CN103623713A - One-step homogeneous cation exchange membrane and molding technology thereof - Google Patents
One-step homogeneous cation exchange membrane and molding technology thereof Download PDFInfo
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- CN103623713A CN103623713A CN201210308922.XA CN201210308922A CN103623713A CN 103623713 A CN103623713 A CN 103623713A CN 201210308922 A CN201210308922 A CN 201210308922A CN 103623713 A CN103623713 A CN 103623713A
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Abstract
The invention relates to a one-step homogeneous cation exchange membrane and a molding technology thereof. The exchange membrane is formed by an enhanced fiber cloth and a water-insoluble polyelectrolyte layer compounded on the enhanced fiber cloth, the enhanced fiber cloth is formed by copolymerizing two types of total monomers containing unsaturated double bonds and an auxiliary material, the total monomers include 30-70% of a monomer containing a cation exchange function and 5-50% of a hydrophobic monomer or a monomer containing a polyvinyl function group, the auxiliary substance is an initiator, and the content of the initiator in the exchange membrane is 0.01-5%. The invention also relates to the molding technology of the exchange membrane. In the invention, the enhance fiber cloth is dipped into a water-insoluble polyelectrolyte solution provided in the invention, and polymerization at a suitable temperature is carried out to form the required homogeneous cation exchange membrane, so the technology has the advantages of production cost reduction, production efficiency increase, suitableness for the large scale production, substantial progress, and good economic and social benefits.
Description
Technical field:
The present invention relates to a kind of isolation technics, more specifically to a kind of one-step method homogeneous phase cation exchange film and moulding process thereof.
Background technology:
Amberplex is a kind of as modern diffusion barrier, in water treatment, and Chemical Engineering, the fields such as new forms of energy have a wide range of applications.At some specific area of water treatment desalination, amberplex has larger advantage with respect to RO film, is that other diffusion barriers are irreplaceable, for example, small-sized sea water desalting equipment, saline sewage partially desalted, ion exchange resin is filled electrodialysis (EDI) and is prepared high purity water etc.; In field of chemical engineering, the application of amberplex can be optimized traditional chemical process greatly, reduces production costs, and realizes cleaner production, for example amino acid whose production, the production of glucose, the desalination of lactalbumin etc.; In new forms of energy industry.Amberplex is the critical materials such as biological fuel cell, fuel cell as proton membrane.
At present the technology of the manufacture homogeneous phase cation exchange film of main flow is mainly the polymer of phenyl ring class to be carried out to sulfonation obtain, and for example, in the technology that the CM series cation-exchange membrane of Japanese A Sitong company and the disclosed coating method of Chinese patent CN941152294 are manufactured cation-exchange membrane, is all that the sulfonation by the phenyl ring in styrene copolymer realizes.
These methods all need to contain sulfonic strong acid sulfonation basement membrane with the concentrated sulfuric acid or chlorosulfonic acid etc. in process of production, and production process control ratio is more difficult, and produces acid waste water.
Summary of the invention:
The object of the invention is provides a kind of one-step method homogeneous phase cation exchange film for prior art weak point.In the manufacturing process of this cation-exchange membrane, without sulfonation, the easy to control and environmental protection of production process does not produce acid waste water.
Another object of the present invention is to provide the moulding process of making this cation-exchange membrane.This technique guarantees that the production of amberplex is easy, and cost is low.
The object of the invention is to realize by following measures: a kind of one-step method homogeneous phase cation exchange film, it is characterized in that, it consists of cloth of reinforcement fibers and the insoluble polyelectrolyte layers of water being compounded in cloth of reinforcement fibers, wherein:
The insoluble polyelectrolyte layers of described water is by the total monomer of two types containing unsaturated double-bond, and auxiliary substance copolymerization forms:
By the molal quantity percentage of total monomer, total monomer is comprised of following component:
A. the monomer 30-70% that cation function of exchange is rolled into a ball
B. hydrophobic monomer or containing many vinyl-functional monomer 5%-50%
The mass percent of auxiliary substance and total monomer is:
Initator 0.01%-5%
Described cloth of reinforcement fibers is woven cloth or nonwoven, and the thickness of described cloth is that the voidage of 0.05-0.5 millimeter, cloth requires to be greater than 30%, is less than 80%.
The monomer that described cation function of exchange is rolled into a ball is optional in following: vinylbenzenesulfonic acid, vinylbenzenesulfonic acid salt, methacrylic acid, methacrylate, acrylic acid, acrylates, methacrylic acid sulfonic acid ethyl ester, acrylic acid sulfonic acid ethyl ester.
Described hydrophobic monomer or optional in following containing many vinyl-functional monomer: divinylbenzene, octadecyl methacrylate, Hexafluorobutyl mathacrylate, ethylene glycol bisthioglycolate ethyl acrylate, glycerine three ethyl acrylates, ethylene glycol bisthioglycolate vinyl ethers.
Described initator is peroxide or diimide class, and peroxide is optional in following: BPO, TBHP, diimide class is optional in following: azo-bis-isobutyl cyanide, azo diisoamyl cyanogen.
Described auxiliary substance can be selected polyvinyl acetate, and its amount is total monomer quality≤1%.
Described auxiliary substance can be selected EP rubbers, and its amount is total monomer quality≤1%.
Described auxiliary substance can be selected ethyl acrylate, and its amount is total monomer quality≤1%.
A moulding process for one-step method homogeneous phase cation exchange film, is characterized in that, concrete steps are as follows:
Step 3, the insoluble polyeletrolyte liquid of the water of configuration is watered on fiber reinforcement cloth, and fully impregnation of fibers strengthens cloth, unnecessary feed liquid flows out from the outlet of mold bottom side;
On step 4, the fiber reinforcement cloth after thorough impregnation, place not sticky barrier film and then put into next fiber reinforcement cloth, then repeating step three;
Step 5, repeating step four, the fiber reinforcement cloth of the not sticky barrier film of multi-disc and multi-disc dipping is alternately shape;
After the dipping of the step 6, the superiors, fiber reinforcement cloth is placed not sticky barrier film, then slowly place a smooth weight identical with finished product cation-exchange membrane size thereon, slowly the sticky barrier film of multilayer and fiber reinforcement cloth below it are applied to the pressure of 0.1-1 kilogram/square metre;
Step 7, in the process of exerting pressure, the outlet of closing molding bottom sides, the insoluble polyeletrolyte liquid of superfluous water squeezing out flows out from fiber reinforcement cloth, and is filled in the gap of fiber reinforcement cloth and groove-shaped mold surrounding;
Step 8, the sticky barrier film of mould and inner laminated thereof and impregnation of fibers are strengthened to cloth put into together explosion-proof baking oven and solidify, solidification temperature and hardening time are decided according to the kind of added initator and addition;
Step 9, each material being cured being taken out from baking oven, peeled off each layer of barrier film, just can obtain the block polyelectrolyte layer that fiber reinforcement cloth strengthens, is also one-step method homogeneous phase cation exchange film.
Initator described in step 8 adopts benzoyl peroxide BPO, and addition is resin 1% time, and solidification temperature is 80 degree, and the time is 17 hours.
Initator described in step 8 adopts TBHP, and addition is resin 2% time, and solidification temperature is 80 degree, and the time is 17 hours.
Initator described in step 8 adopts azo-bis-isobutyl cyanide, 1% addition, and solidification temperature is 70 degree, time 4 hours.
Compared with prior art, a kind of one-step method homogeneous phase cation exchange film and moulding process tool thereof that the present invention proposes have the following advantages: the formula of the insoluble polyeletrolyte liquid of water being provided by the present invention, each component is through being thoroughly mixed to form stable mixed liquor, again fiber reinforcement cloth is impregnated in mixed liquor, at applicable temperature, polymerization just can obtain required amberplex or precursor film, reduced production cost, improve production efficiency, be suitable for large-scale production, obtained significant progress and good economic benefit and social benefit.
Accompanying drawing explanation:
Fig. 1 is the structural representation of one embodiment of the invention.
In figure: the insoluble polyelectrolyte layers of 1-water, 2-fiber reinforcement cloth.
The specific embodiment:
Below in conjunction with accompanying drawing, the specific embodiment is elaborated: a kind of one-step method homogeneous phase cation exchange film, it consists of cloth of reinforcement fibers 2 and the insoluble polyelectrolyte layers 1 of water being compounded in cloth of reinforcement fibers, wherein:
The insoluble polyelectrolyte layers of described water is by the total monomer of two types containing unsaturated double-bond, and auxiliary substance copolymerization forms:
By the molal quantity percentage of total monomer, total monomer is comprised of following component:
A. the monomer 30-70% that cation function of exchange is rolled into a ball
B. hydrophobic monomer or containing many vinyl-functional monomer 5%-50%
The mass percent of auxiliary substance and total monomer is:
Initator 0.01%-5%
Described cloth of reinforcement fibers is woven cloth or nonwoven, and the thickness of described cloth is that the voidage of 0.05-0.5 millimeter, cloth requires to be greater than 30%, is less than 80%.Cloth of reinforcement fibers can be woven cloth, commercially available polypropylene screen cloth for example, glass fabric, polyester screen cloth etc.; Also can be nonwoven, comprise polypropylene non-woven fabric, polyester bonded fabric, polyacrylonitrile bonded fabric etc.The thickness requirement of these cloth is between 0.05-0.5 millimeter, to obtain suitable intensity and operating characteristics.For thinner cloth, although production cost is lower, may causes the reduction of production qualification rate and the reduction of film-strength and not recommend; For thicker cloth, production control is easier, but can cause production cost high, and the relative change of the resistance of final products is large, neither wish.The voidage of cloth requires to be greater than 30%, is less than 80%.Too low voidage can cause the resistance of final products to become large, and certainly, voidage can not be too large, otherwise the burst strength of film product and hot strength will significantly reduce.
The monomer that described cation function of exchange is rolled into a ball is optional in following: vinylbenzenesulfonic acid, vinyl benzene sulphur salt, methacrylic acid, metering system salt, acrylic acid, propylene salt, methacrylic acid sulfonic acid ethyl ester, acrylic acid sulfonic acid ethyl ester.Such monomer need account for the 30-70% of total monomer molar number, and too low amount can cause the too high in resistance of final film forming.Too high molal quantity can cause finally becoming film strength low, and water imbibition is large.
Described hydrophobic monomer or optional in following containing many vinyl-functional monomer: divinylbenzene, octadecyl methacrylate, Hexafluorobutyl mathacrylate, ethylene glycol bisthioglycolate ethyl acrylate, glycerine three ethyl acrylates, ethylene glycol bisthioglycolate vinyl ethers.Such monomer accounts for the 5%-50% of total monomer molar number, gives the water-insoluble of amberplex and the intensity in water, and too low amount can cause film strength to reduce, and water imbibition is large, and too high amount can cause the fragility of film large, and resistance is high.
Described initator is peroxide or diimide class, and peroxide is optional in following: BPO, TBHP, diimide class is optional in following: azo-bis-isobutyl cyanide, azo diisoamyl cyanogen.Initator can be used separately, also can mix multiple initator and jointly use, and the amount of initator can be the 0.01%-5% of total monomer weight, is meeting under curing prerequisite, and the initator that consumption is few is more desirable.The key that initator is selected is can well be dissolved in the mixed solution system needing.
The present invention further takes following measure: described auxiliary substance can be selected polyvinyl acetate or EP rubbers, and its amount is total monomer quality≤1%.Polyvinyl acetate or EP rubbers, as auxiliary substance, add and can regulate the viscosity of mixed liquor on a small quantity, and moulding process is more easily realized.
Described auxiliary substance can be selected ethyl acrylate, and its amount is total monomer quality≤1%.Ethyl acrylate can participate in polymer copolymerization as auxiliary substance, increases the flexibility of film, and the interpolation of such material has certain influence to the performance of telolemma.
A moulding process for one-step method homogeneous phase cation exchange film, concrete steps further illustrate in force.
First, preparation water insoluble polyeletrolyte liquid: by the vinyl P-TOLUENE SULFO ACID 99 lithium of 6 moles, the divinylbenzene of 2 moles, azo two cyanogen in different heptan of 1% percetage by weight, a small amount of isopropyl alcohol mixes that to obtain the mixed liquor of clear stand-by.
Secondly, prepare moulding process:
1) prepare groove-shaped mold, spread the sticky barrier film PET cloth of one deck thereon, and then to spread 80 order thickness be that the PET of 0.12 millimeter strengthens screen cloth, water mixed liquor, unnecessary liquid flows out and collects again stand-by from the bottom side of groove-shaped mold.
2) continue to lay the not sticky barrier film PET cloth of one deck, and then to spread 80 order thickness be the PET fiber reinforcement screen cloth of 0.12 millimeter, water the insoluble polyeletrolyte liquid of water of preparation, dipping PET fiber reinforcement screen cloth, repeat this step, until not sticky barrier film and the PET fiber reinforcement screen cloth of folded 20 layers;
3) in the superiors, cover the sticky barrier film PET cloth of one deck, and then slowly to press in the above a thickness be the steel plate of 1 cm thick, put into baking oven 70 degree and solidify 4 hours
4) each layer of material being cured taken out, peel off each layer of PET barrier film, obtain 20 strong cation exchange films.After testing: thickness is 0.18 millimeter, exchange capacity 2.2 meq/g dry films, moisture content 32%, surface resistance is 3 ohm-sq centimetre.Burst strength is greater than 7 kilograms.
Identical with embodiment 1 step, just vinyl P-TOLUENE SULFO ACID 99 lithium is become to methacrylic acid, obtain the weak cation exchange film containing carboxyl group.After testing: thickness is 0.18 millimeter, exchange capacity 3.2meq/g dry film, moisture content 40%, surface resistance 2 ohm-sq centimetre.
Embodiment 3
Identical with embodiment 1 step, just vinyl P-TOLUENE SULFO ACID 99 lithium is become to methacrylic acid sulfonic acid ethyl ester, divinylbenzene changes ethylene glycol diacrylate into, obtains strong cation exchange film.After testing: thickness is 0.18 millimeter, exchange capacity 2.8meq/g dry film, moisture content 38%, surface resistance 2 ohm-sq centimetre, burst strength is greater than 7 kilograms.
Claims (10)
1. an one-step method homogeneous phase cation exchange film, is characterized in that, it consists of cloth of reinforcement fibers and the insoluble polyelectrolyte layers of water being compounded in cloth of reinforcement fibers, wherein:
The insoluble polyelectrolyte layers of described water is by the total monomer of two types containing unsaturated double-bond, and auxiliary substance copolymerization forms:
By the molal quantity percentage of total monomer, total monomer is comprised of following component:
A. the monomer 30-70% that cation function of exchange is rolled into a ball
B. hydrophobic monomer or containing many vinyl-functional monomer 5%-50%
The mass percent of auxiliary substance and total monomer is:
Initator 0.01%-5%
Described cloth of reinforcement fibers is woven cloth or nonwoven, and the thickness of described cloth is that the voidage of 0.05-0.5 millimeter, cloth requires to be greater than 30%, is less than 80%.
2. one-step method homogeneous phase cation exchange film according to claim 1, it is characterized in that, the monomer that described cation function of exchange is rolled into a ball is optional in following: vinylbenzenesulfonic acid, vinylbenzenesulfonic acid salt, methacrylic acid, methacrylate, acrylic acid, acrylates, methacrylic acid sulfonic acid ethyl ester, acrylic acid sulfonic acid ethyl ester.
3. one-step method homogeneous phase cation exchange film according to claim 1, it is characterized in that, described hydrophobic monomer or optional in following containing many vinyl-functional monomer: divinylbenzene, octadecyl methacrylate, Hexafluorobutyl mathacrylate, ethylene glycol bisthioglycolate ethyl acrylate, glycerine three ethyl acrylates, ethylene glycol bisthioglycolate vinyl ethers.
4. one-step method homogeneous phase cation exchange film according to claim 1, it is characterized in that, described initator is peroxide or diimide class, and peroxide is optional in following: BPO, TBHP, diimide class is optional in following: azo-bis-isobutyl cyanide, azo diisoamyl cyanogen.
5. one-step method homogeneous phase cation exchange film according to claim 1, is characterized in that, described auxiliary substance can be selected polyvinyl acetate or EP rubbers, its amount is total monomer quality≤and 1%.
6. one-step method homogeneous phase cation exchange film according to claim 1, described auxiliary substance can be selected ethyl acrylate, and its amount is total monomer quality≤1%.
7. the moulding process of a kind of one-step method homogeneous phase cation exchange film according to claim 1, is characterized in that, concrete steps are as follows:
Step 1, the corrosion-resistant not sticky mould of selection flute profile, bottom is smooth rectangle, and bottom sides is provided with an outlet, and groove tool inner chamber can hold places multiple cloth of reinforcement fibers and sticky barrier film;
Step 2, first at the sticky barrier film film of groove-shaped mold bottom layer overlay rectangle, then on sticky barrier film, repave the corresponding fiber reinforcement cloth of one deck, each limit of fiber reinforcement cloth and sticky barrier film align;
Step 3, the insoluble polyeletrolyte liquid of the water of configuration is watered on fiber reinforcement cloth, and fully impregnation of fibers strengthens cloth, unnecessary feed liquid flows out from the outlet of mold bottom side;
On step 4, the fiber reinforcement cloth after thorough impregnation, place not sticky barrier film and then put into next fiber reinforcement cloth, then repeating step three;
Step 5, repeating step four, the fiber reinforcement cloth of the not sticky barrier film of multi-disc and multi-disc dipping is alternately shape;
After the dipping of the step 6, the superiors, fiber reinforcement cloth is placed not sticky barrier film, then slowly place a smooth weight identical with finished product cation-exchange membrane size thereon, slowly the sticky barrier film of multilayer and fiber reinforcement cloth below it are applied to the pressure of 0.1-1 kilogram/square metre;
Step 7, in the process of exerting pressure, the outlet of closing molding bottom sides, the insoluble polyeletrolyte liquid of superfluous water squeezing out flows out from fiber reinforcement cloth, and is filled in the gap of fiber reinforcement cloth and groove-shaped mold surrounding;
Step 8, the sticky barrier film of mould and inner laminated thereof and impregnation of fibers are strengthened to cloth put into together explosion-proof baking oven and solidify, solidification temperature and hardening time are decided according to the kind of added initator and addition;
Step 9, each material being cured being taken out from baking oven, peeled off each layer of barrier film, just can obtain the block polyelectrolyte layer that fiber reinforcement cloth strengthens, is also one-step method homogeneous phase cation exchange film.
8. the moulding process of one-step method homogeneous phase cation exchange film according to claim 7, is characterized in that, initator described in described step 8 adopts benzoyl peroxide BPO, and addition is resin 1% time, and solidification temperature is 80 degree, and the time is 17 hours.
9. the moulding process of one-step method homogeneous phase cation exchange film according to claim 7, is characterized in that, initator described in described step 8 adopts TBHP, and when addition is 2%, solidification temperature is 80 degree, and the time is 17 hours.
10. the moulding process of one-step method homogeneous phase cation exchange film according to claim 7, is characterized in that, initator described in described step 8 adopts azo-bis-isobutyl cyanide, 1% addition, and solidification temperature is 70 degree, time 4 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108110197A (en) * | 2017-12-06 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of lithium battery selective membrane and preparation method thereof |
| CN109589809A (en) * | 2018-12-27 | 2019-04-09 | 山东天维膜技术有限公司 | A kind of preparation method of the cation-exchange membrane with multiple cross-linked structure |
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| CN101352657A (en) * | 2008-02-29 | 2009-01-28 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
| CN101497001A (en) * | 2008-02-01 | 2009-08-05 | 北京工商大学 | Single slice type ambipolar ion-exchange membrane and preparation method thereof |
| US20110068002A1 (en) * | 2009-08-26 | 2011-03-24 | Juchui Ray Lin | Ion exchange membranes |
| WO2012045152A1 (en) * | 2010-10-04 | 2012-04-12 | Saltworks Technologies Inc. | Resilient ion exchange membranes |
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Patent Citations (5)
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| CN1104556A (en) * | 1994-09-27 | 1995-07-05 | 核工业北京化工冶金研究院 | Cation exchange membrane and manufacturing method thereof |
| CN101497001A (en) * | 2008-02-01 | 2009-08-05 | 北京工商大学 | Single slice type ambipolar ion-exchange membrane and preparation method thereof |
| CN101352657A (en) * | 2008-02-29 | 2009-01-28 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
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| WO2012045152A1 (en) * | 2010-10-04 | 2012-04-12 | Saltworks Technologies Inc. | Resilient ion exchange membranes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108110197A (en) * | 2017-12-06 | 2018-06-01 | 成都新柯力化工科技有限公司 | A kind of lithium battery selective membrane and preparation method thereof |
| CN108110197B (en) * | 2017-12-06 | 2020-08-28 | 成都新柯力化工科技有限公司 | Selective diaphragm for lithium battery and preparation method thereof |
| CN109589809A (en) * | 2018-12-27 | 2019-04-09 | 山东天维膜技术有限公司 | A kind of preparation method of the cation-exchange membrane with multiple cross-linked structure |
| CN109589809B (en) * | 2018-12-27 | 2021-06-29 | 山东天维膜技术有限公司 | Preparation method of cation exchange membrane with multiple cross-linked structure |
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Application publication date: 20140312 |