CN105220267A - A kind of method preparing perfluorinated sulfonic acid catalysis fibre - Google Patents
A kind of method preparing perfluorinated sulfonic acid catalysis fibre Download PDFInfo
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- CN105220267A CN105220267A CN201510706943.0A CN201510706943A CN105220267A CN 105220267 A CN105220267 A CN 105220267A CN 201510706943 A CN201510706943 A CN 201510706943A CN 105220267 A CN105220267 A CN 105220267A
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- perfluorinated sulfonic
- sulfonic acid
- acid catalysis
- fibre
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Abstract
The invention provides a kind of method preparing perfluorinated sulfonic acid catalysis fibre, after specifically comprising the steps: that granular perfluorinated sulfonic resin is dissolved in solvent, mix a certain amount of water soluble polymer, be prepared into the spinning solution of clarification, recycling electrospinning process prepares perfluorinated sulfonic acid catalysis fibre, fibre diameter 100 ~ 1000 nanometer, can be used for water purification, chemical catalysis, the preparation of biosynthesis fiber and the manufacture of fuel cell barrier film.Equipment and process step required for the present invention is few, and processing conditions is gentle, is easy to operation.
Description
Technical field
The invention belongs to high molecular functional fiber art and catalyst field, be specifically related to a kind of preparation method of perfluorinated sulfonic acid catalysis fibre.
Background technology
Perfluorinated sulfonic resin is a kind of solid super-strong acid, has excellent heat resistance, chemistry and the feature such as electrochemical stability and high mechanical properties, and it has good catalytic activity and selective to many reactions.The film made with perfluorinated sulfonic resin has been widely used in the fields such as chemical catalysis, sewage disposal, the preparation of biosynthesis fiber, gas separaion, fuel cell and chlorine industry, has the advantage that other materials is incomparable.
As Luo Shiping in its " Advance in catalysis of novel perfluorinated resinsulfonic acid catalysts " (chemical research and application, 2004,17 (1), 15-18), described in, perfluorinated sulfonic resin is generally the spherical of densification, specific area is less, the acid centre be buried in fluorocarbon radical body is not easily close by reactant institute, and mass ratio activity is low, therefore increases its specific area, raising can utilize the ratio in acid site, is the important measures improving perfluorinated sulfonic resin catalysis potentiality.In order to increase the specific area of perfluorinated sulfonic resin, to improve catalytic activity, method conventional at present has porous method and load method.Porous method is contacted with pressure fluid by perfluorinated sulfonic resin, carries out swelling, then explosive decompression, fluid gasified and effusion rapidly, produce a lot of hole at perfluorinated sulfonic resin intrinsic silicon.Load method is by perfluorinated sulfonic resin wiring solution-forming under uniform temperature and pressure, then by solution impregnation in inorganic oxide, after certain hour, then by dipping backflow or dipping steam seasoning remove solvent, obtain loaded catalyst.Along with the reach of science, also have new preparation method to continue to bring out, wherein electrostatic spinning is relatively more direct, the efficient method obtaining nano level superfine fiber, perfluorinated sulfonic resin can be prepared into perfluorinated sulfonic acid nano-catalytic fiber.The present invention proposes a kind of method preparing perfluorinated sulfonic acid catalysis fibre, by perfluorinated sulfonic resin particle after dissolving, and add and certain carry polymer to increase the chain entanglement in spinning solution system, then carry out electrostatic spinning, obtain perfluorinated sulfonic acid catalysis fibre.
Summary of the invention
The object of the present invention is to provide the efficient technology of preparing of a kind of dissolving method of perfluorinated sulfonic resin and superfine fibre, can prepare that thickness is homogeneous, the nanoscale perfluorinated sulfonic acid catalysis fibre of good heat resistance, long service life.
The present invention prepares the method for perfluorinated sulfonic acid catalysis fibre, specifically comprises the steps and process conditions:
1) dissolving of perfluorinated sulfonic resin.Perfluorinated sulfonic resin solid particle is put into the mixed solvent of water and organic solvent, after stirring at normal temperature, proceed to autoclave, dissolve 4 to 24 hours under high temperature, naturally cool, obtain limpid perfluor sulfoacid resin solution.
2) by step 1) gained solution mixes with water soluble polymer, magnetic agitation standing and defoaming 1 to 24 hours, as spinning solution.
3) step 2 is got) obtained spinning solution is in centrifugal electrostatic spinning apparatus, and setting spinning condition, voltage 1KV to 50KV, receiving range 5cm to 20cm, obtain perfluorinated sulfonic acid catalysis fibre.
Technical solution of the present invention step 1) in, the molecular structure of described perfluorinated sulfonic resin is:
Wherein M is the integer of 0 ~ 3, N be more than or equal to 2 integer, X is more than or equal to 1, Y, and to be more than or equal to 1, R be SO3M, and wherein M is alkali metal or alkaline-earth metal.
Technical solution of the present invention step 1) in solid perfluorinated sulfonic acid resin quality account for and proceed to 1% to 50% of material gross mass in autoclave.
Technical solution of the present invention step 1) in solution temperature be 100 DEG C to 240 DEG C, pressure is 1MPa ~ 10MPa.
Technical solution of the present invention step 1) in, described organic solvent is methyl alcohol, ethanol, isopropyl alcohol, dimethyl formamide, propylene glycol, and the mixture that is a kind of or wherein many persons in acetone, the mass fraction of described water is 10% ~ 50%.
Technical solution of the present invention step 2) in, described water soluble polymer is the mixing of one or more in polyvinyl alcohol, PVP, polyacrylic acid, Pluronic F-127, and mass fraction is 1% ~ 50%.
Feed particulate material, by dissolving perfluorinated sulfonic resin, then by centrifugal electrospinning process, is prepared into fibrous material, adds specific area by the present invention.Preparation method is succinct, efficient, nontoxic, and preparation capable of circulation, stock utilization is high.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further with embodiment below, but content of the present invention is not only confined to the following examples:
Embodiment 1:
1) prepare the mixed solution 60 grams of water and ethanol, wherein the mass fraction of water is 10%, and adds 4g perfluorinated sulfonic resin, magnetic agitation 30 minutes, proceeds to autoclave, is heated to 100 DEG C after airtight, be incubated and naturally cool to room temperature after 20 hours, take out mixing material.2) mixed solution is mixed with 4 grams of Pluronic F-127s fully stir, leave standstill 1 hour, obtain the spinning solution of clear.3) get spinning solution 30 grams, put into centrifugal electrospinning device, setting voltage 5KV, rotating speed 480rpm, receiving range 15cm, obtain uniform perfluorinated sulfonic acid catalysis fibre of arranging.
Embodiment 2:
1) prepare the mixed solution 40 grams of water and ethanol, wherein the mass fraction of water is 20%, and adds 2g perfluorinated sulfonic resin, magnetic agitation 10 minutes, proceeds to autoclave, is heated to 120 DEG C after airtight, be incubated and naturally cool to room temperature after 15 hours, take out mixing material.2) by mixed solution and 2 grams of PVP, leave standstill 2 hours, obtain the spinning solution of clear.3) get spinning solution 30 grams, put into centrifugal electrospinning device, setting voltage 5KV, rotating speed 720rpm, receiving range 15cm, obtain the perfluorinated sulfonic acid catalysis fibre of a large amount of evenly arrangement.
Embodiment 3:
1) prepare the mixed solution 40 grams of water and dimethyl formamide, wherein the mass fraction of water is 20%, and adds 1g perfluorinated sulfonic resin, magnetic agitation 10 minutes, proceeds to autoclave, is heated to 150 DEG C after airtight, be incubated and naturally cool to room temperature after 8 hours, take out mixing material.2) by mixed solution and 2 grams of PVP, leave standstill 2 hours, obtain the spinning solution of clear.3) get spinning solution 10 grams, put into solution electrospinning device, setting voltage 20KV, flow velocity 1g/h, receiving range 12cm, obtain perfluorinated sulfonic acid catalysis fibre.
Embodiment 4:
1) mixed solution 50 grams of water, ethanol and dimethyl formamide is prepared, wherein the mass fraction of water is 20%, the mass fraction of ethanol is 50%, and add 2.5g perfluorinated sulfonic resin, magnetic agitation 30 minutes, proceeds to autoclave, is heated to 200 DEG C after airtight, be incubated and naturally cool to room temperature after 5 hours, take out mixing material.2) by mixed solution and 2 grams of PVP, leave standstill 4 hours, obtain the spinning solution of clear.3) get spinning solution 10 grams, put into solution electrospinning device, setting voltage 30KV, flow velocity 1.5g/h, receiving range 15cm, obtain perfluorinated sulfonic acid catalysis fibre.
Claims (1)
1. prepare the method for perfluorinated sulfonic acid catalysis fibre for one kind, it is characterized in that, first by graininess perfluorinated sulfonic resin in autoclave through dissolution with solvents, and obtained spinning solution is mixed with water soluble polymer, spin perfluorinated sulfonic acid catalysis fibre by centrifugal electrospinning process, its diameter is 100 ~ 1000 nanometers; Wherein the structure of perfluorinated sulfonic resin is:
Wherein M is the integer of 0 ~ 3, N be more than or equal to 2 integer, X is more than or equal to 1, Y, and to be more than or equal to 1, R be SO
3m, wherein M is alkali metal or alkaline-earth metal; Perfluorinated sulfonic resin quality accounts for 1% to 50% of the mixture gross mass loading reactor; Solvent is the mixture of water and organic solvent, and described organic solvent is methyl alcohol, ethanol, isopropyl alcohol, dimethyl formamide, propylene glycol, the mixture that is a kind of or wherein many persons in acetone, and wherein the mass fraction of water is 10% ~ 50%; Solution temperature is 100 DEG C to 240 DEG C, and pressure is 1MPa ~ 10MPa; Water soluble polymer is one or more mixing in polyvinyl alcohol, PVP, polyacrylic acid, Pluronic F-127, mass fraction 1% ~ 50%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107653504A (en) * | 2016-07-26 | 2018-02-02 | 通用汽车环球科技运作有限责任公司 | Perfluorinated sulfonic acid nanofiber |
| CN110146454A (en) * | 2019-05-16 | 2019-08-20 | 江南大学 | A method of passing through palingenesis between the separable regenerating system verifying antioxidant of building |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103469352A (en) * | 2012-06-06 | 2013-12-25 | 华东理工大学 | Preparation method of polymer nanofiber membrane containing perfluorinated sulfonic acid |
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2015
- 2015-10-28 CN CN201510706943.0A patent/CN105220267A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469352A (en) * | 2012-06-06 | 2013-12-25 | 华东理工大学 | Preparation method of polymer nanofiber membrane containing perfluorinated sulfonic acid |
Non-Patent Citations (5)
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| HONG CHEN ET AL: "Electrospinning and Solution Properties of Nation and Poly(acrylic acid)", 《MACROMOLECULES》 * |
| 吴昌政等: ""离心纺丝技术研究进展"", 《上海纺织科技》 * |
| 宋天丹等: ""离心纺丝的发展现状及前景"", 《纺织导报》 * |
| 张智明等: ""高速离心纺制备纳米纤维研究进展"", 《高分子通报》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107653504A (en) * | 2016-07-26 | 2018-02-02 | 通用汽车环球科技运作有限责任公司 | Perfluorinated sulfonic acid nanofiber |
| CN107653504B (en) * | 2016-07-26 | 2020-07-03 | 通用汽车环球科技运作有限责任公司 | Perfluorosulfonic acid nanofibers |
| CN110146454A (en) * | 2019-05-16 | 2019-08-20 | 江南大学 | A method of passing through palingenesis between the separable regenerating system verifying antioxidant of building |
| CN110146454B (en) * | 2019-05-16 | 2021-07-09 | 江南大学 | Method for verifying regeneration effect between antioxidants by constructing separable regeneration system |
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