Cation group-containing ether bond-free polyfluorene alkylene, preparation method thereof and anion exchange membrane

A technology of cationic groups and polyfluoranes, which is applied in the field of anion exchange membranes, can solve the problems of decreased mechanical properties of anion exchange membranes, decreased performance of anion exchange membranes, excessive swelling of membranes, etc., and achieves the effect of excellent solubility

Active Publication Date: 2019-02-12
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the main chain of traditional anion exchange membranes is either polyolefins that are not resistant to swelling or aromatic ethers with poor alkali stability. Easy to over-swell or degrade the main chain, resulting in a decrease in the mechanical properties of the anion-exchange membrane, which in turn leads to a decrease in the overall performance of the anion-exchange membrane
[0003] The main reason for the degradation of the traditional aromatic main chain is that there are ether bonds on the main chain that are not stable under alkaline conditions. In order to improve the stability of aromatic anion exchange membranes under alkaline conditions, many scholars have designed and prepared a series of ether-free membranes. Bond main chain, such as: polyphenylene main chain synthesized by Diels–Alder reaction (Michael R.Hibbs, et al., Macromolecules 2009, 42, 8316–8321), N-spirocyclic quaternary ammonium synthesized by cyclocondensation reaction The cationic main chain (Patric Jannasch, et al., J.Am.Chem.Soc.2017, 139, 2888-2891) has good alkali resistance, but the preparation method is cumbersome, and the obtained anion The mechanical properties of the membrane are not good

Method used

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  • Cation group-containing ether bond-free polyfluorene alkylene, preparation method thereof and anion exchange membrane
  • Cation group-containing ether bond-free polyfluorene alkylene, preparation method thereof and anion exchange membrane
  • Cation group-containing ether bond-free polyfluorene alkylene, preparation method thereof and anion exchange membrane

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preparation example Construction

[0055] The present invention provides a preparation method of cationic group-containing polyfluorene alkylene without ether bond with structure of formula (I), comprising:

[0056] A) dissolving fluorene-type monomers, comonomers, and ketone monomers of formula (II) in a solvent, and reacting under the condition of superacid as a catalyst, the polymer obtained; the comonomers are selected from the group consisting of One or more of benzene, p-terphenyl, m-terphenyl, naphthalene and anthracene;

[0057] B) dissolving the polymer in an aprotic polar solvent and reacting with one of tertiary amine, imidazole and tertiary phosphine to obtain a cationic group-containing polyfluorene alkylene without ether linkage of the structure of formula (I);

[0058]

[0059] Wherein, Y is one of F, Cl, Br and I; a is 0-11.

[0060] The preparation method of the cationic group-containing non-ether bond polyfluorene alkylene with the structure of formula (I) provided by the present invention...

Embodiment 1

[0104] (1) In a 75mL pressure-resistant bottle with a magnetic stirrer, dissolve 2.32g of a=4 fluorene monomer, 1.54g of biphenyl, and 1.68g of 1,1,1-trifluoroacetone in 11mL of dichloromethane, Under ice-water bath, add 11mL CF 3 SO 3 H. After capping for 6 hours, the system was settled in methanol to obtain a white solid, which was washed several times with methanol and dried in vacuo. The yield is 97%, and the intrinsic viscosity is 0.5dL / g (determined in NMP at 25°C).

[0105] (2) In a 100mL single-necked flask equipped with a magnetic stir bar, add 1g of the obtained white solid and 0.77g image 3 Add 20mL of N,N-dimethylacetamide to dissolve the large sterically hindered imidazole, react at 80°C for 72h, cool to room temperature and precipitate ionized polymer in ether, wash with ether several times, and vacuum dry for 12h to obtain The imidazolium salt group has no ether linkage polyfluorenalkylene. The yield is 95%, and the intrinsic viscosity is 0.8dL / g (determine...

Embodiment 2

[0109] (1) In a 75mL pressure-resistant bottle with a magnetic stirrer, dissolve 1.48g of a=5 fluorene-type monomer and 1.61g of terphenyl, 1.12g of 1,1,1-trifluoroacetone in 15mL of dichloromethane, Under ice water bath, add 10mL SbF 5 After capping and reacting for 3 h, the system was settled in methanol to obtain a white solid, which was washed several times with methanol and dried in vacuo. The yield is 98%, and the intrinsic viscosity is 0.6dL / g (determined in NMP at 25°C).

[0110] (2) In a 75mL pressure-resistant bottle equipped with a magnetic stirrer, add 1g of the obtained white solid and 0.60g of trimethylamine in water, add 20mL of dimethyl sulfoxide to dissolve, react at room temperature for 48h, and then precipitate and ionize in ether After the polymer was washed several times with ether, it was vacuum-dried for 12 hours to obtain a polyfluorene alkylene containing quaternary ammonium cationic groups without ether linkages. The yield is 94%, and the intrinsic ...

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Abstract

The invention provides cation group-containing ether bond-free polyfluorene alkylene with a structure as shown in a formula (I). A polymer, which takes ether bond-free polyfluorene alkylene as a mainchain, is prepared through utilizing super acid-catalyzed Friedel-Crafts reaction, and then the cation group-containing ether bond-free polyfluorene alkylene is obtained through reaction with tertiaryamine or large steric hindrance imidazole or large steric hindrance tertiary phosphine. The method can be used for accurately controlling the positions and number of ion exchange groups; the obtainedcation group-containing ether bond-free polyfluorene alkylene has excellent solubility and is conducive to further functionalized application; the whole polymer molecule structure does not have a group which is not resistant to alkali, and the anion exchange membrane prepared from the polymer is conducive to being used for a long time in a high pH condition.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a cationic group-containing polyfluorene alkylene without ether bonds, a preparation method thereof and an anion exchange membrane. Background technique [0002] Anion exchange membrane fuel cell is a clean, efficient and environmentally friendly new energy technology. Compared with proton exchange membrane fuel cells, hydroxide ion exchange membrane fuel cells have higher electrode catalytic activity under alkaline conditions, and non-precious metal catalysts can be selected to assemble fuel cells to achieve low cost and high performance. However, the main chain of traditional anion exchange membranes is either polyolefins that are not resistant to swelling or aromatic ethers with poor alkali stability. It is easy to excessively swell or degrade the main chain, resulting in a decrease in the mechanical properties of the anion exchange membrane, which in turn leads to ...

Claims

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Application Information

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IPC IPC(8): C08G61/02C08J5/18C08L65/00H01M8/103H01M8/1034
CPCC08G61/02C08G2261/122C08G2261/143C08G2261/146C08G2261/147C08G2261/312C08G2261/3142C08G2261/45C08J5/18C08J2365/00H01M8/103H01M8/1034Y02E60/50
Inventor 李胜海杨宽郭靖张所波
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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