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A kind of crystalline polyaryletherketone porous membrane with adjustable pore size, preparation method and application thereof

A technology of polyaryletherketone and polyaryletherketimine, which is applied in the field of preparation of crystalline polyaryletherketone porous membranes, can solve the problems of affecting comprehensive performance, unstable diluent, solvent resistance and high temperature, and achieves The preparation process is simple and easy, the cost of raw materials can be recovered, and the cost of raw materials is low

Active Publication Date: 2022-02-01
JILIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Chinese patent (CN101234304A) discloses a polyether ether ketone porous membrane prepared by a thermally induced phase separation method: mix polyether ether ketone with a diluent, and form a porous structure by high-temperature dissolution and low-temperature phase separation. However, this method requires It is carried out at high temperature and requires a high-temperature-resistant diluent. Compared with the immersion phase inversion method and the steam-induced phase inversion method in the present invention, the process cost and operational difficulty are increased, and some diluents are not stable at high temperatures, affecting craft effect
Chinese patent (CN103816820A) discloses a preparation method of a semi-crystalline polyetheretherketone porous membrane: polyetheretherketone and polyetherimide are blended and extruded to form a film, and then the polyetherimide is dissolved and removed to obtain Polyetheretherketone porous membrane, this method also needs to be carried out at high temperature, and it is necessary to select a suitable pore-forming agent. Compared with the immersion phase inversion method and the steam-induced phase inversion method in the present invention, the process cost and operation are increased. Difficulty, and limited by the content and dispersion state of the pore-forming agent, it is impossible to obtain a wide pore size distribution, and it is also impossible to form a finger-shaped pore morphology that can be applied to filtration and other fields, so the application is very limited
Chinese patent (CN107611322A) discloses a production process of polyetheretherketone lithium battery diaphragm: polymerizing halogenated ketone compounds and bishydroxy compounds into polyetheretherketone, and melting, extruding and stretching at high temperature to form polyether Etherketone nanofibrous membrane, but this method not only needs to be carried out at high temperature, which increases the process cost and operational difficulty, and compared with the immersion phase inversion method, water vapor induced phase inversion method and template method in the present invention, the obtained The polymer loses the original crystallinity of PEEK
According to the theory of polymer physics, the higher the symmetry of the molecular chain, the easier it is to form crystals, and the existence of the methyl structure of the side chain of the polymer in this invention makes it asymmetric, so the porous membrane prepared by it does not have crystallinity. Not resistant to solvents and high temperatures, which will affect the overall performance in practical applications

Method used

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  • A kind of crystalline polyaryletherketone porous membrane with adjustable pore size, preparation method and application thereof
  • A kind of crystalline polyaryletherketone porous membrane with adjustable pore size, preparation method and application thereof
  • A kind of crystalline polyaryletherketone porous membrane with adjustable pore size, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0054] Dissolve the soluble polyether ether ketone precursor—polyether ether ketone-1,3-dioxolane (see literature [1, 2] for the preparation method) (1.0g) in the polar polymer good solvent NMP (4mL) , the mass concentration of the solution is 20%, and it is airtightly stirred at room temperature for 15 hours to prepare a clear and transparent casting solution; pour the casting solution on the surface of a horizontal glass plate, spread it evenly with a scraper, and then place it in a constant humidity box 10 minutes, and then made a polymer porous membrane; soak the obtained polymer porous membrane in deionized water for 50 hours, take it out and dry it at 80°C under vacuum, remove the residual polymer polar good solvent and place it in Soak in hydrochloric acid for 28 hours, take it out, rinse with deionized water, remove excess acid, and then dry it at 60°C under vacuum to obtain a polyetheretherketone porous membrane with adjustable pore size; the polyetheretherketone porou...

Embodiment 2

[0057] The preparation process of the crystalline polyetheretherketone porous membrane described in Example 1 is the same, and the DSC curve of the prepared crystalline polyaryletherketone porous membrane with adjustable pore size is similar to that of Example 1, and its crystallinity is 27%. , the pore diameter is 3 μm, the porosity is 80%, the pore morphology is sponge-like pores, and the thickness is 10 μm. Then, the prepared crystalline polyetheretherketone porous membrane was assembled into a supercapacitor according to the literature [4] for cyclic voltammetry curve test, using an electrochemical workstation (CHI 660A) in the voltage range of 0.0-3.0V, and the scan rate was 5mV s -1 , Tested at ambient temperature.

[0058] The linear sweep voltammetry curves of the supercapacitor conventional gel electrolyte (GPE-20) and cross-linked gel electrolyte (NGPE-CL-20) prepared in Example 2 are shown in the appendix Figure 8 ; The figure shows that both NGPE-CL-20 and GPE-2...

Embodiment 3

[0060] The same as in Example 1, except that the pore forming agent dibutyl phthalate (0.9g) was added to the casting solution, the ratio of its mass dosage to the polymer was 0.9:1, and the stirring was continued for 5 hours to make the pore forming agent Disperse evenly in the polymer solution; pour the casting solution with the porogen added on the surface of a horizontal glass plate, place it in an oven at 60°C, 80°C, and 100°C for 12 hours each, and then dry it in vacuum at 120°C for 12 hours. Solvent was completely removed. After taking out the membrane, place the membrane in a Soxhlet extractor, extract it with ethanol for 8 hours, and dry it in vacuum at 60°C for 12 hours to obtain a polymer porous membrane; soak the obtained polymer porous membrane in hydrochloric acid for 28 hours, take it out and use deionized Rinse with water to remove excess acid, then dry at 60°C under vacuum to obtain a polyether ether ketone porous membrane with adjustable pore size; heat-treat...

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Abstract

A crystalline polyaryletherketone porous membrane with adjustable pore diameter, a preparation method and its application belong to the technical field of polymer materials. The soluble polyaryletherketone precursor solution is prepared by the immersion phase inversion method, the steam-induced phase inversion method or the template method to prepare a porous membrane, and then crystallized by acidification and heat treatment, thereby preparing the adjustable pore size film of the present invention. The crystalline polyaryletherketone porous membrane; the crystallinity of the prepared crystalline polyaryletherketone porous membrane with adjustable pore size is 26-29%, the pore diameter range is 0.01-5μm, the porosity is 50-80%, and the pores The morphology is finger-like pores or sponge-like pores, and the thickness is 10-130 μm. The method is simple to operate, low in cost, and can be produced on a large scale, and the immersion phase inversion method and the water vapor induced phase inversion method do not require external additives, further saving process costs, and can be widely used in fuel cells, supercapacitors, and lithium-ion batteries and ultrafiltration membranes.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and in particular relates to a crystalline polyaryletherketone porous membrane with adjustable aperture, a preparation method and its application in fuel cells, supercapacitors, lithium ion batteries and ultrafiltration membranes. Background technique [0002] High-performance membrane materials are the core materials of the contemporary chemical industry. They are strategic materials for solving water resources, energy, environmental problems and traditional industrial technologies. They have been widely used in important fields such as water resources, energy, environment, traditional industries and national defense. Compared with traditional materials, it has the characteristics of high efficiency, low energy consumption, simple operation and environmental friendliness, and is easy to integrate with other technologies to play a role, showing huge advantages. [0003] Polyaryletherket...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08J5/22B01D71/72B01D69/02B01D67/00B01D61/14H01M50/414H01M50/489H01M50/491H01G11/52
CPCC08J5/2256B01D71/72B01D69/02B01D67/0079B01D61/145H01G11/52H01M50/411Y02E60/13Y02E60/10
Inventor 王贵宾张重阳杨砚超栾加双张淑玲张梅
Owner JILIN UNIV
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