CN104292800A - Polyoxometallate-polymer nano reinforced composite material and preparation method thereof - Google Patents
Polyoxometallate-polymer nano reinforced composite material and preparation method thereof Download PDFInfo
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- CN104292800A CN104292800A CN201410481627.3A CN201410481627A CN104292800A CN 104292800 A CN104292800 A CN 104292800A CN 201410481627 A CN201410481627 A CN 201410481627A CN 104292800 A CN104292800 A CN 104292800A
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Abstract
The invention relates to a polyoxometallate-polymer nano reinforced composite material. The nano reinforced composite material is formed by blending pegylated polyoxometallate and polyethylene glycol, wherein molfraction of pegylated polyoxometallate is 2-50%, and balance is polyethylene glycol. A preparation method of the nano reinforced composite material comprises the following steps: mixing pegylated polyoxometallate and polyethylene glycol solids in molar ratio, adding deionized water, stirring, and then annealing at constant temperature of 25 DEG C to obtain a precursor solution; keeping the precursor solution in a dark place, carrying out vacuum drying at constant temperature, quickly putting the dried material into liquid nitrogen to obtain a sample, and drying again, so that a nano composite material can be obtained. The preparation method of the nano reinforced composite material is simple in technology, low in cost and good in repeatability; above a melting point of polyethylene glycol, shearing storage modulus of the nano composite material is obviously increased; and the nano composite material reserves excellent performances of each component and has a potential application value in the aspects of catalysis, materials, medicines and the like.
Description
Technical field
The invention belongs to technical field of composite preparation, relate to a kind of nano reinforced composites and preparation method thereof, particularly nano composite material of forming of a kind of polyethyleneglycol modified polyoxometallate and polyoxyethylene glycol and preparation method thereof.
Background technology
Matrix material to have two kinds or two or more materials of different performance, and by physics or chemical process, on both macro and micro, composition has the elite clone of multiple performance.Nano composite material is then the part of wherein most magnetism, and the dispersion level mainly due to system reaches nano level, dispersed, excellent material performance.
Polyoxometallate is had by early transition metal atom the negatively charged ion unit molecule duster compound determining structure by a class of oxygen coordination bridging, wherein with elements such as vanadium, molybdenum, tungsten for main representative.Polyoxometallate has good performance due to it, all demonstrates tempting application prospect, thus receive much concern in catalysis, photoelectricity, the energy, material, biology, medicine and other fields.But polyoxometallate is as a kind of inorganic salt, be subject to the constraint of its structure and inherent nature, from the angle of material, it is a kind of material not easily processed, and limits its development and application in actual industrial to a great extent.Therefore, the material that the new method of effort exploitation is prepared based on polyoxometallate is very important.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.
Polyoxometallate is having very large difference, therefore about the work of the matrix material of polyoxometallate rarely has report in nature as inorganics and organic polymer thing.Keggin-type many metal-salts hydrochlorate and agarose compound are obtained soft photic sensitive membrane (Ying Ma et al. by a study group, Adv. Mater., 21,1737 (2009)), owing to directly carrying out compound, if obtain mixture to store easily generation macroface separation for a long time.In the application for a patent for invention of disclosed No. 2013100959150 " Pegylation polyoxometallate and preparation method thereof ", we illustrate a kind of covalent linkage that adopts and connect the preparation method preparing polyoxometallate-polymkeric substance.We carry out organic decoration by the means of covalent linkage to polyoxometallate, improve consistency and the stability of many metal-salts hydrochlorate and polymkeric substance, thus realize nanometer composite technology.
Summary of the invention
The object of the invention is to provide a kind of simple and practical, with low cost and be easy to realize polyoxometallate-polymer nanocomposite reinforced composite and the preparation method of suitability for industrialized production.
The present invention adopt the Pegylation polyoxometallate hybrid be connected by covalent linkage as disperse phase and molecular weight be 5000 polyoxyethylene glycol to carry out nanometer as external phase blended, thus obtain a kind of matrix material with nanometer enhancing.Use Pegylation polyoxometallate to improve consistency and the stability of polyoxometallate and polymkeric substance, when adding many metal-salts hydrochlorate of minute quantity in the composite, just can show the functional of excellence.
The present invention provide firstly a kind of polyoxometallate-polymer nanocomposite reinforced composite, described nano reinforced composites is formed by Pegylation polyoxometallate and polyethylene glycol blending, wherein Pegylation polyoxometallate molar content is 2 ~ 50%, and all the other components are polyoxyethylene glycol.The molecular weight of the polyoxometallate of described Pegylation is 10500 g/mol, and the molecular weight of polyoxyethylene glycol is 5000 g/mol.
Described nano reinforced composites is by the laminated structure of 2 dimension nano-scales, the crystallization of polyoxyethylene glycol, the crystallization of Pegylation polyoxometallate and Pegylation polyoxometallate and polyoxyethylene glycol cocrystallization composition.
When temperature is on 60 DEG C, the storage shear modulus of matrix material (
g ') be 2.7 ~ 5.5 × 10
5pa, adds along with Pegylation polyoxometallate the increase that storage shear modulus is the order of magnitude.
Invention also provides the preparation method of a kind of polyoxometallate-polymer nanocomposite reinforced composite, step is as follows:
1st, the preparation of precursor aqueous solution
The solid sample of Pegylation polyoxometallate and polyoxyethylene glycol is configured by mol ratio, add deionized water, described solid sample and the amount ratio of water are 0.01 ~ 0.05 g/mL, 50 ~ 80 DEG C are stirred abundant mixed dissolution 1 ~ 4 h, then at 25 DEG C of cycle annealing 12 ~ 48 h, precursor aqueous solution is obtained; Described mol ratio is Pegylation polyoxometallate 2 ~ 50 parts, polyoxyethylene glycol 50 ~ 98 parts;
2nd, the preparation of nano reinforced composites
Proceeded to by precursor aqueous solution prepared by the 1st step in polyethylene terephthalate (PET) container, lucifuge is placed; In the thermostatic drying chamber of 25 DEG C, dry under vacuum tightness is 0.01 MPa, after dry 5 ~ 7 d, taken out by the sample after complete drying, place in liquid nitrogen rapidly, sample is separated with container.Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 12 ~ 48 h, can obtain the nano reinforced composites of Pegylation polyoxometallate and polyoxyethylene glycol.
Nano reinforced composites performance
As shown in Figure 1, Pegylation polyoxometallate obtains the advantage highly significant of matrix material.When temperature is on 60 DEG C, the material of pure PEG
g '=6.2 × 10
-2pa, it is liquid.The increase adding the storage shear modulus magnitude differences making material of a small amount of Pegylation polyoxometallate.When Pegylation polyoxometallate amount molar fraction is 2%, the storage shear modulus of matrix material is
g '=2.7 Pa, the material compared to pure PEG has the increase of 2 orders of magnitude.When Pegylation polyoxometallate amount molar fraction is 20%, the storage shear modulus of matrix material is
g '=1.0 × 10
3pa is 1.7 × 10 of the material of pure PEG
4doubly.This excellent properties is difficult to find in traditional nano composite material.
advantage of the present invention and positively effect:
Nano composite material prepared by the present invention has the nanometer result of multilayer level, observed by projection electron microscope, nano composite material is by the laminated structure of 2 dimension nano-scales, the crystallization of polyoxyethylene glycol, the crystallization of Pegylation polyoxometallate and Pegylation polyoxometallate and polyoxyethylene glycol cocrystallization composition.Pegylation polyoxometallate be dispersed in polyoxyethylene glycol mutually in, both consistencies are fine.On the fusing point of polyoxyethylene glycol, the storage shear modulus of the matrix material obtained significantly is increasing.Preparation method's technique is simple, and processing ease is with low cost, reproducible.The matrix material of the polyoxometallate that this method obtains is with a wide range of applications in practice.
Accompanying drawing explanation
Fig. 1 is the spectrogram of storage shear modulus to temperature of polyoxyethylene glycol, Pegylation polyoxometallate and nano composite material.
When Fig. 2 is 80 DEG C, storage shear modulus is to the spectrogram of different Pegylation polyoxometallate molar fraction.
The micro image that Fig. 3 observes under transmission electron microscope for the nano composite material described in embodiment 1.
The micro image that Fig. 4 observes under transmission electron microscope for the nano composite material described in embodiment 2.
The micro image that Fig. 5 observes under transmission electron microscope for the nano composite material described in embodiment 3.
The micro image that Fig. 6 observes under transmission electron microscope for the nano composite material described in embodiment 4.
The micro image that Fig. 7 observes under transmission electron microscope for the nano composite material described in embodiment 5.
Embodiment
First utilize No. 2013100959150 " Pegylation polyoxometallate and preparation method thereof " to prepare Pegylation polyoxometallate hybridized polymer that molecular weight is 10500 g/mol, wherein polyoxometallate is Dawson structure phosphorus tungsten vanadium multi-metal oxygen acid organic ammonium salt (n-C
4h
9)
6h
3p
2w
15v
3o
62; The molecular weight of polyoxyethylene glycol is 5000 g/mol, is modified by its end group and connects upper Tutofusin tris, be then connected by covalent linkage with many metal-salts hydrochlorate, obtain Pegylation polyoxometallate.
embodiment 1
In molar ratio heavily by Pegylation polyoxometallate 2 parts, polyoxyethylene glycol 98 parts of solids mixings, add deionized water, configuration concentration is the solution of 0.05 g/mL.Stirring and dissolving 1 h at temperature is 50 DEG C, then temperature control is at 25 DEG C of cycle annealing 12 h, obtains precursor aqueous solution.
Be transferred to by precursor aqueous solution in pet container, lucifuge is placed.At 25 DEG C, vacuum tightness is dry 7 d in the constant temperature oven of 0.01 MPa, is taken out by the sample after complete drying, and place in liquid nitrogen rapidly, sample is separated with container.Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 48 h, can obtain the nano composite material of Pegylation polyoxometallate and polyoxyethylene glycol, called after P-2.The micro image observed under transmission electron microscope as shown in Figure 3.
embodiment 2
In molar ratio heavily by Pegylation polyoxometallate 5 parts, polyoxyethylene glycol 95 parts of solids mixings, add deionized water, configuration concentration is the solution of 0.04 g/mL.Stirring and dissolving 1 h at temperature is 50 DEG C, then temperature control is at 25 DEG C of cycle annealing 20 h, obtains precursor aqueous solution.Be transferred to by solution in pet container, lucifuge is placed.At 25 DEG C, vacuum tightness is dry 6 d in the constant temperature oven of 0.01 MPa, is taken out by the sample after complete drying, and place in liquid nitrogen rapidly, sample is separated with container.Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 36 h, can obtain the nano composite material of Pegylation polyoxometallate and polyoxyethylene glycol, called after P-5.The micro image observed under transmission electron microscope as shown in Figure 4.
embodiment 3
In molar ratio heavily by Pegylation polyoxometallate 10 parts, polyoxyethylene glycol 90 parts of solids mixings, add deionized water, configuration concentration is the solution of 0.03 g/mL.Stirring and dissolving 2 h at temperature is 60 DEG C, then temperature control is at 25 DEG C of cycle annealing 24 h, obtains precursor aqueous solution.Be transferred to by solution in pet container, lucifuge is placed.At 25 DEG C, vacuum tightness is dry 6 d in the constant temperature oven of 0.01MPa, is taken out by the sample after complete drying, and place in liquid nitrogen rapidly, sample is separated with container.Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 24 h, can obtain the nano composite material of Pegylation polyoxometallate and polyoxyethylene glycol, called after P-10.The micro image observed under transmission electron microscope as shown in Figure 5.
embodiment 4
In molar ratio heavily by Pegylation polyoxometallate 20 parts, polyoxyethylene glycol 80 parts of solids mixings, add deionized water, configuration concentration is the solution of 0.02 g/mL.Stirring and dissolving 3 h at temperature is 70 DEG C, then temperature control is at 25 DEG C of cycle annealing 38 h, obtains precursor aqueous solution.Be transferred to by solution in pet container, lucifuge is placed.At 25 DEG C, vacuum tightness is dry 5 d in the constant temperature oven of 0.01 MPa, is taken out by the sample after complete drying, and place in liquid nitrogen rapidly, sample is separated with container.Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 18 h, can obtain the nano composite material of Pegylation polyoxometallate and polyoxyethylene glycol, called after P-20.The micro image observed under transmission electron microscope as shown in Figure 6.
embodiment 5
In molar ratio heavily by Pegylation polyoxometallate 50 parts, polyoxyethylene glycol 50 parts of solids mixings, add deionized water, configuration concentration is the solution of 0.01 g/mL.Stirring and dissolving 4 h at temperature is 80 DEG C, then temperature control is at 25 DEG C of cycle annealing 48 h, obtains precursor aqueous solution.Be transferred to by solution in pet container, lucifuge is placed.At 25 DEG C, vacuum tightness is dry 5 d in the constant temperature oven of 0.01MPa, is taken out by the sample after complete drying, and place in liquid nitrogen rapidly, sample is separated with container.Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 12 h, can obtain the nano composite material of Pegylation polyoxometallate and polyoxyethylene glycol, called after P-50.The micro image observed under transmission electron microscope as shown in Figure 7.
Claims (5)
1. polyoxometallate-polymer nanocomposite reinforced composite, described nano reinforced composites is formed by Pegylation polyoxometallate and polyethylene glycol blending, wherein Pegylation polyoxometallate molar content is 2 ~ 50%, and all the other components are polyoxyethylene glycol.
2. polyoxometallate according to claim 1-polymer nanocomposite reinforced composite, is characterized in that the molecular weight of the polyoxometallate of described Pegylation is 10500 g/mol, and the molecular weight of polyoxyethylene glycol is 5000 g/mol.
3. polyoxometallate according to claim 1 and 2-polymer nanocomposite reinforced composite, is characterized in that when temperature is more than 60 DEG C, and the storage shear modulus of matrix material is 2.7 ~ 5.5 × 10
5pa, adds along with Pegylation polyoxometallate the increase that storage shear modulus is the order of magnitude.
4. polyoxometallate according to claim 1 and 2-polymer nanocomposite reinforced composite, it is characterized in that described nano reinforced composites is by the laminated structure of 2 dimension nano-scales, the crystallization of polyoxyethylene glycol, the crystallization of Pegylation polyoxometallate and Pegylation polyoxometallate and polyoxyethylene glycol cocrystallization composition.
5. a preparation method for polyoxometallate according to claim 1-polymer nanocomposite reinforced composite, is characterized in that the step of the method is as follows:
1st, the preparation of precursor aqueous solution
The solid sample of Pegylation polyoxometallate and polyoxyethylene glycol is configured by mol ratio, add deionized water, described solid sample and the amount ratio of water are 0.01 ~ 0.05 g/mL, 50 ~ 80 DEG C are stirred abundant mixed dissolution 1 ~ 4 h, then at 25 DEG C of cycle annealing 12 h ~ 48 h, precursor aqueous solution is obtained; Described mol ratio is Pegylation polyoxometallate 2 ~ 50 parts, polyoxyethylene glycol 50 ~ 98 parts;
2nd, the preparation of nano reinforced composites
Proceeded to by precursor aqueous solution prepared by the 1st step in polyethylene terephthalate (PET) container, lucifuge is placed; In the thermostatic drying chamber of 25 DEG C, vacuum tightness is 0.01 MPa, and after dry 5 ~ 7 d, taken out by the sample after complete drying, place in liquid nitrogen rapidly, sample is separated with container; Sample is put into again the thermostatic drying chamber of 25 DEG C, under vacuum tightness is 0.1 MPa, dry 12 ~ 48 h, can obtain the nano reinforced composites of Pegylation polyoxometallate and polyoxyethylene glycol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114469993A (en) * | 2022-02-15 | 2022-05-13 | 山西白求恩医院 | Preparation method and application of water-soluble organic hybrid polyoxometallate |
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| WO2006110166A2 (en) * | 2004-09-02 | 2006-10-19 | Cornell Research Foundation, Inc. | Functionalized nanostructures with liquid-like behavior |
| CN101124251A (en) * | 2004-03-26 | 2008-02-13 | 阿拉巴马大学 | Polymer dissolution and blend formation in ionic liquids |
| CN103145978A (en) * | 2013-03-25 | 2013-06-12 | 南开大学 | Pegylation polyoxometallate and preparation method thereof |
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2014
- 2014-09-22 CN CN201410481627.3A patent/CN104292800B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101124251A (en) * | 2004-03-26 | 2008-02-13 | 阿拉巴马大学 | Polymer dissolution and blend formation in ionic liquids |
| WO2006110166A2 (en) * | 2004-09-02 | 2006-10-19 | Cornell Research Foundation, Inc. | Functionalized nanostructures with liquid-like behavior |
| CN103145978A (en) * | 2013-03-25 | 2013-06-12 | 南开大学 | Pegylation polyoxometallate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIE CHEN ET AL.: "Preparation and photochromism of nanocomposite thin film based on polyoxometalate and polyethyleneglycol", 《MATERIALS LETTERS》 * |
| YAOKUN HAN ET AL.: "Synthesis of Polyoxometalate-Polymer Hybrid Polymers and Their Hybrid Vesicular Assembly", 《MACROMOLECULES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114469993A (en) * | 2022-02-15 | 2022-05-13 | 山西白求恩医院 | Preparation method and application of water-soluble organic hybrid polyoxometallate |
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