CN109908758A - A kind of preparation method of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane - Google Patents
A kind of preparation method of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane Download PDFInfo
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Abstract
The present invention relates to a kind of Thief zones, the preparation method of anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane, this method passes through the interface polymerization reaction between polyamine and polynary acyl chlorides, attapulgite-silver nano-grain composite material is successfully embedded into the aramid layer generated by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride reaction, compared with traditional TFC film, since attapulgite-silver nano-grain composite material has very strong hydrophily, greatly increase the hydrophily on reverse osmosis membrane surface, make film to the adhesion strength very little of dirt, therefore, obtained reverse osmosis membrane stain resistance is very strong, in addition, additional aquaporin is formed in the concave convex rod insertion aramid layer of crystal bar pencil, promote the fast transportation of hydrone, and pollutant cannot pass through, increase the infiltration rate of reverse osmosis membrane, the reverse osmosis of high osmosis is obtained Permeable membrane increases the infiltration rate of reverse osmosis membrane.
Description
Technical field
The present invention relates to the systems of a kind of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane
Preparation Method belongs to membrane preparation technology field.
Background technique
World today's water resource critical shortage obtains the fresh water of high quality in order to solve this problem, and sea water desalination is recognized
For a kind of effective ways for being solution water resources crisis.In the means of numerous sea water desalinations, reverse osmosis technology has high take off because of it
Salt rate, low energy consumption, it is easy to operate the advantages that, be widely used in sea water desalination.Wherein pass through interface polymerization reaction
The utilized thin film composite membranes (thin film composite, TFC) of preparation be using at most, but in actual operation, fouling membrane
" upper limit balance " problem between phenomenon and water flux and salt-stopping rate always exists, and restricts its further development.With biography
The TFC film of system is compared, and thin layer nano composite membrane (the thin film that different nano materials obtain is added in polyamide separating layer
Nanocomposite, TFN) there is better separation property and excellent antibacterial, stain resistance, therefore this method becomes people
The emphasis studied.
Attapulgite is the aqueous magnesium alumino metasilicate salt clay mineral of a kind of layer of chain structure, because of its special architectural characteristic
It is widely used in fields such as chemical, environmental protections.Its nanochannel feature cross-section product is 0.37 × 0.63nm2,
It can be hydrone by providing additional nanochannel, while its surface contains there are many hydrophilic radical, has good
Hydrophily.In recent years, attapulgite had been used for the preparation of water-oil separationg film, products obtained therefrom in permeability, thermal stability and
Better performance is shown in terms of soil resistance, there are the very big potentiality applied to wastewater treatment.
Biodeterioration and bacterium attachment are two major issues faced in reverse osmosis operational process, will lead to the water of film
Flux declines to a great extent, and increases operating cost and shortens membrane lifetime.According to the literature, by the nano grain of silver with excellent antibacterial ability
It can the significant bacteriostasis for increasing film in son incorporation film.However, only by the aramid layer of silver nano-grain insertion composite membrane
In, fenestra can be blocked, to cause the violent decline of water flux and salt-stopping rate, be unable to reach expected effect.
In addition, current reverse osmosis membrane is without antifouling property, due to solid particulate matter, colloid, organic matter and microorganism
Etc. will be adsorbed on film surface, thus film is in use for some time, and the dirt that colloid can occurs in film surface is stifled, biological pollution and change
Incrustation etc. is learned, the aperture of ultrafiltration membrane will reduce, and water flux reduces, and also pollutes to ultrafiltration membrane, and then will lead to the stabilization of film
Property etc. the separating effects such as performances and water flux sharply decline, or even shorten film service life.
Summary of the invention
In view of the deficiencies of the prior art, it is compound to provide a kind of Thief zone, anti-fouling type doped attapulgite-silver nanoparticle by the present invention
The preparation method of the reverse osmosis membrane of material.
Technical scheme is as follows:
A kind of preparation method of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane, including
Steps are as follows:
(1) attapulgite-silver nano-grain composite material preparation
It takes natural attapulgite powder to be added in Tris-HCl buffer solution and is ultrasonically treated 0.5-2h, DOPA is then added
Amine obtains mixed solution, and mixed solution is stirred to react 1~10h at room temperature, obtained product centrifugation removal solution, washing, vacuum
It is dry, the solids after drying is added in silver nitrate solution, heating reaction, obtained product centrifugation removal solution, washing, very
Sky is dry, obtains attapulgite-silver nano-grain composite material；
(2) prepared by aqueous phase solution:
Water is added to be configured to attapulgite-silver nano-grain composite material water in attapulgite-silver nano-grain composite material
Solution is added polyamine, surfactant, stirs evenly, obtain aqueous phase solution；
(3) dissolution of polynary acyl chlorides the preparation of oil-phase solution: is configured to oil-phase solution in organic solvent；
(4) interface polymerization reaction: aqueous phase solution is poured on basement membrane, and after keeping 30~180s, it is molten to remove extra water phase
Liquid, naturally dry are subsequently poured into oil-phase solution, and extra oil-phase solution is removed after reaction, drying, obtain the doping oxidation of anti-pollution type
The reverse osmosis membrane of cerium and silver nano-grain.
Above-mentioned preparation method, it is preferred that in step (1), the Tris-HCl buffer concentration is 10~60mmol/
L, pH are 6~9.
Above-mentioned preparation method, it is preferred that in step (1), the concentration of attapulgite is 0.1~5g/L in mixed solution；It is more
The concentration of bar amine is 0.1~4g/L.
Above-mentioned preparation method, it is preferred that in step (1), the concentration of silver nitrate solution is 10~60mmol/L, after dry
The additional amount of solids and the mass volume ratio of silver nitrate solution are as follows: (0.1-5): (10-200), unit, g/mL.
Above-mentioned preparation method, it is preferred that in step (1), heating reaction temperature be 55~65 DEG C, the reaction time be 5~
18h。
Above-mentioned preparation method, it is preferred that in step (1), centrifugation removal solution is under 6500~12000rpm revolving speed
It is centrifuged 5~20min.
In the preparation of attapulgite of the present invention-silver nano-grain composite material, Tris-HCl buffer solution makes reaction system
Constant pH is maintained, group on attapulgite is activated, so that more groups is participated in reaction, the addition of dopamine is first is that by nitric acid
Silver is reduced into silver nano-grain, second is that the silver nano-grain after reduction is adhered to concave convex rod crystal bar surface by dopamine, so that silver-colored
Nano particle is firmly attached to concave convex rod crystal bar surface, avoids in use process silver nano-grain from falling off and causes failure (structure
As shown in Figure 1, it can be seen from the figure that circle silver nano-grain is firmly attached to concave convex rod surface), the modification of silver nano-grain
Attachment makes composite material assign sterilizing function.
Above-mentioned preparation method, it is preferred that silver is concave-convex in step (2) attapulgite-silver nano-grain composite material aqueous solution
Stick stone-silver nano-grain composite material concentration is 0.01-0.5g/L, it is preferred that attapulgite-silver nano-grain composite material
The concentration of silver-colored attapulgite-silver nano-grain composite material is 0.05-0.15g/L in aqueous solution.
Above-mentioned preparation method, it is preferred that the mass concentration of polyamine is 0.5-3% in step (2) aqueous phase solution, preferably
, the mass concentration of polyamine is 1-3%.
Above-mentioned preparation method, it is preferred that in step (2), polyamine is o-phenylenediamine, p-phenylenediamine, m-phenylene diamine (MPD) or piperazine
One of piperazine, it is preferred that polyamine is m-phenylene diamine (MPD).
Above-mentioned preparation method, it is preferred that in step (2), the surfactant is dodecyl sodium sulfate (SDS),
The mass concentration of surfactant is 0.1~0.2% in aqueous phase solution.
Above-mentioned preparation method, it is preferred that in step (3), polynary acyl chlorides is pyromellitic trimethylsilyl chloride, three formyl chloride of isophthalic, ring
Three acyl chlorides of hexane, three acyl chlorides of pentamethylene, the third three one of acyl chlorides or penta 3 acyl chlorides；Organic solvent is n-hexane, normal heptane, ten
One of dioxane or the tetradecane.
Above-mentioned preparation method, it is preferred that in step (3), in oil-phase solution the mass concentration of polynary acyl chlorides be 0.02~
0.2%.
Above-mentioned preparation method, it is preferred that in step (4), the basement membrane is polysulfones, polyether sulfone, polyethylene, polyamide Asia
Amine, polypropylene or polyacrylonitrile.
Above-mentioned preparation method, it is preferred that in step (4), basement membrane first carries out pretreatment and reuses, the preprocessing process
It is as follows: first to impregnate 4~10h in 50% ethanol solution, to remove product film sealer, and be swollen fenestra moderately, so
Unnecessary alcohol is rinsed well afterwards, it is spare to impregnate 24-30h in deionized water.
Above-mentioned preparation method, it is preferred that in step (4), after pouring into aqueous phase solution, 90~150s of retention time pours into oil
The reaction time is 10-120s after phase solution, it is preferred that the reaction time is 40-80s after pouring into oil-phase solution.
Above-mentioned preparation method, it is preferred that in step (4), for drying temperature at 50~95 DEG C, drying time is 2~10min.
Preparation method of the invention, is first made attapulgite-silver nano-grain composite material for concave convex rod, and attapulgite removes
Have outside hydroxyl abundant, by being prepared into attapulgite-silver nano-grain composite material, makes the negative electrical charge on attapulgite surface
Increase, make composite material that there is very strong hydrophily, by attapulgite-silver nano-grain composite material dissolution in aqueous phase solution
In, along with the generation of interface polymerization reaction, attapulgite-silver nano-grain composite material be successfully embedded by m-phenylene diamine (MPD) and
In the aramid layer that pyromellitic trimethylsilyl chloride reaction generates, since attapulgite-silver nano-grain composite material has very strong parent
It is aqueous, the hydrophily on reverse osmosis membrane surface is greatly increased, makes film to the adhesion strength very little of dirt, therefore, what is obtained is reverse osmosis
Film stain resistance is very strong, in addition, forming additional aquaporin in the concave convex rod insertion aramid layer of crystal bar pencil, hydrone is along recessed
The aquaporin on convex stick surface is quickly through promoting the fast transportation of hydrone, and pollutant cannot pass through, and increase reverse osmosis
The infiltration rate of film has obtained the reverse osmosis membrane of high osmosis, and compared to the TFC film for the composite material that undopes, water flux has greatly
Width improves, and is still maintained at higher level to the rejection of NaCl solution, and antifouling property is excellent, bactericidal activity is strong, permeability is high,
Filtering rate is improved, can be widely applied to the fields such as sea water desalination, reusing sewage.
Thief zone of the invention, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane and the prior art
Compared to following excellent results:
1. the present invention is by the interface polymerization reaction between polyamine and polynary acyl chlorides, by attapulgite-silver nano-grain
Composite material is successfully embedded into the aramid layer generated by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride reaction, has been made a kind of novel
TFN film.Compared with traditional TFC film, since attapulgite-silver nano-grain composite material has very strong hydrophily, make reverse osmosis
The hydrophily of permeable membrane surface greatly increases, and makes film to the adhesion strength very little of dirt, and therefore, obtained reverse osmosis membrane stain resistance is very
By force, in addition, forming additional aquaporin, water of the hydrone along concave convex rod surface in the concave convex rod insertion aramid layer of crystal bar pencil
Channel is quickly through promoting the fast transportation of hydrone, and pollutant cannot pass through, increase the infiltration speed of reverse osmosis membrane
Rate has obtained the reverse osmosis membrane of high osmosis, increases the infiltration rate of reverse osmosis membrane, and the permeability and separation performance of TFN film obtains
It is obviously improved.
2. attapulgite of the present invention-silver nano-grain composite material preparation process is simple, silver nano-grain is firmly attached
On concave convex rod surface, it is not easy to fall off, composite material have negative electrical charge abundant, thus enhance gained TFN film surface
Electronegativity.Pollutant and bacterium have negative electrical charge mostly, because of the repulsion effect between identical charges, the film surface with negative electrical charge
It is not easy to adsorb pollutant, antifouling property is significantly improved.
3. the silver nano-grain in attapulgite produced by the present invention-silver nano-grain composite material has sterilizing ability,
Gained TFN film has excellent anti-microbial property, can effectively inhibit the growth and breeding of film surface bacterium, and extend film uses the longevity
Life.
4, reverse osmosis membrane of the invention has both high water flux and strong bactericidal property, reduces the bacterium of filter membrane surface
It breeds and breeds, enhance ultrafiltration membrane service life, filter effect lasting stability, membrane lifetime is long, and preparation method is simple.
Detailed description of the invention
Fig. 1 is attapulgite-argentum nano composite material electromicroscopic photograph made from embodiment 1；
Fig. 2 is the long-play stability curve graph of reverse osmosis membrane made from embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but institute's protection scope of the present invention is without being limited thereto.
Attapulgite in embodiment, derives from Jiangsu Jiu Chuan nanosecond science and technology Co., Ltd, which has typical case
Rod-like shape, diameter be 30~60nm, length is about 500~800nm.
Embodiment 1:
A kind of preparation method of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane, including
Steps are as follows:
(1) it attapulgite-silver nano-grain composite material preparation: is added into 100mL Tris-HCl buffer solution
0.1g natural attapulgite powder, ultrasonic 1h；The concentration of Tris-HCl buffer solution is 0.01mol/L, pH=8.5, backward
0.1g dopamine is wherein added, obtains mixed solution, mixed solution is stirred to react 6h at room temperature, obtained product centrifugation removal is molten
It is molten the silver nitrate that 100mL concentration is 0.01mol/L to be added in solids 1g after drying by liquid, washing, 60 DEG C of vacuum drying 10h
Liquid, after 60 DEG C of stirring 12h, gains are centrifuged and wash, and attapulgite-silver nano-grain composite material is obtained after vacuum drying；
(2) preparation of aqueous phase solution: adding water to be configured to concentration in attapulgite-silver nano-grain composite material is 0.05g/
The attapulgite of L-silver nano-grain composite material aqueous solution, is added m-phenylene diamine (MPD) dodecyl sodium sulfate, and ultrasound makes its mixing
Uniformly, aqueous phase solution is obtained；The mass concentration of polyamine is 2% in aqueous phase solution, dodecyl sodium sulfate in aqueous phase solution
Mass concentration is 0.15%.
(3) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride is dissolved in and obtains the oil that mass concentration is 0.1% in n-hexane
Phase solution, ultrasound are uniformly mixed it, obtain oil-phase solution.
(4) interface polymerization reaction: the PS membrane cut being clamped with film fixture, aqueous phase solution is poured on PS membrane,
The aqueous phase solution of excess surface, uniform naturally dry are poured out after 120s；Backward film surface topple over oil-phase solution, after contacting 60s
The oil-phase solution for removing excess surface is put into 80 DEG C of baking ovens drying 5min after natural drying, and it is recessed to obtain Thief zone, anti-fouling type doping
The reverse osmosis membrane of convex stick stone-argentum nano composite material, Jiang Qipao enters spare in deionized water.
Embodiment 2:
With the system of Thief zone described in embodiment 1, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane
Preparation Method, the difference is that:
Silver-colored attapulgite-silver nano-grain composite wood in step (2) attapulgite-silver nano-grain composite material aqueous solution
The concentration of material is 0.1g/L,
Step (4) oil-phase solution and film surface time of contact are 120s, and other conditions press the progress of embodiment 1.
Embodiment 3:
With the system of Thief zone described in embodiment 1, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane
Preparation Method, the difference is that:
Step (4) oil-phase solution and film surface time of contact are 120s, and other conditions press the progress of embodiment 1.
Application effect test
One, change in embodiment 1 silver-colored attapulgite-in step (2) attapulgite-silver nano-grain composite material aqueous solution
The concentration of silver nano-grain composite material changes the dosage of nanocomposite, namely to 0,0.05 (embodiment
1), 0.1,0.15,0.2g/L obtain five groups of different reverse osmosis membranes.This five groups of reverse osmosis membranes are used to handle the salt of high concentration
Solution separates permeance property to test it, is elaborated as follows: the membrane module structure that reverse osmosis test device is placed in parallel by three
At the validity test area of each membrane module is 18.75cm2, material liquid is the sodium chloride solution of 2g/L, passes through the side of cross-flow
Formula, coutroi velocity 44.4cm/s, pressure are that 16bar is tested.Reverse osmosis membrane is fixed on membrane module, is first transported instrument
Row 30min or so when stable postscript and is sampled, the quality and conductivity of measurement gained permeate, to calculate film
Water flux and salt-stopping rate further calculate out solvent transmission coefficient and solute transmission coefficient.The water flux of reverse osmosis membrane and cut
Salt rate is as shown in table 1, and solvent transmission coefficient and solute transmission coefficient are as shown in table 2.
The water flux and salt-stopping rate of 1 reverse osmosis membrane of table
The solvent transmission coefficient and solute transmission coefficient of 2 reverse osmosis membrane of table
As can be seen from the above table, with the increase of attapulgite-silver nano-grain composite material dosage, reverse osmosis membrane
Water flux significantly increases.When material dosage is 0.15g/L, it is not add material that the water flux of reverse osmosis membrane, which is 39.31LMH,
1.6 times for expecting film, while salt-stopping rate remains at 98.2%.When material dosage is further promoted to 0.2g/L, salt-stopping rate
Occur being decreased obviously.Therefore, adding appropriate attapulgite-silver nano-grain composite material (lower than 0.15g/L) can be effective
The separation permeance property for improving film, the integrality without destroying reverse osmosis membrane selection layer.
Two, reverse osmosis membrane obtained in embodiment 1 is used to handle the salting liquid of high concentration, carries out the test of duration 36h
To probe into the stability of film, acquired results are as shown in Figure 1.As shown, reverse osmosis membrane prepared by the present invention was tested entirely
Water flux and salt-stopping rate are maintained at a stable level in journey, substantially there is no variation, illustrate doped attapulgite-Yin Na
The reverse osmosis membrane of rice grain composite material is with good stability, will not be destroyed with the increase of runing time.
Three, two groups of different reverse osmosis membranes that nanocomposite dosage is respectively 0,0.15g/L are subjected to pollution resistance
It can test, be elaborated as follows: common protein pollutant being respectively represented with bovine serum albumin(BSA) and humic acid and is had naturally
Machine object pollute by way of cross-flow-cleaning-and is restored to test using reverse osmosis unit.Reverse osmosis membrane is fixed on film
Chi Zhong uses the sodium chloride solution of 2g/L to carry out 3h test as material liquid, cow's serum is added into material liquid after flux stabilized
Albumin or humic acid carry out pollution experiment, when Contamination measurement a length of 21h.It is reverse osmosis after rinsing pollution with deionized water later
Film, flushing process continue 2h.Material liquid is finally changed to the sodium chloride solution of 2g/L, the recovery flux of a length of 3h is surveyed when carrying out
Examination.The antifouling property of reverse osmosis membrane is with flux recovery rate (FRR, %) and gross contamination rate (Rt, %) and it is indicated, acquired results are such as
Shown in table 3.
The antifouling property of 3 reverse osmosis membrane of table is tested
It can be seen that, for two different pollutants, compared to the film for not adding composite material, dosage is from table
The reverse osmosis membrane of 0.15g/L has higher flux recovery rate and lower gross contamination, and the doping prepared by the present invention of this explanation is recessed
The reverse osmosis membrane of convex stick stone-silver nano-grain composite material has better antifouling property.
Four, two groups of different reverse osmosis membranes that nanocomposite dosage is respectively 0,0.15g/L are subjected to antibiotic property
It can test, be elaborated as follows: Escherichia coli (strain ATCC25922) are added in the LB meat soup of sterilized 250mL,
It is placed in 37 DEG C of constant-temperature tables and cultivates for 24 hours.Escherichia coli after culture are centrifugated 5min under 10000rpm revolving speed, with life
Reason salt water is diluted to its concentration about 1.0 × 106cfu/mL.Then the film that area is 3cm × 3cm is added to containing above-mentioned bacterium
In the conical flask of suspension, it is placed in 37 DEG C of constant-temperature tables and cultivates 2h.Later with the above-mentioned film of 5ml normal saline flushing to collect it
The Escherichia coli on surface.0.1ml is rinsed the bacterial suspension being collected into be coated on LB agar medium, it is uniform with spreading rod
Coating, is cultivated for 24 hours at 37 DEG C.Culture medium is taken out, clump count is obtained using colony counting method and calculates bacteriostasis rate, acquired results
As shown in table 4.
The anti-microbial property test of 4 reverse osmosis membrane of table
As can be seen from the above table, compared to the film for not adding composite material, dosage is the suppression of the reverse osmosis membrane of 0.15g/L
Bacterium rate is up to 97.6%, has excellent anti-microbial property, can effectively inhibit the growth and breeding of film surface bacterium.
Claims (10)
1. a kind of preparation method of the reverse osmosis membrane of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material, including step
It is rapid as follows:
(1) attapulgite-silver nano-grain composite material preparation
It takes natural attapulgite powder to be added in Tris-HCl buffer solution and is ultrasonically treated 0.5-2h, dopamine is then added, obtains
Mixed solution is stirred to react 1~10h by mixed solution at room temperature, obtained product centrifugation removal solution, washing, vacuum drying,
By in the solids addition silver nitrate solution after drying, heating reaction, obtained product centrifugation removal solution, washing, vacuum are done
It is dry, obtain attapulgite-silver nano-grain composite material；
(2) prepared by aqueous phase solution:
Water is added to be configured to attapulgite-silver nano-grain composite material aqueous solution in attapulgite-silver nano-grain composite material,
Polyamine, surfactant is added, stirs evenly, obtains aqueous phase solution；
(3) dissolution of polynary acyl chlorides the preparation of oil-phase solution: is configured to oil-phase solution in organic solvent；
(4) interface polymerization reaction: aqueous phase solution is poured on basement membrane, after keeping 30~180s, removes extra aqueous phase solution, from
So dry, be subsequently poured into oil-phase solution, extra oil-phase solution is removed after reaction, dry, obtain anti-pollution type doped cerium oxide with
The reverse osmosis membrane of silver nano-grain.
2. preparation method according to claim 1, which is characterized in that in step (1), the Tris-HCl buffer solution
Concentration is 10~60mmol/L, and pH is 6~9.
3. preparation method according to claim 1, which is characterized in that in step (1), attapulgite is dense in mixed solution
Degree is 0.1~5g/L；The concentration of dopamine is 0.1~4g/L.
4. preparation method according to claim 1, which is characterized in that in step (1), the concentration of silver nitrate solution is 10~
60mmol/L, the additional amount of the solids after drying and the mass volume ratio of silver nitrate solution are as follows: (0.1-5): (10-200), it is single
Position, g/mL.
5. preparation method according to claim 1, which is characterized in that in step (1), heating reaction temperature is 55~65
DEG C, the reaction time is 5~18h, and centrifugation removal solution is that 5~20min is being centrifuged under 6500~12000rpm revolving speed.
6. preparation method according to claim 1, which is characterized in that step (2) attapulgite-silver nano-grain composite wood
The concentration for expecting silver-colored attapulgite-silver nano-grain composite material in aqueous solution is 0.01-0.5g/L, it is preferred that attapulgite-silver
The concentration of silver-colored attapulgite-silver nano-grain composite material is 0.05-0.15g/L in nano particle composite material aqueous solution.
7. preparation method according to claim 1, which is characterized in that the quality of polyamine is dense in step (2) aqueous phase solution
Degree is 0.5-3%, it is preferred that the mass concentration of polyamine is 1-3%, and polyamine is o-phenylenediamine, p-phenylenediamine, m-phenylene diamine (MPD)
Or one of piperazine, it is preferred that polyamine is m-phenylene diamine (MPD), and the surfactant is dodecyl sodium sulfate (SDS),
The mass concentration of surfactant is 0.1~0.2% in aqueous phase solution.
8. preparation method according to claim 1, which is characterized in that in step (3), polynary acyl chlorides is equal three formyl of benzene
Chlorine, three formyl chloride of isophthalic, three acyl chlorides of hexamethylene, three acyl chlorides of pentamethylene, the third three one of acyl chlorides or penta 3 acyl chlorides；Organic solvent
For one of n-hexane, normal heptane, dodecane or tetradecane, in oil-phase solution the mass concentration of polynary acyl chlorides be 0.02~
0.2%.
9. preparation method according to claim 1, which is characterized in that the basement membrane be polysulfones, polyether sulfone, polyethylene,
Polyamide-imide, polypropylene or polyacrylonitrile, basement membrane first carry out pretreatment and reuse, and the preprocessing process is as follows: first existing
4~10h is impregnated in 50% ethanol solution, to remove product film sealer, and is swollen fenestra moderately, then by extra second
Alcohol is rinsed well, and it is spare to impregnate 24-30h in deionized water.
10. preparation method according to claim 1, which is characterized in that in step (4), after pouring into aqueous phase solution, when holding
Between 90~150s, pouring into the reaction time after oil-phase solution is 10-120s, it is preferred that the reaction time is 40- after pouring into oil-phase solution
80s, for drying temperature at 50~95 DEG C, drying time is 2~10min.
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| CN111298651A (en) * | 2019-12-11 | 2020-06-19 | 恩泰环保科技（常州）有限公司 | Biological pollution resistant composite reverse osmosis membrane and preparation method thereof |
| CN112516799A (en) * | 2020-12-18 | 2021-03-19 | 山东建筑大学 | Reverse osmosis membrane and preparation method thereof |
| CN114481602A (en) * | 2022-02-24 | 2022-05-13 | 中国地质大学（北京） | Mineral composite moisture absorption fiber textile and preparation method thereof |
| CN115007000A (en) * | 2021-12-02 | 2022-09-06 | 淮阴师范学院 | Modified attapulgite polylactic acid separation membrane, preparation method and application |
| CN115606587A (en) * | 2022-10-13 | 2023-01-17 | 河北工业大学 | Method for preparing silver chloride/low-grade attapulgite clay composite antibacterial agent by using seawater |
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