CN107789995A - A kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation method and application - Google Patents

A kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation method and application Download PDF

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CN107789995A
CN107789995A CN201711007030.5A CN201711007030A CN107789995A CN 107789995 A CN107789995 A CN 107789995A CN 201711007030 A CN201711007030 A CN 201711007030A CN 107789995 A CN107789995 A CN 107789995A
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ether
polyaniline
ketone
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halloysite nanotubes
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王永洪
张新儒
侯蒙杰
刘成岑
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Taiyuan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
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    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract

The invention discloses a kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation method and application, belong to UF membrane field.The mixed substrate membrane containing nano-grade molecular sieve is made up of sulfonated polyether-ether-ketone matrix and the halloysite nanotubes of composite Polyaniline-modified, wherein, the ratio of halloysite nanotubes and polyaniline is 1 in composite：（1‑3）, the halloysite nanotubes of Polyaniline-modified and the mass ratio of sulfonated polyether-ether-ketone are 0.1 ~ 5:95~99.9.Its preparation method includes：In the halloysite nanotubes aqueous dispersion liquid of purifying, the home position polymerization reaction of polyaniline is carried out, obtains the halloysite nanotubes of Polyaniline-modified；Polyaniline-modified halloysite nanotubes obtain casting solution with sulfonated polyether-ether-ketone using solution blended process, and the mixed substrate membrane containing nano-grade molecular sieve is made through the tape casting.Preparation process simplicity of the present invention is controllable, and obtained mixed substrate membrane containing nano-grade molecular sieve is applied to CO2/N2Gas separates, and has higher selectivity and permeability.

Description

A kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified And its preparation method and application
Technical field
The present invention relates to a kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation Methods and applications, belong to technical field of membrane separation.
Background technology
Organic and inorganic mixed substrate membrane containing nano-grade molecular sieve has mixing due to the advantages of having high molecular polymer and inorganic material film concurrently Derivative new advantage afterwards, progressively as film and the forward position in UF membrane field.The combination side of multiple polymers matrix and inorganic material Formula causes mixed substrate membrane containing nano-grade molecular sieve to have very big development potentiality and space in terms of preparation is designed.So far, mixed-matrix film preparation Method mainly has physical blending process, sol-gal process and biomimetic mineralization method.Traditional physical blending process prepares organic and inorganic mixing Matrix membrane is directly to be distributed to the inorganic material of micron or nano-scale in polymer matrix in a manner of physical blending.The party Method is simple and easy to do, controllability and versatile；But the restriction of some non-ideal factors occurs in operation, such as due to Scattered inequality caused by inorganic material nature and addition, phenomena such as particle agglomeration.Other polymer substrate and nothing The interface problem of machine material also governs the lifting of mixed-matrix film properties.It is uniformly dispersed to prepare, good interface compatibility Organic and inorganic mixed substrate membrane containing nano-grade molecular sieve, some researchers begin to try to develop some new inorganic nano membrane materials, still The exploitation of new inorganic material is often faced with the problem in terms of some preparations, such as raw material costliness, preparation process complexity etc.. And the surface progress that other researchers then start to inorganic material is organically-modified, after some organic groups are introduced, The interface compatibility between inorganic particulate and macromolecule is not only increased, the inorganic material of functionalization can also play to object gas Certain Selective Separation effect, to improve permeability of the membrane and separating property, promotes the development of membrane technology.
In the gas separation process of reality, it will usually there is the presence of some vapor, and most of membrane material is water-fast Stability is simultaneously bad, and which greatly limits the selection of gas separation membrane material.In organic and inorganic mixed substrate membrane containing nano-grade molecular sieve The water-resistant stability of high-molecular matrix material is most important for its actual prospects for commercial application；In addition, in shape existing for water Under state, amino carrier can be preferably played to CO2Faciliated diffusion.
The sulfonated polyether-ether-ketone (SPEEK) obtained after polyether-ether-ketone (PEEK) Direct Sulfonation, still with polyether-ether-ketone Good thermal stability and mechanical strength, and the introducing of sulfonic acid group causes SPEEK to have good film forming, workability. It is good that the organic and inorganic mixed substrate membrane containing nano-grade molecular sieve of the halloysite nanotubes of sulfonated polyether-ether-ketone/Polyaniline-modified has had SPEEK films concurrently Pliability, film forming and workability, and the feature such as the high temperature resistant of halloysite nanotubes, corrosion-resistant and high mechanical properties, and incite somebody to action Halloysite nanotubes can not only improve two-phase interface compatibility after polyaniline-modified, improve boundary defect, moreover it is possible to improve film Gas separating property.
The hollow tubular nanostructured of halloysite nanotubes provides the better channels of size adjustable, gas for the transmission of molecule Body can obtain high flux when passing through halloysite nanotubes.Molecular dynamics model in recent years shows, because to not Congener molecule Preferential adsorption is different, and nanotube shows certain selectivity to mixture.Halloysite nanotubes are one The nontoxic natural material of kind, mechanical property is good, unique structure, has compared with high length-diameter ratio；And inside and outside tube wall and defect Some oh groups are contained at place, are easy to functional modification, therefore caliber can be adjusted on nanoscale, have unique separation property Can, it is a kind of excellent inorganic nano material.Most importantly, halloysite nanotubes are easily obtained and cheap, and this makes Obtain it has more preferable prospect compared with other inorganic nano materials in actual applications.The amino group contained on polyaniline molecule chain With sour gas CO2Between there is soda acid affinity interaction, aniline is modified inside and outside halloysite nanotubes by situ aggregation method Between wall and tube layer.The halloysite nanotubes of Polyaniline-modified in mixed substrate membrane containing nano-grade molecular sieve are not only CO2Gas transmission provides The high-speed transfer passage of multilayer tubular, moreover it is possible to improve polymer matrix and the interface compatibility of inorganic material.Up to the present, sulphur Change the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of polyether-ether-ketone/Polyaniline-modified and use it for gas separation and be showed no document report Road.
The content of the invention
The present invention is intended to provide a kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its Preparation method and application.Preparation method provided by the invention is simple to operate, green, and preparation-obtained gas separation membrane can For separating CO2/N2Mixed gas, there is good separating effect.
The invention provides a kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified, the sulphur It is 5-60 microns to change polyether-ether-ketone/Polyaniline-modified halloysite nanotubes mixed-matrix film thickness, by sulfonated polyether-ether-ketone matrix Formed with the halloysite nanotubes of composite Polyaniline-modified, wherein, halloysite nanotubes and polyaniline in composite Quality proportioning be 1：（1-3）, the halloysite nanotubes of Polyaniline-modified and the mass ratio of sulfonated polyether-ether-ketone are 0.1 ~ 5:95 ~99.9.The sulfonation degree of the sulfonated polyether-ether-ketone is 50-70%.
The invention provides the preparation method of sulfonated polyether-ether-ketone/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve, Comprise the following steps：
Step 1, first, purified halloysite nanotubes is distributed in deionized water, it is 0.5%- to be configured to mass fraction 2% aqueous solution, it is agitated to be divided after ultrasonic 10-120min (ultrasonic frequency range 20-51KHz, 25-70 DEG C of ultrasonic temperature) Dissipate uniform galapectite pipe suspension liquid of aqueous phase A；It is according to aniline and halloysite nanotubes mass ratio（1-3）：1 ratio, is weighed Aniline and concentrated hydrochloric acid are added in deionized water, are prepared in the hydrochloric acid solution B as the 2mol/L containing aniline；By the molten of same volume After liquid A and solution B mixing, solution C is obtained, wherein, the mass fraction of halloysite nanotubes is 0.25%-1% in solution C, aniline Mass fraction be 0.25%-3%；Solution C is added in three-necked flask, keeping temperature is 2-10 DEG C, lasting stirring, makes its point Dissipate uniform；
Step 2, according to the mol ratio of ammonium persulfate and aniline it is（0.8-1.5）：1, take solid ammonium persulfate to be dissolved into 1mol/L Hydrochloric acid solution D in, measure the solution D with solution C same volume, and be slowly added into foregoing solution C；It is added dropwise Afterwards, keeping temperature is 2-10 DEG C, it is reacted 4-6h under conditions of no external interference.Reaction is finished, and mixed liquor is spent Ionized water repeatedly filter, wash after, obtain dirty-green pureed solid, by it in 35-50 DEG C of dry 36-72h, obtained pure The halloysite nanotubes composite of net Polyaniline-modified；
Step 3, in temperature it is 25-35 DEG C, under conditions of lasting stirring, the sulfonated polyether-ether-ketone that sulfonation degree is 50-70% is added Enter into N,N-dimethylformamide solvent to be configured to the sulfonated polyether-ether-ketone solution that mass concentration is 5-15%；
Step 4, the galapectite of Polyaniline-modified is received as made from the sulfonated polyether-ether-ketone in sulfonated polyether-ether-ketone solution with step 2 Mitron mass ratio is 95 ~ 99.9：0.1 ~ 5, it is molten that the halloysite nanotubes of Polyaniline-modified are scattered in DMF Agent is configured to the suspension that mass concentration is 0.1-0.5%, ultrasonic 4-12h, and the sulfonated polyether-ether-ketone added obtained by step 3 is molten In liquid, 24-48h is stirred, stands 2-6h deaerations, obtains the halloysite nanotubes casting solution of sulfonated polyether-ether-ketone/Polyaniline-modified；
Step 5, the halloysite nanotubes casting solution for the sulfonated polyether-ether-ketone/Polyaniline-modified for obtaining step 4 are poured over glass Casting film-forming in mould, after 50-70 DEG C of dry 12-24 h of temperature, then in 80-120 DEG C of temperature heat treatment 4-12 h, obtain sulphur Change the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of polyether-ether-ketone/Polyaniline-modified.
In step 1 and step 4, ultrasonic detailed process is：Ultrasonic frequency range 20-51KHz, 25-70 DEG C of ultrasonic temperature；
Solution D in step 2 is slowly dropped in solution C, must strictly control the speed being added dropwise dropwise；General control rate of addition For 0.5-5mL/min.
Heat treatment temperature is 80-120 DEG C in step 5, and the time of heat treatment is 4-12h, must heating and cooling in heat treatment process Speed.Heating and rate of temperature fall all should must ensure heat treatment time in the range of 0.5-2 DEG C/min, after reaching preset temperature.
The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified of the present invention is in CO2/N2Point Application from.Concrete application operating process is as follows：Gas permeability test device is built by this laboratory, in experiment test Film to be tested is fixed in membrane cisterna, upstream side pressure scope is 0.1MPa-2.0MPa, and gas permeation test temperature is 20- 60 DEG C, the humidity of feed side gas is regulated and controled by the humidifying pot of temperature-controllable；He or H is used in the downstream of membrane cavity2As Purge gass are purged, and purge gass flow control is detected using gas-chromatography to downstream component in 2-80sccm.
In above-mentioned application, obtained film thickness is separated, containing 0.9% composite polyphenyl for gas in 5-60 microns The mixed substrate membrane containing nano-grade molecular sieve of amine-modified halloysite nanotubes possesses high CO2Permeation flux and CO2/N2It is selective, surveyed under hygrometric state condition Examination, gaseous mixture test CO2Permeation flux reaches 1294Barrer（1Barrer=10-10cm3(STP)cm/(cm2s cmHg)）, CO2/ N2Selectivity is 83.
Beneficial effects of the present invention：
（1）The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve preparation process simplicity of sulfonated polyether-ether-ketone/Polyaniline-modified is controllable, raw material valency Honest and clean to be easy to get, modified condition is gentle, and obtained mixed substrate membrane containing nano-grade molecular sieve is used for CO2/N2The gas separation of binary mixture.
（2）The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified improves interface compatibility, structure CO is built2High-speed transfer passage, promote CO2Transmission, there is excellent gas separating property.
（3）The mixed substrate membrane containing nano-grade molecular sieve has higher CO2/N2Permeability and selectivity, divide compared with pure sulfonated polyether-ether-ketone film 255% and 210% are not improved.
（4）Add machine of the sulfonated polyether-ether-ketone film than pure sulfonated polyether-ether-ketone film of the halloysite nanotubes of Polyaniline-modified Tool performance improves, anti-pressure ability enhancing.
（5）Halloysite nanotubes wide material sources, cost are low, are advantageous to the galapectite of sulfonated polyether-ether-ketone/Polyaniline-modified The industrialization of nanotube mixed substrate membrane containing nano-grade molecular sieve, there is good prospects for commercial application.
Brief description of the drawings
Fig. 1 is the section partial sweep electron microscope picture of pure sulfonated polyether-ether-ketone homogeneous membrane made from comparative example 1；
Fig. 2 is the section office of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified made from embodiment 1 Portion's scanning electron microscope diagram；
Fig. 3 is the section office of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified made from embodiment 2 Portion's scanning electron microscope diagram；
Fig. 4 is the section office of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified made from embodiment 3 Portion's scanning electron microscope diagram；
Fig. 5 is the section office of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified made from embodiment 4 Portion's scanning electron microscope diagram.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Comparative example 1：Pure sulfonated polyether-ether-ketone homogeneous membrane is prepared, the film thickness is 40 microns, the sulfonated polyether-ether-ketone Sulfonation degree is 60%.
Weigh 0.64g sulfonated polyether-ether-ketones to be added in 8g DMF solvent, magnetic force stirs at 25 DEG C 24h is mixed, obtains sulfonated polyether-ether-ketone solution homogeneously, the impurity of some indissolubles is fallen using screen filtration, 2h deaerations is stood, is poured into Clean smooth glass（14cm×14cm）In mould, the glass mold for having toppled over casting solution is stood into 10min in the environment, then It is transferred in 60 DEG C of baking oven and dries 12h, be then heat-treated 4h at 100 DEG C, it is equal obtains the sulfonated polyether-ether-ketone that thickness is 40 microns Plasma membrane；The pure sulfonated polyether-ether-ketone homogeneous membrane is subjected to CO under the conditions of 25 DEG C, 0.1MPa2/N2The permeance property of binary gas Test, CO2Infiltration coefficient is respectively 364Barrer, CO2/N2Selectivity is 27.
Embodiment 1：
The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified is by sulfonated polyether-ether-ketone matrix and composite wood Expect that the halloysite nanotubes of Polyaniline-modified are formed, its thickness is 40 microns, wherein, sulfonated polyether-ether-ketone and Polyaniline-modified Halloysite nanotubes mass ratio is 99.7:0.3, the sulfonation degree of the sulfonated polyether-ether-ketone is 60%.Prepare Polyaniline-modified Halloysite nanotubes：0.5g HNTs is dispersed in 100 ml deionized water, in frequency 20KHz ultrasonic cleaner It is agitated to obtain finely dispersed galapectite pipe suspension liquid of aqueous phase A after ultrasonic 60min；1g aniline is taken to be added to 100ml's In 2mol/L HCl solution, solution B is obtained；Solution A is mixed with solution B, obtains homogeneous suspension liquid C.Suspension C is added Into three-necked flask, keeping temperature is 5 DEG C of conditions, lasting stirring.2.5g ammonium persulfate is dissolved into 200ml HCl （1mol/L）Solution D is obtained in solution, and it is slowly added to dropwise（Rate of addition is 2mL/min）To foregoing mixed solution In C；After being added dropwise, keeping temperature makes it react 4 h under conditions of not interfering with.After completion of the reaction, mixed liquor is spent Ionized water repeatedly filter, wash after, obtain dirty-green pureed solid, by it in 40 DEG C of dry 72 h, obtained pure The halloysite nanotubes solid powder of Polyaniline-modified.
Weigh 0.64g sulfonated polyether-ether-ketones to be added in 6g DMF solvent, magnetic force stirs at 25 DEG C 12h is mixed, until macromolecule all dissolves, obtains sulfonated polyether-ether-ketone solution homogeneously.By 0.00192g polyphenyl obtained above Amine-modified halloysite nanotubes are added in 2g DMF, are surpassed in frequency 20KHz ultrasonic cleaner Sound 12h, obtain homogeneous suspension liquid and add it in above-mentioned sulfonated polyether-ether-ketone solution, continue to stir 12h, use screen cloth The impurity of some indissolubles is filtered, stands 6h deaerations, is poured into clean smooth glass（14cm×14cm）In mould, it will topple over The glass mold of casting solution stands 10min in the environment, is then transferred in 60 DEG C of baking oven and dries 12h, then at 100 DEG C at heat 6h is managed, obtains the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve for sulfonated polyether-ether-ketone/Polyaniline-modified that thickness is 40 microns.
By the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified of above-mentioned gained 25 DEG C, CO is carried out under the conditions of 0.1MPa2/N2The permeance property test of binary gas, CO2Infiltration coefficient is respectively 634Barrer, CO2/ N2Selectivity is 47.2.
Fig. 1 shows the section partial sweep electron microscopic for the pure sulfonated polyether-ether-ketone homogeneous membrane that comparative example 1 is prepared Mirror figure, Fig. 2 show the section of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of the present embodiment sulfonated polyether-ether-ketone/Polyaniline-modified Partial sweep electron microscope picture.Compare the halloysite nanotubes mass fraction that Fig. 1, Fig. 2 can be seen that in Polyaniline-modified to account for Obvious change occurs for the interface configuration structure of 0.3% mixed substrate membrane containing nano-grade molecular sieve (embodiment 1) of polymer substrate mass fraction, It is changed into the raised structure with the arrangement of directive tubulose, and the keramite nano-tube nano of Polyaniline-modified from more smooth Dispersiveness of the grain in film very well, has no obvious boundary defect and existed, illustrate that Polyaniline-modified improves nothing to a certain extent The dispersiveness of machine particle.Compared by the gas separating property of comparative example 1 and embodiment 1, sulfonated polyether-ether-ketone/Polyaniline-modified The gas separating property of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve be improved.
Embodiment 2：
The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified is by sulfonated polyether-ether-ketone matrix and composite wood Expect that the halloysite nanotubes of Polyaniline-modified are formed, its thickness is 40 microns, wherein, sulfonated polyether-ether-ketone and Polyaniline-modified Halloysite nanotubes mass ratio is 99.4:0.6, the sulfonation degree of the sulfonated polyether-ether-ketone is 60%.
The halloysite nanotubes of Polyaniline-modified are prepared using method same as Example 1.
Weigh 0.64g sulfonated polyether-ether-ketones to be added in 6g DMF solvent, magnetic force stirs at 25 DEG C 12h is mixed, until macromolecule all dissolves, obtains sulfonated polyether-ether-ketone solution homogeneously.By 0.00384g polyphenyl obtained above Amine-modified halloysite nanotubes are added in 2g DMF, are surpassed in frequency 28KHz ultrasonic cleaner Sound 12h, obtain homogeneous suspension liquid and add it in above-mentioned sulfonated polyether-ether-ketone solution, continue to stir 12h, use screen cloth The impurity of some indissolubles is filtered, stands 6h deaerations, is poured into clean smooth glass（14cm×14cm）In mould, it will topple over The glass mold of casting solution stands 10min in the environment, is then transferred in 60 DEG C of baking oven and dries 12h, then at 100 DEG C at heat 6h is managed, obtains the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve for sulfonated polyether-ether-ketone/Polyaniline-modified that thickness is 40 microns.
By the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified of above-mentioned gained 25 DEG C, CO is carried out under the conditions of 0.1MPa2/N2The permeance property test of binary gas, CO2Infiltration coefficient is respectively 790Barrer, CO2/ N2Selectivity is 61.5.
Fig. 3 shows the disconnected of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of the present embodiment sulfonated polyether-ether-ketone/Polyaniline-modified Face partial sweep electron microscope picture.Compare Fig. 1, Fig. 3 and can be seen that halloysite nanotubes mass fraction in Polyaniline-modified Obvious change occurs for the interface configuration structure for accounting for 0.6% mixed substrate membrane containing nano-grade molecular sieve (embodiment 2) of polymer substrate mass fraction； Compared with Example 1, it can be seen that the halloysite nanotubes of Polyaniline-modified in the polymer matrix scattered more crypto set and Arragement direction is more obvious.In addition, improve content of the keramite nano-tube nano particle of Polyaniline-modified in film not Have an impact the dispersiveness of nano particle, illustrate the halloysite nanotubes of Polyaniline-modified and the interface compatibility of sulfonated polyether-ether-ketone Well.
By the gas separating property of comparative example 1, embodiment 1 and embodiment 2, sulfonated polyether-ether-ketone/Polyaniline-modified The gas separating property of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve is improved compared to pure sulfonated polyether-ether-ketone film, and is improved poly- Mass fraction of the halloysite nanotubes of aniline modification in film improves the CO of mixed substrate membrane containing nano-grade molecular sieve to a certain extent2Separation property Energy.
Embodiment 3：
The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified is by sulfonated polyether-ether-ketone matrix and composite wood Expect that the halloysite nanotubes of Polyaniline-modified are formed, its thickness is 40 microns, wherein, sulfonated polyether-ether-ketone and Polyaniline-modified Halloysite nanotubes mass ratio is 99.1:0.9, the sulfonation degree of the sulfonated polyether-ether-ketone is 60%.
Using the halloysite nanotubes that Polyaniline-modified is prepared with the identical method of embodiment 1.
Weigh 0.64g sulfonated polyether-ether-ketones to be added in 6g DMF solvent, magnetic force stirs at 25 DEG C 12h is mixed, until macromolecule all dissolves, obtains sulfonated polyether-ether-ketone solution homogeneously.By 0.00576g polyphenyl obtained above Amine-modified halloysite nanotubes are added in 2g DMF, are surpassed in frequency 40KHz ultrasonic cleaner Sound 12h, obtain homogeneous suspension liquid and add it in above-mentioned sulfonated polyether-ether-ketone solution, continue to stir 12h, use screen cloth The impurity of some indissolubles is filtered, stands 6h deaerations, is poured into clean smooth glass（14cm×14cm）In mould, it will topple over The glass mold of casting solution stands 10min in the environment, is then transferred in 60 DEG C of baking oven and dries 12h, then at 100 DEG C at heat 6h is managed, obtains the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve for sulfonated polyether-ether-ketone/Polyaniline-modified that thickness is 40 microns.
By the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified of above-mentioned gained 25 DEG C, CO is carried out under the conditions of 0.1MPa2/N2The permeance property test of binary gas, CO2Infiltration coefficient is respectively 1294Barrer, CO2/N2Selectivity is 83.
Fig. 4 shows the disconnected of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of the present embodiment sulfonated polyether-ether-ketone/Polyaniline-modified Face part SEM schemes.From Fig. 1, the halloysite nanotubes mass fraction that Fig. 4 can be seen that in Polyaniline-modified accounts for polymer substrate Obvious change occurs for the interface configuration structure of 0.9% mixed substrate membrane containing nano-grade molecular sieve (embodiment 3) of mass fraction：With embodiment 1, Embodiment 2 is compared, it can be seen that the halloysite nanotubes of Polyaniline-modified form a kind of with certain side in the polymer matrix The network structure of tropism, and the halloysite nanotubes of Polyaniline-modified are tightly combined with sulfonated polyether-ether-ketone matrix, interface is compatible Property is good.
Pass through the gas separating property of comparative example 1, embodiment 1, embodiment 2 and embodiment 3, sulfonated polyether-ether-ketone/polyphenyl The gas separating property of amine-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve is improved relative to pure sulfonated polyether-ether-ketone film, The raising of mass fraction of the halloysite nanotubes of Polyaniline-modified in film have impact on the fine structure of mixed substrate membrane containing nano-grade molecular sieve, so as to Improve the CO of mixed substrate membrane containing nano-grade molecular sieve2Separating property.
Embodiment 4：
The halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified is by sulfonated polyether-ether-ketone matrix and composite wood Expect that the halloysite nanotubes of Polyaniline-modified are formed, its thickness is 40 microns, wherein, sulfonated polyether-ether-ketone and Polyaniline-modified Halloysite nanotubes mass ratio is 98.8:1.2, the sulfonation degree of the sulfonated polyether-ether-ketone is 60%.
Using the halloysite nanotubes that Polyaniline-modified is prepared with the identical method of embodiment 1.
Weigh 0.64g sulfonated polyether-ether-ketones to be added in 6g DMF solvent, magnetic force stirs at 25 DEG C 12h is mixed, until macromolecule all dissolves, obtains sulfonated polyether-ether-ketone solution homogeneously.By 0.00768 g polyphenyl obtained above Amine-modified halloysite nanotubes are added in 2g DMF, are surpassed in frequency 51KHz ultrasonic cleaner Sound 12h, obtain homogeneous suspension liquid and add it in above-mentioned sulfonated polyether-ether-ketone solution, continue to stir 12h, use screen cloth The impurity of some indissolubles is filtered, stands 6h deaerations, is poured into clean smooth glass（14cm×14cm）In mould, it will topple over The glass mold of casting solution stands 10min in the environment, is then transferred in 60 DEG C of baking oven and dries 12h, then at 100 DEG C at heat 6h is managed, obtains the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve for sulfonated polyether-ether-ketone-Polyaniline-modified that thickness is 40 microns.
By the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified of above-mentioned gained 25 DEG C, CO is carried out under the conditions of 0.1MPa2/N2The permeance property test of binary gas, CO2Infiltration coefficient is respectively 1570Barrer, CO2/N2Selectivity is 61.4.
Fig. 5 shows the disconnected of the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of the present embodiment sulfonated polyether-ether-ketone/Polyaniline-modified Face partial sweep electron microscope picture.Compare Fig. 1, Fig. 5 and can be seen that halloysite nanotubes mass fraction in Polyaniline-modified Obvious become occurs for the interface configuration structure for accounting for 1.2% mixed substrate membrane containing nano-grade molecular sieve (embodiment 4) of polymer substrate mass fraction Change;With embodiment 1, embodiment 2, example 3 is compared, it can be seen that in the film of example 4, the halloysite nanotubes of Polyaniline-modified exist The more crypto set disperseed in polymer substrate, good interface compatibility, but there is slight agglomeration.
By comparing comparative example 1, the gas separating property of embodiment 4, the galapectite of sulfonated polyether-ether-ketone-Polyaniline-modified The gas separating property of nanotube mixed substrate membrane containing nano-grade molecular sieve is improved relative to pure sulfonated polyether-ether-ketone film；Pass through comparison example 3 With the gas separating property of example 4, the content of halloysite nanotubes increases again in mixed substrate membrane containing nano-grade molecular sieve, can influence in mixed substrate membrane containing nano-grade molecular sieve The arrangement situation of the halloysite nanotubes of Polyaniline-modified, in turn result in the CO of mixed substrate membrane containing nano-grade molecular sieve2Separating property declines.

Claims (8)

  1. A kind of 1. halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified, it is characterised in that：The sulfonation gathers The thickness of ether ether ketone/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve is 5-60 microns, by sulfonated polyether-ether-ketone matrix with The halloysite nanotubes of composite Polyaniline-modified are formed, wherein, halloysite nanotubes and polyaniline in composite Ratio is 1：（1-3）, the halloysite nanotubes of Polyaniline-modified and the mass ratio of sulfonated polyether-ether-ketone are 0.1 ~ 5:95~99.9.
  2. 2. the halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified according to claim 1, it is special Sign is：The sulfonation degree of the sulfonated polyether-ether-ketone is 50-70%.
  3. A kind of 3. system of sulfonated polyether-ether-ketone/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve described in claim 1 or 2 Preparation Method, it is characterised in that comprise the following steps：
    Step 1, first, purified halloysite nanotubes is distributed in deionized water, it is 0.5%- to be configured to mass fraction 2% aqueous solution, it is agitated to obtain finely dispersed galapectite pipe suspension liquid of aqueous phase A after ultrasonic 10-120min；According to aniline with Halloysite nanotubes mass ratio is（1-3）：1, weigh aniline and concentrated hydrochloric acid is added in deionized water, preparation turns into concentration of aniline For 2mol/L hydrochloric acid solution B；After the solution A of same volume and solution B are mixed, solution C is obtained, wherein, galapectite in solution C The mass fraction of nanotube is 0.25%-1%, and the mass fraction of aniline is 0.25%-3%；Solution C is added in three-necked flask, Keeping temperature is 2-10 DEG C, lasting stirring, it is uniformly dispersed；
    Step 2, according to the mol ratio of ammonium persulfate and aniline it is（0.8-1.5）：1, take solid ammonium persulfate to be dissolved into 1mol/L Hydrochloric acid solution D in, measure the solution D with solution C same volume, and be slowly added into foregoing solution C；It is added dropwise Afterwards, keeping temperature is 2-10 DEG C, it is reacted 4-6h under conditions of no external interference；Reaction is finished, and mixed liquor is spent Ionized water repeatedly filter, wash after, obtain dirty-green pureed solid, by it in 35-50 DEG C of dry 36-72h, obtained pure The halloysite nanotubes composite of net Polyaniline-modified；
    Step 3, in temperature it is 25-35 DEG C, under conditions of lasting stirring, the sulfonated polyether-ether-ketone that sulfonation degree is 50-70% is added Enter into N,N-dimethylformamide solvent to be configured to the sulfonated polyether-ether-ketone solution that mass concentration is 5-15%；
    Step 4, the galapectite of Polyaniline-modified is received as made from the sulfonated polyether-ether-ketone in sulfonated polyether-ether-ketone solution with step 2 Mitron mass ratio is 95 ~ 99.9：0.1 ~ 5, it is molten that the halloysite nanotubes of Polyaniline-modified are scattered in DMF Agent is configured to the suspension that mass concentration is 0.1-0.5%, ultrasonic 4-12h, and is added to sulfonated polyether-ether-ketone made from step 3 In solution, 24-48h is stirred, stands 2-6h deaerations, obtains the halloysite nanotubes casting solution of sulfonated polyether-ether-ketone/Polyaniline-modified；
    Step 5, the halloysite nanotubes casting solution for the sulfonated polyether-ether-ketone/Polyaniline-modified for obtaining step 4 are poured over glass Casting film-forming in mould, after 50-70 DEG C of dry 12-24 h of temperature, then it is heat-treated, obtains sulfonated polyether-ether-ketone/polyphenyl Amine-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve.
  4. 4. the preparation of sulfonated polyether-ether-ketone according to claim 3/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve Method, it is characterised in that：In step 1 and step 4, ultrasonic frequency range 20-51KHz, 25-70 DEG C of ultrasonic temperature.
  5. 5. the preparation of sulfonated polyether-ether-ketone according to claim 3/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve Method, it is characterised in that：Solution D in step 2 is slowly dropped in solution C, rate of addition 0.5-5mL/min.
  6. 6. the preparation of sulfonated polyether-ether-ketone according to claim 3/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve Method, it is characterised in that：Heat treatment temperature is 80-120 DEG C in step 5, and the time of heat treatment is 4-12h.
  7. 7. sulfonated polyether-ether-ketone/Polyaniline-modified halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve described in a kind of claim 1 or 2 exists CO2/N2Application in separation, it is characterised in that：Film to be tested is fixed in membrane cisterna in experiment test, upstream side pressure model It is 20-60 DEG C to enclose for 0.1MPa-2.0MPa, gas permeation test temperature, humidity the adding by temperature-controllable of feed side gas Wet tank regulation and control；He or H is used in the downstream of membrane cavity2Purged as purge gass, purge gass flow control is adopted in 2-80sccm Downstream component is detected with gas-chromatography.
  8. 8. application according to claim 7, it is characterised in that：Obtained film thickness is in 5-60 microns, for gas point From the mixed substrate membrane containing nano-grade molecular sieve of the halloysite nanotubes containing 0.9% composite Polyaniline-modified possesses high CO2Permeation flux and CO2/N2It is selective, tested under hygrometric state condition, gaseous mixture test CO2Permeation flux reaches 1294Barrer, 1Barrer=10-10cm3 (STP)cm/(cm2S cmHg), CO2/N2Selectivity is 83.
CN201711007030.5A 2017-10-25 2017-10-25 A kind of halloysite nanotubes mixed substrate membrane containing nano-grade molecular sieve of sulfonated polyether-ether-ketone/Polyaniline-modified and its preparation method and application Pending CN107789995A (en)

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CN108745002A (en) * 2018-06-08 2018-11-06 太原理工大学 A kind of sulfonated polyether-ether-ketone mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application of doping carbon quantum dot in situ
CN108816063A (en) * 2018-06-08 2018-11-16 太原理工大学 A kind of polyvinylamine film and its preparation method and application with branched network structure
CN109647233A (en) * 2019-02-19 2019-04-19 太原理工大学 A kind of preparation method and application of polyvinylamine/inierpeneirating network structure carbon composite mixed substrate membrane containing nano-grade molecular sieve
CN109647233B (en) * 2019-02-19 2021-07-27 太原理工大学 Preparation method and application of polyvinylamine/interpenetrating network structure carbon composite material mixed matrix membrane
CN113956473A (en) * 2021-08-16 2022-01-21 丽水学院 Halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater by photocatalysis and preparation method thereof
CN113956473B (en) * 2021-08-16 2023-12-12 丽水学院 Halloysite nanotube composite material for adsorbing and degrading antibiotics in wastewater by photocatalysis and preparation method thereof
CN113896220A (en) * 2021-10-22 2022-01-07 天津工业大学 Cerium fluoride porous nanosheet adjusted mixed matrix membrane and preparation method and application thereof
CN113967412A (en) * 2021-10-22 2022-01-25 天津鼎芯膜科技有限公司 Mixed matrix membrane regulated by ionic liquid modified cerium fluoride porous nanosheets and preparation method and application thereof
CN113967412B (en) * 2021-10-22 2024-01-19 天津鼎芯膜科技有限公司 Mixed matrix membrane regulated by ionic liquid modified cerium fluoride porous nano-sheet, and preparation method and application thereof
CN114441604A (en) * 2022-01-17 2022-05-06 电子科技大学 Halloysite nanotube morphology modification polymer gas sensor and preparation method thereof

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