CN104998546B - Ternary mixed ionic polymer and preparation method and application thereof - Google Patents
Ternary mixed ionic polymer and preparation method and application thereof Download PDFInfo
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- CN104998546B CN104998546B CN201510383495.5A CN201510383495A CN104998546B CN 104998546 B CN104998546 B CN 104998546B CN 201510383495 A CN201510383495 A CN 201510383495A CN 104998546 B CN104998546 B CN 104998546B
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- hybrid ionic
- ternary hybrid
- ionic polymer
- ternary
- polysulfones
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001226 reprecipitation Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920002492 poly(sulfone) Polymers 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 9
- 238000000108 ultra-filtration Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 210000001772 blood platelet Anatomy 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 102000004506 Blood Proteins Human genes 0.000 description 1
- 108010017384 Blood Proteins Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a ternary mixed ionic polymer, which is prepared by the following method: mixing styrene, dimethyl carbonate and acrylic acid in ethanol serving as a solvent, adding an ethanol solution of azodiisobutyronitrile serving as an initiator, reacting for 1-20 hours at 50-80 ℃ under the protection of nitrogen, then placing the reaction mixture in a drying oven, drying at 50-70 ℃ in vacuum to obtain a crude product, and purifying the crude product by using a dissolution-reprecipitation method to obtain the ternary mixed ionic polymer; the invention also provides an ultrafiltration membrane modified by the ternary mixed ionic polymer; the invention adopts a blending method to dope the ternary mixed ionic polymer in the whole ultrafiltration membrane, so that the ternary mixed ionic polymer can not be lost in the filtration process to keep the stability of the membrane, and the hydrophilicity, the flux and the biocompatibility of the membrane are greatly improved.
Description
(1) technical field
The present invention relates to a kind of ternary hybrid ionic polymer with carboxyl and amino and preparation method thereof, one is further related to
Milipore filter of ternary hybrid ionic polymer modification described in kind utilization and preparation method thereof, and the milipore filter is in UF membrane
During application.
(2) background technology
Membrane separation technique refer to by one have selection performance film mixture is separated under external force,
Purification, a kind of separation method of concentration.Because its separative efficiency is high, pollution-free, easy to operate, floor space is small, it is easy to and other
The advantages of technology is combined is widely used in the fields such as water process, chemical industry, medicine, food processing, military and national defense.Ultrafiltration can be with
The materials such as bacterium, larger molecular organics matter, colloidal particles, virus in trap water.Hyperfiltration technique is while its advantage is shown
Also some shortcomings, such as fouling membrane have been manifested.Fouling membrane easily causes flux to decline, operating pressure increase and film service life are dropped
Low harm.The main matter of Pollution of Ultrafiltration Membrane has organic matter, colloid and microorganism.At present, it is reduction fouling membrane, the parent of film
Water is modified to be widely studied.Its method mainly has cladding process, Graft Method and blending method.Blending method is because of its modified firmly, operation
The simple emphasis for turning into research with the features such as industrializing is easy to.Hybrid ionic polymer is total to because of its unique hydrophilicity
It is mixed to be added to the absorption that film interior energy effectively changes the surface contaminant of film.
(3) content of the invention
Ternary hybrid ionic polymer it is an object of the invention to provide a kind of high-hydrophilic and preparation method thereof, while also
A kind of milipore filter of ternary hybrid ionic polymer modification described in and preparation method thereof is provided, and the milipore filter exists
Application in membrane separating process.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of ternary hybrid ionic polymer, the ternary hybrid ionic polymer is prepared as follows obtaining：
Styrene (St), dimethyl carbonate (DMC), acrylic acid (AA) are mixed in etoh solvent, initiation is subsequently adding
The ethanol solution of agent azodiisobutyronitrile (AIBN), under nitrogen protection, 1~20h is reacted at 50~80 DEG C, afterwards mixes reaction
Thing is placed in baking oven, and vacuum drying obtains crude product at 50~70 DEG C, and gained crude product is purified with Solution reprecipitation method,
Obtain described ternary hybrid ionic polymer (PSt-DMC-AA)；
The ratio between the styrene and dimethyl carbonate, the amount of acrylic acid material that feeds intake are 4~9：1：1；The solvent second
The volumetric usage of alcohol is calculated as 1~2mL/mmol with the amount of acrylic acid material；The ethanol of the initiator azodiisobutyronitrile is molten
The volumetric usage of liquid is calculated as 0.3~0.7mL/mmol with the amount of acrylic acid material；The second of the initiator azodiisobutyronitrile
The concentration of azodiisobutyronitrile is 0.3~0.7mmol/mL in alcoholic solution.
Ternary hybrid ionic polymer of the present invention, in the preparation method, preferable reaction temperature is 70~80 DEG C, during reaction
Between be 4~8h.
It is described purification crude product Solution reprecipitation method be：First crude product is dissolved in ethanol, the precipitation that then adds water is heavy
Starch, is collected by filtration sediment, repeats above procedure 3 times, collects last time gained sediment and dries, and obtains ternary mixing
Ionomer.
Present invention also offers a kind of milipore filter using described ternary hybrid ionic polymer modification, the milipore filter
It is prepared as follows obtaining：
The ternary hybrid ionic copolymer and polysulfones are dissolved in dimethylacetylamide (DMAc), are stirred at 70~90 DEG C
Mix and uniformly obtain casting solution, 10~20min of ultrasound removes bubble after gained casting solution is stood into 20~40min, then uses scraper
The casting solution casting of bubble will be stripped of on a glass, after 5~60s of evaporation, be put into 0~5 DEG C of deionized water and solidified 50
~70s, obtains final product described milipore filter, and gained milipore filter is stored in 2wt%~5wt% formalins；
Gross mass based on ternary hybrid ionic copolymer and polysulfones, the quality percentage of the ternary hybrid ionic copolymer
Number is 1%~30% (preferably 10%), balance of polysulfones；The volumetric usage of the dimethylacetylamide is common with ternary hybrid ionic
The quality summation of polymers and polysulfones is calculated as 6~10mL/g；Casting solution casting thickness on a glass is 180~220 μm.
Milipore filter of the present invention is finger-like composite membrane, and thickness is 80~120 μm, and aperture is 10~30nm, and porosity is big
In 75%.
Application of the film of the present invention in ultrafiltration, the method for the application is pressure filtration, cross film pressure be 0.1~
0.4MPa。
Compared with prior art, the beneficial effects of the present invention are：
(1) positively charged is polymerized with electronegative Orqanics Monomer using the method for easy polymerisation in solution to be formed mixing from
Sub- polymer；
(2) method using blending is polymer-doped in whole milipore filter by ternary hybrid ionic, makes it will not be in mistake
It is lost in keep the stability of film during filter.
(3) ternary hybrid ionic polymer blending modification, can greatly improve hydrophily, flux and the bio-compatible of film
Property.
(4) illustrate
Fig. 1 is the SEM figures of the milipore filter prepared by the embodiment of the present invention 2.
Fig. 2 is the SEM figures of the milipore filter prepared by comparative example of the present invention 1.
(5) specific embodiment
Technical scheme is described further below by specific embodiment, but protection scope of the present invention
Not limited to this.
Embodiment 1
(1) PSt-DMC-AA is prepared：Weigh St (4.17g, 40mmol), DMC (0.90g, 10mmol), AA (0.72g,
10mmol), it is mixed in etoh solvent (15mL), then mixed liquor is transferred in four-hole boiling flask, is subsequently added into 0.5mmol/
The ethanol solution (5mL) of mL initiator As IBN, under nitrogen protection, 6h is reacted at 70 DEG C, and reactant mixture is placed in into 50 DEG C afterwards
Vacuum drying oven is dried, and obtains crude product, is used Solution reprecipitation method to purify, and removes autopolymer and monomer.Method of purification is：
Gained crude product about 1.3g is dissolved in ethanol (20mL), then add water (40mL) precipitation sediment, and sediment is collected by filtration,
Repeat above procedure 3 times, collect last time gained sediment and dry, obtain ternary hybrid ionic polymer about 1.2g.
(2) milipore filter is prepared：Ternary hybrid ionic copolymer (0.03g) and polysulfones (2.97g) that step (1) is obtained are molten
In DMAc (24mL), casting solution is uniformly mixing to obtain at 70 DEG C, ultrasound 15min takes off after gained casting solution is stood into 30min
Bubble removing, the casting solution that then will be stripped of bubble with scraper is cast on a glass, and casting thickness is 200 μm, evaporates 30s
Afterwards, it is put into 5 DEG C of deionized waters and solidifies 60s, obtain described milipore filter, after placing 2 days in deionized water, is stored in
2wt% formalins, in order to avoid the growth of microorganism.
The pure water flux of film is detected, after tested, the pure water flux of film is 187.38 (L/m2/ h), gained film is to BSA albumen
The rejection of matter is 95.3%, and non-reversible pollution is 8%, and gained film is zero to blood platelet and bacterial adsorption.
Embodiment 2
(1) PSt-DMC-AA is prepared：With the step of embodiment 1 (1).
(2) milipore filter is prepared：In addition to inventory ternary hybrid ionic copolymer (0.3g) and polysulfones (2.7g), remaining
With the step of embodiment 1 (2).
The pure water flux of film is detected, after tested, the pure water flux of film is 258.32 (L/m2/ h), gained film is to BSA albumen
The rejection of matter is 93.2%, and non-reversible pollution is 0%, and gained film is zero to blood platelet and bacterial adsorption.
Embodiment 3
(1) PSt-DMC-AA is prepared：Outside inventory St (7.29g, 70mmol), remaining is with the step of embodiment 1
(1)。
(2) milipore filter is prepared：In addition to inventory ternary hybrid ionic copolymer (0.9g) and polysulfones (2.1g), remaining
With the step of embodiment 1 (2).
The pure water flux of film is detected, after tested, the pure water flux of film is 344.68 (L/m2/ h), gained film is to BSA albumen
The rejection of matter is 91.3%, and non-reversible pollution is 0%, and gained film is zero to blood platelet and bacterial adsorption.
Embodiment 4
(1) PSt-DMC-AA is prepared：Outside inventory St (9.37g, 90mmol), remaining is with the step of embodiment 1
(1)。
(2) milipore filter is prepared：In addition to inventory ternary hybrid ionic copolymer (0.03g) and polysulfones (2.97g), its
The remaining step of same embodiment 1 (2).
The pure water flux of film is detected, after tested, the pure water flux of film is 178.32 (L/m2/ h), gained film is to BSA albumen
The rejection of matter is 98.2%, and non-reversible pollution is 3%, and gained film is zero to blood platelet and bacterial adsorption.
Comparative example 1
To embody the advantage of hybrid ionic polymer addition, pure PS membrane is prepared, preparation method is with the step of embodiment 1
(2) ternary hybrid ionic copolymer, is simply added without in casting solution, the pure water flux of gained film is 73.72 (L/m2/ h), it is right
The rejection 95.8% of BSA protein, blood platelet and bacterium have a large amount of absorption on film surface.
Claims (5)
1. a kind of ternary hybrid ionic polymer, it is characterised in that the ternary hybrid ionic polymer is prepared as follows
Obtain：
Styrene, dimethyl carbonate, acrylic acid are mixed in etoh solvent, the second of initiator azodiisobutyronitrile is subsequently adding
Alcoholic solution, under nitrogen protection, 1~20h is reacted at 50~80 DEG C, reactant mixture is placed in baking oven afterwards, at 50~70 DEG C
Lower vacuum drying obtains crude product, and gained crude product is purified with Solution reprecipitation method, obtains described ternary hybrid ionic and gathers
Compound；
The ratio between the styrene and dimethyl carbonate, the amount of acrylic acid material that feeds intake are 4~9：1：1；The etoh solvent
Volumetric usage is calculated as 1~2mL/mmol with the amount of acrylic acid material；The ethanol solution of the initiator azodiisobutyronitrile
Volumetric usage is calculated as 0.3~0.7mL/mmol with the amount of acrylic acid material；The ethanol of the initiator azodiisobutyronitrile is molten
The concentration of azodiisobutyronitrile is 0.3~0.7mmol/mL in liquid.
2. ternary hybrid ionic polymer as claimed in claim 1, it is characterised in that reaction temperature is 70~80 DEG C, reaction
Time is 4~8h.
3. ternary hybrid ionic polymer as claimed in claim 1, it is characterised in that the dissolving of the purification crude product-again
The precipitation method are：First crude product is dissolved in ethanol, then add water precipitation sediment, sediment is collected by filtration, repeat above mistake
Journey 3 times, collects last time gained sediment and dries, and obtains ternary hybrid ionic polymer.
4. the milipore filter of the ternary hybrid ionic polymer modification described in a kind of utilization claim 1, it is characterised in that described super
Filter membrane is prepared as follows obtaining：
The ternary hybrid ionic copolymer and polysulfones are dissolved in dimethylacetylamide（DMAc）In, stir equal at 70~90 DEG C
Even to obtain casting solution, 10~20min of ultrasound removes bubble after gained casting solution is stood into 20~40min, then will be de- with scraper
Except bubble casting solution casting on a glass, after 5~60s of evaporation, be put into solidification 50 in 0~5 DEG C of deionized water~
70s, obtains final product described milipore filter, and gained milipore filter is stored in 2wt%~5wt% formalins；
Gross mass based on ternary hybrid ionic copolymer and polysulfones, the mass percent of the ternary hybrid ionic copolymer is
1%~30%, balance of polysulfones；The volumetric usage of the dimethylacetylamide is with ternary hybrid ionic copolymer and the quality of polysulfones
Summation is calculated as 6~10mL/g；Casting solution casting thickness on a glass is 180~220 μm.
5. milipore filter as claimed in claim 4, it is characterised in that the total matter based on ternary hybrid ionic copolymer and polysulfones
Amount, the mass percent of the ternary hybrid ionic copolymer is 10%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220121A (en) * | 2008-01-22 | 2008-07-16 | 张武兴 | Green acrylic resin and preparation method for green acrylic resin road surface reticule paint |
| CN103357277A (en) * | 2013-07-24 | 2013-10-23 | 浙江师范大学 | Ultrafiltration membrane with heavy metal ion adsorption function, and preparation method thereof |
| CN103441230A (en) * | 2013-08-21 | 2013-12-11 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane, preparation method thereof and electrochemical device |
-
2015
- 2015-06-30 CN CN201510383495.5A patent/CN104998546B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220121A (en) * | 2008-01-22 | 2008-07-16 | 张武兴 | Green acrylic resin and preparation method for green acrylic resin road surface reticule paint |
| CN103357277A (en) * | 2013-07-24 | 2013-10-23 | 浙江师范大学 | Ultrafiltration membrane with heavy metal ion adsorption function, and preparation method thereof |
| CN103441230A (en) * | 2013-08-21 | 2013-12-11 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane, preparation method thereof and electrochemical device |
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