CN108409981A - A kind of preparation method of modified metal organic frame and composite nanometer filtering film - Google Patents
A kind of preparation method of modified metal organic frame and composite nanometer filtering film Download PDFInfo
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- CN108409981A CN108409981A CN201810261143.6A CN201810261143A CN108409981A CN 108409981 A CN108409981 A CN 108409981A CN 201810261143 A CN201810261143 A CN 201810261143A CN 108409981 A CN108409981 A CN 108409981A
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- B01D61/027—Nanofiltration
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Abstract
The invention discloses a kind of preparation methods of modified metal organic frame and composite nanometer filtering film.The preparation method of the modified metal organic frame is：While using plant polyphenol modified metal organic frame surface, hollow structure is formed inside metal organic frame, obtains modified metal organic frame.The preparation method of the composite nanometer filtering film of the organic frame containing modified metal is：Modified metal organic frame is loaded to by interfacial polymerization in the aromatic polymer Motor cortex of porous support membrane in situ.Modified metal organic frame well loaded in the composite nanometer filtering film of the present invention is on film, there is chemical bond interaction between cortex polymer, it is not only advantageous to the raising of the water flux, hydrophily and antifouling property of composite membrane, and the structural stability and chlorine resistance of composite nanometer filtering film can be improved.The method of the present invention is simple, and production cost is relatively low, significantly improves film comprehensive performance, has good industrialized production basis and wide application prospect.
Description
Technical field
A kind of preparation method of modified metal organic frame and composite nanometer filtering film of the present invention, belongs to technical field of membrane.
Background technology
Nanofiltration is a kind of membrane process between reverse osmosis between ultrafiltration, and pore diameter range is in several rans.Nanofiltration
Process has higher rejection to the organic matter of divalent or polyvalent mineral ion and molecular weight between 200-1000Da, has
It is easy to operate, it is the advantages that low energy consumption, and separative efficiency is high, pure in drinking-water softening, solution decoloration, dye desalination concentration and biochemical substances
Change and be widely used in the industrial productions such as concentration and daily life, produces certain economic results in society.But it is wide at present
The problem of general straight polymer NF membrane generally existing flux used is relatively low, and antifouling property is poor, anti-chlorine poor performance.And it will be inorganic
Nanometer particle material is combined to the comprehensive performance that NF membrane can be effectively improved in NF membrane, becomes the traditional straight polymer nanofiltration of breakthrough
The effective scheme of film development bottleneck.
The characteristics of metal organic framework (MOFs) has high-specific surface area, and high porosity and structure are easily adjusted.Therefore, it
Catalysis, gas absorption, separation, load medicine etc. show ideal application prospect.Recently, MOFs in terms of water process gradually by
Extensive concern is arrived.Such as：《Materials chemistry A》(Journal of Materials Chemistry A 2016,4,16368-
16376) it reports to be combined to be made in aramid layer by metal organic frame ZIF-8 by the method for suction filtration and has machine frame containing metal
The composite nanometer filtering film of frame, the film show certain promotion of flux.《ACS application materials and surface》(ACS Applied
Materials and Interfaces 2016,8,25508-25519) it reports ZIF-8@GO particles is combined to polyamide
The stable against biological contamination NF membrane comprising metal organic frame is prepared in functional layer.《Membrane science》(Journal of
Membrane science 2015,476,303-310) it reports ZIF-8 is combined to polyamide functional layer and is prepared compound anti-
The work of permeable membrane.Relative to straight polymer film, these compound membrane fluxs for containing metal organic frame are promoted.But
The metal organic frame surface hydrophobicity mainly studied at present, the bad dispersibility in film water are unfavorable for the promotion of water flux, or even meeting
Reduce the antifouling property of film.Therefore, by being reasonably modified so that metal organic frame hydrophily is promoted, and is used for
Prepare composite nanometer filtering film so that the comprehensive performance of the composite nanometer filtering film containing metal organic frame, which is further promoted, still compels in eyebrow
Eyelash.
Invention content
Problem to be solved by this invention is：How on the basis of not reducing the antifouling property of film, promoting metal has
Dispersibility of the machine frame in film water improves water flux.
To solve the above-mentioned problems, the present invention provides a kind of preparation method of modified metal organic frame, feature exists
In while using plant polyphenol modified metal organic frame surface, forming hollow structure inside metal organic frame, obtain
Modified metal organic frame.
Preferably, specially：Metal organic frame is dispersed in plant polyphenol aqueous solution, lower reaction is stirred, is changed
Property metal organic frame.
It is highly preferred that the metal organic frame is ZIF series materials or MIL series materials.
It is highly preferred that the plant polyphenol is any one in tannic acid, gallic acid, gallic acid and polyvinyl
Kind is several.
It is highly preferred that a concentration of 0.1~100mg/mL of the plant polyphenol aqueous solution.
It is highly preferred that the time of the reaction is 1~60min.
The present invention also provides a kind of preparation method of the composite nanometer filtering film of organic frame containing modified metal, feature exists
In modified metal organic frame made from the preparation method of above-mentioned modified metal organic frame is negative in situ by interfacial polymerization
It is downloaded in the aromatic polymer Motor cortex of porous support membrane, obtains the composite nanometer filtering film of the organic frame containing modified metal.
Preferably, specially：Porous support membrane is immersed in aqueous phase solution, takes out the discharge excessive solution in surface, so
After be immersed in oil-phase solution and react, then thermally treated, rinsing makes porous support membrane in one layer of loaded modified gold of its Surface Creation
The aromatic polymer Motor cortex for belonging to organic frame, obtains the composite nanometer filtering film of the organic frame containing modified metal；Wherein, water phase is molten
Liquid is the aqueous solution comprising the first reaction monomers and modified metal organic frame, and oil-phase solution is having comprising the second reaction monomers
Machine solution.
It is highly preferred that first reaction monomers are using piperazine, N- (2- aminopropyls)-piperazine, N, N- diaminopiperazines, first
In base diethanol amine, triethanolamine, polyethyleneimine, m-phenylene diamine (MPD), o-phenylenediamine and triethylene tetramine any one or it is several
Kind, the mass percent in aqueous phase solution is 0.01~10%；The quality hundred of modified metal organic frame in aqueous phase solution
Divide than being 0.005~5%.
It is highly preferred that second reaction monomers using m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride,
Any one or a few in four formyl chloride of pyromellitic trimethylsilyl chloride and equal benzene, the mass percent in oil-phase solution is 0.01~
10%.
The present invention modifies and etches metal organic frame using the metal ion chelating effect of plant polyphenol and faintly acid,
The hollow modified metal organic frame in acquisition surface cladding plant polyphenol, inner cavity, surface have good hydrophily, can be very well
Ground is dispersed in aqueous phase solution, and the phenolic hydroxyl group of institute's band can be reacted with oil phase monomer, so as to polymerize with the Motor cortex of composite membrane
Object has chemical bond interaction.
Modified metal organic frame method of modifying is simple, and operating process is simple, and reaction condition is mild, of low cost, green
Environmental protection.The compatibility of obtained product and polymer is good, stable quality, is suitable for industrial scale and produces.
Modified metal organic frame is scattered in aqueous phase solution, by interfacial polymerization by modified metal organic frame with
Chemical bond form loads in the polymers function cortex of composite nanometer filtering film.Modified metal organic frame is chemically bonded to composite membrane
Polymeric surface layer in so that the contact of inorganic-organic two-phase is even closer, and compatibility is more preferable, and the structure of film is more stable.It is modified
Metal organic frame carries hydrophilic functional group, is conducive to carrying for the water flux of composite nanometer filtering film, hydrophily and antifouling property
It is high.Modified metal organic frame is unique porous and hollow structure can provide additional preferential transmission by film for hydrone and lead to
Road is conducive to composite nanometer filter membrane flux and is further promoted.The phenolic groups that modified metal organic frame carries have free radical
Capturing ability can enhance the anti-chlorine performance of composite nanometer filtering film and stability is used for a long time.
In addition, composite nanometer filtering film production process is easy, of low cost, it is easy to mass, large-scale production；It is obtained compound
NF membrane operating pressure is low, and comprehensive separating property significantly improves, and has good industrialized production basis.
The present invention modifies metal organic frame by plant polyphenol, this not only make metal organic frame surface from
Hydrophobicity is transformed into hydrophily, has been formed simultaneously unique hollow structure.Then, modified metal organic frame is combined to
In the Motor cortex for closing NF membrane.A large amount of plant polyphenols are wrapped up on modified metal organic frame surface, and advantageous film surface is hydrophilic
It is promoted, while metal organic frame and Motor cortex can be made to form covalent bond, enhance the stability of film；Film surface it is hydrophilic
Property because the addition of modified metal organic frame is also enhanced, the promotion of this also advantageous water flux and antifouling property；Modified gold
Additional Water transport channel can be provided in hymeniderm layer by belonging to the unique porous and hollow structure of organic frame so that membrane flux is into one
Step is promoted.In addition, the reproducibility of plant polyphenol can effectively promote the chlorine resistance of film.
Description of the drawings
Fig. 1 is the comparison diagram of unmodified (a) and the TEM figures of modified (b) metal organic frame；
Fig. 2 is the comparison of unmodified (a, a1) and modified (b, b1) metal organic frame photo and Hydrophilic Characterization of Hydrophilic photo
Figure.
Specific implementation mode
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is coordinated to be described in detail below.
Embodiment 1
A kind of preparation method of the composite nanometer filtering film containing modified metal organic frame：
(1) 500mg ZIF-8 (one kind of metal organic frame) additions 200mL is contained to the tannic acid (TA) of 3mg/mL
In aqueous solution, it is quickly stirred to react 5min.Then, centrifugation is precipitated, multiple deionized water washing precipitation, freeze-drying, i.e.,
Obtain modified metal organic frame (ZIF-8@TA)；
(2) preparation of aqueous phase solution：By the piperazine of a concentration of 0.5wt%, 0.2wt% sodium hydroxides are dissolved in deionized water
In, a concentration of 0.03wt%ZIF-8@TA are added, ultrasound makes it be uniformly dispersed in 5 minutes；The polysulfones support membrane of hygrometric state is immersed
Aqueous phase solution, dip time 5min roll support film surface with squeegee after taking-up, extract；
(3) preparation of oil-phase solution：The pyromellitic trimethylsilyl chloride of a concentration of 0.15wt% is dissolved in n-hexane；It will support
Film immerses oil-phase solution, and reaction time 1min takes out；
(4) composite membrane is heat-treated 30 minutes in 70 DEG C of baking ovens.Then it with after deionized water rinsing for several times, obtains containing changing
The composite nanometer filtering film of property metal organic frame.
Embodiment 2
A kind of preparation method of the composite nanometer filtering film containing modified metal organic frame：
(1) 500mg ZIF-8 (one kind of metal organic frame) additions 200mL is contained to the tannic acid (TA) of 3mg/mL
In aqueous solution, it is quickly stirred to react 5min.Then, centrifugation is precipitated, multiple deionized water washing precipitation, freeze-drying, i.e.,
Obtain modified metal organic frame (ZIF-8@TA)；
(2) preparation of aqueous phase solution：By the piperazine of a concentration of 0.5wt%, 0.2wt% sodium hydroxides are dissolved in deionized water
In, a concentration of 0.06wt%ZIF-8@TA are added, ultrasound makes it be uniformly dispersed in 5 minutes；The polysulfones support membrane of hygrometric state is immersed
Aqueous phase solution, dip time 5min roll support film surface with squeegee after taking-up, extract；
(3) preparation of oil-phase solution：The pyromellitic trimethylsilyl chloride of a concentration of 0.15wt% is dissolved in n-hexane；It will support
Film immerses oil-phase solution, and reaction time 1min takes out；
(4) composite membrane is heat-treated 30 minutes in 70 DEG C of baking ovens.Then it with after deionized water rinsing for several times, obtains containing changing
The composite nanometer filtering film of property metal organic frame.
Embodiment 3
A kind of preparation method of the composite nanometer filtering film containing modified metal organic frame：
(1) 500mg ZIF-8 (one kind of metal organic frame) additions 200mL is contained to the tannic acid (TA) of 3mg/mL
In aqueous solution, it is quickly stirred to react 5min.Then, centrifugation is precipitated, multiple deionized water washing precipitation, freeze-drying, i.e.,
Obtain modified metal organic frame (ZIF-8@TA)；
(2) preparation of aqueous phase solution：By the piperazine of a concentration of 0.5wt%, 0.2wt% sodium hydroxides are dissolved in deionized water
In, a concentration of 0.10wt%ZIF-8@TA are added, ultrasound makes it be uniformly dispersed in 5 minutes；The polysulfones support membrane of hygrometric state is immersed
Aqueous phase solution, dip time 5min roll support film surface with squeegee after taking-up, extract；
(3) preparation of oil-phase solution：The pyromellitic trimethylsilyl chloride of a concentration of 0.10wt% is dissolved in n-hexane；It will support
Film immerses oil-phase solution, and reaction time 1min takes out；
(4) composite membrane is heat-treated 30 minutes in 70 DEG C of baking ovens.Then it with after deionized water rinsing for several times, obtains containing changing
The composite nanometer filtering film of property metal organic frame.
Embodiment 4
A kind of preparation method of the composite nanometer filtering film containing modified metal organic frame：
(1) 500mg ZIF-8 (one kind of metal organic frame) additions 200mL is contained to the tannic acid (TA) of 3mg/mL
In aqueous solution, it is quickly stirred to react 5min.Then, centrifugation is precipitated, multiple deionized water washing precipitation, freeze-drying, i.e.,
Obtain modified metal organic frame (ZIF-8@TA)；
(2) preparation of aqueous phase solution：By the piperazine of a concentration of 0.5wt%, 0.2wt% sodium hydroxides are dissolved in deionized water
In, a concentration of 0.2wt%ZIF-8@TA are added, ultrasound makes it be uniformly dispersed in 5 minutes；The polysulfones support membrane of hygrometric state is immersed into water
Phase solution, dip time 5min roll support film surface with squeegee after taking-up, extract；
(3) preparation of oil-phase solution：The pyromellitic trimethylsilyl chloride of a concentration of 0.15wt% is dissolved in n-hexane；It will support
Film immerses oil-phase solution, and reaction time 1min takes out；
(4) composite membrane is heat-treated 30 minutes in 70 DEG C of baking ovens.Then it with after deionized water rinsing for several times, obtains containing changing
The composite nanometer filtering film of property metal organic frame.
Comparative example 1
A kind of preparation method of the straight polymer composite nanometer filtering film without any metal organic frame：
(1) preparation of aqueous phase solution：By the piperazine of a concentration of 0.5wt%, 0.2wt% sodium hydroxides are dissolved in deionized water
In；The polysulfones support membrane of hygrometric state is immersed into aqueous phase solution, dip time 5min rolls support membrane table after taking-up with squeegee
Face is extracted；
(2) preparation of oil-phase solution：The pyromellitic trimethylsilyl chloride of a concentration of 0.15wt% is dissolved in n-hexane；It will support
Film immerses oil-phase solution, and reaction time 1min takes out；
(3) composite membrane for obtaining step (2) is heat-treated 30 minutes in 70 DEG C of baking ovens.Then number is rinsed with deionized water
After secondary, the straight polymer composite nanometer filtering film without any metal organic frame is obtained.
Comparative example 2
A kind of preparation method of the composite nanometer filtering film of the unmodified metal organic frame of addition：
(1) preparation of aqueous phase solution：By the piperazine of a concentration of 0.5wt%, 0.2wt% sodium hydroxides are dissolved in deionized water
In, the unmodified metal organic frames of 0.10wt% (ZIF-8) are added；The polysulfones support membrane of hygrometric state is immersed into aqueous phase solution, dipping
Time is 5min, rolls support film surface with squeegee after taking-up, extracts；
(2) preparation of oil-phase solution：The pyromellitic trimethylsilyl chloride of a concentration of 0.15wt% is dissolved in n-hexane；It will support
Film immerses oil-phase solution, and reaction time 1min takes out；
(3) composite membrane for obtaining step (2) is heat-treated 30 minutes in 70 DEG C of baking ovens.Then number is rinsed with deionized water
After secondary, the composite nanometer filtering film containing unmodified metal organic frame is obtained.
Fig. 1 is the comparison diagram of the TEM figures for modification (b) metal organic frame that unmodified (a) is obtained with embodiment 1；Fig. 2 is
The comparison for modification (b, b1) the metal organic frame photo and Hydrophilic Characterization of Hydrophilic photo that unmodified (a, a1) is obtained with embodiment 1
Figure.
Embodiment 1-4, comparative example the 1-2 composite nanometer filtering film prepared are preserved in water, in the aqueous sodium sulfate of 5mmol/L
Liquid, operating pressure test its desalting performance under the conditions of being 0.6MPa, and the results are shown in Table 1.
Table 1
As shown in Table 1, when modified metal organic frame content is 0.10wt% in water phase, the performance of film obtains optimal
Change, water flux is about not 2.3 times of metal organic frame composite membrane of polymer flux under identical preparation condition, while can be kept pair
In the higher cutoff performance of the aqueous sodium persulfate solution of 5mmol/L；Although the composite nanometer filtering film containing unmodified metal organic frame is logical
Amount has a small amount of promotion, but rejection is decreased obviously, and in contrast, the composite nanometer filtering film of addition modified metal organic frame also embodies
Go out clear superiority.
In conclusion metal organic frame is modified and etched to plant polyphenol in the present invention, obtain surface cladding plant polyphenol,
The hollow modified metal organic frame in inner cavity, surface have good hydrophily, can be well dispersed in aqueous phase solution, institute
The phenolic hydroxyl group of band can be reacted with oil phase monomer, so as to have chemical bond interaction with the Motor cortex polymer of composite membrane.Change
Property metal organic frame method of modifying is simple, and operating process is simple, and reaction condition is mild, of low cost, environmentally protective.It obtains
The compatibility of product and polymer is good, stable quality, is suitable for industrial scale and produces.
Modified metal organic frame is scattered in aqueous phase solution, by interfacial polymerization by modified metal organic frame with
Chemical bond form loads in the polymers function cortex of composite nanometer filtering film.Modified metal organic frame is chemically bonded to composite membrane
Polymeric surface layer in so that the contact of inorganic-organic two-phase is even closer, and compatibility is more preferable, and the structure of film is more stable.It is modified
Metal organic frame carries hydrophilic functional group, is conducive to carrying for the water flux of composite nanometer filtering film, hydrophily and antifouling property
It is high.Modified metal organic frame is unique porous and hollow structure can provide additional preferential transmission by film for hydrone and lead to
Road is conducive to composite nanometer filter membrane flux and is further promoted.The phenolic groups that modified metal organic frame carries have free radical
Capturing ability can enhance the anti-chlorine performance of composite nanometer filtering film and stability is used for a long time.
In addition, composite nanometer filtering film production process is easy, of low cost, it is easy to mass, large-scale production；It is obtained compound
NF membrane operating pressure is low, and comprehensive separating property significantly improves, and has good industrialized production basis.
Claims (10)
1. a kind of preparation method of modified metal organic frame, which is characterized in that utilize plant polyphenol modified metal organic frame
While surface, hollow structure is formed inside metal organic frame, obtains modified metal organic frame.
2. the preparation method of modified metal organic frame as described in claim 1, which is characterized in that be specially：Metal is had
Machine frame is dispersed in plant polyphenol aqueous solution, is stirred lower reaction, is obtained modified metal organic frame.
3. the preparation method of modified metal organic frame as claimed in claim 2, which is characterized in that the metal organic frame
For ZIF series materials or MIL series materials.
4. the preparation method of modified metal organic frame as claimed in claim 2, which is characterized in that the plant polyphenol is single
Rather any one or a few in acid, gallic acid, gallic acid and polyvinyl.
5. the preparation method of the modified metal organic frame as described in claim 2 or 4, which is characterized in that the plant polyphenol
A concentration of 0.1~100mg/mL of aqueous solution.
6. the preparation method of modified metal organic frame as claimed in claim 2, which is characterized in that the time of the reaction is
1~60min.
7. a kind of preparation method of the composite nanometer filtering film of organic frame containing modified metal, which is characterized in that appoint claim 1-6
Modified metal organic frame made from the preparation method of modified metal organic frame described in meaning one passes through interfacial polymerization original
Position loads in the aromatic polymer Motor cortex of porous support membrane, obtains the composite nanometer filtering film of the organic frame containing modified metal.
8. the preparation method of the composite nanometer filtering film of the organic frame containing modified metal as claimed in claim 7, which is characterized in that tool
Body is：Porous support membrane is immersed in aqueous phase solution, the discharge excessive solution in surface is taken out, is then immersed in oil-phase solution
Reaction, then thermally treated, rinsing keep porous support membrane poly- in the fragrance of its one layer of loaded modified metal organic frame of Surface Creation
Object Motor cortex is closed, the composite nanometer filtering film of the organic frame containing modified metal is obtained；Wherein, aqueous phase solution is single comprising the first reaction
The aqueous solution of body and modified metal organic frame, oil-phase solution are the organic solution for including the second reaction monomers.
9. the preparation method of the composite nanometer filtering film of the organic frame containing modified metal as claimed in claim 8, which is characterized in that institute
The first reaction monomers are stated using piperazine, N- (2- aminopropyls)-piperazine, N, N- diaminopiperazines, methyl diethanolamine, three ethyl alcohol
Any one or a few in amine, polyethyleneimine, m-phenylene diamine (MPD), o-phenylenediamine and triethylene tetramine, in aqueous phase solution
Mass percent be 0.01~10%；The mass percent of modified metal organic frame is 0.005~5% in aqueous phase solution.
10. the preparation method of the composite nanometer filtering film of the organic frame containing modified metal as claimed in claim 8, which is characterized in that
Second reaction monomers use m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, pyromellitic trimethylsilyl chloride and equal benzene
Any one or a few in four formyl chlorides, the mass percent in oil-phase solution are 0.01~10%.
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