CN102389724A - Preparation method and use of carboxyl-modified polyacrylonitrile nano fiber membrane - Google Patents
Preparation method and use of carboxyl-modified polyacrylonitrile nano fiber membrane Download PDFInfo
- Publication number
- CN102389724A CN102389724A CN2011102877955A CN201110287795A CN102389724A CN 102389724 A CN102389724 A CN 102389724A CN 2011102877955 A CN2011102877955 A CN 2011102877955A CN 201110287795 A CN201110287795 A CN 201110287795A CN 102389724 A CN102389724 A CN 102389724A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile nano
- tunica fibrosa
- water
- nano tunica
- carboxyl modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method and use of a carboxyl-modified polyacrylonitrile nano fiber membrane. In the method, a polyacrylonitrile nano fiber membrane prepared by an electrostatic spinning technique is used as a raw material, the polyacrylonitrile nano fiber membrane is subjected to carboxyl modification by alkali solution, and thus, the carboxyl-modified polyacrylonitrile nano fiber membrane is obtained. The carboxyl-modified polyacrylonitrile nano fiber membrane obtained by the method can be used for purifying running water polluted by metal ions so as to improve the life quality of people. The running water treated by the method disclosed by the invention has a very obvious metal ion separation effect.
Description
Technical field
The present invention relates to a kind of carboxyl modified the polyacrylonitrile nano tunica fibrosa the preparation method and be used for the purposes of the water purification of metal ion pollution.
Background technology
In recent years; The nano fibrous membrane of electrostatic spinning technique preparation has obtained broad research; The nano fibrous membrane of this method preparation has that fibre diameter is little, specific area is high, porosity is high, and therefore, the nano fibrous membrane of electrostatic spinning technique preparation is easy to be applied to water purification as filter membrane material.In addition, this method can be mass-produced because of its manufacturing process is simple, makes this technology have bigger application potential in the film field.Yet common high polymer nanometer fiber membrane has chemical inertness, except filtration and as there not being special function the backing material.Therefore will expand its application greatly to the further rhetorical functionization of high polymer nanometer fiber membrane.Polyacrylonitrile nano tunica fibrosa with electrostatic spinning technique preparation is a raw material in the present invention, synthetic a kind of polyacrylonitrile nano fiber film material in order to the carboxyl modified of removing the metal ion in the water.
Summary of the invention
The object of the invention is, in order to solve the chemically inert problem of existing high polymer nanometer fiber membrane, and a kind of preparation method of polyacrylonitrile nano tunica fibrosa of carboxyl modified is provided.This method is a raw material with the polyacrylonitrile nano tunica fibrosa of electrostatic spinning technique preparation, uses alkaline solution that the polyacrylonitrile nano tunica fibrosa is carried out carboxyl modified, thereby obtains the polyacrylonitrile nano tunica fibrosa of carboxyl modified.The polyacrylonitrile nano tunica fibrosa of the carboxyl modified that obtains through this method can be applicable to purify the running water of metal ion pollution.
The preparation method of the polyacrylonitrile nano tunica fibrosa of carboxyl modified of the present invention follows these steps to carry out:
A, the polyacrylonitrile nano tunica fibrosa under agitation placed contain the aqueous solution that alkali is NaOH, ammoniacal liquor or potassium hydroxide 5-25%;
B, be heated to temperature 30-90 ℃, after reaction time 0.5-3 hour, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, with the polyacrylonitrile nano tunica fibrosa that step b obtains carboxyl modified, through water washing 5 times, can obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified.
The step a aqueous solution is deionized water, distilled water or polymer solution in water.
Step b is described to be heated to be water-bath heating, oil bath heating, sand bath heating or air bath heating.
The described water washing of step c is deionized water, distilled water, soda water, salt solution or running water washing.
The purposes of polyacrylonitrile nano tunica fibrosa in the water purification from the beginning of metal ion pollution of the carboxyl modified that said method obtains.
Described metal ion is copper, cadmium, lead, calcium or magnesium ion.
The Preparation method and use of the polyacrylonitrile nano tunica fibrosa of carboxyl modified of the present invention, the reaction equation of this method is:
The Preparation method and use of the polyacrylonitrile nano tunica fibrosa of carboxyl modified of the present invention; The polyacrylonitrile partial hydrolysis in aqueous slkali that is based in the nano fibrous membrane forms carboxyl; Thereby the polyacrylonitrile nano tunica fibrosa of carboxyl modified is applied to the water purification from the beginning of metal ion pollution; Carboxyl be easy to water in copper, cadmium, lead, calcium or magnesium ion combine and adsorb, so bigger value will be arranged in water purification from the beginning.
Description of drawings
Fig. 1 is a stereoscan photograph of the present invention, and wherein 1 for before modifying, 2 be carboxyl modified after.
Fig. 2 is an infrared spectrogram of the present invention, and wherein 1 for before modifying, 2 be carboxyl modified after.
Fig. 3 purifies copper ions water effect contrast figure for the present invention, and wherein 1 is Cu concentration in the water before handling, and 2 are Cu concentration in the water behind the use polyacrylonitrile nano Fibrous membrane filtration, and 3 are Cu concentration in the water behind the polyacrylonitrile nano Fibrous membrane filtration that uses carboxyl modified.
The specific embodiment
A, under agitation with polyacrylonitrile nano tunica fibrosa 1g, placing 10ml concentration is 5% to contain the deionized water solution that alkali is NaOH;
B, with step a solution water-bath heating, temperature is 90 ℃, after 0.5 hour reaction time, obtains the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, step b is obtained the polyacrylonitrile nano tunica fibrosa of carboxyl modified,, promptly obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified through deionized water washing 5 times.
The application of polyacrylonitrile nano tunica fibrosa in the running water that metal copper ion pollutes purifies of the carboxyl modified that obtains through this method.
A, under agitation with polyacrylonitrile nano tunica fibrosa 1g, placing 25ml concentration is 10% to contain the polymer solution in water of alkali NaOH;
B, with step a solution sand bath heating, 50 ℃ of temperature after 1 hour reaction time, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, step b is obtained the polyacrylonitrile nano tunica fibrosa of carboxyl modified,, promptly obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified through running water washing 5 times.
The application of the polyacrylonitrile nano tunica fibrosa of the carboxyl modified that said method obtains in the running water that metal copper ion pollutes purifies.
A, under agitation with polyacrylonitrile nano tunica fibrosa 1g, placing 50ml concentration is 15% to contain the distilled water solution of alkali NaOH;
B, with step a solution air bath heating, 60 ℃ of temperature after 1.5 hours reaction time, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, step b is obtained the polyacrylonitrile nano tunica fibrosa of carboxyl modified,, promptly obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified through distilled water washing 5 times.
The application of polyacrylonitrile nano tunica fibrosa in the running water of metallic lead ionic soil purifies of the carboxyl modified that obtains through this method.
Embodiment 4
A, under agitation with polyacrylonitrile nano tunica fibrosa 1g, placing 80ml concentration is 18% to contain the deionized water solution of alkali potassium hydroxide;
B, with step a solution sand bath heating, 75 ℃ of temperature after 2 hours reaction time, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, step b is obtained the polyacrylonitrile nano tunica fibrosa of carboxyl modified,, promptly obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified through soda water washing 5 times.
The application of polyacrylonitrile nano tunica fibrosa in the running water of calcium metal ionic soil purifies of the carboxyl modified that obtains through this method.
Embodiment 5
A, under agitation with polyacrylonitrile nano tunica fibrosa 1g, placing 100ml concentration is 25% to contain the polymer solution in water of alkali ammoniacal liquor;
B, with step a solution oil bath heating, 30 ℃ of temperature after 3 hours reaction time, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, step b is obtained the polyacrylonitrile nano tunica fibrosa of carboxyl modified,, promptly obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified through brine wash 5 times.
The application of polyacrylonitrile nano tunica fibrosa in the running water of magnesium metal ionic soil purifies of the carboxyl modified that obtains through this method.
Embodiment 6
A, under agitation with polyacrylonitrile nano tunica fibrosa 1g, placing 80ml concentration is 20% to contain the polymer solution in water of alkali NaOH;
B, with step a solution water-bath heating, 80 ℃ of temperature after 2.5 hours reaction time, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, step b is obtained the polyacrylonitrile nano tunica fibrosa of carboxyl modified,, promptly obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified through deionized water washing 5 times.
The application of the polyacrylonitrile nano tunica fibrosa of the carboxyl modified that said method obtains in the running water that metal copper ion pollutes purifies.
The preparation method of the polyacrylonitrile nano tunica fibrosa of carboxyl modified of the present invention; The polyacrylonitrile nano tunica fibrosa has a large amount of hole (Fig. 1); Aqueous slkali can be easy to get in the film, contacts with the nanofiber surface, and makes the polyacrylonitrile part group hydrolysis of fiber surface.The ESEM picture of sample was as shown in Figure 1 before and after the polyacrylonitrile nano tunica fibrosa was modified; Among Fig. 11 is polyacrylonitrile nano tunica fibrosa ESEM picture before modifying; The polyacrylonitrile nano fibre diameter is at 100-300nm; The fiber porous fibre film that together forms straggly, tunica fibrosa has than the diameter of homogeneous and hole; Among Fig. 12 modifies back polyacrylonitrile nano tunica fibrosa ESEM picture, and after modifying, the polyacrylonitrile nano tunica fibrosa has kept the porous nano-fibre membrane property of original nano fibrous membrane.
FT-IR detects and has shown that further it is respectively polyacrylonitrile nano tunica fibrosa and the FFIR (FTIR) of polyacrylonitrile nano tunica fibrosa after NaOH is carboxy-modified that the polyacrylonitrile nano tunica fibrosa is successfully modified carboxyl: Fig. 2; As shown in Figure 2, modify former and later two samples at 2245cm
-1All occur very strong characteristic absorption peak respectively, this is the characteristic absorption peak of cyanic acid (C ≡ N).This also explains and uses the NaOH modification, is the local modifications such as surface to the polyacrylonitrile nano fiber, so the nano fibrous membrane after the NaOH modification still contains a large amount of cyanic acid.Through two spectrograms relatively, after carboxyl modified in the polyacrylonitrile nano tunica fibrosa, at 1668cm
-1A carboxylic carbonyl infrared signature vibration peak (v clearly appears
C=0) absworption peak, show that NaOH successfully modifies the polyacrylonitrile nano tunica fibrosa to have gone up carboxyl.Is feasible with alkali to the method for polyacrylonitrile nano tunica fibrosa modification, can make the part itrile group hydrolysis on the polyacrylonitrile nano tunica fibrosa generate carboxyl.
With the copper ion is example: elect in the water copper ion as typical metal ion, Fig. 3 has shown that initial concentration is the water polyacrylonitrile nano Fibrous membrane filtration adsorption effect through polyacrylonitrile nano tunica fibrosa, carboxyl modified respectively of 6ppm cupric.Experiment finds that initial concentration is the cupric water of 6ppm, and the polyacrylonitrile nano tunica fibrosa has only adsorbed 10.11% copper; And the polyacrylonitrile nano tunica fibrosa of carboxyl modified has adsorbed 93.20% copper, and the polyacrylonitrile nano tunica fibrosa after the carboxyl modified is remarkable to the adsorption of metal ions effect.
Claims (6)
1. the preparation method of the polyacrylonitrile nano tunica fibrosa of a carboxyl modified is characterized in that following these steps to carrying out:
A, the polyacrylonitrile nano tunica fibrosa under agitation placed contain the aqueous solution that alkali is NaOH, ammoniacal liquor or potassium hydroxide 5-25%;
B, be heated to temperature 30-90 ℃, after reaction time 0.5-3 hour, obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified;
C, with the polyacrylonitrile nano tunica fibrosa that step b obtains carboxyl modified, through water washing 5 times, can obtain the polyacrylonitrile nano tunica fibrosa of carboxyl modified.
2. method according to claim 1 is characterized in that the step a aqueous solution is deionized water, distilled water or polymer solution in water.
3. method according to claim 2 is characterized in that step b is described to be heated to be water-bath heating, oil bath heating, sand bath heating or air bath heating.
4. method according to claim 3 is characterized in that the described water washing of step c is deionized water, distilled water, soda water, salt solution or running water washing.
5. the purposes of polyacrylonitrile nano tunica fibrosa in the water purification from the beginning of metal ion pollution of the carboxyl modified that method according to claim 1 obtains.
6. purposes according to claim 5 is characterized in that described metal ion is copper, cadmium, lead, calcium or magnesium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102877955A CN102389724A (en) | 2011-09-26 | 2011-09-26 | Preparation method and use of carboxyl-modified polyacrylonitrile nano fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102877955A CN102389724A (en) | 2011-09-26 | 2011-09-26 | Preparation method and use of carboxyl-modified polyacrylonitrile nano fiber membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102389724A true CN102389724A (en) | 2012-03-28 |
Family
ID=45857181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102877955A Pending CN102389724A (en) | 2011-09-26 | 2011-09-26 | Preparation method and use of carboxyl-modified polyacrylonitrile nano fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102389724A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349916A (en) * | 2013-06-13 | 2013-10-16 | 东华大学 | In-situ preparation method of functional nano-grade zero-valent iron/polymer composite film |
| CN104264453A (en) * | 2014-09-09 | 2015-01-07 | 天津工业大学 | Manufacturing method of adsorption cationic fiber membrane |
| CN108061716A (en) * | 2017-12-15 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of carboxy-functionalized modified acrylic fibre is to the selective absorbing detection method of heavy metal cadmium ion |
| CN110804856A (en) * | 2019-10-21 | 2020-02-18 | 南通大学 | Acrylic fabric for photocatalytic degradation of reactive dye and preparation method thereof |
| CN111672328A (en) * | 2020-06-04 | 2020-09-18 | 中国科学技术大学 | Carboxylated polyacrylonitrile porous membrane for removing fluorine and preparation method thereof |
| CN112892248A (en) * | 2021-01-28 | 2021-06-04 | 吉林大学 | Coating modified PAN nanofiber filtering membrane, preparation method and application thereof, PAN filtering material and application thereof |
| CN114007743A (en) * | 2019-06-20 | 2022-02-01 | 日本爱克兰工业株式会社 | Ion exchange fiber and ion exchange filter containing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4113418A1 (en) * | 1991-04-25 | 1992-10-29 | Bayer Ag | Hollow fibres of polyacrylonitrile for membrane applications - are made swellable on sepn.-active face by hydrolysis with strong alkali to improve sepn. limits |
| CN101507903A (en) * | 2009-02-27 | 2009-08-19 | 北京工业大学 | Polyacrylonitrile ultrafiltration membrane surface hydrolysis method |
| CN101844041A (en) * | 2010-06-07 | 2010-09-29 | 苏州信望膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
-
2011
- 2011-09-26 CN CN2011102877955A patent/CN102389724A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4113418A1 (en) * | 1991-04-25 | 1992-10-29 | Bayer Ag | Hollow fibres of polyacrylonitrile for membrane applications - are made swellable on sepn.-active face by hydrolysis with strong alkali to improve sepn. limits |
| CN101507903A (en) * | 2009-02-27 | 2009-08-19 | 北京工业大学 | Polyacrylonitrile ultrafiltration membrane surface hydrolysis method |
| CN101844041A (en) * | 2010-06-07 | 2010-09-29 | 苏州信望膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
Non-Patent Citations (9)
| Title |
|---|
| 《浙江理工大学学报》 20100908 陈勇 水解PAN纳米纤维膜对Cu(Ⅱ)离子的吸附性能 第529-532页 1-6 第27卷, 第4期 * |
| 《精细石油化工进展》 20091231 李玲等 聚丙烯腈离子交换纤维的制备 第27-29页 1-6 第10卷, 第12期 * |
| 华东石油学院: "《钻井泥浆》", 30 June 1975 * |
| 孙小莉等: "聚丙烯腈基离子交换纤维制备研究进展", 《合成纤维》 * |
| 李玲等: "聚丙烯腈离子交换纤维的制备", 《精细石油化工进展》 * |
| 李留忠等: "废腈纶水解物的制备与表征", 《高分子材料科学与工程》 * |
| 梁志宏等: "羧酸钠型离子交换纤维对Cu~(2+)的吸附性能研究", 《合成纤维工业》 * |
| 郭静等: "腈纶废丝的水解及其产物的应用", 《合成纤维工业》 * |
| 陈勇: "水解PAN纳米纤维膜对Cu(Ⅱ)离子的吸附性能", 《浙江理工大学学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349916A (en) * | 2013-06-13 | 2013-10-16 | 东华大学 | In-situ preparation method of functional nano-grade zero-valent iron/polymer composite film |
| CN103349916B (en) * | 2013-06-13 | 2015-07-08 | 东华大学 | In-situ preparation method of functional nano-grade zero-valent iron/polymer composite film |
| CN104264453A (en) * | 2014-09-09 | 2015-01-07 | 天津工业大学 | Manufacturing method of adsorption cationic fiber membrane |
| CN108061716A (en) * | 2017-12-15 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of carboxy-functionalized modified acrylic fibre is to the selective absorbing detection method of heavy metal cadmium ion |
| CN114007743A (en) * | 2019-06-20 | 2022-02-01 | 日本爱克兰工业株式会社 | Ion exchange fiber and ion exchange filter containing the same |
| CN114007743B (en) * | 2019-06-20 | 2023-09-15 | 日本爱克兰工业株式会社 | Ion exchange fiber and ion exchange filter containing the same |
| CN110804856A (en) * | 2019-10-21 | 2020-02-18 | 南通大学 | Acrylic fabric for photocatalytic degradation of reactive dye and preparation method thereof |
| CN111672328A (en) * | 2020-06-04 | 2020-09-18 | 中国科学技术大学 | Carboxylated polyacrylonitrile porous membrane for removing fluorine and preparation method thereof |
| CN111672328B (en) * | 2020-06-04 | 2021-10-22 | 中国科学技术大学 | Carboxylated polyacrylonitrile porous membrane for removing fluorine and preparation method thereof |
| CN112892248A (en) * | 2021-01-28 | 2021-06-04 | 吉林大学 | Coating modified PAN nanofiber filtering membrane, preparation method and application thereof, PAN filtering material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102389724A (en) | Preparation method and use of carboxyl-modified polyacrylonitrile nano fiber membrane | |
| CN110026091B (en) | Ionic liquid modified positively charged composite nanofiltration membrane and preparation method thereof | |
| Huang et al. | Electrospun fibrous membranes for efficient heavy metal removal | |
| US20110163035A1 (en) | Nanofiber-containing membrane, a composite membrane, a process for producing them and their use | |
| CN109295713B (en) | Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers | |
| CN113769593B (en) | Nanofiltration membrane for extracting lithium from salt lake and preparation method thereof | |
| CN110975821A (en) | Silicon dioxide and calcium alginate composite metal ion adsorbent, preparation method and application | |
| CN111921388B (en) | Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof | |
| CN111282456B (en) | Forward osmosis membrane for efficiently intercepting heavy metals and preparation method and application thereof | |
| Chong et al. | Adsorptive membranes for heavy metal removal–A mini review | |
| CN112195566A (en) | Composite fiber membrane for heavy metal sewage treatment and preparation method thereof | |
| CN102701497A (en) | Method for recycling cyanide from electroplating cyanide-containing wastewater | |
| CN111804149A (en) | Production method of super-hydrophobic, wetting-resistant and scaling-resistant hybrid nanofiber composite membrane for membrane distillation | |
| CN113600147A (en) | Preparation method of heavy metal ion adsorption fiber membrane material | |
| CN104707573A (en) | Preparation method of cadmium removal agent of thiolated chitosan microsphere | |
| JP2010138430A (en) | Metal recovery material and method for recovering platinum group metal | |
| KR102033119B1 (en) | Antibacterial and antiviral positive electric charge-filter and method of manufacturing using the same | |
| CN112191233A (en) | Three-dimensional net-shaped composite magnetic material for sewage treatment and preparation method thereof | |
| CN109364774B (en) | Ionic polymer and graphene oxide nano composite membrane and preparation method and application thereof | |
| CN104289199A (en) | Preparation method of magnetic HPCS/GO adsorbing agent for removing heavy metals and application | |
| CN110655138A (en) | Preparation method and application of MOFs composite material | |
| Nthumbi et al. | Method development for flow adsorption and removal of lead and copper in contaminated water using electrospun nanofibers of chitosan blend | |
| CN112316753B (en) | Preparation method of high-flux loose hollow fiber nanofiltration membrane | |
| KR100727576B1 (en) | Ion-exchange fiber filter for absorbing lithium, method for manufacturing the same, and method for recovering lithium | |
| CN113304730A (en) | Preparation method of special adsorbent for cobalt recovery in waste ternary batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120328 |