CN106582333A - Manufacturing method of monolithic bipolar membrane - Google Patents
Manufacturing method of monolithic bipolar membrane Download PDFInfo
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- CN106582333A CN106582333A CN201510685315.9A CN201510685315A CN106582333A CN 106582333 A CN106582333 A CN 106582333A CN 201510685315 A CN201510685315 A CN 201510685315A CN 106582333 A CN106582333 A CN 106582333A
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- bipolar membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005341 cation exchange Methods 0.000 claims abstract description 25
- 239000004698 Polyethylene Substances 0.000 claims abstract description 22
- 229920000573 polyethylene Polymers 0.000 claims abstract description 22
- -1 polypropylene Polymers 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000004743 Polypropylene Substances 0.000 claims abstract description 12
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 229920001155 polypropylene Polymers 0.000 claims abstract description 9
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 7
- 238000007731 hot pressing Methods 0.000 claims abstract description 7
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 92
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000000806 elastomer Substances 0.000 claims description 20
- 229920001169 thermoplastic Polymers 0.000 claims description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 6
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229940059939 kayexalate Drugs 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 7
- 238000005576 amination reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 4
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 39
- 239000000047 product Substances 0.000 description 20
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- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
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- 238000006460 hydrolysis reaction Methods 0.000 description 6
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- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical class COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- FAIFRACTBXWXGY-JTTXIWGLSA-N COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 Chemical compound COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 FAIFRACTBXWXGY-JTTXIWGLSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000002091 cationic group Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001566735 Archon Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- BBJUQZWVBVNTJM-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC(C)=C.C=C.C1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC(C)=C.C=C.C1=CC=CC=C1 BBJUQZWVBVNTJM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 238000010345 tape casting Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a manufacturing method of a monolithic bipolar membrane. The manufacturing method comprises the steps that 1, a rolled dry sulfonated polystyrene-polyethylene cation exchange dry membrane and a thermoplastic elastomer thin-membrane roll containing polystyrene are respectively unrolled and then are superposed, and then a composite anode membrane roll with one surface coated with a thermoplastic elastomer containing polystyrene through hot pressing of a four-roll calender, cooling of a five-roll cooler and rolling of a rolling machine; 2, the composite anode membrane roll is cut off, is covered by a polyester protection membrane and a stainless steel plate and then is put on a flat-plate vulcanization machine, cooling and pressure relief are performed, and firmly bonded composite anode membrane pieces are obtained after taking out; 3, the uncoated surfaces of the two composite anode membrane pieces are bonded and then are superposed with a polypropylene separation screen, loose arrangement and multi-layer combined piling are performed, the pieces are put in a reaction tank, chloromethyl ether and a catalyst are successively added to carry out chloromethylation reaction, a dimethylamine and trimethylamine mixed solution performs amination reaction, the pieces are taken out after thorough cleaning, a polypropylene separation screen are peeled off, a wet membrane is collected, and the monolithic bipolar membrane is prepared.
Description
Technical field
The invention belongs to functional polymer thin film fabrication and technical field of membrane separation, more particularly to a kind of monolithic type
The industrialization production method of Bipolar Membrane product.
Background technology
Bipolar Membrane (full name is ambipolar ion-exchange membrane) generally by cation exchange film layer (referred to as positive layer),
Anion exchange membrane facing (referred to as cloudy layer) and intermediate transition zone (alternatively referred to as Catalytic Layer) compound composition.
When the reverse applied voltage of Bipolar Membrane (cloudy aspect to positive pole, positive aspect is to negative pole), charged ion will be
Migrate from intermediate transition zone to bulk solution in the presence of DC electric field；Original salt ion is quickly moved in film
After being shifted out, Catalytic Layer start be catalyzed hydrone occur dissociation and constantly produce hydrogen ion and hydroxyl from
Son, the hydrone for being consumed then is permeated incessantly to intermediate transition zone by the water in surrounding medium and is obtained
Timely supplement.As a result, compared with the direct hydrolysis mode without Bipolar Membrane, bipolar membrane electrodialysis device
Only consume the electricity of relatively small amount, you can continuously generate sour (hydrogen ion) and alkali (hydrogen-oxygen
Radical ion), become " factory " that soda acid is manufactured by salt.
The production method of Bipolar Membrane, there is at present five kinds：The adhesion-molded method of two-layer hot pressing formation process, two-layer, (one
Layer is on another layer) doctor-blade casting process, (two-layer difference) independent functionalization method, (one layer on another layer)
The electro-deposition method of forming (bibliography：Fu Rong is strong etc., the progress of Preparation Technology of Bipolar Membrane,《Water technology》,
The 2nd phase of volume 2003,29, page 67～69).Wherein, the Bipolar Membrane electricity that pressure sintering and Method for bonding are obtained
Resistance is higher, and two-layer is easily disengaged in use, and service life is not long, it is difficult to is formed and has competitiveness
Mature industry product.At present, the bipolar film manufacturing method of industrial comparative maturity is the 3rd kind and (is cast into
Type method) and the 4th kind (independent functionalization method).Such as, Japanese Aston companies and Fumatech companies of Germany,
All Bipolar Membrane is prepared using the enhanced individual layer difference the tape casting of screen cloth, i.e., the first coating on screen cloth is strengthened forms sun
Layer (either cloudy layer), it is coated forming cloudy layer (or positive layer), it is also possible to introduce Catalytic Layer among coating
Or a certain layer is coated with repeatedly to reach required thickness in monolayer.This method can continuous prodution with
To the Bipolar Membrane product of rolling, large-scale industry manufacture is also easily achieved.But some difficult problems are there is also,
As coating process control is complicated, require that " bubbling " causes film in the easy film of higher, Long-Time Service to strengthening screen cloth
Can decay etc..In contrast to this, United States Patent (USP) US 4024043 and Chinese Patent Application No.
201010281997.4 then all adopt polyethylene for main body film be basilar memebrane, be impregnated with by styrene and diethyl
The polymerized monomer solution of alkenyl benzene composition, forms the compound substrate membranes containing polystyrene after polymerization, then distinguishes
Positive layer is formed with concentrated acid sulfonation, implements chloromethylation and aminating reaction to form cloudy layer in another side in one side.
So, it is very firm (because both are all based in itself same Zhang Ji that resulting Bipolar Membrane the moon layer and positive layer is combined
Film), service life can be with longer.But the method for this manufacture Bipolar Membrane there is also some problems demands and solve.
For example, the course of reaction such as sulfonation, chloromethylation, amination all hold it is susceptible to various factors, especially
The sulfonation process that the first step is carried out, it is difficult to accurately controlled.So, the positive thickness between batch can be caused
Degree has differences, and then causes the performance of cloudy thickness degree and Bipolar Membrane to be difficult to stablize.
The content of the invention
The invention provides a kind of surfacing, negative and positive bed boundary is clear, film thickness is homogeneous, film properties are stable,
And can realize the manufacture method of the industrial monolithic type Bipolar Membrane product of large-scale.
Using monolithic type Bipolar Membrane product obtained in the inventive method, surfacing, interface is clear, ion are handed over
Change group be evenly distributed, film thickness it is homogeneous, and easily realize large-scale industry manufacture, film properties of product are steady
It is fixed, it is adapted to the engineer applied in electrodialysis field.
Technical scheme is as follows：A kind of manufacture method of monolithic type Bipolar Membrane, it enters as follows
OK：
Step 1), by the sulfonated polystyrene of rolling-polyethylene-based cation exchange dry film roll and containing polystyrene
Thermoplastic elastomer thin film volume is unreeled respectively, is overlapped afterwards, then in turn through four-roll calender hot pressing, five rollers
The cooling of cooling unit and winder winding, obtain one side and apply the compound sun containing thermoplastic polystyrene elastomer
Film roll；
Step 2), compound anode membrane is rolled up into severing, after adding a cover polyester diaphragm and stainless-steel sheet, it is placed in flat board
Hot pressing on vulcanizer, obtains the compound anode membrane piece being firmly combined with after cooling, release, taking-up；
Step 3), the clad can that is not coated with of two compound anode membrane pieces is fitted, then overlap with polypropylene filter, loosely
Arrangement, multiple layer combination is piled up, and in being placed in reactive tank, successively adds chloromethyl ether and catalyst to implement chloromethylation
Reaction, dimethylamine and trimethylamine mixed solution implement aminating reaction, take out after washes clean, peel off poly- third
Alkene filter, collects wet film, you can described monolithic type Bipolar Membrane is obtained.
Preferably, step 1) in, sulfonated polystyrene-polyethylene-based cation exchange dry film contains polyethylene
Based on can thermal plastic high polymer skeleton and kayexalate bear Electricity Functional macromolecule.
Preferably, step 1) in, described sulfonated polystyrene-polyethylene-based cation exchange dry film, sun
Ion exchange capacity is 1.5～2.2 mMs of every gram of dry films.
Preferably, step 1) in, described sulfonated polystyrene-polyethylene-based cation exchange dry film is thick
Spend for 0.10～0.15 millimeter.
Preferably, step 1) in, described film containing thermoplastic polystyrene elastomer, the polyphenyl of material choosing
Ethylene-vinyl alternate copolymer (PSE), SBS (SBS), benzene
Ethene-isoprene styrene triblock copolymer (SIS), the styrene-ethylene/butylene-styrene three of hydrogenation
One or more mixing in block copolymer (SEBS).
Preferably, film containing thermoplastic polystyrene elastomer, the mass content of polystyrene component is
20～42%.
Preferably, step 1) in, described film containing thermoplastic polystyrene elastomer, thickness be 0.04～
0.08 millimeter.
Preferably, step 3) in, the described dimethylamine for aminating reaction and trimethylamine mixed solution, its
In, trimethylamine is 100 with the mass ratio of dimethylamine：5～100：20.
Preferably, the thickness of wet film is 0.16～0.25 millimeter.
The manufacture method of monolithic type Bipolar Membrane according to the present invention：
Sulfonated polystyrene in step (1)-polyethylene-based cation exchange dry film, as Bipolar Membrane manufacture
Basilar memebrane, it simultaneously containing based on polyethylene can thermoplastic component and kayexalate bear Electricity Functional
Macromolecule.Generally, this cationic ion exchange substrate film is obtained by the following method with step manufacture：A) with poly-
Ethene particle and a small amount of flexibilizing agent particle (such as polyisobutene, ethylene propylene diene rubber, ethylene-octene copolymerization
Body (i.e. thermoplastic polyolefin elastomer, POE) etc.) melt blending, granulation, be impregnated with again afterwards styrene and
The comonomer solution of divinyl composition, polymerization obtains Polystyrene-Polyethylene system high polymer alloy Archon；b)
By this alloy Archon concentrated acid sulfonation, the cation exchange high polymer alloy resin of sulfonation is obtained；C) by this
Alloy resin obtains described sulfonated polystyrene-poly- after mill, continuous calendering, cooling, winding
Ethene cation exchanges dry film roll.It is preferred that Liaoning Yi Chenmo Science and Technology Ltd.s production LCM series sun from
Son exchanges homogeneous membrane, used as the basilar memebrane that Bipolar Membrane is subsequently manufactured.The LCM series cation exchange homogeneous membranes
Product manufacturing technology maturation, using the teaching of the invention it is possible to provide the dry film product of rolling, and film thickness, cation exchange capacity,
The Key Performance Indicators such as wet film moisture content are stablized, therefore suitable as the base of described monolithic type Bipolar Membrane product
Counterdie.The ion exchange capacity of this cationic ion exchange substrate film is preferably controlled to 1.5～2.2 mMs of every gram of dry films,
It is too high to cause the unbalanced of chemical composition between Bipolar Membrane the moon layer and positive layer, can not form rational in infrastructure bipolar
Film product is too low that the membrane surface resistance of Bipolar Membrane can be caused to sharply increase.The build of this basilar memebrane is preferably controlled
0.10～0.15 millimeter is made as, thickness is too small to reduce the mechanical strength of Bipolar Membrane product, and cannot get surface
Smooth Bipolar Membrane product, thickness is excessive, can dramatically increase the membrane surface resistance of Bipolar Membrane product.
Film containing thermoplastic polystyrene elastomer in step (1), material includes poly- (styrene-ethylene)
Alternate copolymer (PSE), SBS (SBS), styrene-isoamyl
Styrene triblock copolymer (SIS), the styrene-ethylene/butylene-styrene triblock copolymer of hydrogenation
Thing (SEBS), or they with the mixture of arbitrary proportion.Wherein, the quality of polystyrene component contains
Measure as 20～42%.If the content of polystyrene component is too low or too high, chloromethylation, amination it
The anion-exchange capacity of the cloudy layer for obtaining afterwards occurs deficiency or excess, can not all form chemical composition equal
The Bipolar Membrane of weighing apparatus.In addition to polystyrene component, what is contained in this kind of elastomer thin film can thermoplastic component
(such as polyethylene, polybutadiene, polyisoprene, Ethylene/Butylene random copolymer) is in the great majority, matter
Amount percentage is up to 58～80%.Therefore, basilar memebrane is exchanged with the Polystyrene-Polyethylene cation of sulfonation
Thermoplastic component (based on polyethylene) between compatibility preferably, can be tight after hot pressing, sulfuration
It is combined together.Using it complete by common membrane blowing production line (such as the fresh-keeping film production line of polyethylene) as described in
Containing thermoplastic polystyrene elastomer film rolling manufacture.Its thickness is preferably controlled to 0.04～0.08 milli
Rice.Thickness is too little to cause Bipolar Membrane the moon layer content not enough and Bipolar Membrane surface wrinkling pleat, then can make greatly very much double
The cloudy layer resistance of pole film is increased dramatically.
The dimethylamine for aminating reaction/trimethylamine mixed solution in step (3), wherein, trimethylamine and two
The mass ratio of methylamine is 100：5～20.Generally, the alkalescence of tertiary amine groups not as quaternary amine base it is strong.Therefore, if
The content of dimethylamine is too big in amination liquid, and the quaternary amine base that may result in Bipolar Membrane the moon layer is not enough, i.e., cloudy layer electricity
Resistance is increased dramatically；But if the content of dimethylamine is too little and the tertiary amines group content in Catalytic Layer can be caused not enough,
I.e. catalytic capability declines, and the hydrolysis efficiency for making Bipolar Membrane weakens.Some situations, in order to promote aminating process in
Compound anode membrane volume it is swelling, to promote the carrying out of aminating reaction, can add that some can be miscible with water is molten
Swollen dose of such as acetone, methyl alcohol, ethanol, to increase the speed and degree of aminating reaction.But these swellers
Addition is not necessary, by liter high reaction temperature and prolongation reaction time, often can be obtained same
Aminating reaction result.
In addition, the four-roller machine hot press operation in step (1) is more crucial, should control between each roller
Temperature and gap, temperature should gradient successively decrease, roller space should also be as control precisely (as between each roller and single
Gap error inside roller should be less than 0.01 millimeter).Press cure step in step (2) is also critically important,
Curing temperature, pressure and time need to be controlled.Furthermore, it is desirable to pressure is laid down again after cooling " annealing ",
Take out pressed material.During sulfuration, needs install resistant to elevated temperatures diaphragm additional between every film, to ensure
To the compound anode membrane piece of surfacing.The wet-film thickness of last obtained monolithic type Bipolar Membrane is 0.16～0.25
Millimeter.If too thin, the mechanical strength of product is inadequate, and cloudy layer and positive bed boundary can thicken；If too thick,
Then the membrane surface resistance of Bipolar Membrane can increase to insufferable degree.
The invention has the beneficial effects as follows：
1) sulfonated polystyrene-polyethylene-based cation exchange dry film roll for employing rolling is basilar memebrane, and it is thick
The performance indications such as degree, exchange capacity, wet film moisture content are sufficiently stable, that is, positive thickness degree and performance completely may be used
Control, therefore, be conducive to obtaining the Bipolar Membrane product of stable performance on this basis.
2) the cationic ion exchange substrate film for adopting, itself containing based on polyethylene can thermoplastic composition, and will
Apply film layer containing thermoplastic polystyrene elastomer (in addition to polystyrene, main material be polyethylene,
The thermoplastics such as polybutadiene, polyisoprene or ethylene-butylene random copolymer) material compatibility
Preferably, it is combined with reference to firm monolithic type therefore, it is possible to be formed after through rolling compound, press cure
Anode membrane piece, last obtained Bipolar Membrane Product Interface is clear, with suitable service behaviour.
3) the sulfonating reaction step for being difficult to precise control has been prevented, meanwhile, because chloromethylation and aminating reaction
Can be realized (as reaction conversion ratio reaches 98%) by the way of reacting completely, it is so final obtained
The exchange capacity of the cloudy layer of Bipolar Membrane is also relatively stable, so as to reduce the uncertain risk of manufacturing process.
Description of the drawings
Fig. 1 is the manufacture method flow chart of monolithic type Bipolar Membrane of the present invention.
Specific embodiment
The present invention is further explained below by way of specific embodiment.
Embodiment 1：
Step 1：The dry film roll of LCM series cation exchange homogeneous membranes is (limited by the easy occasion film science and technology in Liaoning
Company provides, and performance indications are as follows：Width is 60.0 centimetres, and thickness is 0.12 millimeter, and length is 200 meters,
Cation exchange capacity is 2.13 mMs of every gram of dry films) and SEBS elastomer thin films volume (Asahi Chemical Industry's strain formula
Commercial firm, trade mark H1041, polystyrene content 30%；Film width is 63.0 centimetres, and thickness is 0.04 millimeter,
Length is 300 meters), all unreel according to 3.2 ms/min of linear velocity, after overlapping (elastomer thin film upper,
All cover following anode membrane) enter four-roll calender, the temperature of four-roller is followed successively by 125,123,121,
120 DEG C, each roller space of accurate adjustment is 0.13～0.14 millimeter, after the cooling unit cooling of five rollers immediately
Into identical tension winder, continuous winding obtains the compound anode membrane volume that one side is coated with SEBS elastomers.
Step 2：Compound anode membrane volume is cut into into the diaphragm of 120 centimetre lengths, with polyester diaphragm (i.e. PET
Film, thickness is 0.125 millimeter, and width is 70.0 centimetres, and length is 130.0 centimetres) 6 layers of interval covering is (i.e.
7 PET protection films, 6 compound anode membranes), above and below stainless steel mirror board (thickness is 2.0 millimeters,
Width is 70.0 centimetres, and length is 130.0 centimetres) clamp, in sending into vulcanizing press, in 140～145
DEG C, vulcanize 45 minutes under 17～20MPa, less than 50 DEG C are cooled to afterwards, release, taking-up is dismantled stainless
Steel plate and PET protection film, collect the compound anode membrane piece that must be suppressed.The membrane surface is smooth, smooth, thick
Spend for 0.15～0.16 millimeter.
Step 3：The clad can (i.e. sunny side) that is not coated with of two compound anode membrane pieces is fit together, i.e. coated side court
Outward, then with polypropylene filter piece (thickness be 0.7 millimeter, width be 70.0 centimetres, length be 130.0 centimetres)
Loose overlapping, so combination, 150 groups altogether, among being placed in closed reactive tank.First put into 40 kilograms of nothings
Water zinc chloride, injects 600 liters of industrial chloromethyl ethers (content 40～42%), closed, room temperature interior circulation reaction 2
Hour, 45～50 DEG C are warmed up to, confined reaction 15 hours；It is passed through chuck and is water-cooled to room temperature, drains remnants
Reactant liquor, washed 3 times with 500 liters of dimethoxym ethanes, then drain；Add the mixed of 600 liters of dimethylamine/trimethylamines
Conjunction solution (dimethylamine concentration 2.1%, trimethylamine concentration 18%), confined reaction 12 hours at 42～45 DEG C,
It is cooled to after room temperature and extracts the reactant liquor of remnants out, be neutral with originally water washing to washing lotion, take out, peels off poly-
Propylene filter, wet film is collected separately, and carries out necessary cutting edge process, that is, described monolithic type is obtained bipolar
Film.
After testing, the performance indications of the monolithic type Bipolar Membrane product obtained by the present embodiment are as follows：Wet-film thickness
For 0.17～0.19 millimeter, transmembrane voltage is that (test fluid is 10% aqueous sodium persulfate solution to 1.57V, tests electric current
Density is 50mA/cm2), hydrolysis efficiency is more than 98%, and wet film burst strength is more than 0.35MPa.
Embodiment 2：
Step 1：The dry film roll of LCM series cation exchange homogeneous membranes is (limited by the easy occasion film science and technology in Liaoning
Company provides, and performance indications are as follows：Width is 60.0 centimetres, and thickness is 0.10 millimeter, and length is 200 meters,
Cation exchange capacity be 2.02 mMs of every gram of dry films) and blending elastomer thin film roll up【Material is consisted of：
SEBS (section of the U.S. rises, trade mark G1654H, polystyrene content 31%)：SBS (rise, the trade mark by section of the U.S.
D1155BJ, polystyrene content 40%)=4：6 (mass ratioes), film width is 63.0 centimetres, thickness
For 0.04 millimeter, length is 300 meters】, all unreel according to 2.4 ms/min of linear velocity, (bullet after overlapping
Gonosome film all covers following anode membrane upper) four-roll calender is entered, the temperature of four-roller is followed successively by
121st, 119,117,115 DEG C, each roller space of accurate adjustment is 0.11～0.12 millimeter, through five roller coolers
Identical tension winder is immediately entered after group cooling, continuous winding obtains one side and be coated with co-blending elastic body
Compound anode membrane volume.
Step 2：Compound anode membrane volume is cut into into the diaphragm of 120 centimetre lengths, with polyester diaphragm (i.e. PET
Film, thickness is 0.125 millimeter, and width is 70.0 centimetres, and length is 130.0 centimetres) 8 layers of interval covering is (i.e.
9 PET protection films, 8 compound anode membranes), above and below stainless steel mirror board (thickness is 2.0 millimeters,
Width is 70.0 centimetres, and length is 130.0 centimetres) clamp, in sending into vulcanizing press, in 138～142
DEG C, vulcanize 40 minutes under 16～20MPa, less than 50 DEG C are cooled to afterwards, release, taking-up is dismantled stainless
Steel plate and PET protection film, collect the compound anode membrane piece that must be suppressed.The membrane surface is smooth, smooth, thick
Spend for 0.13～0.14 millimeter.
Step 3：The clad can (i.e. sunny side) that is not coated with of two compound anode membrane pieces is fit together, i.e. coated side court
Outward, then with polypropylene filter piece (thickness be 0.7 millimeter, width be 70.0 centimetres, length be 130.0 centimetres)
Loose overlapping, so combination, 152 groups altogether, among being placed in closed reactive tank.First put into 40 kilograms of nothings
Water zinc chloride, injects 600 liters of industrial chloromethyl ethers (content 40～42%), closed, room temperature interior circulation reaction 2
Hour, 45～50 DEG C are warmed up to, confined reaction 10 hours；It is passed through chuck and is water-cooled to room temperature, drains remnants
Reactant liquor, washed 3 times with 500 liters of dimethoxym ethanes, then drain；Add the mixed of 600 liters of dimethylamine/trimethylamines
Solution (dimethylamine concentration 2.4%, trimethylamine concentration 21.2%) is closed, confined reaction 10 is little at 42～45 DEG C
When, it is cooled to after room temperature and extracts the reactant liquor of remnants out, it is neutral with originally water washing to washing lotion, take out, stripping
From polypropylene filter, wet film is collected separately, carries out necessary cutting edge process, that is, described monolithic type is obtained
Bipolar Membrane.
After testing, the performance indications of the monolithic type Bipolar Membrane product obtained by the present embodiment are as follows：Wet-film thickness
For 0.16～0.18 millimeter, transmembrane voltage is that (test fluid is 10% aqueous sodium persulfate solution to 1.49V, tests electric current
Density is 50mA/cm2), hydrolysis efficiency is more than 98%, and wet film burst strength is more than 0.32MPa.
Embodiment 3：
Step 1：The dry film roll of LCM series cation exchange homogeneous membranes is (limited by the easy occasion film science and technology in Liaoning
Company provides, and performance indications are as follows：Width is 60.0 centimetres, and thickness is 0.11 millimeter, and length is 230 meters,
Cation exchange capacity is 1.95 mMs of every gram of dry films) and poly- (styrene-ethylene) alternate copolymer elasticity
Body thin film rolls up (PSE, Ningbo karr new material Co., Ltd, trade mark K7033, polystyrene content 33%；
Film width is 62.0 centimetres, and thickness is 0.05 millimeter, and length is 250 meters), all according to 2.7 ms/min
Linear velocity is unreeled, and (elastomer thin film upper, all cover following anode membrane) enters four-roller after overlapping
Calender, the temperature of four-roller is followed successively by 130,128,126,125 DEG C, and each roller space of accurate adjustment is 0.13～0.14
Millimeter, after the cooling unit cooling of five rollers identical tension winder is immediately entered, and continuous winding obtains
One side is coated with the compound anode membrane volume of PSE elastomers.
Step 2：Compound anode membrane volume is cut into into the diaphragm of 120 centimetre lengths, with polyester diaphragm (i.e. PET
Film, thickness is 0.125 millimeter, and width is 70.0 centimetres, and length is 130.0 centimetres) 6 layers of interval covering is (i.e.
7 PET protection films, 6 compound anode membranes), above and below stainless steel mirror board (thickness is 2.0 millimeters,
Width is 70.0 centimetres, and length is 130.0 centimetres) clamp, in sending into vulcanizing press, in 145～150
DEG C, vulcanize 40 minutes under 18～20MPa, less than 50 DEG C are cooled to afterwards, release, taking-up is dismantled stainless
Steel plate and PET protection film, collect the compound anode membrane piece that must be suppressed.The membrane surface is smooth, smooth, thick
Spend for 0.15～0.16 millimeter.
Step 3：The clad can (i.e. sunny side) that is not coated with of two compound anode membrane pieces is fit together, i.e. coated side court
Outward, then with polypropylene filter piece (thickness be 0.7 millimeter, width be 70.0 centimetres, length be 130.0 centimetres)
Loose overlapping, so combination, 150 groups altogether, among being placed in closed reactive tank.First put into 40 kilograms of nothings
Water zinc chloride, injects 600 liters of industrial chloromethyl ethers (content 40～42%), closed, room temperature interior circulation reaction 2
Hour, 45～50 DEG C are warmed up to, confined reaction 16 hours；It is passed through chuck and is water-cooled to room temperature, drains remnants
Reactant liquor, washed 3 times with 500 liters of dimethoxym ethanes, then drain；Add the mixed of 600 liters of dimethylamine/trimethylamines
Conjunction solution (dimethylamine concentration 1.8%, trimethylamine concentration 20%), confined reaction 12 hours at 42～45 DEG C,
It is cooled to after room temperature and extracts the reactant liquor of remnants out, be neutral with originally water washing to washing lotion, take out, peels off poly-
Propylene filter, wet film is collected separately, and carries out necessary cutting edge process, that is, described monolithic type is obtained bipolar
Film.
After testing, the performance indications of the monolithic type Bipolar Membrane product obtained by the present embodiment are as follows：Wet-film thickness
For 0.18～0.20 millimeter, transmembrane voltage is that (test fluid is 10% aqueous sodium persulfate solution to 1.69V, tests electric current
Density is 50mA/cm2), hydrolysis efficiency is more than 98%, and wet film burst strength is more than 0.38MPa.
Embodiment 4：
Step 1：The dry film roll of LCM series cation exchange homogeneous membranes is (limited by the easy occasion film science and technology in Liaoning
Company provides, and performance indications are as follows：Width is 60.0 centimetres, and thickness is 0.13 millimeter, and length is 200 meters,
Cation exchange capacity be 2.16 mMs of every gram of dry films) and blending elastomer thin film roll up【Material is consisted of：
Poly- (styrene-ethylene) alternate copolymer (PSE, Ningbo karr new material Co., Ltd, trade mark K7033,
Polystyrene content 33%)：SIS (SIS, section of the U.S. rises,
Trade mark D1193P, polystyrene content 24%)=9：1, film width is 63.0 centimetres, and thickness is 0.05
Millimeter, length is 250 meters】, all unreeling according to 2.8 ms/min of linear velocity, (elastomer is thin after overlapping
Film all covers following anode membrane upper) enter four-roll calender, the temperature of four-roller is followed successively by 131,129,
127th, 125 DEG C, each roller space of accurate adjustment is 0.14～0.15 millimeter, after the cooling unit cooling of five rollers
Identical tension winder is immediately entered, continuous winding obtains the compound anode membrane that one side is coated with co-blending elastic body
Volume.
Step 2：Compound anode membrane volume is cut into into the diaphragm of 120 centimetre lengths, with polyester diaphragm (i.e. PET
Film, thickness is 0.125 millimeter, and width is 70.0 centimetres, and length is 130.0 centimetres) 6 layers of interval covering is (i.e.
7 PET protection films, 6 compound anode membranes), above and below stainless steel mirror board (thickness is 2.0 millimeters,
Width is 70.0 centimetres, and length is 130.0 centimetres) clamp, in sending into vulcanizing press, in 145～150
DEG C, vulcanize 50 minutes under 18～20MPa, less than 50 DEG C are cooled to afterwards, release, taking-up is dismantled stainless
Steel plate and PET protection film, collect the compound anode membrane piece that must be suppressed.The membrane surface is smooth, smooth, thick
Spend for 0.17～0.18 millimeter.
Step 3：The clad can (i.e. sunny side) that is not coated with of two compound anode membrane pieces is fit together, i.e. coated side court
Outward, then with polypropylene filter piece (thickness be 0.7 millimeter, width be 70.0 centimetres, length be 130.0 centimetres)
Loose overlapping, so combination, 150 groups altogether, among being placed in closed reactive tank.First put into 40 kilograms of nothings
Water zinc chloride, injects 600 liters of industrial chloromethyl ethers (content 40～42%), closed, room temperature interior circulation reaction 1
Hour, 45～50 DEG C are warmed up to, confined reaction 13 hours；It is passed through chuck and is water-cooled to room temperature, drains remnants
Reactant liquor, washed 3 times with 500 liters of dimethoxym ethanes, then drain；Add the mixed of 600 liters of dimethylamine/trimethylamines
Conjunction solution (dimethylamine concentration 2.5%, trimethylamine concentration 20%), confined reaction 12 hours at 43～45 DEG C,
It is cooled to after room temperature and extracts the reactant liquor of remnants out, be neutral with originally water washing to washing lotion, take out, peels off poly-
Propylene filter, wet film is collected separately, and carries out necessary cutting edge process, that is, monolithic type Bipolar Membrane is obtained.
After testing, the performance indications of the monolithic type Bipolar Membrane product obtained by the present embodiment are as follows：Wet-film thickness
For 0.20～0.21 millimeter, transmembrane voltage is that (test fluid is 10% aqueous sodium persulfate solution to 1.73V, tests electric current
Density is 50mA/cm2), hydrolysis efficiency is more than 98%, and wet film burst strength is more than 0.40MPa.
Above-described embodiment is, for explaining and illustrating the present invention, rather than to limit the invention.At this
Within the spirit and scope of the claims of invention, to any modifications and changes done by the present invention,
Fall within protection scope of the present invention.
Claims (9)
1. a kind of manufacture method of monolithic type Bipolar Membrane, it is carried out as follows：
Step 1), by the sulfonated polystyrene of rolling-polyethylene-based cation exchange dry film roll and containing polystyrene
Thermoplastic elastomer thin film volume is unreeled respectively, is overlapped afterwards, then in turn through four-roll calender hot pressing, five rollers
The cooling of cooling unit and winder winding, obtain one side and apply the compound sun containing thermoplastic polystyrene elastomer
Film roll；
Step 2), compound anode membrane is rolled up into severing, after adding a cover polyester diaphragm and stainless-steel sheet, it is placed in flat board
Hot pressing on vulcanizer, obtains the compound anode membrane piece being firmly combined with after cooling, release, taking-up；
Step 3), the clad can that is not coated with of two compound anode membrane pieces is fitted, then overlap with polypropylene filter, loosely
Arrangement, multiple layer combination is piled up, and in being placed in reactive tank, successively adds chloromethyl ether and catalyst to implement chloromethylation
Reaction, dimethylamine and trimethylamine mixed solution implement aminating reaction, take out after washes clean, peel off poly- third
Alkene filter, collects wet film, you can described monolithic type Bipolar Membrane is obtained.
2. the manufacture method of monolithic type Bipolar Membrane according to claim 1, it is characterised in that：Step 1)
In, described sulfonated polystyrene-polyethylene-based cation exchange dry film contain based on polyethylene can thermoplasticity
Macromolecular scaffold and kayexalate bear Electricity Functional macromolecule.
3. the manufacture method of monolithic type Bipolar Membrane according to claim 1, it is characterised in that：Step 1)
In, described sulfonated polystyrene-polyethylene-based cation exchange dry film, cation exchange capacity is 1.5～2.2
MM every gram of dry film.
4. the manufacture method of the monolithic type Bipolar Membrane according to any one of claim 1-3, it is characterised in that：
Step 1) in, sulfonated polystyrene-polyethylene-based cation exchange dry film, thickness is 0.10～0.15 millimeter.
5. the manufacture method of monolithic type Bipolar Membrane according to claim 1, it is characterised in that：Step 1)
In, described film containing thermoplastic polystyrene elastomer, the polystyrene-ethylene alternate copolymer of material choosing,
SBS, SIS,
One or more mixing in the styrene-ethylene/butylene-styrene triblock copolymer of hydrogenation.
6. the manufacture method of monolithic type Bipolar Membrane according to claim 1 or 5, it is characterised in that：Institute
The film containing thermoplastic polystyrene elastomer stated, the mass content of polystyrene component is 20～42%.
7. the manufacture method of the monolithic type Bipolar Membrane according to claim 1-3 or 5 any one, its feature
It is：Step 1) in, film containing thermoplastic polystyrene elastomer, thickness is 0.04～0.08 millimeter.
8. the manufacture method of monolithic type Bipolar Membrane according to claim 1, it is characterised in that：Step 3)
In, the described dimethylamine for aminating reaction and trimethylamine mixed solution, wherein, trimethylamine and dimethylamine
Mass ratio be 100：5～100：20.
9. the manufacture method of the monolithic type Bipolar Membrane according to claim 1 or 8, it is characterised in that：Institute
The thickness for stating wet film is 0.16～0.25 millimeter.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106968108A (en) * | 2017-05-03 | 2017-07-21 | 厦门大学 | A kind of application of monolithic type Bipolar Membrane in flow battery |
| CN109821423A (en) * | 2019-03-27 | 2019-05-31 | 苏州交创石墨烯新材料有限公司 | The solid solution casting technique and device of heterogeneous anion-exchange membrane |
| CN109876678A (en) * | 2019-04-02 | 2019-06-14 | 浙江迪萧环保科技有限公司 | A kind of bipolar membrane and preparation method |
| CN111905569A (en) * | 2020-08-18 | 2020-11-10 | 巨轮智能装备股份有限公司 | Continuous manufacturing method of partition board for electrodialysis membrane stack |
| CN112516809A (en) * | 2021-01-11 | 2021-03-19 | 浙江工业大学 | Preparation method of semi-homogeneous bipolar membrane |
| CN112915793A (en) * | 2021-01-21 | 2021-06-08 | 衢州蓝然新材料有限公司 | Single-sheet bipolar membrane roll with screen cloth support and manufacturing method thereof |
| WO2022155854A1 (en) * | 2021-01-21 | 2022-07-28 | 衢州蓝然新材料有限公司 | Single piece-type bipolar film roll with mesh cloth support and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106968108A (en) * | 2017-05-03 | 2017-07-21 | 厦门大学 | A kind of application of monolithic type Bipolar Membrane in flow battery |
| CN109821423A (en) * | 2019-03-27 | 2019-05-31 | 苏州交创石墨烯新材料有限公司 | The solid solution casting technique and device of heterogeneous anion-exchange membrane |
| CN109876678A (en) * | 2019-04-02 | 2019-06-14 | 浙江迪萧环保科技有限公司 | A kind of bipolar membrane and preparation method |
| CN111905569A (en) * | 2020-08-18 | 2020-11-10 | 巨轮智能装备股份有限公司 | Continuous manufacturing method of partition board for electrodialysis membrane stack |
| CN111905569B (en) * | 2020-08-18 | 2022-03-11 | 巨轮智能装备股份有限公司 | Continuous manufacturing method of partition board for electrodialysis membrane stack |
| CN112516809A (en) * | 2021-01-11 | 2021-03-19 | 浙江工业大学 | Preparation method of semi-homogeneous bipolar membrane |
| CN112915793A (en) * | 2021-01-21 | 2021-06-08 | 衢州蓝然新材料有限公司 | Single-sheet bipolar membrane roll with screen cloth support and manufacturing method thereof |
| WO2022155854A1 (en) * | 2021-01-21 | 2022-07-28 | 衢州蓝然新材料有限公司 | Single piece-type bipolar film roll with mesh cloth support and manufacturing method therefor |
| CN112915793B (en) * | 2021-01-21 | 2022-08-02 | 衢州蓝然新材料有限公司 | Single-sheet bipolar membrane roll with screen cloth support and manufacturing method thereof |
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