Proton-type and alkali-metal-ion-type polyacid hybrid polymer with polymerization degree of 100 and preparation method thereof

An alkali metal ion and polymer technology, which is applied to the proton type and alkali metal ion type polyacid hybrid polymer with a degree of polymerization of 100 and the field of preparation thereof, and can solve the problems of limited application, ineffective ionization, insolubility, etc. , to achieve the effect of simple experimental processing

Active Publication Date: 2021-04-20
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, since poly(POM-TBA) cannot ionize effectively in organic solvents and cannot be dissolved in water, its application in electrochemical fields including ion conduction and chemical batteries is limited.

Method used

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  • Proton-type and alkali-metal-ion-type polyacid hybrid polymer with polymerization degree of 100 and preparation method thereof
  • Proton-type and alkali-metal-ion-type polyacid hybrid polymer with polymerization degree of 100 and preparation method thereof
  • Proton-type and alkali-metal-ion-type polyacid hybrid polymer with polymerization degree of 100 and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Example 1: The proton-type multi-acid hybrid polyelectrolyte poly(POM-6H with a degree of polymerization of 100 + ) 100 (Theoretical molecular weight is 438.4kDa) preparation

[0043] Take 25 mL of the treated cation exchange resin and pack it into the chromatographic column and add deionized water to wet it, and dissolve 50 mg of polyacid polymer poly(POM-6TBA) with a degree of polymerization of 100 and tetrabutylammonium ion as a counter ion with 1 mL of acetonitrile. ) 100 (theoretical molecular weight is 583.3kDa), the acetonitrile solution is dropped into the ion exchange column by wet loading. Rinse the resin column with water as the mobile phase, receive a clear and transparent yellow aqueous solution below, remove the mobile phase by vacuum evaporation, and obtain brown-yellow powder poly(POM-6H + ) 100 Such as figure 2 As shown, the yield was 33 mg, and the yield was 88%. product of 1 H NMR spectrum as image 3 as shown, 31 P NMR spectrum as Figure ...

Embodiment 2

[0044] Example 2: The lithium-ion type polyacid hybrid polyelectrolyte poly(POM-6Li with a degree of polymerization of 100 + ) 100 (Theoretical molecular weight is 442.0kDa) preparation

[0045] To 50mg of polyacid polymer poly(POM-6TBA) 100 Add 0.7mL of LiTFSI in THF solution (1mol / L) to form a suspension system, and ion exchange occurs after vigorous stirring. The ion-exchange solution was replaced every 8 hours, and the precipitate was washed with MeCN and THF after repeated 5 times, and the dark green powder poly(POM-6Li + ) 100 Such as figure 2 As shown, the yield was 33 mg, and the yield was 88%. product of 1 H NMR spectrum as Figure 5 as shown, 31 P NMR spectrum as Figure 6 shown; the concentration of 0.1mmol / L poly(POM-6Li + ) 100 Li at 0.1mol / L 2 SO 4 In the supporting electrolyte solution, the CV curves at different scanning speeds are as follows Figure 16 shown.

Embodiment 3

[0046] Embodiment 3: the sodium ion type multi-acid hybrid polyelectrolyte poly(POM-6Na + ) 100 (Theoretical molecular weight is 451.6kDa) preparation

[0047] To 50mg of polyacid polymer poly(POM-6TBA) 100 Add 0.7mL of NaTFSI in THF solution (1mol / L) to form a suspension system, and ion exchange occurs after vigorous stirring. The ion-exchange solution was replaced every 8 hours, and after repeated 5 times, the precipitate was washed with MeCN and THF, and vacuum-dried to obtain poly(POM-6Na + ) 100 Such as figure 2 As shown, the yield was 34 mg, and the yield was 89%. product of 1 H NMR spectrum as Figure 7 as shown, 31 P NMR spectrum as Figure 8 shown; the concentration of 0.1mmol / L poly(POM-6Na + ) 100 Na at 0.1mol / L 2 SO 4 In the supporting electrolyte solution, the CV curves at different scanning speeds are as follows Figure 17 shown.

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Abstract

The invention relates to a proton-type and alkali-metal-ion-type polyacid hybrid polymer with a polymerization degree of 100 and a preparation method thereof. According to the invention, two different cation exchange methods are creatively adopted to convert a polyoxometallate (polyacid) polymer taking tetrabutylammonium ions as counter ions into a proton type polyacid hybrid polymer and an alkali metal ion type polyacid hybrid polymer respectively, and a nuclear magnetic resonance spectrogram of the hybrid polymers is measured; and the molar ratio of the peripheral alkali metal ions to the central metal in the polyacid cluster is determined through a plasma emission spectrum. The method has the advantages that the target hybrid polymer can be obtained through a simple, convenient, efficient and rapid ion exchange process, the experimental method is simple, and industrialization is easy to realize. The polymer retains the covalent linkage of a polyacid cluster and a polymer chain and has good water solubility, and an aqueous solution of the polymer has good electrochemical oxidation-reduction reversibility, so that the polymer has potential application value in the fields of catalysis, materials, medicines, electrochemistry and the like.

Description

technical field [0001] The present invention relates to macromolecule polymer, organic, inorganic and material chemistry, especially the method for preparing proton type and alkali metal ion type polyacid polymer by two different cation exchange methods, utilize this method to polymerize polyacid The tetrabutylammonium counter ions on the periphery of the compound were directly replaced by protons and alkali metal ions, respectively, and a new type of water-soluble conductive multi-acid hybrid polymer was obtained. Background technique [0002] Inorganic polyoxometalate clusters (polyoxometalate, referred to as POM) are composed of pre-transition metals such as tungsten (W), vanadium (V), molybdenum (Mo) in the highest oxidation state and central atoms such as phosphorus (P) and silicon (Si) and A class of monomolecular clusters with a definite structure formed by oxygen coordination. With their specific architecture, fixed geometry, and size of 1–2 nm, they are widely used...

Claims

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Application Information

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IPC IPC(8): B01J39/26C08F8/44C08F132/08
CPCY02E60/50
Inventor 王维鲁卓群颜雨坤张兰兰
Owner NANKAI UNIV
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