CN103145978B - Pegylation polyoxometallate and preparation method thereof - Google Patents
Pegylation polyoxometallate and preparation method thereof Download PDFInfo
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- CN103145978B CN103145978B CN201310095915.0A CN201310095915A CN103145978B CN 103145978 B CN103145978 B CN 103145978B CN 201310095915 A CN201310095915 A CN 201310095915A CN 103145978 B CN103145978 B CN 103145978B
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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, the polyoxyethylene glycol of different molecular weight can be connected on tungstenic polyoxometallate thus to obtain novel hybrid inorganic-organic compound by profit in this way.
Background technology
Polyoxometallate is also known as multi-metal oxygen cluster (Polyoxometalates, be abbreviated as POMs, be called for short polyacid),, by early transition metal atom, be there is by a class of oxygen coordination bridging the negatively charged ion unit molecule duster compound determining structure, wherein with elements such as vanadium, molybdenum, tungsten for main representative.Because polyoxometallate has transmission, the storage power of good electronics and proton, special redox potential and stronger Bronsted acidity, it all demonstrates tempting application prospect in catalysis, photoelectricity, the energy, material, biology, medicine and other fields, therefore causes the extensive concern of various countries scientist in recent years gradually.But polyoxometallate exists with the form of crystal or powder usually as a kind of inorganic materials, badly be dissolved in common solvent, be difficult to machine-shaping, and it has high lattice energy, pH stability is low, with the poor compatibility of other materials, therefore from the angle of material, it is a kind of material not easily processed.These factors greatly limit it as the actual development of material and device and application.Therefore, make great efforts that the new method of exploitation prepares molecule based on polyoxometallate, device is very important.The method of preparation is divided into non covalent bond and covalent linkage two kinds.The hybrid compounds that non covalent bond obtains, is easily separated when processing treatment, unstable in nature, therefore in application, receives certain restriction.The mode that we are devoted to covalent linkage connects obtains hybrid compounds, its stable in properties, more can be widely used in practice.
Polymkeric substance is contemporary the most widely used organic synthesis material, and have the advantage that easy processing, easy modification, resolvability, good stability etc. are numerous, these advantages can make up polyoxometallate deficiency in actual applications.The polymkeric substance selected 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 the market, and molecular weight distribution all very narrow (PDI < 1.1).The simultaneously soluble in water and multiple organic solvent of polyoxyethylene glycol, and have good intermiscibility with many organic matter components, nontoxic, nonirritant, having good stability, is current scientist research one of polymkeric substance the most widely.Therefore, polyoxyethylene glycol and polyoxometallate link together by the method that we utilize covalent linkage to modify, thus obtain the novel hybrid inorganic-organic compound of a class.
Summary of the invention
The present invention be directed to above-mentioned technical Analysis, there is provided a kind of simple and practical, with low cost and be easy to realize suitability for industrialized production utilize chemical synthesis process, profit obtains the hybrid compounds of the Pegylation polyoxometallate that can obtain different molecular weight in this way.
Technical scheme of the present invention:
Synthetic method utilizes R-C (CH
2oH)
3(R=CH
3, NO
2, CH
2oH) with [P
2w
15v
3o
62l
9-there is esterification, namely replace bridging at V with alkoxyl group
3sauerstoffatom on bunch carrys out covalently bound polyoxometallate.Can obtain one end connection polyoxometallate in this way 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) synthesis of carboxy polyethylene glycol
Under argon shield, by polyoxyethylene glycol, succinyl oxide and DMAP are dissolved in dry toluene, stir and are warming up to 80 DEG C, reaction 12h.Be spin-dried for after reaction, dissolve, use the aqueous hydrochloric acid of PH=2 successively with methylene dichloride, saturated sodium-chloride water solution extracts.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid.
2) synthesis of trishydroxymethyl polyoxyethylene glycol
Under argon shield, by 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 DEG C, reaction 24h.Be spin-dried for after reaction, dissolve with methylene dichloride, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid.
3) synthesis of Pegylation polyoxometallate hybrid compounds
Under argon shield, by trishydroxymethyl polyoxyethylene glycol and polyoxometallate TBA
6h
3p
2w
15v
3o
62be dissolved in DMF, stir and be warming up to 80 DEG C, 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-1,2-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: polyoxyethylene glycol and polyoxometallate link together by first Application covalent linkage of the present invention, and the hybrid molecule of synthesis can be dissolved in more organic solvent compared to simple polyoxometallate, enhances its stability greatly.The method synthesis technique is simple, mild condition, easy handling, reaction easily controls, product purity is high, be convenient to realize suitability for industrialized production and apply.
Accompanying drawing explanation
Fig. 1 is for adopting the GPC spectrogram of molecule described in embodiment 1.
Fig. 2 is molecule described in employing embodiment 1
1h NMR spectrogram.
Fig. 3 is for adopting the GPC spectrogram of molecule described in embodiment 2.
Fig. 4 is molecule described in employing embodiment 2
1h NMR spectrogram.
Fig. 5 is for adopting the GPC spectrogram of molecule described in embodiment 3.
Fig. 6 is molecule described in employing embodiment 3
1h NMR spectrogram.
Fig. 7 is molecule described in employing embodiment 1, example 2 and example 3
31p NMR spectrogram.
Specific implementation method
Embodiment 1:
The molecular-weight average using polyoxyethylene glycol is 1000, and one end is-OH, and one end is-OCH
3.
1) synthesis of carboxy polyethylene glycol
Under argon shield, by 8g cetomacrogol 1000,1.2g succinyl oxide, 0.98g4-Dimethylamino pyridine is dissolved in 50mL dry toluene, stirs and is warming up to 80 DEG C, reaction 12h.Be spin-dried for after reaction, dissolve, use the aqueous hydrochloric acid of PH=2 successively with methylene dichloride, saturated sodium-chloride water solution extracts.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid 5.0g, productive rate 56.8%.
2) synthesis of trishydroxymethyl polyoxyethylene glycol
Under argon shield, by 0.5g carboxy polyethylene glycol 1000,0.15g2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline, 0.08g Tutofusin tris is dissolved in 30mL anhydrous acetonitrile, stirs and is warming up to 80 DEG C, reaction 24h.Be spin-dried for after reaction, dissolve with methylene dichloride, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid 0.21g, productive rate 38.9%.
3) synthesis of Pegylation polyoxometallate hybrid compounds
Under argon shield, by 0.14g trishydroxymethyl cetomacrogol 1000,0.58g polyoxometallate TBA
6h
3p
2w
15v
3o
62, be dissolved in 50mL DMF, stir and be warming up to 80 DEG C, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid 0.6g, productive rate 83.3%.
Embodiment 2:
The molecular-weight average using polyoxyethylene glycol is 2000, and one end is-OH, and one end is-OCH
3.
1) synthesis of carboxy polyethylene glycol
Under argon shield, by 5g Macrogol 2000,0.38g succinyl oxide, 0.32g4-Dimethylamino pyridine is dissolved in 50mL dry toluene, stirs and is warming up to 80 DEG C, reaction 12h.Be spin-dried for after reaction, dissolve, use the aqueous hydrochloric acid of PH=2 successively with methylene dichloride, saturated sodium-chloride water solution extracts.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid 4.5g, productive rate 85.7%.
2) synthesis of trishydroxymethyl polyoxyethylene glycol
Under argon shield, by 0.4g carboxy polyethylene glycol 2000,0.07g2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline, 0.03g Tutofusin tris is dissolved in 30mL anhydrous acetonitrile, stirs and is warming up to 80 DEG C, reaction 24h.Be spin-dried for after reaction, dissolve with methylene dichloride, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid 0.37g, productive rate 88.0%.
3) synthesis of Pegylation polyoxometallate hybrid compounds
Under argon shield, by 0.15g trishydroxymethyl Macrogol 2000,0.37g polyoxometallate TBA
6h
3p
2w
15v
3o
62, be dissolved in 50mL DMF, stir and be warming up to 80 DEG C, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid 0.48g, productive rate 92.3%.
Embodiment 3:
The molecular-weight average using polyoxyethylene glycol is 5000, and one end is-OH, and one end is-OCH
3.
1) synthesis of carboxy polyethylene glycol
Under argon shield, by 5g polyoxyethylene glycol 5000,0.12g succinyl oxide, 0.13g4-Dimethylamino pyridine is dissolved in 50mL dry toluene, stirs and is warming up to 80 DEG C, reaction 12h.Be spin-dried for after reaction, dissolve, use the aqueous hydrochloric acid of PH=2 successively with methylene dichloride, saturated sodium-chloride water solution extracts.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid 4.8g, productive rate 94.3%.
2) synthesis of trishydroxymethyl polyoxyethylene glycol
Under argon shield, by 0.4g carboxy polyethylene glycol 5000,0.029g2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline, 0.012g Tutofusin tris is dissolved in 30mL anhydrous acetonitrile, stirs and is warming up to 80 DEG C, reaction 24h.Be spin-dried for after reaction, dissolve with methylene dichloride, extract with saturated sodium-chloride water solution.Collect organic phase, spend the night, carry out suction filtration afterwards to it with anhydrous sodium sulfate drying, concentrated, precipitate in ether, vacuum-drying obtains white solid 0.38g, productive rate 92.7%.
3) synthesis of Pegylation polyoxometallate hybrid compounds
Under argon shield, by 0.2g trishydroxymethyl methyl polyoxyethylene glycol 5000,0.23g polyoxometallate TBA
6h
3p
2w
15v
3o
62, be dissolved in 50mL DMF, stir and be warming up to 80 DEG C, reaction 7d.Concentrated after reaction, precipitate in ether, vacuum-drying obtains yellow solid 0.38g, productive rate 88.4%.
Claims (3)
1. a preparation method for Pegylation polyoxometallate replaces bridging at V with alkoxyl group
3sauerstoffatom on bunch carrys out covalently bound polyoxometallate, it is characterized in that, comprises the following steps:
Under argon shield, by polyoxyethylene glycol, succinyl oxide and DMAP are dissolved in dry toluene, stirring and refluxing, 80 DEG C of reaction 12h, are spin-dried for after reaction, dissolve with methylene dichloride, use the aqueous hydrochloric acid of PH=2 successively, saturated sodium-chloride water solution extracts, organic phase, spends the night with anhydrous sodium sulfate drying, carries out suction filtration afterwards to it, concentrated, precipitate in ether, vacuum-drying obtains white solid, and its name is called carboxy polyethylene glycol; Under argon shield, by carboxy polyethylene glycol, 2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline and Tutofusin tris are dissolved in anhydrous acetonitrile, stirring and refluxing, 80 DEG C of reaction 24h, be spin-dried for after reaction, dissolve with methylene dichloride, extract with saturated sodium-chloride water solution, organic phase, spends the night with anhydrous sodium sulfate drying, carries out suction filtration afterwards to it, concentrated, precipitate in ether, vacuum-drying obtains white solid, and its name is called trishydroxymethyl polyoxyethylene glycol; Under argon shield, by 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 DEG C, react after 7 days, concentrated, precipitate in ether, vacuum-drying obtains yellow solid, is Pegylation polyoxometallate hybrid compounds.
2. preparation method according to claim 1, is characterized in that the molecular-weight average of described polyoxyethylene glycol is the polyoxyethylene glycol of 1000,2000 and 5000.
3. preparation method according to claim 1, is characterized in that:
The mol ratio of described polyoxyethylene glycol, succinyl oxide and DMAP is 1: 1.2-2: 1.0-1.3; The mol ratio of carboxy polyethylene glycol, 2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-dihydroquinoline and Tutofusin tris is 1: 1.2-2: 1.2-2.
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