CN103223305A - Polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy film preparation method - Google Patents
Polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy film preparation method Download PDFInfo
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Abstract
The invention discloses a polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy film preparation method, which comprises the following steps: dissolving polyvinylidene fluoride firstly, uniformly mixing the polyvinylidene fluoride and a polymerized monomer solution containing styrene, a cross-linking agent and an initiator, and then heating for copolymerization, extruding, solidifying, granulating, drying, crushing and other steps for obtaining polystyrene/polyvinylidene fluoride alloy powder; obtaining a quaternary ammonium type anion exchange alloy powder by applying chloromethylation reaction and amination reaction to alloy powder finally using a hot pressing moulding method, adding auxiliary material, banburying, milling, pulling sheet, hot pressing, cooling and obtaining polystyrene/polyvinylidene fluoride quaternary ammonium type anion exchange alloy membrane. The quaternary ammonium type anion exchange alloy membrane prepared by the invention has the advantages of high-molecular interpenetrating network structure, which completely eliminates the structure defect that the anion exchange resin powder and the high-molecular binder in the traditional interphase anion exchange membrane are not compatible with low resistor.
Description
Technical field
The invention belongs to the functional polymer film preparing technical field, particularly a kind of preparation method with polystyrene/Kynoar quaternary ammonium type anion exchange high polymer alloy film of inierpeneirating network structure.
Background technology
Amberplex is the immobilized group that ion-exchange (or conduction) effect can take place on film generally, can exchange cation (as sodium ion) as immobilized sulfonic group, and immobilized quaternary amine base can exchange anion (as chlorion).Because amberplex has unique ion-exchange (conduction) characteristic; make it bring into play more and more important effect, be particularly suitable for that modern industry utilizes desalination separation, new forms of energy, energy-conservation, low-grade raw material and the needs of environmental pollution improvement again at aspects such as cleaner production, environmental protection, energy conversions.
According to the structure difference, amberplex can be divided into heterogeneous membrane, half homogeneous membrane and homogeneous membrane.Wherein, heterogeneous ion-exchange membrane generally adopts the hot press forming technology manufacturing, and the ion exchange resin that is about to be provided by ion exchange resin factory is pulverized, and adds thermoplastic binder polymer (as low density polyethylene (LDPE)), mixes back hot pressing and forms.Its manufacture process is simple Polymer Physics process, and technology is simple relatively, pollutes little (exhaust emission that generally has only a spot of thermoplastic processing to produce), and production cost is lower.But, because the polarity that plays the hydrophobicity cohesive polymers of skeleton supporting role and play between the hydrophilic resin cosmetics that ionic conduction (exchange) acts on differs bigger, make heterogeneous ion-exchange membrane separate when using and occur the structure segregation phenomenon easily, have significantly " shedding " and " hole " defective in electric drive membrane.On the other hand, the manufacturing of homogeneous ion-exchange membrane, normally pre-XianCheng basement membrane reacts basement membrane enforcement functionalizing and introduces ion-exchange group.As the polystyrene anion-exchange membrane, the polystyrene basement membrane need be implemented earlier chloromethylation, implement aminating reaction again and get.And to implement the functionalizing reaction to whole film, course of reaction is difficult to accurately control, and is all very high to the requirement of process control and equipment, and is difficult to guarantee the stability of each batch products performance.
Till, in conjunction with the technology and equipment condition of utilizing existing ion exchange resin industry of China and heterogeneous ion-exchange membrane industry, a kind of preparation method's (Chinese invention patent application number 201110417296.3) of polystyrene ion-exchange alloy film has been proposed before us.Consider hear resistance, chemical stability, film-forming flexibility and the thermoplastic processability of Kynoar excellence subsequently, further proposed preparation method's (Chinese invention patent application number 201210259047.0) of a kind of polystyrene/Kynoar cation-exchange membrane.The present invention is the actual conditions of making in conjunction with anion exchange resin production and out-phase anion-exchange membrane on the bigger purity, and integrated, as to be connected two industries process route proposes the preparation method of a kind of polystyrene/Kynoar quaternary ammonium type anion exchange membrane.
Summary of the invention
The objective of the invention is in order to promote the combination property of traditional polystyrene out-phase anion-exchange membrane comprehensively, a kind of preparation method with polystyrene/Kynoar quaternary ammonium type anion exchange alloy film of macromolecule inierpeneirating network structure is provided, the structure and the performance of the anion-exchange membrane that this method is made, all be better than the anion exchange heterogeneous membrane, and approach homogeneous membrane.
The objective of the invention is to be achieved through the following technical solutions: the preparation method of a kind of polystyrene/Kynoar quaternary ammonium type anion exchange alloy film, this method may further comprise the steps:
1, the monomer solution of earlier styrene, crosslinking agent and initator being formed by quality proportioning 100:2 ~ 10:1 ~ 10, slowly be added drop-wise among the Kynoar solution, the quality proportioning of monomer solution and Kynoar solution is 5 ~ 40:100, fully mix, obtain uniform styrene/Kynoar composite solution;
2, composite solution is heated to 65 ~ 105 ℃, polymerization obtains polystyrene/Kynoar jelly after 5 ~ 20 hours; With jelly extrude, water sedimentation curing, wire drawing, granulation, obtain polystyrene/polyvinylidene fluoride alloy particle; With the alloying pellet oven dry, pulverize, obtain polystyrene/polyvinylidene fluoride alloy powder;
3, add chloromethyl ether and anhydrous zinc chloride, implemented chloromethylation 4 ~ 12 hours at 35 ~ 50 ℃ of following p-poly-phenyl ethene/polyvinylidene fluoride alloy powder, the quality proportioning of chloromethyl ether, anhydrous zinc chloride and polystyrene/polyvinylidene fluoride alloy powder is 200 ~ 800:60 ~ 120:100; With chloromethylation products for several times, make the chloromethylation alloyed powder with the dimethoxym ethane washing;
4, add amination solution, under 25 ~ 50 ℃ the chloromethylation alloyed powder was implemented aminating reaction 2 ~ 12 hours, the use amount of amination solution is 250% ~ 800% of a chloromethylation alloyed powder quality; Washing, the dry quaternary ammonium type anion exchange alloyed powder that promptly makes afterwards;
5, quaternary ammonium type anion is exchanged alloyed powder and drop into banbury, add auxiliary materials such as pigment, flexibilizing agent, antioxidant and releasing agent, 160 ~ 210 ℃ of following banburyings 15 ~ 60 minutes, discharging; Send into mill then, under 150 ~ 200 ℃, open refining 10 ~ 30 minutes, pulling-on piece; Send in the hot press, hot pressing is 15 ~ 60 minutes under 160 ~ 210 ℃, 20 ~ 60 MPas again, and cooling makes described polystyrene/Kynoar quaternary ammonium type anion exchange alloy film.
The invention has the beneficial effects as follows: prepared polystyrene/Kynoar quaternary ammonium type anion exchange alloy film, play the vinylidene component of basement membrane effect and rise between the quaternary ammoniated polystyrene component of ion exchange and twine mutually, has the high polymer alloy structure that runs through mutually, eliminated in traditional out-phase anion-exchange membrane inconsistent fault of construction between the resin-oatmeal and high polymer binder, film resistance greatly reduces, the electrochemistry combination property of film is better than the anion exchange heterogeneous membrane, and approaches the anion exchange homogeneous membrane.And, fully use for reference and utilized the production technology of anion exchange resin, can directly polystyrene/polyvinylidene fluoride alloy powder be implemented chloromethylation and aminating reaction in anion exchange resin workshop (factory), obtain quaternary ammonium type anion exchange alloyed powder, be used for the described anion exchange alloy film of hot-forming processing and manufacturing.Simultaneously, avoided and be difficult to control, caused the inhomogenous functionalizing reaction of film properties easily, when being very beneficial for suitability for industrialized production the alloy film product has been carried out quality control basement membrane (or intermediate coat).
Description of drawings
Fig. 1 is a manufacturing process flow diagram of the present invention.
The specific embodiment
As shown in Figure 1, the preparation method of polystyrene of the present invention/Kynoar quaternary ammonium type anion exchange alloy film may further comprise the steps:
1, the monomer solution of earlier styrene, crosslinking agent and initator being formed by quality proportioning 100:2 ~ 10:1 ~ 10, slowly be added drop-wise among the Kynoar solution, the quality proportioning of monomer solution and Kynoar solution is 5 ~ 40:100, fully mix, obtain uniform styrene/Kynoar composite solution.
The monomer solution that is adopted is evenly mixed by styrene, crosslinking agent and initator.The crosslinking agent that is adopted in the described step (1) is a divinylbenzene, and use amount is 2% ~ 10% of a styrene quality; The too little meeting of ratio causes the water content of film and swellbility excessive, and ratio then is difficult to carry out follow-up thermoplastic processing film forming too greatly.The initator that is adopted is benzoyl peroxide or azodiisobutyronitrile, and the dosage of initator is 1% ~ 10% of a styrene quality.The solvent of the dissolving Kynoar that is adopted is included as dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or N-methyl pyrrolidone; Can be wherein a kind of, also can be two or more mixture with any mass ratio.Solvent adding amount is 2 ~ 10 times of Kynoar quality, can not dissolve Kynoar fully very little, and too conference causes waste, can increase the wastewater treatment pressure of subsequent thermal water sedimentation step simultaneously.Solution temperature is 50 ~ 120 ℃, and high again temperature helps dissolving, but can increase the volatilization loss amount of solvent.Look solution temperature, generally need 60 ~ 150 minutes ability to dissolve fully.Separate out in order to prevent that styrene polymerization solution from precipitating among Kynoar solution, need under the condition of high-speed stirred styrene monomer solution slowly be added among the Kynoar solution.The quality proportioning of monomer solution and Kynoar solution is 5 ~ 40:100.Ratio is too high, can cause the thermoplasticity of alloying pellet to disappear, and the hot press operation that can't carry out for the 5th step obtains alloy film; Ratio is too low, then can cause the exchange capacity of the anion exchange alloy film that finally makes not enough, and face resistance is bigger than normal.
2, composite solution is heated to 65 ~ 105 ℃, polymerization obtains polystyrene/Kynoar jelly after 5 ~ 20 hours; With jelly extrude, water sedimentation curing, wire drawing, granulation, obtain polystyrene/polyvinylidene fluoride alloy particle; With the alloying pellet oven dry, pulverize, obtain polystyrene/polyvinylidene fluoride alloy powder.
Temperature during heated polymerizable generally maintains 65 ~ 105 ℃, and controls temperature polymerization 5 ~ 20 hours, so that styrene and crosslinking agent copolymerzation with cross-linking are complete.Can take programmed temperature method, as 65 ℃ of polymerizations 2 hours, 75 ℃ of polymerizations 2 hours, 85 ℃ of polymerizations 8 hours.Obtain the polystyrene/Kynoar jelly of jelly shape after the polymerization.To jelly implement to extrude, operations such as water sedimentation curing, wire drawing, granulation, can on integrated extruding granulator, carry out continuously.The coolant-temperature gage of sedimentation basin is controlled at 40 ~ 90 ℃, and the size of the polystyrene that granulation obtains/polyvinylidene fluoride alloy particle is controlled at below 3 millimeters, is beneficial to thorough oven dry.With the alloying pellet of oven dry, mechanical crushing to 0.2 ~ 1.0 millimeter are beneficial to the carrying out of chloromethylation and aminating reaction subsequently.
3, add chloromethyl ether and anhydrous zinc chloride, implemented chloromethylation 4 ~ 12 hours at 35 ~ 50 ℃ of following p-poly-phenyl ethene/polyvinylidene fluoride alloy powder, the quality proportioning of chloromethyl ether, anhydrous zinc chloride and polystyrene/polyvinylidene fluoride alloy powder is 200 ~ 800:60 ~ 120:100; With chloromethylation products for several times, make the chloromethylation alloyed powder with the dimethoxym ethane washing.
Chloromethylation is at room temperature used industrial chloromethyl ether swelling with polystyrene/polyvinylidene fluoride alloy powder earlier, adds anhydrous zinc chloride then, and the control temperature is carried out chloromethylation.The use amount of chloromethyl ether is 200% ~ 800% of polystyrene/polyvinylidene fluoride alloy opaque amount, and the use amount of anhydrous zinc chloride is 60% ~ 120% of polystyrene/polyvinylidene fluoride alloy opaque amount.Reaction was generally carried out between 35 ~ 50 ℃ 4 ~ 12 hours, and is can chloromethylation complete.After chloromethylation is finished, drain and react residual night, add dimethoxym ethane washing 3 ~ 4 times, can add 300% ~ 600% of polystyrene/polyvinylidene fluoride alloy opaque amount at every turn, stir to wash after 1 hour and drain, promptly get the chloromethylation alloyed powder.
4, add amination solution, under 25 ~ 50 ℃ the chloromethylation alloyed powder was implemented aminating reaction 2 ~ 12 hours, the use amount of amination solution is 250% ~ 800% of a chloromethylation alloyed powder quality; Washing, the dry quaternary ammonium type anion exchange alloyed powder that promptly makes afterwards.
The amination solution that is adopted is trimethylamine aqueous solution, and its mass percent concentration is 10% ~ 30%.The use amount of amination solution is 250% ~ 800% of a chloromethylation alloyed powder quality, and the aminating reaction temperature is 25 ~ 50 ℃, and the reaction time is 2 ~ 12 hours, can add 4% liquid caustic soda, and pH is adjusted to more than 12, promotes that aminating reaction is complete.Drain and add clear water after the reaction residue, wash to pH less than 8.0.Add dilute hydrochloric acid solution (mass concentration 3% ~ 10%) again, soaked 1 ~ 5 hour, film is changed into the chlorine type by the hydrogen-oxygen type, add again at last clear water wash to pH greater than 6.0.To wash product and take out, obtain quaternary ammonium type anion exchange alloyed powder after 80 ~ 120 ℃ of heated-air dryings.
5, quaternary ammonium type anion is exchanged alloyed powder and drop into banbury, add auxiliary materials such as pigment, flexibilizing agent, antioxidant and releasing agent, 160 ~ 210 ℃ of following banburyings 15 ~ 60 minutes, discharging; Send into mill then, under 150 ~ 200 ℃, open refining 10 ~ 30 minutes, pulling-on piece; Send in the hot press, hot pressing is 15 ~ 60 minutes under 160 ~ 210 ℃, 20 ~ 60 MPas again, and cooling makes described polystyrene/Kynoar quaternary ammonium type anion exchange alloy film.
Pigment can adopt phthalocyanine blue, and addition is 0.1 ~ 1% of a quaternary ammonium type anion exchange alloyed powder quality; Flexibilizing agent generally adopts polyisobutene (trade mark B200), and addition is 0 ~ 10% of a quaternary ammonium type anion exchange alloyed powder quality; When less input as polymerization single polymerization monomer solution (for example with the mass ratio of Kynoar less than 0.4), can not add described flexibilizing agent; As polymerization single polymerization monomer solution input (for example with the mass ratio of Kynoar greater than 0.8) more for a long time, can add described flexibilizing agent to improve the pliability of dry film.Antioxidant can adopt pentaerythritol ester, and addition is 0.01 ~ 0.1% of a quaternary ammonium type anion exchange alloyed powder quality; Releasing agent can adopt calcium stearate, organosilicon or high melting point paraffin, and addition is 0.1 ~ 1% of a quaternary ammonium type anion exchange alloyed powder quality.The banburying temperature is 160 ~ 210 ℃, and the banburying time is 15 ~ 60 minutes.Mixing temperature is 150 ~ 200 ℃, and opening the refining time is 10 ~ 30 minutes.By adjusting the distance between mill two rollers, the thickness of film is 0.3 ~ 0.6 millimeter before the control hot pressing.Hot pressing temperature is 160 ~ 210 ℃, and pressure is 20 ~ 60 MPas, and hot pressing time is 15 ~ 60 minutes.After the hot pressing, the thickness of film is 0.2 ~ 0.5 millimeter.Film is taken out, and individual curls, and with the polybag encapsulation, charges into rare salting liquid (being generally the sodium chloride solution of mass concentration 5%) in the bag, promptly makes polystyrene/Kynoar quaternary ammonium type anion exchange alloy film that hygrometric state is preserved.
Below by the specific embodiment the present invention is further explained explanation.
Embodiment 1
1) in 500 liters of glassed steel reaction vessels, add 50 kilograms of Kynoar powder (trade mark DF-1, limit company is liked to be rich in Shanghai three), pour 200 liters of dimethylacetylamides, be heated to 90 ℃, stirred 2 hours, form and dissolve Kynoar solution completely.Among 50 liters of glass reaction stills, add 36 kilograms of styrene, 4 kilograms of divinylbenzenes (purity is 63.2%, and Shangyu pul resin Co., Ltd provides) and 2.4 kilograms of benzoyl peroxides, stirred 1 hour under the room temperature, get the styrene polymerization monomer solution.With styrene monomer solution, slowly join by head tank in the Kynoar solution of quick stirring, within 30 minutes, add, continue again afterwards to stir 30 minutes, obtain uniform styrene/Kynoar composite solution.
2) subsequently, composite solution is emitted from 500 liters of glassed steel reaction vessels,, tighten lid to adding a cover (400 liters of volumes) in the stainless steel aggregation container, by the chuck heating that heats up, 65 ℃ of polymerizations 2 hours, 75 ℃ of polymerizations 2 hours, 85 ℃ of polymerizations 10 hours.Unload lid, polystyrene/Kynoar jelly that polymerization is obtained takes out, and is transferred in the loading hopper of double screw extruder in batches; extrude, through 70 ~ 80 ℃ of hot water sedimentation basins, wire drawing; be cut into 3 millimeters following length with pelleter, obtain polystyrene/polyvinylidene fluoride alloy particle.Alloying pellet is placed the fluid bed hot-air drier, and 105 ℃ of oven dry are crushed to below 0.5 millimeter with mechanical crusher then, obtain polystyrene/polyvinylidene fluoride alloy powder.
3) above-mentioned powder (about 83 kilograms) is put in 500 liters of glassed steel reaction vessels, added 400 liters of industrial chloromethyl ethers and 80 kilograms of anhydrous zinc chlorides, stirred swelling 1 hour under the room temperature.Be warming up to 43 ~ 45 ℃ of reactions 10 hours then, be cooled to rapidly below 25 ℃, drain reactant liquor by bottom screen.Add the dimethoxym ethane agitator treating 3 times, add 400 liters at every turn, stir and drain after 1 hour.
4) adding concentration is 400 liters of 20% trimethylamine aqueous solutions, adds 25 liters of 4% liquid caustic soda, regulates more than the pH to 12, and the control temperature is 42 ~ 45 ℃, stirring reaction 8 hours.By the filter screen of bottom the amination liquid of remnants is extracted out afterwards; Add a large amount of clear water, wash to pH approaching neutral; Add 300 mass per liter concentration again and be 4% dilute hydrochloric acid solution, stirred 2 hours, change into the chlorine type by the hydrogen-oxygen type.Add again clear water wash to pH greater than 6.0, be discharged in the centrifuge, dry, place 105 ℃ of oven dry in the fluid bed hot-air drier, promptly get quaternary ammonium type anion and exchange alloyed powder (about 91 kilograms).
5) get 50 kilograms of above-mentioned quaternary ammonium type anion exchange alloyed powders, with 40 gram pentaerythritol esters, 200 gram phthalocyanine blues, 250 gram silicone releases, 2.5 kilograms of polyisobutene (trade mark B200, BASF AG) premix 5 minutes in high-speed mixer, send in the banbury, 180 ℃ of left and right sides banburyings 30 minutes, discharging.The banburying product is sent in the mill, opened refining 20 minutes about 165 ℃, discharging is after two-roll calendar is pulled out diaphragm, and by two roll spacings from controlling diaphragm thickness.Send into hydraulic press, in hot pressing about 175 ℃, under gauge pressure 40 MPas 30 minutes.Take out the cooling back fast, promptly makes described polystyrene/Kynoar quaternary ammonium type anion exchange alloy film.
According to the described assay method of national standard (HY/T 034.2-1994), it is as follows to measure prepared anion exchange alloy film performance parameter: the film average thickness is 0.31 millimeter, moisture content is 39.7%, and exchange capacity is 1.72 mmol/g dry films, and face resistance is 5.3 Ω ﹒ cm
2, it is 96.2% that ion is selected transmitance, the film burst strength is 0.42 MPa.
Embodiment 2
With 46 kilograms of styrene, 4 kilograms of divinylbenzenes (content is 80.5%) and 3 kilograms of azodiisobutyronitriles, preparation styrene monomer solution replaces the styrene monomer solution among the embodiment 1, and remaining material proportion and method of operating are constant.According to the method identical, make described polystyrene/Kynoar quaternary ammonium type anion exchange alloy film with embodiment 1.
According to the described assay method of national standard (HY/T 034.2-1994), it is as follows to measure prepared anion exchange alloy film performance parameter: the film average thickness is 0.32 millimeter, moisture content is 50.7%, and exchange capacity is 2.21 mmol/g dry films, and face resistance is 3.7 Ω ﹒ cm
2, it is 96.2% that ion is selected transmitance, the film burst strength is 0.43 MPa.
The foregoing description is to be used for explaining and to illustrate of the present invention, rather than limits the invention.Within the protection domain of spirit of the present invention and claim, any modification and change to the present invention has done all fall within protection scope of the present invention.
Claims (7)
1. the preparation method of a polystyrene/Kynoar quaternary ammonium type anion exchange alloy film is characterized in that this method may further comprise the steps:
(1) monomer solution of earlier styrene, crosslinking agent and initator being formed by quality proportioning 100:2 ~ 10:1 ~ 10, slowly be added drop-wise among the Kynoar solution, the quality proportioning of monomer solution and Kynoar solution is 5 ~ 40:100, fully mix, obtain uniform styrene/Kynoar composite solution;
(2) composite solution is heated to 65 ~ 105 ℃, polymerization obtains polystyrene/Kynoar jelly after about 5 ~ 20 hours; With jelly extrude, water sedimentation curing, wire drawing, granulation, obtain polystyrene/polyvinylidene fluoride alloy particle; With the alloying pellet oven dry, pulverize, obtain polystyrene/polyvinylidene fluoride alloy powder;
(3) add chloromethyl ether and anhydrous zinc chloride, implemented chloromethylation about 4 ~ 12 hours at 35 ~ 50 ℃ of following p-poly-phenyl ethene/polyvinylidene fluoride alloy powder, the quality proportioning of chloromethyl ether, anhydrous zinc chloride and polystyrene/polyvinylidene fluoride alloy powder is 200 ~ 800:60 ~ 120:100; With chloromethylation products for several times, make the chloromethylation alloyed powder with the dimethoxym ethane washing;
(4) add amination solution, under 25 ~ 50 ℃ the chloromethylation alloyed powder was implemented aminating reaction about 2 ~ 12 hours, the use amount of amination solution is 250% ~ 800% of a chloromethylation alloyed powder quality; Washing, the dry quaternary ammonium type anion exchange alloyed powder that promptly makes afterwards;
(5) quaternary ammonium type anion is exchanged alloyed powder and drop into banbury, add auxiliary materials such as pigment, flexibilizing agent, antioxidant and releasing agent, 160 ~ 210 ℃ of following banburyings 15 ~ 60 minutes, discharging; Send into mill then, under 150 ~ 200 ℃, open refining 10 ~ 30 minutes, pulling-on piece; Send in the hot press, hot pressing is 15 ~ 60 minutes under 160 ~ 210 ℃, 20 ~ 60 MPas again, and cooling makes described polystyrene/Kynoar quaternary ammonium type anion exchange alloy film.
2. the preparation method of polystyrene according to claim 1/Kynoar quaternary ammonium type anion exchange alloy film is characterized in that the crosslinking agent that is adopted in the described step (1) is a divinylbenzene.
3. the preparation method of polystyrene according to claim 1/Kynoar quaternary ammonium type anion exchange alloy film, it is characterized in that the organic solvent that is adopted in the described step (1) is dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide or N-methyl pyrrolidone; Can be wherein a kind of, also can be two or more mixture with any mass ratio.
4. the preparation method of polystyrene according to claim 1/Kynoar quaternary ammonium type anion exchange alloy film is characterized in that in the described step (1), described initator is benzoyl peroxide or azodiisobutyronitrile.
5. the preparation method of polystyrene according to claim 1/Kynoar quaternary ammonium type anion exchange alloy film is characterized in that the amination solution in the described step (4) is trimethylamine aqueous solution, and mass percent concentration is 10% ~ 30%.
6. the preparation method of polystyrene according to claim 1/Kynoar quaternary ammonium type anion exchange alloy film, it is characterized in that, flexibilizing agent in the described step (5) is a polyisobutene, and addition is and 0 ~ 10% of quaternary ammonium type anion exchange alloyed powder quality.
7. the preparation method of polystyrene according to claim 1/Kynoar quaternary ammonium type anion exchange alloy film is characterized in that build is 0.2 ~ 0.5 millimeter.
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| CN106512761A (en) * | 2015-09-09 | 2017-03-22 | 杭州华恒膜技术有限公司 | Manufacture method of semihomogeneous anion-exchange membrane |
| CN108080039A (en) * | 2017-07-11 | 2018-05-29 | 衢州蓝然新材料有限公司 | A kind of manufacturing method of alcohol-soluble quaternary amine type or tertiary amine-type anion exchange resin |
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| CN112452160A (en) * | 2020-11-24 | 2021-03-09 | 南通市赛孚环保科技有限公司 | Preparation method of heterogeneous anion exchange membrane |
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Application publication date: 20130731 |