CN1305570C - Method for preparing full fluorinion exchange resin - Google Patents
Method for preparing full fluorinion exchange resin Download PDFInfo
- Publication number
- CN1305570C CN1305570C CNB2004100213945A CN200410021394A CN1305570C CN 1305570 C CN1305570 C CN 1305570C CN B2004100213945 A CNB2004100213945 A CN B2004100213945A CN 200410021394 A CN200410021394 A CN 200410021394A CN 1305570 C CN1305570 C CN 1305570C
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- CN
- China
- Prior art keywords
- solvent
- polymer waste
- base polymer
- chelating agent
- waste material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a method for preparing full-fluorine ion-exchange resin. Full-fluorine type polymer waste is immersed in a chelating agent for 1 to 4 hours for pretreatment, wherein the weight ratio of the full-fluorine type polymer waste to the chelating agent is 1: (0.1 to 1.1); then, solvent is prepared according to the weight ratio of the full-fluorine type polymer waste to the solvent as 1:3 to 1:100, and the solvent is composed of water accounting for 5 to 90 percent of the gross weight of the solvent, and the mixture of at least three components of monohydric alcohols, dihydric alcohols or polyalcohols, wherein the mixture accounts for 10 to 95 percent of the gross weight of the solvent; the solvent is mixed with the treated full-fluorine type polymer waste, and a finished product is prepared under the conditions of the reaction temperature of 0 to 180 DEG C and the reaction time of 0.5 to 4 hours. The present invention has the advantages of simple process, low requirements for technological conditions and low preparing cost, and the prepared finished product has stable performance and high yield.
Description
Technical field
The invention belongs to the preparation method of chemicals, particularly a kind of preparation method of perfluorinated ion exchange resin.
Background technology
Perfluorinated ion exchange resin contains the functional group of the salt of sulfonic acid and hydroxy-acid group or sulfonic acid and carboxylic acid, it is of many uses, as in fuel cell, electrolytic cell and alkaline water generating apparatus, using, in many chemical reactions, also can be used as catalyst and use and in the multiple choices process of osmosis, use as film.Say that generally these polymer become required product with melt-processed, polymer is the sulfuryl fluoride predecessor of melt-processable, and hydrolysis converts ion exchange resin membrane to then, but also has many products to make with liquid compound.The present domestic producer that does not also have to produce in a large number in batch this resinoid, and tetrafluoroethene, perfluoro propene oxid, perfluor oxygen base sulfuryl fluoride, perfluor oxygen yl carboxylic acid ester that external general employing makes with hydrofluoric acid are raw material, get by copolymerization, this complex process, process conditions require height, manufacturing cost is high, yield is low.
Summary of the invention
The objective of the invention is to solve the problems referred to above that prior art exists, the preparation method of the perfluorinated ion exchange resin that provide that a kind of technology is simple, process conditions requires low, low cost of manufacture, prepared end properties is stable, yield is high.
First kind of technical solution of the present invention is: get and contain-SO
3M and-the perfluor base polymer waste material of COOM ion soaks through chelating agent and carried out preliminary treatment in 1～4 hour, wherein M is H, Na, K or NR
4, R is H, CH
3Or C
3H
5, said chelating agent is sulfamic acid or EDTA, perfluor base polymer waste material and chelating agent weight ratio are 1: 0.1～1: 1; Be to get solvent in 1: 3～1: 100 by the weight ratio of perfluor base polymer waste material and solvent again, with described solvent with mix through pretreated perfluor base polymer waste material, in reaction temperature is that 0～180 ℃, reaction time are under 0.5～4 hour the condition, make perfluorinated ion exchange resin, said solvent is made up of the water that accounts for solvent gross weight 5～90%, the ethanol that accounts for solvent gross weight 10～95%, propyl alcohol and PPG.
Second kind of technical solution of the present invention is:
Get and contain-SO
3M and-the perfluor base polymer waste material of COOM ion soaks through chelating agent and carried out preliminary treatment in 1～4 hour, wherein M is H, Na, K or NR
4, R is H, CH
3Or C
3H
5, said chelating agent is sulfamic acid or EDTA, perfluor base polymer waste material and chelating agent weight ratio are 1: 0.1～1: 1; Be to get solvent at 1: 50 by the weight ratio of perfluor base polymer waste material and solvent again, with described solvent with mix through pretreated perfluor base polymer waste material, 25～150 ℃ of following immersion treatment 0.5 hour, make perfluorinated ion exchange resin, said solvent is by according to weight ratio 2.4: 1.6: 1.6: 0.4 water, ethanol, propyl alcohol and triethylene glycol are formed.
Advantage of the present invention is that technology is simple, process conditions require low, low cost of manufacture, prepared end properties is stable, yield is high, be applicable to the recovery of waste material in the preparation membrane process or use before damaged the recovery of film, the useless film in fuel cell or the recovery of the film on electrolytic cell, used.
The specific embodiment
Embodiment 1:
Get 100 kilograms of perfluor base polymer waste materials, said perfluor base polymer waste material contains-SO
3M and-COOM, M is H, Na, K or NR
4, R is H, CH
3Or C
3H
5Add 10～100 kilograms of chelating agents, said chelating agent can adopt sulfamic acid or EDTA, soaked 1～4 hour, carry out preliminary treatment, put into reactor after the preliminary treatment, add 300～10000 kilograms of solvents, said solvent is by the water that accounts for solvent gross weight 5～90%, account for the ethanol of solvent gross weight 10～95%, propyl alcohol and PPG are formed, wherein ethanol, propyl alcohol and PPG weight ratio are 1.4: 1.4: 0.2 (ethanol, the weight of propyl alcohol and PPG is proportioning arbitrarily also), mix, put into still, soaked 0.5～4 hour down, compound is taken out separate then at 0～180 ℃, behind the edulcoration purification, washing and drying gets product.
Embodiment 2:
Get 100 kilograms of perfluor base polymer waste materials, soaked 1～4 hour with 10～100 kilograms of chelating agents, said chelating agent can adopt sulfamic acid or EDTA, after the preliminary treatment, put into reactor, add 5000 kilograms of solvents of forming by water, ethanol, propyl alcohol and triethylene glycol again, water in the said solvent: ethanol: propyl alcohol: the triethylene glycol weight ratio is 2.4: 1.6: 1.6: 0.4, mix, put into still, immersion is after 30 minutes down at 25～150 ℃, and taking-up separates, behind the edulcoration purification, washing and drying gets product.
Embodiment 3:
Get 100 kilograms of perfluor base polymer waste materials, soaked 1～4 hour with 10～100 kilograms of chelating agents, said chelating agent can adopt sulfamic acid or EDTA, after the preliminary treatment, put into reactor, get 3000 kilograms by water, ethanol, propyl alcohol, the solvent that glycerine and PPG are formed, water in the said solvent: ethanol: propyl alcohol: glycerine: the PPG weight ratio is 2: 2: 2: 1 or 7: 1: 1: 1, mix, and put into still, after heating between 0～180 ℃ and refluxing 30 minutes, stop heating, be cooled to 18～25 ℃ of room temperatures, take out and separate, and purifying, washing and drying gets product.
Embodiment 4:
Get 100 kilograms of perfluor base polymer waste materials, soaked 1～4 hour through 10～100 kilograms of chelating agents, said chelating agent can adopt sulfamic acid or EDTA, after the preliminary treatment, puts into reactor; Get 8000 kilograms of solvents of forming by water, ethanol, isopropyl alcohol, triethylene glycol and PPG, wherein water, ethanol, isopropyl alcohol, triethylene glycol, PPG weight ratio are 1: 1: 2: 1: 0.5 or 10: 1: 1: 1: 1, put into reactor, in 0～180 ℃ of scope the heating and refluxed 30 minutes after, stop heating, be cooled to 15～25 ℃ of room temperatures, take out and separate, and purifying, washing and drying gets product.
Embodiment 5:
Get 100 kilograms of perfluor base polymer waste materials, soaked 1～4 hour through 10～100 kilograms of chelating agents, said chelating agent can adopt sulfamic acid or EDTA, after the preliminary treatment, puts into reactor; Get 10000 kilograms of solvents of forming by water, ether, isopropyl alcohol, triethylene glycol and PPG, wherein water, ether, isopropyl alcohol, triethylene glycol, PPG weight ratio are 1: 1: 2: 1: 0.5 or 10: 2: 1: 1: 0.5, put into reactor, after heating between 0～180 ℃ and refluxing 30 minutes, stop heating, be cooled to 10～20 ℃ of room temperatures, take out and separate, and purifying, washing and drying gets product.
Embodiment 6:
Get 100 kilograms of perfluor base polymer waste materials, soaked 1～4 hour with 10～100 kilograms of chelating agents, said chelating agent can adopt sulfamic acid or EDTA, after the preliminary treatment, puts into reactor; Get 4000 kilograms of solvents of forming by water, isopropyl ether, isopropyl alcohol, triethylene glycol and PPG, wherein water, isopropyl ether, isopropyl alcohol, triethylene glycol, PPG weight ratio are 1: 1: 2: 1: 0.5 or 5: 1: 1: 1: 0.5, put into reactor, after heating between 0～180 ℃ and refluxing 30 minutes, stop heating, be cooled to 15～25 ℃ of room temperatures, take out and separate, and purifying, washing and drying gets product.
Claims (2)
1, a kind of preparation method of perfluorinated ion exchange resin is characterized in that: get and contain-SO
3M and-the perfluor base polymer waste material of COOM ion soaks through chelating agent and carried out preliminary treatment in 1～4 hour, wherein M is H, Na, K or NR
4, R is H, CH
3Or C
3H
5, said chelating agent is sulfamic acid or EDTA, perfluor base polymer waste material and chelating agent weight ratio are 1: 0.1～1: 1; Be to get solvent in 1: 3～1: 100 by the weight ratio of perfluor base polymer waste material and solvent again, with described solvent with mix through pretreated perfluor base polymer waste material, in reaction temperature is that 0～180 ℃, reaction time are under 0.5～4 hour the condition, make perfluorinated ion exchange resin, said solvent is made up of the water that accounts for solvent gross weight 5～90%, the ethanol that accounts for solvent gross weight 10～95%, propyl alcohol and PPG.
2, a kind of preparation method of perfluorinated ion exchange resin is characterized in that: get and contain-SO
3M and-the perfluor base polymer waste material of COOM ion soaks through chelating agent and carried out preliminary treatment in 1～4 hour, wherein M is H, Na, K or NR
4, R is H, CH
3Or C
3H
5, said chelating agent is sulfamic acid or EDTA, perfluor base polymer waste material and chelating agent weight ratio are 1: 0.1～1: 1; Be to get solvent at 1: 50 by the weight ratio of perfluor base polymer waste material and solvent again, with described solvent with mix through pretreated perfluor base polymer waste material, 25～150 ℃ of following immersion treatment 0.5 hour, make perfluorinated ion exchange resin, said solvent is by according to weight ratio 2.4: 1.6: 1.6: 0.4 water, ethanol, propyl alcohol and triethylene glycol are formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100213945A CN1305570C (en) | 2004-03-14 | 2004-03-14 | Method for preparing full fluorinion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100213945A CN1305570C (en) | 2004-03-14 | 2004-03-14 | Method for preparing full fluorinion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1562486A CN1562486A (en) | 2005-01-12 |
| CN1305570C true CN1305570C (en) | 2007-03-21 |
Family
ID=34479805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100213945A Expired - Fee Related CN1305570C (en) | 2004-03-14 | 2004-03-14 | Method for preparing full fluorinion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1305570C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415679A (en) * | 1981-10-26 | 1983-11-15 | E. I. Du Pont De Nemours & Co. | Process for esterifying fluorinated carboxylic acid polymer |
| CN85100496B (en) * | 1985-04-01 | 1988-02-10 | 中国科学院上海有机化学研究所 | Method to manufacture monomers of perfluoro-carboxylic acid ion-exchanging resin |
-
2004
- 2004-03-14 CN CNB2004100213945A patent/CN1305570C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415679A (en) * | 1981-10-26 | 1983-11-15 | E. I. Du Pont De Nemours & Co. | Process for esterifying fluorinated carboxylic acid polymer |
| CN85100496B (en) * | 1985-04-01 | 1988-02-10 | 中国科学院上海有机化学研究所 | Method to manufacture monomers of perfluoro-carboxylic acid ion-exchanging resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1562486A (en) | 2005-01-12 |
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Granted publication date: 20070321 Termination date: 20140314 |