g trishydroxymethyl cetomacrogol 1000,0.58g polyoxometallate TBA
6H
3P
2W
15V
3O
62, be dissolved in the 50mL DMF, stir and be warming up to 80 ℃, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid 0.6g, productive rate 83.3%.
Embodiment 2:
Using the molecular-weight average of polyoxyethylene glycol is that 2000, one ends are-OH, and an end is-OCH
3
1) carboxy polyethylene glycol is synthetic
Under argon shield, with the 5g Macrogol 2000,0.38g succinyl oxide, 0.32g4-Dimethylamino pyridine are dissolved in the 50mL dry toluene, stir and are warming up to 80 ℃, reaction 12h.Be spin-dried for after reaction, with the methylene dichloride dissolving, use successively the aqueous hydrochloric acid of PH=2, the saturated sodium-chloride water solution extraction.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid 4.5g, productive rate 85.7%.
2) the trishydroxymethyl polyoxyethylene glycol is synthetic
Under argon shield, with 0.4g carboxy polyethylene glycol 2000,0.07g2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-dihydroquinoline, the 0.03g Tutofusin tris is dissolved in the 30mL anhydrous acetonitrile, stirs and is warming up to 80 ℃, reaction 24h.Be spin-dried for after reaction, with the methylene dichloride dissolving, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid 0.37g, productive rate 88.0%.
3) Pegylation polyoxometallate hybrid compounds is synthetic
Under argon shield, with 0.15g trishydroxymethyl Macrogol 2000,0.37g polyoxometallate TBA
6H
3P
2W
15V
3O
62, be dissolved in the 50mL DMF, stir and be warming up to 80 ℃, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid 0.48g, productive rate 92.3%.
Embodiment 3:
Using the molecular-weight average of polyoxyethylene glycol is that 5000, one ends are-OH, and an end is-OCH
3
1) carboxy polyethylene glycol is synthetic
Under argon shield, with 5g polyoxyethylene glycol 5000,0.12g succinyl oxide, 0.13g4-Dimethylamino pyridine are dissolved in the 50mL dry toluene, stir and are warming up to 80 ℃, reaction 12h.Be spin-dried for after reaction, with the methylene dichloride dissolving, use successively the aqueous hydrochloric acid of PH=2, the saturated sodium-chloride water solution extraction.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid 4.8g, productive rate 94.3%.
2) the trishydroxymethyl polyoxyethylene glycol is synthetic
Under argon shield, with 0.4g carboxy polyethylene glycol 5000,0.029g2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-dihydroquinoline, the 0.012g Tutofusin tris is dissolved in the 30mL anhydrous acetonitrile, stirs and is warming up to 80 ℃, reaction 24h.Be spin-dried for after reaction, with the methylene dichloride dissolving, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid 0.38g, productive rate 92.7%.
3) Pegylation polyoxometallate hybrid compounds is synthetic
Under argon shield, with 0.2g trishydroxymethyl methyl polyoxyethylene glycol 5000,0.23g polyoxometallate TBA
6H
3P
2W
15V
3O
62, be dissolved in the 50mL DMF, stir and be warming up to 80 ℃, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid 0.38g, productive rate 88.4%.
Claims (4)
1. invention utilizes the mode of covalent linkage that polyoxyethylene glycol and polyoxometallate are coupled together first, the hybridized polymer of synthesizing polyethylene glycol tungstenic polyoxometallate.
2. according to claim 1, synthetic method is to replace the Sauerstoffatom of bridging on V3 bunch with alkoxyl group to come covalently bound polyoxometallate.Its feature synthesis step is as follows:
Under argon shield, with polyoxyethylene glycol, succinyl oxide and DMAP are dissolved in dry toluene, stirring and refluxing is spin-dried for after reaction, dissolves with methylene dichloride, use successively the aqueous hydrochloric acid of PH=2, saturated sodium-chloride water solution extraction, organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid, and its name is called carboxy polyethylene glycol; Under argon shield, with carboxy polyethylene glycol, 2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline and Tutofusin tris are dissolved in anhydrous acetonitrile, and stirring and refluxing is spin-dried for after reaction, with the methylene dichloride dissolving, with saturated sodium-chloride water solution extraction, organic phase, spend the night with anhydrous sodium sulfate drying, afterwards it is carried out suction filtration, concentrated, precipitate in ether, vacuum-drying obtains white solid, and its name is called the trishydroxymethyl polyoxyethylene glycol; Under argon shield, with trishydroxymethyl polyoxyethylene glycol and polyoxometallate ((C
4H
9)
4N)
6H
3P
2W
15V
3O
62Be dissolved in DMF, stir and be warming up to 80 ℃, concentrated after reacting a couple of days, precipitate in ether, vacuum-drying obtains yellow solid, is Pegylation polyoxometallate hybrid compounds.
3. synthetic method according to claim 2 can obtain peg molecule chain one end connection polyoxometallate and be similar to A-B type hybrid compounds.
4. the preparation method of the Pegylation polyoxometallate hybrid compounds that obtains of synthetic method according to claim 2 is characterized in that:
The mol ratio of described polyoxyethylene glycol, succinyl oxide and DMAP is 1: 1.2-2: 1.0-1.3; Carboxy polyethylene glycol, 2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-dihydroquinoline and the mol ratio of Tutofusin tris be 1: 1.2-2: 1.2-2.
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| CN104292800A (en) * | 2014-09-22 | 2015-01-21 | 南开大学 | Polyoxometallate-polymer nano reinforced composite material and preparation method thereof |
| CN106750538A (en) * | 2016-12-07 | 2017-05-31 | 中北大学 | A kind of polyoxomolybdate polyethylene glycol hybrid and preparation method thereof |
| CN108495820A (en) * | 2016-02-04 | 2018-09-04 | 埃克森美孚化学专利公司 | Include the polyoxometallate of noble metal and corresponding metal cluster compound |
| WO2020258605A1 (en) * | 2019-06-27 | 2020-12-30 | 华南理工大学 | Polyacid-based electrolyte conductor material and preparation method and application thereof |
| CN108465486B (en) * | 2018-03-19 | 2021-02-02 | 山西大学 | Preparation method and application of temperature-sensitive interface catalyst |
| CN114213669A (en) * | 2021-12-20 | 2022-03-22 | 东华大学 | Polyoxometallate giant surfactant and preparation method and application thereof |
| CN116023669A (en) * | 2021-10-27 | 2023-04-28 | 兰州大学 | Hybrid arm supermolecule star copolymer, and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292800A (en) * | 2014-09-22 | 2015-01-21 | 南开大学 | Polyoxometallate-polymer nano reinforced composite material and preparation method thereof |
| CN104292800B (en) * | 2014-09-22 | 2016-08-24 | 南开大学 | A kind of polyoxometallate-polymer nanocomposite strengthens composite and preparation method |
| CN108495820A (en) * | 2016-02-04 | 2018-09-04 | 埃克森美孚化学专利公司 | Include the polyoxometallate of noble metal and corresponding metal cluster compound |
| CN106750538A (en) * | 2016-12-07 | 2017-05-31 | 中北大学 | A kind of polyoxomolybdate polyethylene glycol hybrid and preparation method thereof |
| CN108465486B (en) * | 2018-03-19 | 2021-02-02 | 山西大学 | Preparation method and application of temperature-sensitive interface catalyst |
| WO2020258605A1 (en) * | 2019-06-27 | 2020-12-30 | 华南理工大学 | Polyacid-based electrolyte conductor material and preparation method and application thereof |
| CN116023669A (en) * | 2021-10-27 | 2023-04-28 | 兰州大学 | Hybrid arm supermolecule star copolymer, and preparation method and application thereof |
| CN116023669B (en) * | 2021-10-27 | 2023-12-15 | 兰州大学 | Hybrid arm supermolecule star copolymer, and preparation method and application thereof |
| CN114213669A (en) * | 2021-12-20 | 2022-03-22 | 东华大学 | Polyoxometallate giant surfactant and preparation method and application thereof |
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