阅读说明：本技术 一种均相阴离子交换膜的制备方法 (A kind of preparation method of homogeneous-phase anion exchange film ) 是由 王建友 刘颖 于 2019-08-13 设计创作，主要内容包括：本发明涉及阴离子交换膜技术领域,公开了一种均相阴离子交换膜的制备方法,该方法包括以下步骤：以聚砜为基质材料,通过三甲基氯硅烷、多聚甲醛和无水四氯化锡体系对其进行氯甲基化,制得高取代度的氯甲基化聚砜；将氯甲基化聚砜溶于N-甲基吡咯烷酮中,加入三乙胺对其进行季胺化,即得季胺化聚砜；将季胺化聚砜的铸膜液于玻璃板上,流延成型后,置于真空烘箱中蒸发溶剂,即制得聚砜基阴离子交换膜。本发明的优点是在25℃下反应24h,即可制得氯甲基化程度高达1.95的氯甲基化聚砜。同时,本发明中所制备的阴离子交换膜离子交换容量可高达1.85毫克当量/克干膜,面电阻约为6.5Ω/cm2,迁移数97％。(The present invention relates to anion exchange technical field of membrane, disclose a kind of preparation method of homogeneous-phase anion exchange film, method includes the following steps: using polysulfones as host material, chloromethylation is carried out to it by trim,ethylchlorosilane, paraformaldehyde and anhydrous stannic chloride system, the chloromethyl polysulphone of high substituted degree is made；Chloromethyl polysulphone is dissolved in N-Methyl pyrrolidone, addition triethylamine carries out it quaternary ammoniated to get quaternary ammoniated polysulfones；By the casting solution of quaternary ammoniated polysulfones on glass plate, after tape casting, it is placed in vacuum drying oven evaporation solvent, obtains polysulfones base anion-exchange membrane.It can be prepared by the chloromethyl polysulphone that chloromethylation degree is up to 1.95 for 24 hours it is an advantage of the invention that reacting at 25 DEG C.Meanwhile prepared anion-exchange membrane ion exchange capacity may be up to 1.85 milliequivalents/gram dry film in the present invention, surface resistance is about 6.5 Ω/cm2, transport number 97%.)

1. a kind of preparation method of homogeneous-phase anion exchange film, which is characterized in that specifically includes the following steps:

S1, it is firstly added polysulfones into reaction flask, and is dissolved using solvent, trim,ethylchlorosilane, poly is being added later Formaldehyde and anhydrous stannic chloride carry out chloromethylation to the polysulfones, obtain chloromethyl polysulphone；

During the chloromethylation, 25-40 DEG C of reaction temperature, reaction time 18-24h, anhydrous stannic chloride dosage is 1- 2.5mL；

S2, the chloromethyl polysulphone is dissolved in N-Methyl pyrrolidone, triethylamine is then added and carries out quaternary ammonium reaction, water Bath heating, reaction temperature are 35 DEG C -40 DEG C, and reaction time 20-24 hour obtains quaternary ammoniated polysulfones；

Then S3, the quaternary ammoniated polysulfones for obtaining the step S2 pass through evaporation solvent system in surface of plate glass tape casting Standby anion-exchange membrane, 80-120 DEG C of evaporating temperature, time 18-24 hour.

2. a kind of preparation method of homogeneous-phase anion exchange film according to claim 1, which is characterized in that the step S1 In, polysulfones: paraformaldehyde: trim,ethylchlorosilane: anhydrous stannic chloride is that 1: 10: 10: 2 progress are anti-according to the ratio between amount of substance It answers, reaction temperature is 25 DEG C, and the reaction time is for 24 hours.

3. a kind of preparation method of homogeneous-phase anion exchange film according to claim 1, which is characterized in that the step S1 In, charging sequence are as follows: paraformaldehyde, trim,ethylchlorosilane, anhydrous stannic chloride.

4. a kind of preparation method of homogeneous-phase anion exchange film according to claim 1, which is characterized in that the step S1 In, 1-2.5mL anhydrous stannic chloride is dissolved in 20-50mL methylene chloride using constant pressure funnel, is then added dropwise to In reaction vessel.

5. a kind of preparation method of homogeneous-phase anion exchange film according to claim 1, which is characterized in that described anhydrous four Stannic chloride dosage is 2.5mL.

6. a kind of preparation method of homogeneous-phase anion exchange film according to claim 1, which is characterized in that the step S1 After reaction, product is poured into the beaker for filling dehydrated alcohol, there is white precipitate precipitation, filtered, product dehydrated alcohol Be respectively washed repeatedly with deionized water, be placed in vacuum drying oven later, freeze-day with constant temperature to get arrive chloromethyl polysulphone.

7. a kind of preparation method of homogeneous-phase anion exchange film according to claim 1, which is characterized in that the step S3 Detailed process be casting solution to be hung with knifing machine after film is made on a glass, stood in vacuum drying oven, it is molten to volatilize Agent is subsequently placed in deionized water, and film will fall off from glass plate automatically.

8. a kind of preparation method of homogeneous-phase anion exchange film according to claim 7, which is characterized in that the step S3 In, vacuum drying temperature is 40 DEG C -80 DEG C, vacuum drying time 12-48h.

9. a kind of preparation method of homogeneous-phase anion exchange film according to claim 7, which is characterized in that by the step Film obtained in S3, is soaked in KOH solution, then is washed with deionized repeatedly to get to colorless and transparent polysulfones anion Exchange membrane.

10. a kind of preparation method of homogeneous-phase anion exchange film according to claim 8, which is characterized in that the KOH is molten The concentration of liquid is 0.1molL^-1, soaking time 48h.

Technical field

The present invention relates to anion exchange technical field of membrane, and in particular to a kind of preparation side of homogeneous-phase anion exchange film Method.

Background technique

Anion-exchange membrane is widely used in alkaline fuel cell, water process, the fields such as ion isolation.Therefore, domestic It is growing for the demand of the anion-exchange membrane of efficient stable outside.Polysulfones (PSF) is a kind of thermoplasticity being widely used High molecular material, the degree of polymerization is up to up to a million.Due to containing phenyl ring and sulfuryl on main chain, there is the aromatic compound good Chemical stability, thermoplasticity and mechanical performance.Therefore, polysulfones base anion-exchange membrane receives the favor of researcher.

The method for preparing polysulfones anion-exchange membrane most commonly utilizes the electrophilic substitution reaction on aromatic ring to polymer It carries out halomethylation reaction (chloromethylation, bromomethylation etc.), then by quaternized and basification, and then obtains anion Exchange membrane.Therefore, chloromethylation process is to prepare the most basic and most important step of anion-exchange membrane, chloromethylation degree Determine the ion-exchange capacity of anion-exchange membrane.Common chloromethylation process is divided into direct chloromethylation and indirect chloromethane Two kinds of baseization.Direct chloromethylation utilizes nucleophilic substitution, directly uses chloromethylation reagents and catalyst, makes on phenyl ring It directly is connected into chloromethyl, then quaternized introducing quaternary ammonium group again, finally alkalizes, prepare anion-exchange membrane.

It is commonly used in research process and efficient chloromethylation reagents is chloromethyl ether and bischlormethyl ether, their activity are higher, The reaction time can be shortened, improve chloromethylation degree, still, since chloromethyl ether is volatile, there is strong carcinogenic toxicity, In It is used by limitation within 1970.In recent years, researcher starts to carry out chlorine to polysulfones using the trim,ethylchlorosilane without carcinogenic toxicity Methylation, by the optimization of parameter and technique to reaction process, has obtained chloromethyl polysulphone.But compared with chloromethyl ether, though Right trim,ethylchlorosilane is without carcinogenic toxicity, but the reaction time is longer, generally requires 72 hours or more, meanwhile, it needs strictly to control Reaction condition processed is easy to cause the generation of the side reactions such as gel in reaction process, leads to obtained chloromethyl polysulphone Chloromethyl degree is not high, and yield is relatively low, and the repeatability of experiment is relatively low.Therefore, it designs a kind of using the chlorine without carcinogenic toxicity Methylating reagent realizes the system of the anion-exchange membrane of the chloromethyl polysulphone based on high substituted degree under mild experiment condition Preparation Method has important economic value and realistic meaning.

Summary of the invention

In view of the deficiencies of the prior art, the present invention intends to provide a kind of preparation of homogeneous-phase anion exchange film Method, this method may be implemented under relatively mild experiment condition, using the chloromethylation reagents and solvent of no carcinogenic toxicity, Prepare the chloromethyl polysulphone of Perchloromethyl degree.

To achieve the goals above, the invention provides the following technical scheme:

A kind of preparation method of homogeneous-phase anion exchange film, specifically includes the following steps:

S1, be firstly added polysulfones into reaction flask, and dissolved using solvent, later be added trim,ethylchlorosilane, Paraformaldehyde and anhydrous stannic chloride carry out chloromethylation to the polysulfones, obtain chloromethyl polysulphone；

During the chloromethylation, 25-40 DEG C of reaction temperature, reaction time 18-24h, anhydrous stannic chloride dosage is 1-2.5mL；

S2, the chloromethyl polysulphone is dissolved in N-Methyl pyrrolidone, it is quaternary ammoniated anti-that triethylamine progress is then added It answers, heating water bath, reaction temperature is 35 DEG C -40 DEG C, in reaction time 20-24 hour, quaternary ammoniated polysulfones is obtained, used in reaction The mass concentration of chloromethyl polysulphone is 15%-25%, and the mass concentration of triethylamine is 6%-12%；

S3, by the quaternary ammoniated polysulfones in surface of plate glass tape casting, then by evaporate solvent prepare anion Exchange membrane, 80-120 DEG C of evaporating temperature, time 18-24 hour.

In the present invention, it is preferred to, in the step S1, polysulfones: paraformaldehyde: trim,ethylchlorosilane: anhydrous four chlorination Tin is that 1:10:10:2 is reacted according to the ratio between amount of substance, 25-40 DEG C of reaction temperature, reaction time 18-24h, anhydrous tetrachloro Change tin dosage 1-2.5mL.

In the present invention, it is preferred to, in the step S1, reaction temperature is 25 DEG C, reaction time 124h, anhydrous tetrachloro Change tin dosage is 2.5mL.

In the present invention, it is preferred to, in the step S1, charging sequence are as follows: paraformaldehyde, trim,ethylchlorosilane, anhydrous Tin tetrachloride is generated without gel in reaction process, and the chloromethylation degree of chloromethyl polysulphone obtained is up to 1.95.

In the present invention, it is preferred to, in the step S1, using constant pressure funnel by 1-2.5mL anhydrous stannic chloride It is dissolved in 20-50mL methylene chloride, is then added dropwise in reaction vessel.

In the present invention, it is preferred to, the anhydrous stannic chloride dosage is 2.5mL.

In the present invention, it is preferred to, product after reaction, is poured into the beaker for filling dehydrated alcohol by the step S1 In, have white precipitate precipitation, filter, product dehydrated alcohol and deionized water be respectively washed repeatedly, be placed on vacuum drying oven In, freeze-day with constant temperature to get arrive chloromethyl polysulphone.

In the present invention, it is preferred to, the detailed process of the step S3 is to be hung casting solution on a glass with knifing machine It after film is made, stands in vacuum drying oven, with solvent flashing, is subsequently placed in deionized water, film will take off from glass plate automatically It falls, film is soaked in 0.1molL^-1KOH solution in 48h, then be washed with deionized repeatedly to get to colorless and transparent poly- Sulfone anion-exchange membrane.

In the present invention, it is preferred to, in the step S3, vacuum drying temperature is 40 DEG C -80 DEG C, vacuum drying time For 12-48h.

In the present invention, it is preferred to, the chloromethylation degree of the chloromethyl polysulphone is up to 1.25-1.95, yield Up to 55-80%

Compared with prior art, the beneficial effects of the present invention are:

Chloromethylation reagents and solvent of the use without carcinogenic toxicity of the invention are realized high under mild experiment condition The preparation of the anion-exchange membrane of functionalization degree.At 25 DEG C, the reaction time for 24 hours, the chloromethylation degree of polysulfones up to 1.95, 1.85 milliequivalents/gram dry film, face are up to using the ion exchange capacity of anion-exchange membrane made from the chloromethyl polysulphone About 6.5 Ω cm of resistance², moisture content 28.5%, transport number 97%.

Detailed description of the invention

Fig. 1 is the preparation process figure of chloromethyl polysulphone in present embodiment.

Fig. 2 is the material object of the anion-exchange membrane of chloromethyl polysulphone in present embodiment.

Fig. 3 is the gelatin phenomenon in present embodiment during polysulfones chloromethylation.

Main element symbol description in attached drawing: 1- chloromethyl polysulphone, the anion-exchange membrane of 2- chloromethyl polysulphone, 3- Gel.

Specific embodiment

Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.

It should be noted that it can be directly on another component when component is referred to as " being fixed on " another component Or there may also be components placed in the middle.When a component is considered as " connection " another component, it, which can be, is directly connected to To another component or it may be simultaneously present component placed in the middle.When a component is considered as " being set to " another component, it It can be and be set up directly on another component or may be simultaneously present component placed in the middle.Term as used herein is " vertical ", " horizontal ", "left", "right" and similar statement for illustrative purposes only.

Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases Any and all combinations of the listed item of pass.