CN1299811C - Method for preparing cation exchange membrane with high content of sodium sulfonate group - Google Patents
Method for preparing cation exchange membrane with high content of sodium sulfonate group Download PDFInfo
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- CN1299811C CN1299811C CN 200410067791 CN200410067791A CN1299811C CN 1299811 C CN1299811 C CN 1299811C CN 200410067791 CN200410067791 CN 200410067791 CN 200410067791 A CN200410067791 A CN 200410067791A CN 1299811 C CN1299811 C CN 1299811C
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Abstract
The present invention relates to a preparation method of cation exchange membranes with high content of sodium sulfonate groups, particularly to a preparation method for preparing cation exchange membranes with high content of sodium sulfonate groups by a pre-radiation grafting technology initiated by cathode beams, and the present invention belongs to the technical field of functional polymer material preparation and irradiation chemistry. The method has the preparation steps: a water solution of acrylic acid and sodium styrene sulfonate is firstly prepared, and the acidity of a grafting reaction liquid system is regulated to be used; a sealed high density polyethylene basal body film containing nitrogen is positioned under accelerator electron beam flow with 200kGy dynamic irradiation; the irradiated high density polyethylene film is immersed into a container with grafting reaction solution, and then, the film is pumped to vacuum, charged with nitrogen and sealed; the entire reaction device is arranged in a thermostatic waterbath device to react for 18 hours in 40 DEG C, and finally, cation exchange membranes with high content of sodium sulfonate groups are obtained. The method of the present invention has the advantages of simple process, low cost, high product grafting ratio, high stability, low resistance and high current efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of high sodium group cation-exchange membrane, particularly a kind of electron beam causes the preparation method that the pre-irradiation grafting technology prepares the cation-exchange membrane of high sodium sulfonate group mass contg, preparation of function of dominant macromolecular material and irradiation technical field of chemistry.
Background technology
The commercial at present sulfonic acid type cation exchange membrane of using is generally by blend or chemical copolymerization method preparation.The heterogeneous ion-exchange membrane of blending method preparation remains in defectives such as cation exchange groups skewness and mechanical strength are relatively poor, and improving one's methods of having is to add reinforcing material, but the chemical property of film and ion selectivity are reduced.The Nafion of E.I.Du Pont Company series perfluoro sulfonic acid membrane is prepared by chemical copolymerization method, though its chemical stability and ionic conductivity are good, still exists not enoughly on some performance, and when higher, electrical conductivity obviously descends as or temperature lower in water content.In addition, this film costs an arm and a leg, and has limited being extensive use of of it.
The cation-exchange membrane of radiation graft process preparation mainly comprises two types: carboxylic acid type Subacidity cation exchange membrane and sulfonic acid type highly acidic cation exchange membrane.Before a kind of exchange membrane by monomers such as acrylic acid or derivatives thereof methacrylic acids to the preparation of the radiation grafted method of polymer, at home and abroad appear in the newspapers repeatly for preparation method, structural behaviour test and the real application research of this type graft copolymer membrane.And, report less in this respect for sulfonic acid type highly acidic cation exchange membrane.The hydrophily that mainly is sodium group is strong, and this makes that the polyolefin film of it and hydrophobic is incompatible, so report that at present radiation graft process prepares the sulfonic acid type film and all adopts indirect method.Indirect method mainly contains two kinds of implementations: the one, and polymeric matrix elder generation radiation grafting styrene compound is again to the phenyl ring sulfonation; The 2nd, polymeric matrix elder generation radiation grafting vinylic chemical compound, after making its surface obtain hydrophily, thereby further radiation grafting contains the vinyl monomer of sulfonic acid group, and this is the experimental procedure complexity not only, and the ubiquity sulfonate groups introducing amount problem that can not further improve.
Summary of the invention
The objective of the invention is some defective of existing at present business-like sulfonic acid type cation exchange membrane and now prepare the problem that this film percent grafting can not further improve, specially propose directly radiation initiation grafting in binary graft reaction reagent and obtain the method for the cation-exchange membrane of high sodium sulfonate group mass contg with radiation method.
The preparation method of the cation-exchange membrane of a kind of high sodium sulfonate group mass contg of the present invention, the main radiation graft process that adopts, it is characterized in that: utilize electronics to cause bundle binary graft reaction system, on the high density polyethylene (HDPE) matrix, directly introduce the sodium vinyl sulfonate monomer, thereby obtain the cation-exchange membrane of high sodium sulfonate group mass contg; Reagent composition and molar concentration in the binary graft reaction reagent system are:
Acrylic acid 1.0-1.6mol/L;
Sodium p styrene sulfonate 0.4-1.0mol/L;
Its technical process and step are as follows:
Clean clean and oven dry with ketone density polyethylene film with high, the density polyethylene film with high after weighing is put into polythene film bag, and in bag, charge into high pure nitrogen, seal to be placed on and carry out irradiation in the electron beam irradiation chamber; Electronic beam current intensity is 3mA, and total irradiation dose is 200kGy; Density polyethylene film with high behind irradiation is stacked with the gasket material polypropylene non-woven fabric again, it is positioned in the binary graft reaction reagent system then, promptly put in the reagent solution of acrylic acid and sodium p styrene sulfonate, and be 1.08 with the pH value of hydrochloric acid conditioned reaction system; Then reaction vessel is placed constant temperature water bath apparatus, reaction is 18 hours under 40 ℃ of temperature; Final acquisition has the cation-exchange membrane of the density polyethylene film with high of sodium group grafting.
The chemical reaction process and the mechanism of the inventive method are as described below:
Acrylic acid is grafted to earlier on the high density polyethylene (HDPE) matrix during reaction beginning, make the hydrophily of film obtain to improve, two kinds of monomer acrylic acid and sodium p styrene sulfonate are competed the free radical activity position on the matrix jointly then, thereby introduce hydroxy-acid group and sodium group on the high density polyethylene (HDPE) matrix.After the grafting system adds hydrochloric acid, the pH value reduces acid the increase, can suppress the ionization of acrylic monomers and homopolymers thereof or copolymer, make the repulsive interaction between the polyacrylic acid chain weaken, wherein the partial polymer chain becomes rolled state by stretched condition, cause system viscosity to reduce, thereby help the diffusion of grafted monomers to matrix.But higher amplitude improves the percent grafting of sodium p styrene sulfonate to density polyethylene film with high.
The characteristics and the advantage of the inventive method are as follows:
1. the inventive method utilizes electron beam to cause the directly high cation-exchange membrane of the high sodium sulfonate group mass contg of preparation of pre-irradiation grafting method, and this cation-exchange membrane good stability, resistance is low, current efficiency is high; This kind exchange membrane is logical to the proton road, to electronic isolation, is the functional polymer film that a kind of selection sees through, and can be used as the solid electrolyte of Proton Exchange Membrane Fuel Cells, plays proton transport.Because of sulphonate-base mass contg height, face resistance is low, and it helps the heavy-current discharge of battery during as accumulator diaphragm such as zinc-silver oxide.This kind sulfonic acid type cation exchange membrane is also having potential use aspect the separation of water treatment, constant boiling mixture in addition.
2. by controlling the addition of hydrochloric acid, the introducing amount of flexibly changing sodium group; The adding of hydrochloric acid can significantly improve the diffusion rate of monomer to matrix.
3. the adding of gasket material polypropylene non-woven fabric helps to accelerate the diffusion rate of monomer to matrix, when improving percent grafting, can get the ion-exchange composition in return at the homodisperse exchange membrane of graft copolymer membrane diverse location.
4. replace copolymerization method with radiation graft process, technology is simple, cost is low; Owing to do not use any chemical initiator, so the gained graft copolymer does not contain initator, environment is pure, the favorable environment protection.
The specific embodiment
Now in conjunction with the embodiments, the present invention is described in further detail as follows:
Embodiment 1
The concrete processing step of the embodiment of the invention is as follows:
1. as requested, designing and calculating binary graft reaction system chemical reagent composition and molar concentration:
Acrylic acid 1.33mol/L
Sodium p styrene sulfonate 0.67mol/L
2. density polyethylene film with high is cut into the rectangle of 7 * 13cm, behind the acetone scrub, places baking oven to be dried to constant weight for 50 ℃ again;
3. the density polyethylene film with high after the weight of having weighed is put into polythene film bag, and charges into high pure nitrogen repeatedly in bag, and repeatedly surplus air is driven in extruding away; Seal to be placed on to push on the flat bogie and carry out dynamic radioaction in the electron beam irradiation chamber, beam intensity 3mA, total irradiation dose 200kGy gives the 50kGy exposure dose at every turn, intermittently continues irradiation after 5 minutes, carries out altogether four times;
4. density polyethylene film with high behind the irradiation and gasket material polypropylene non-woven fabric are stacked together, it is cylindric with the glass bar to be that the axle center is rolled into then, puts into the acrylic acid that fills certain mol proportion and the ground reaction vessel of sodium p styrene sulfonate mixed solution after tying up with cotton thread again; Three vacuum nitrogen filling gas repeatedly, and seal it; It is 1.08 that mixed reaction solution needs to regulate its pH value with hydrochloric acid in advance, makes it be highly acid;
5. the entire reaction container is placed constant water bath box, reaction is 18 hours under 40 ℃ of temperature;
6. take out the sintetics graft copolymer membrane, wash repeatedly with deionized water earlier, place 70 ℃ of deionized waters to soak again, remove homopolymers or copolymer; Take out this graft copolymer membrane after 24 hours again, vacuum drying then, the final cation-exchange membrane that obtains to contain sodium group.
Test to graft copolymer membrane: adopt weight method to measure the total percent grafting of two monomers to density polyethylene film with high, titration is measured the percent grafting of sodium p styrene sulfonate to density polyethylene film with high.When two total monomer are 2mol/L, its amount of substance is than acrylic acid: sodium p styrene sulfonate=2: 1, during system pH=1.08, graft reaction is after carrying out 18 hours under 40 ℃ of temperature, recording acrylic acid and sodium p styrene sulfonate is 346.1% to total percent grafting of density polyethylene film with high, and sodium p styrene sulfonate is 103.4% to the percent grafting of density polyethylene film with high.
When total percent grafting when 20.5-362.3% changes, the final thickness that obtains to contain the cation-exchange membrane of sodium group is 16-26 μ m.
Claims (1)
1. the preparation method of a high sodium group cation-exchange membrane mainly adopts radiation graft process, it is characterized in that:
Utilize electron beam to cause the binary radiation graft process, on the high density polyethylene (HDPE) matrix, directly introduce the sodium vinyl sulfonate monomer, thereby obtain the cation-exchange membrane of high sodium sulfonate group mass contg; In the binary graft reaction reagent system
Reagent composition and molar concentration are:
Acrylic acid 1.0-1.6mol/L;
Sodium p styrene sulfonate 0.4-1.0mol/L;
Its technical process and step are as follows:
Clean clean and oven dry with ketone density polyethylene film with high, the density polyethylene film with high after weighing is put into polythene film bag, and in bag, charge into high pure nitrogen, seal to be placed on and carry out irradiation in the electron beam irradiation chamber; Electronic beam current intensity is 3mA, and total irradiation dose is 200kGy; Density polyethylene film with high behind irradiation is stacked with the gasket material polypropylene non-woven fabric again, it is positioned in the binary graft reaction reagent system then, promptly put in the reagent solution of acrylic acid and sodium p styrene sulfonate, and be 1.08 with the pH value of hydrochloric acid conditioned reaction system in advance; Then reaction vessel is placed constant temperature water bath apparatus, reaction is 18 hours under 40 ℃ of temperature; Final acquisition has the cation-exchange membrane of the density polyethylene film with high of sodium group grafting.
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| CN 200410067791 CN1299811C (en) | 2004-11-03 | 2004-11-03 | Method for preparing cation exchange membrane with high content of sodium sulfonate group |
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| CN 200410067791 CN1299811C (en) | 2004-11-03 | 2004-11-03 | Method for preparing cation exchange membrane with high content of sodium sulfonate group |
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| CN1299811C true CN1299811C (en) | 2007-02-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321266B (en) * | 2011-07-13 | 2012-08-15 | 上海大学 | Preparation method of proton exchange membrane for fuel batteries |
| CN103242552B (en) * | 2013-05-23 | 2015-02-11 | 北京大学 | Preparation method of quaternized amphoteric ion exchange membrane |
| CN105013355B (en) * | 2015-06-30 | 2017-06-16 | 四川大学 | Heparan polyether sulphone hollow fibre film and preparation method thereof and purposes |
| CN113813792B (en) * | 2021-09-26 | 2023-12-01 | 湖北吉星化工集团有限责任公司 | Process for producing hypophosphorous acid by bipolar membrane electrodialysis |
| 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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