CN108129666B - Polymetallic oxygen cluster based ring-crosslinked polyphosphazene hybrid polymer material and preparation method thereof - Google Patents

Polymetallic oxygen cluster based ring-crosslinked polyphosphazene hybrid polymer material and preparation method thereof Download PDF

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CN108129666B
CN108129666B CN201810033506.0A CN201810033506A CN108129666B CN 108129666 B CN108129666 B CN 108129666B CN 201810033506 A CN201810033506 A CN 201810033506A CN 108129666 B CN108129666 B CN 108129666B
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polyphosphazene
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闫毅
苗志良
张军平
颜静
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Northwestern Polytechnical University
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Abstract

The invention relates to a polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material and a preparation method thereof, in particular to a preparation technology for preparing the polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material by using a precipitation polymerization technology. The ring-crosslinked polyphosphazene hybrid material prepared by the invention has a chemical structure of organically modified polymetallic oxygen cluster and hexachlorocyclotriphosphazene crosslinking, and can select functional groups and POMs of required monomers according to specific application requirements to realize regulation and control of properties and functions. The preparation process is completed in one step by a one-pot method, expensive catalysts are not needed, the operation is simple and easy, the reaction conditions are mild, and the reaction efficiency is high. The target polyoxometalate-based ring-crosslinked polyphosphazene hybrid material can be applied to: heterogeneous catalyst, electrochromic material, chemical weapon protection, magnetic resonance contrast agent and other fields.

Description

Polymetallic oxygen cluster based ring-crosslinked polyphosphazene hybrid polymer material and preparation method thereof
Technical Field
The invention belongs to the technical field of organic-inorganic hybrid polymer materials, relates to polymer chemistry, organic chemistry, inorganic chemistry and material chemistry, and particularly relates to a polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material and a preparation method thereof. The preparation method is a preparation technology for preparing the polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid high polymer material by using a precipitation polymerization technology, and the polymetallic oxygen cluster functionalized by a plurality of active groups can be directly polymerized by using the polymerization method to obtain the novel polymetallic oxygen cluster-based hybrid polyphosphazene material.
Background
Polyoxometalates (POMs) are monomolecular cluster compounds which are formed by connecting and polycondensing early transition metal atoms such as vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W) and the like with heteroatoms such as silicon (Si), phosphorus (P) and the like through oxygen and have determined structures and compositions. The structure and the composition of the polymetallic oxygen cluster are rich and various, and about more than 70 elements can be introduced into the polymetallic oxygen cluster; meanwhile, the coordination atoms are mostly in the highest oxidation state, and the characteristics endow the polyoxometalate with many excellent physicochemical properties such as oxidation-reduction property, magnetism, photoresponse, catalytic activity and biological activity. More importantly, unlike typical inorganic nanomaterials, the polyoxometalate clusters are generally crystalline materials whose size is well defined, and which perfectly compensate for the 1-5nm scale range that typical nanomaterials cannot cover. However, because of its own crystalline material characteristics and inherent properties, the polyoxometalate as a material has the disadvantages of poor stability, poor organic or polymer compatibility, difficult processing, difficult recovery, etc., which severely limits the range of practical applications.
The polyoxometalate is organically modified through covalent bonds, so that the stability and the organic compatibility of the polyoxometalate can be improved, and a new organic active site is introduced on the surface of the polyoxometalate, so that the polyoxometalate can be further organically functionalized and endowed with more functionality. The polymer is the most widely used synthetic material at present, and has the advantages of easy processing, easy modification, good solubility, high stability and the like. Therefore, the organic modified polyoxometalate is introduced into a polymer system as a functional element, so that the multifunctional property and the excellent processability of the polymer can be effectively combined, the synergistic effect of the organic-inorganic hybrid material is expected to be realized, and the depth and the width of the organic-inorganic hybrid material in the fields of basic research and application are deepened and widened. However, because of poor compatibility of polyoxometalate with radical polymerization, few studies have been reported on polyoxometalate-containing polymers.
Polyphosphazene materials are known as "inorganic rubbers". The cyclocrosslinked polyphosphazene is generally prepared by precipitation polymerization of hexachlorocyclotriphosphazene with bifunctional or more nucleophilic monomers under mild reaction conditions by a one-pot method. Due to the special framework structure and the ring-crosslinking characteristic, the ring-crosslinked polyphosphazene has excellent biocompatibility and photochemical stability and also has good thermal stability, so that the ring-crosslinked polyphosphazene has wide application and prospect in the fields of flame-retardant materials, biomedical materials, separation membranes, bioluminescence imaging and the like. Since the first example of ring-crosslinked polyphosphazenes was reported, a variety of organic nucleophilic monomers have been used to synthesize a wide variety of polyphosphazene materials. However, the work of preparing the organic modified polymetallic oxygen cluster hybridized ring-crosslinked polyphosphazene hybrid material by using a precipitation polymerization method has not been reported yet.
The synthesis and purification processes are simple and easy, and the obtained product not only has the characteristics of the ring-crosslinked polyphosphazene, but also embodies the functions of the polyoxometalate, and the synergistic effect of the two is an important characteristic of the new material.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material and a preparation method thereof, and the polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material is prepared by a simple and rapid polymerization method, namely, the organic modified polymetallic oxygen cluster and hexachlorocyclotriphosphazene are subjected to precipitation polymerization reaction to obtain the target hybrid polyphosphazene material so as to improve the defects of the polymetallic oxygen cluster in the aspect of materials.
Technical scheme
A polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material is characterized by having the following structural formula:
Figure GDA0002724682730000021
wherein: r ═ NH2,-OH,-C6H4NH2,-C6H4OH。
A method for preparing the polyoxometallate-based ring-crosslinked polyphosphazene hybrid polymer material is characterized by comprising the following steps:
step 1: dissolving 1 part of hexachlorocyclotriphosphazene and 1.5-3 parts of functional group organic modified polyoxometalate in 1-3 ml of anhydrous acetonitrile solvent;
step 2: adding 9-18 parts of triethylamine as an acid-binding agent and a catalyst for nucleophilic substitution reaction, and introducing nitrogen to remove oxygen for 10-30 min;
and step 3: reacting the reaction solution in a Schlenk bottle at 80-95 ℃ for 12-48 h under the protection of nitrogen to obtain a suspension;
and 4, step 4: and (3) centrifuging the suspension, repeatedly washing the suspension by using an organic solvent, and drying the suspension for 12-48 h by using a vacuum oven to obtain the target product, namely the polymetallic oxygen cluster-based ring-crosslinked hybrid polyphosphazene material, which is solid powder.
The organic solvent in the step 4 is acetonitrile and ethanol.
The repeated washing treatment refers to 3-4 times of washing respectively by acetonitrile and ethanol.
And introducing nitrogen to remove oxygen for 20 min.
The reaction solution in the step 3 is reacted for 24 hours at 90 ℃ in a Schlenk bottle to obtain a suspension.
And 4, drying in a vacuum oven for 24 hours.
Advantageous effects
The invention provides a polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material and a preparation method thereof, which are a preparation technology for preparing the polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid polymer material by using a precipitation polymerization technology.
Compared with the prior art, the highly crosslinked polymetallic oxygen cluster based polyphosphazene hybrid material prepared by the invention belongs to an organic-inorganic hybrid high polymer material, and has more advantages than the traditional single organic polymer material. The ring-crosslinked polyphosphazene hybrid material prepared by the invention has a chemical structure of organically modified polymetallic oxygen cluster and hexachlorocyclotriphosphazene crosslinking, and can select functional groups and POMs of required monomers according to specific application requirements to realize regulation and control of properties and functions. The preparation process is completed in one step by a one-pot method, expensive catalysts are not needed, the operation is simple and easy, the reaction conditions are mild, and the reaction efficiency is high. The target polyoxometalate-based ring-crosslinked polyphosphazene hybrid material can be applied to: heterogeneous catalyst, electrochromic material, chemical weapon protection, magnetic resonance contrast agent and other fields.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a polyoxometalate-based ring-crosslinked polyphosphazene hybrid material.
A is a polymetallic oxygen cluster
FIG. 2 is a digital photograph of the preparation process of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material.
FIG. 3 is a scanning electron micrograph of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material.
FIG. 4 is a thermogravimetric curve of a polyoxometalate-based ring-crosslinked polyphosphazene hybrid material in a nitrogen atmosphere.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the general structural formula of the polyoxometallate-based ring-crosslinked polyphosphazene hybrid polymer material is as follows:
Figure GDA0002724682730000041
wherein: r ═ NH2,-OH,-C6H4NH2,-C6H4OH；
Figure GDA0002724682730000042
Wherein X is the counterion Tetrabutylammonium (TBA)+)。
The following examples illustrate the invention in detail:
example 1
The preparation of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material is realized by the following steps:
step one, 0.012g of hexachlorocyclotriphosphazene and MnMo is added into a 10mL Schlenk bottle6-C6H4OH0.200g, dissolved well with 2.40mL of anhydrous acetonitrile.
And step two, adding 0.04mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.058g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is orange solid powder.
Effect diagram of the embodiment:
FIG. 1 is a Fourier transform infrared spectrum of a polyoxometalate-based ring-crosslinked polyphosphazene hybrid material. The curve A is organic modified polymetallic oxygen cluster MnMo6-C6H4And the OH and B curves are the target product of the cyclocrosslinking polyphosphazene hybrid material. Wherein 3420cm in Panel A-1The stretching shock absorption attributed to-OH, which is significantly attenuated in panel B, indicates that the phenolic hydroxyl group is substituted. 2920cm can be seen in FIG. B-1Absorption of stretching vibration corresponding to-CH, 1223cm-1Corresponds to the resonance absorption peak of P ═ N in the phosphazene skeleton, 915cm-1Corresponding to Mo ═ O stretching vibration, 790cm-1Asymmetric stretching vibration of 670cm-1The position corresponds to the stretching vibration of Mo-O-Mo. The data fully indicate that the product structure is MnMo6-C6H4A cross-linked condensation structure of OH and hexachlorocyclotriphosphazene.
FIG. 2 is a digital photograph of the preparation process of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material. It can be seen that before the precipitation polymerization reaction, the organic modified polyoxometalate can be uniformly dispersed and stably exist in the organic solvent; after triethylamine serving as an acid-binding agent and a catalyst is added, the color is changed from orange to light white, but the system is still a stable heterogeneous system; after the precipitation polymerization reaction is completed, phase separation occurs and the target product, which is pale white, precipitates out of the solvent, indicating the successful progress of the precipitation polymerization reaction.
FIG. 3 is a scanning electron micrograph of the polyoxometallate-based ring-crosslinked polyphosphazene hybrid material with deionized water as a dispersant, from which many microspheres with a particle size of 500-900nm can be clearly seen, the microspheres have smooth surfaces and no pores, and the microspheres are adhered to each other.
FIG. 4 is a thermogravimetric curve of a polyoxometalate-based ring-crosslinked polyphosphazene hybrid material in a nitrogen atmosphere. It can be seen from the figure that the reaction monomer MnMo6-C6H4The initial OH decomposition temperature in nitrogen atmosphere was greater than 247 deg.C, and the residual rate was 36.80% at temperatures up to 800 deg.C. Light appearance of target hybrid polyphosphazene product at about 200 DEG CThe slight weight loss is caused by volatilization of the solvent remaining in the polymer. The weight loss of the polyphosphazene hybrid material under the nitrogen atmosphere has only one step, and the epitaxial initial decomposition temperature is higher than 227 ℃. The polyphosphazene hybrid material is not completely decomposed in the nitrogen atmosphere, and the residual rate is still higher than 55 percent even at the temperature of 800 ℃. The high residual rate may be attributed to the introduction of a phosphazene monomer (HCCP) having a rigid structure, resulting in a significant increase in the thermal stability of the polymer.
Example 2
The preparation of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material is realized by the following steps:
step one, 0.037g of hexachlorocyclotriphosphazene and MnMo is added into a 10mL Schlenk bottle6-NH20.300g was dissolved well with 5.40mL of anhydrous acetonitrile.
And step two, adding 0.06mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.048g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is orange solid powder.
Example 3
The preparation of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material is realized by the following steps:
step one, adding 0.055g of hexachlorocyclotriphosphazene and MnMo into a 10mL Schlenk bottle60.100g of-OH was sufficiently dissolved in 1.0mL of anhydrous acetonitrile.
And step two, adding 0.10mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.018g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is orange solid powder.
Example 4
The preparation of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material is realized by the following steps:
step one, adding 0.006g hexachlorocyclotriphosphazene and MnMo into a 10mL Schlenk bottle6-C6H40.100g of OH was dissolved thoroughly in 1.0mL of anhydrous acetonitrile and 1.00mL of methanol.
And step two, adding 0.04mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm for 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.058g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is orange solid powder.
Example 5
The preparation of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material is realized by the following steps:
step one, adding 0.028g hexachlorocyclotriphosphazene and V into a 10mL Schlenk bottle6O13-OH 0.300g, dissolved well with 5.50mL of anhydrous acetonitrile.
And step two, adding 0.20mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.102g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is orange solid powder.
Example 6
The preparation of the polyoxometalate-based ring-crosslinked polyphosphazene hybrid material is realized by the following steps:
step one, 0.013g of hexachlorocyclotriphosphazene and PW were added to a 10mL Schlenk flask11O39-NH30.200g was dissolved well with 5.50mL of anhydrous acetonitrile.
And step two, adding 0.04mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.167g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is white solid powder.
Example 7
Step one, adding 0.006g hexachlorocyclotriphosphazene and SiW into a 10mL Schlenk bottle11O39-NH30.200g was dissolved well with 2.20mL of anhydrous acetonitrile.
And step two, adding 0.20mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.045g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is white solid powder.
Example 8
Step one, 0.010g of hexachlorocyclotriphosphazene, [ Mn ] was added to a 10mL Schlenk flask12(OOCC6H4OH)16(H2O)4]0.200g was dissolved well with 2.20mL of anhydrous acetonitrile.
And step two, adding 0.20mL of triethylamine serving as an acid-binding agent and a catalyst for nucleophilic substitution reaction into the solution, and introducing nitrogen to remove oxygen for 20 min.
Step three, sealing a Schlenk bottle, and refluxing in an oil bath kettle at 90 ℃ for 24 hours;
and step four, cooling to room temperature after the reaction is finished, centrifuging the polyphosphazene suspension (8000rpm, 10min), repeatedly washing the obtained solid for 3 times by using acetonitrile and ethanol, and finally drying for 24h by using a vacuum oven to obtain 0.045g of the target product polymetallic oxygen cluster-based ring-crosslinked polyphosphazene hybrid material which is black solid powder.

Claims (6)

1. A method for preparing a polyoxometallate-based ring-crosslinked polyphosphazene hybrid polymer material is characterized by comprising the following steps:
step 1: dissolving 1 part of hexachlorocyclotriphosphazene and 1.5-3 parts of functional group organic modified polyoxometalate in 1-3 ml of anhydrous acetonitrile solvent;
step 2: adding 9-18 parts of triethylamine as an acid-binding agent and a catalyst for nucleophilic substitution reaction, and introducing nitrogen to remove oxygen for 10-30 min;
and step 3: reacting the reaction solution in a Schlenk bottle at 80-95 ℃ for 12-48 h under the protection of nitrogen to obtain a suspension;
and 4, step 4: centrifuging the suspension, repeatedly washing the suspension by using an organic solvent, and drying the suspension for 12-48 h by using a vacuum oven to obtain a target product, namely the polymetallic oxygen cluster-based ring cross-linked hybrid polyphosphazene material, which is solid powder;
the polyoxometalate organically modified by the functional group is X2[V6O13{(OCH2)3CCH2R}2]、X4[SiW11O39{O(SiC3H8R)2}]、X3[PW11O39{O(SiC3H8R)2}]、X6[P2W17O61{O(SiC3H8R)2}]Or [ Mn12(OOCR)16(H2O)4](ii) a Wherein R is-NH2，-OH，-C6H4NH2or-C6H4OH; x is tetrabutylammonium.
2. The method of claim 1, wherein: the organic solvent in the step 4 is acetonitrile and ethanol.
3. The method of claim 1, wherein: the repeated washing treatment refers to 3-4 times of washing respectively by acetonitrile and ethanol.
4. The method of claim 1, wherein: and introducing nitrogen to remove oxygen for 20 min.
5. The method of claim 1, wherein: the reaction solution in the step 3 is reacted for 24 hours at 90 ℃ in a Schlenk bottle to obtain a suspension.
6. The method of claim 1, wherein: and 4, drying in a vacuum oven for 24 hours.
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