CN1244615C - Double functional group anion exchange membrane preparation method - Google Patents
Double functional group anion exchange membrane preparation method Download PDFInfo
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- CN1244615C CN1244615C CN 200410017965 CN200410017965A CN1244615C CN 1244615 C CN1244615 C CN 1244615C CN 200410017965 CN200410017965 CN 200410017965 CN 200410017965 A CN200410017965 A CN 200410017965A CN 1244615 C CN1244615 C CN 1244615C
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- exchange membrane
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Abstract
The present invention relates to an anion exchange membrane, particularly to a double functional group anion exchange membrane preparation method which comprises a carboxylic acid group and a sulfonic acid group prepared by radiation grafting initiated by gamma-ray, and the present invention belongs to the technical field of chemical polymerization reaction and radiation chemistry. The present invention relates to a double functional group anion exchange membrane preparation method, which prepares the double functional group cation exchange membrane with the carboxylic acid group and the sulfonic acid group via an irradiation initiation grafting method of gamma-ray. The present invention has the steps: a solution of acrylic acid (AA), sodium 4-vinylbenzenesulfonate (SSS), copper sulfate and sodium acetate is firstly prepared, and a high density polyethylene basal body membrane is prepared; the prepared grafting reaction solution and the high density polyethylene basal body membrane are positioned in a specific gamma-ray irradiation pipe and are pumped to vacuum, charged by nitrogen and sealed. The irradiation pipe is arranged in a cobalt bomb chamber and is irradiated for 18 hours in the dosage rate of 1.67 kGy/h and the temperature of 35 DEG C, and finally, the hydrophilic double functional group cation exchange membrane can be obtained.
Description
Technical field
The present invention relates to ion-exchange membrane, particularly a kind of gamma-rays causes the preparation method that radiation grafting prepares carboxy-containing acid group and sulfonic acid group dual-functional group cationic exchange membrane, belongs to chemical polymerization and irradiation technical field of chemistry.
Background technology
Making a general survey of domestic and international present Research, is that the sulfonic acid type cation exchange membrane of skeleton mainly contains three kinds of preparation methods with the polyolefine.Polymeric film direct function method, radiation graft copolymerization method and blend or multipolymer film forming function method.The direct function method realizes that by oleum or chlorsulfonic acid because the strong oxidizing property of reaction reagent, the mechanical property of film often is subjected to havoc.Hydrophobic character in view of polyolefin film, highly Ionized sulfonic acid group easily forms spherical hydrated ion, it is incompatible with hydrophobic polyolefin film, therefore hindering sulfonic acid group diffuses into film inside and forms graft copolymer, so preparing the sulfonic acid type film, radiation graft process adopts indirect method more, polymeric matrix elder generation radiation grafting styrene monomer, then graft copolymer membrane is immersed the long-time down reaction of comparatively high temps in the chlorsulfonic acid of high density or the sulfuric acid, thereby on phenyl ring, introduce sulfonic acid group, preparation process complexity not only, there is the impaired problem of the physical strength of film equally in violent reaction conditions.
The ion-exchange membrane of commercial applications is by blend or chemical copolymerization method preparation at present.The heterogeneous ion-exchange membrane of blending method preparation remains in defectives such as cation exchange groups skewness and physical strength are relatively poor, and its range of application is restricted.Improved method is that vinylbenzene, Vinylstyrene and other composition muddle are strengthened on the net at polyvinyl chloride or polypropylene, and post-heating makes basement membrane, introduces sulfonic acid group by chemical reaction again.But strongthener can make the chemical property of film such as specific conductivity and ion selectivity reduce.The Nafion series perfluoro sulfonic acid membrane of E.I.Du Pont Company is prepared by chemical copolymerization method, and chemical stability is good, and ionic conductivity is big, but still exist not enough on the performance, the ionic conductance and the water content of this class film are in close relations, and when lower or temperature was higher in water content, specific conductivity obviously descended.In addition, this film costs an arm and a leg, and what this held it back is extensive use of.
Summary of the invention
The objective of the invention is to for some defective that overcomes at present business-like cationic exchange membrane existence and the process complexity that now prepares this film the special radiation grafting sulfonation that proposes to utilize binary grafting system single stage method realization high density polyethylene(HDPE) matrix with radiation method.
Another object of the present invention is to realize that single stage method introduces hydroxy-acid group and sulfonic acid group and make the method for dual-functional group cationic exchange membrane on the polyethylene matrix.For achieving the above object, the present invention adopts following technical proposals:
A kind of preparation method of dual-functional group cationic exchange membrane is characterized in that, this method utilizes gamma-ray irradiation initiation grafting legal system to be equipped with carboxy-containing acid group and sulfonic acid group dual-functional group cationic exchange membrane, and its concrete steps are as follows:
A. design calculation and preparation graft reaction solution system chemical ingredients and concentration: the chemical ingredients of this system and corresponding volumetric molar concentration are:
Vinylformic acid AA 0.33-2.0mol/L
Sodium p styrene sulfonate SSS 0.17-1.0mol/L
Copper sulfate 1.94 * 10
-3-1.64 * 10
-2Mol/L
Sodium acetate, anhydrous 0.4-1.3mol/L
B. preparing and adopting high density polyethylene(HDPE) is base film, and its thickness is 15 μ m, and weight is 100-130mg, and this base film and graft reaction solution do not dissolve each other;
C. the graft reaction solution for preparing is put into specific gamma-ray irradiation pipe, the high density polyethylene(HDPE) base film that will weigh up weight is simultaneously put into graft reaction solution;
D. will fill the irradiation tube of grafting sample, vacuumize for three times repeatedly, and charge into nitrogen, and seal it; Then irradiation tube is placed chamber, cobalt source, irradiation 18h under 1.67 kilogray (kGy)s/hour dose rate and 35 ℃ of temperature;
E. take out the sintetics graft copolymer membrane, place 70 ℃ of deionized waters to soak, remove homopolymer or multipolymer, take out graft copolymer membrane after 24 hours, vacuum-drying then finally obtains wetting ability dual-functional group cationic exchange membrane.
Above-mentioned vinylformic acid is analytical pure, and stopper is removed in first underpressure distillation before using; Described sodium p styrene sulfonate is a chemical pure, carries out recrystallization with ethanol before using.
The chemical reaction process and the mechanism of the inventive method are as follows: Acrylic Acid Monomer is grafted to earlier on the high density polyethylene(HDPE) base film during reaction beginning, make the wetting ability of film obtain to improve, two kinds of monomers are competed the free radical activity position on the matrix jointly then, thereby introduce hydroxy-acid group and sulfonic acid group on the high density polyethylene(HDPE) matrix.Like this, polymeric matrix can directly go grafting with form of film, has saved casting film-forming or calendering film process that copolymerization or blending method prepare ion-exchange membrane; The irradiation grafting preparation process of dual-functional group cationic exchange membrane has been simplified in the employing of single stage method crosslinking technology.Compare with prior art, the present invention utilizes gamma-rays to cause binary grafting system to prepare the dual-functional group cationic exchange membrane and have following conspicuous outstanding advantage and distinguishing feature:
1. the process of whole preparation ion-exchange membrane is not used any chemical initiator, does not pollute so product has chemical initiator;
2. can realize the grafting of HDPE different depths by experiment conditions such as control irradiation dose, graft reaction times, and the introducing amount of flexibly changing sulfonic acid group and hydroxy-acid group;
3. by introduce cheap strong base-weak acid salt in the grafting system, can keep the loading capacity of graft copolymer membrane not reduce under the condition that reduces irradiation dose, this have created condition for low-cost preparation dual-functional group ion-exchange membrane.
Description of drawings
Fig. 1 prepares the device synoptic diagram of dual-functional group ion-exchange membrane for the inventive method.
The meaning of each digital code is as follows among the figure: 1-
60The source takes place in the Co gamma-rays; The 2-temperature controller; The temperature sensitive probe of 3-; The 4-dose jar; The 5-irradiation tube; The 6-water-bath.
Embodiment
Now in conjunction with the accompanying drawings the embodiment of the inventive method is described in the back:
Embodiment one: referring to Fig. 1, Fig. 1 is the device synoptic diagram for preparing the dual-functional group ion-exchange membrane with the inventive method, and the preparation facilities of graft copolymer membrane is gamma-ray by emission
60Co radioactive source 1, temperature controller 2, temperature sensitive probe 3, dose jar 4, the irradiation tube 5 that fills sample and water-bath 6 constitute,
60The gamma-rays that Co sends, be radial to around emission, by the absorption of sample in the irradiation tube, be used for initiation grafting reaction in a distance, the absorption dose of sample is measured by the potassium bichromate quantimeter that is bundled on the irradiation tube.Thermostatically-controlled equipment is used for regulating the graft reaction temperature, and the temperature control effect realizes by the temperature sensitive probe that is inserted in the water-bath.
In the present embodiment, comprise the following steps:
1, according to required design calculation graft reaction solution system chemical ingredients of reaction and concentration: the chemical ingredients of this system and corresponding volumetric molar concentration are as follows:
Vinylformic acid (AA) 2mol/L
Sodium p styrene sulfonate (SSS) 1mol/L
Copper sulfate 4.16 * 10
-3Mol/L
Sodium acetate, anhydrous 0.49mol/L
Be mixed with solution with deionized water
2, preparing and adopt high density polyethylene(HDPE) is base film, and its thickness is 15 μ m, and weight is 120mg, and this base film and graft reaction solution do not dissolve each other;
3, the graft reaction solution for preparing is put into specific gamma-ray irradiation pipe, simultaneously high density polyethylene(HDPE) base film and cushioning material polypropylene non-woven fabric are stacked together, it is cylindric with the glass stick to be that the axle center is rolled into then, puts into after tying up with cotton thread to fill the fixing graft reaction solution of forming;
4, will fill the irradiation tube that the grafting sample is a polyethylene film, vacuumize for three times repeatedly, and charge into nitrogen, and seal it; Then irradiation tube is placed chamber, cobalt source;
5. take out the sintetics graft copolymer membrane, wash repeatedly with deionized water earlier, place 70 ℃ of deionized waters to soak again, remove homopolymer or multipolymer, take out graft copolymer membrane after 24 hours, vacuum-drying then finally obtains wetting ability dual-functional group cationic exchange membrane.
Used vinylformic acid is analytical pure, and stopper is removed in first underpressure distillation before using; Described sodium p styrene sulfonate is a chemical pure, carries out recrystallization with ethanol before using.
Adopt weighting method to measure the percentage of grafting of two monomers to density polyethylene film with high.When two total monomer are 3mol/L, its amount of substance is than being AA: SSS=2: 1, and stopper copper sulfate add-on is 4.16 * 10
-3Mol/L, the Glacial acetic acid na concn is 0.49mol/L, radiation dose rate is 1.67 kilogray (kGy)s/hour kGy/h, when graft reaction carries out 18h 35 ℃ of temperature, measurement learns that two monomer solutions are 131.4% to total percentage of grafting of density polyethylene film with high, and it is 0.05 Ω cm that AC impedence method records grafting face resistance
-2
Claims (2)
1. the preparation method of a dual-functional group cationic exchange membrane is characterized in that, this method utilizes gamma-ray irradiation initiation grafting legal system to be equipped with carboxy-containing acid group and sulfonic acid group dual-functional group cationic exchange membrane, and its concrete steps are as follows:
A. design calculation and preparation graft reaction solution system chemical ingredients and concentration: the chemical ingredients of this system and corresponding volumetric molar concentration are:
Vinylformic acid .AA 0.33-2.0mol/L
Sodium p styrene sulfonate SSS 0.17-1.0mol/L
Copper sulfate 1.94 * 10
-3-1.64 * 10
-2Mol/L
Sodium acetate, anhydrous 0.4-1.3mol/L
B. adopting high density polyethylene(HDPE) is base film, and its thickness is 15 μ m, and weight is 100-130mg, and this base film and graft reaction solution do not dissolve each other;
C. the graft reaction solution for preparing is put into specific gamma-ray irradiation pipe, the high density polyethylene(HDPE) base film that will weigh up weight is simultaneously put into graft reaction solution;
D. will fill the irradiation tube of grafting sample, vacuumize for three times repeatedly, and charge into nitrogen, and seal it; Then irradiation tube is placed chamber, cobalt source, irradiation is 18 hours under 1.67 kilogray (kGy)s/hour dose rate and 35 ℃ of temperature;
E. take out the sintetics graft copolymer membrane, place 70 ℃ of deionized waters to soak, remove homopolymer or multipolymer, take out graft copolymer membrane after 24 hours, vacuum-drying then finally obtains wetting ability dual-functional group cationic exchange membrane.
2. the preparation method of a kind of dual-functional group cationic exchange membrane according to claim 1 is characterized in that described vinylformic acid is analytical pure, and stopper is removed in first underpressure distillation before using; Described sodium p styrene sulfonate is a chemical pure, carries out recrystallization with ethanol before using.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410017965 CN1244615C (en) | 2004-04-27 | 2004-04-27 | Double functional group anion exchange membrane preparation method |
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| CN 200410017965 CN1244615C (en) | 2004-04-27 | 2004-04-27 | Double functional group anion exchange membrane preparation method |
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| CN1244615C true CN1244615C (en) | 2006-03-08 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0813227D0 (en) * | 2008-07-18 | 2008-08-27 | Fuji Film Mfg Europ B V | Process for preparing membranes |
| CN103242552B (en) * | 2013-05-23 | 2015-02-11 | 北京大学 | Preparation method of quaternized amphoteric ion exchange membrane |
| CN108126537B (en) * | 2018-03-20 | 2020-03-06 | 苏州普希环保科技有限公司 | Polyamide composite forward osmosis membrane for wastewater desalination |
| CN108187506B (en) * | 2018-03-20 | 2020-03-10 | 山西山安碧泉海绵城市科技有限公司 | Forward osmosis membrane for wastewater desalination |
| CN108339402B (en) * | 2018-03-20 | 2020-01-10 | 深圳市盛源环境科技有限公司 | Preparation method of forward osmosis membrane for wastewater desalination |
| CN115228444A (en) * | 2022-06-08 | 2022-10-25 | 湖北科技学院 | Radiation preparation method of loofah sponge-based adsorbent capable of efficiently adsorbing cationic dye |
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