CN105664736A - Polymer blend containing ammonium and phosphate radical zwitterionic groups and preparation method thereof - Google Patents
Polymer blend containing ammonium and phosphate radical zwitterionic groups and preparation method thereof Download PDFInfo
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- CN105664736A CN105664736A CN201610013279.6A CN201610013279A CN105664736A CN 105664736 A CN105664736 A CN 105664736A CN 201610013279 A CN201610013279 A CN 201610013279A CN 105664736 A CN105664736 A CN 105664736A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a blend of two polymers with skeletons respectively containing ammonium ionic group and phosphate radical ionic group and a preparation method thereof. The method consists of: firstly dissolving two polymers containing amino and phosphate group in an aprotic polar solvent according to certain proportion, and then performing sedimentation in deionized water so as to obtain the blend. The polymers are subjected to acidification and heating treatment to obtain a polymer blend material with the skeleton containing zwitterionic groups, the materials have nanofiltration/reverse osmosis desalination performance, and can be applied to the field of water treatment.
Description
Present patent application obtain the young Nsfc Projects of country (project number is: 51503151) and Tianjin science and technology support key special subjects project (contract number is: subsidy 12ZCDZSF07000).
Technical field
The invention belongs to technical field of polymer materials, relate to the preparation field of nanofiltration, anti-penetration wastewater disposal membrane material, particularly to structure of blend polymer containing ammonium root and phosphonate radical amphion group and preparation method thereof, it is a kind of containing amphion membrane for water treatment material and preparation method thereof in particular.
Background technology
In recent years, amphoteric ion polymer (not only containing cation unit but also contain anionic units in polymer) has become as good resistant to pollution material. coating the polymer of class phospholipid on ultrafilter membrane, the both sexes functional group units wherein contained can improve the flux of film and reduce pollution (PolymerInternational, 2009,58 (12): 1350-1361). the existence of relative charge in material so that amphion surface can form the hydration layer of " Free water ", and makes material have good biocompatibility and contamination resistance. at first, (JournalofMembraneScience, 1995,107 (3) 209-218 such as Hawes, JournalofMembraneScience, 2010, 362 (1-2): 326-333) utilize plasma etching technology that amphion graftedzwitterionic2-methacryloyloxy-ethylphosphorylchol ine2-metering system acyloxy-Ethylphosphocholine is grafted to micro-filtration membrane technique [19] .Afterthat of ontosurfacesofpoly (vinylidenefluoride) (PVDF) andcellulose Kynoar (PVDF) and cellulose acetate acetate (CA) microfiltrationmembraneswiththeplasmaetching (CA), the surface of Zhaoetal.tetheredthezwitterionic, improve water and process the performance of micro-filtration membrane. but owing to surface grafting preparation process is complicated, need specific instrument, thus it is unsuitable for a large amount of preparation. (the JournalofMembraneScience such as Jiang, 2009,340 (1): 164-170) being prepared for the random polyacrylonitrile base polymer containing sulfonic acid and ammonium root by direct polymerization and blended with polyacrylonitrile (PAN) be prepared for asymmetric ultrafilter membrane, water flux and the contamination resistance of film all increase. 2012, Cao[Deng (JournalofMembraneScience, 2012, adopt aqueous phase radical reaction to be prepared for novel amphoteric ion polymer PDHD 390-391 (3): 243-253.): and by surface-coated in polysulfone supporting layer after, prepare the NF membrane of compound again with glutaraldehyde cross-linking, obtain higher water flux and contamination resistance.But the preparation of these materials is difficult to control to, and poor chemical stability, easily decomposes.
Polyether aromatic phosphine (or thioether) polymer is high due to its chemical stability, and mechanical performance, heat resistance are good, processes and proton or anion-exchange membrane fuel cells field have a wide range of applications at film water. Functional groups amino in polyether aromatic phosphine (or thioether) polymer of ammonification, is possible not only to directly crosslinking and obtains novel cross-linked polymer compound, and the novel high polymer material that the hydrophilic that can be converted into skeleton cation is controlled. The polyether aromatic phosphine (or thioether) containing ammonium radical ion application in film water process at present rarely has report. Through prior art literature retrieval is found, as far back as nineteen eighty-two Kesting, R.E. just it is prepared for cellulose acetate and the complex reverse osmosis membrane of quaternised poly-piperazine phthalamide, there is good heat stability and chlorine resistance [Report (1982), 49pp]; Kovacs in 2011, JasonR utilizes scattered method layer by layer, it is prepared for the reverse osmosis composite membrane of diallyl dimethyl ammoniumchloride/4-sulfonate polystyrene/montmorillonite, improves the selectivity [PMSEPreprints (2011)] of reverse osmosis membrane.
Macromolecular material containing phosphonic acids has heat stability height, antioxygenic property easy formation hydrogen bond remarkable, intermolecular, content are likely to time higher and keep the very low feature such as swelling. But relatively difficult owing to synthesizing phosphonylation polymer, therefore study relatively fewer for the polymeric material of this class.
The research simultaneously containing the macromolecular material of phosphonic acids and the amino group being connected on macromolecular scaffold with covalent bond in Polymer Blending System at home and abroad still belongs to blank, the strategy of the organic and inorganic doping currently mainly adopted, inorganic salt blended in the macromolecule containing nitrogen or amino phosphoric acid and polymer thereof or phosphoric acid. First phosphoric acid can make nitrogen-atoms protonate, phosphoric acid unnecessary afterwards is present in system with the form of acid freely, improve material hydrophilic, but owing to being non-covalent linkage, the very easily eluted problem of phosphoric acid is not yet solved at present, largely limits their further development and application. Therefore blended containing the macromolecular material of the phosphonic acids macromolecule and the amido-containing group that are connected with covalent bond, both the loss of phosphonic acids can have been avoided, reduce the difficulty of the material of synthesis high molecular, strong hydrogen bonding effect and the ammonium radical ion selectivity to different valence state ion of phosphonyl group can be played again.
Summary of the invention
It is contemplated that prepare a series of chemical stability high, cheap and easily-available, containing zwitterionic macromolecular material, be applied to reverse osmosis, in nanofiltration field.
The invention discloses a kind of can as novel structure and composition containing zwitterionic blend polymer of membrane for water treatment material and preparation method thereof. The structure of two base polymers of blend and composition blend is shown below:
M=0 or 1;
N=1 or 2;
0 < p, q≤1; R, t=1 or 2;
Y=oxygen or sulfur;
X=F,Cl,Br,I,NO3,HSO3,HSO4Or NaSO4;
M=H, first family alkali metal, amine NR1R2R3(R1, R2, R3=H, C1-C6Alkyl or aryl).
Heretofore described, that skeleton contains the polyblend of ammonium root and phosphonium acid ion group respectively preparation method, it is characterised in that undertaken by the steps:
(1) A-poly and P-poly two kinds is contained the polymer of amino and phosphonate group respectively according to certain ratio, be dissolved in high boiling non-protonic solvent, obtain certain density solution;
(2) above-mentioned solution is slowly poured in deionized water, obtains fibrous polymer, then soak 5-10 hour under 60-80 DEG C of condition, repeat 3-5 time, filter, then soak 5-10 hour in 1M aqueous acid, under 60-80 DEG C of condition, repeat 2-3 time, and then soak 5-10 hour in deionized water under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum drying, obtains containing zwitterionic polyblend A-blend-P(m=1, n=2);
(3) the N-Methyl pyrrolidone solution (NMP) (w/v) of the 20% of the A-blend-S prepared from 1M hydrochloric acid is heated to backflow, and keep 1 hour, reduce temperature to 120 DEG C, be then poured into while hot in deionized water, obtain fibrous polymer, then soak 5-10 hour under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum drying, obtains containing zwitterionic polyblend A-blend-P(m=0, n=1).
Heretofore described preparation method, the ratio of A-Poly and P-Poly therein is the ratio of the molal quantity containing amino and phosphonate group, ranges for 0.02:1 to 1:0.02.
Heretofore described preparation method, high boiling point aprotic solvent therein is dimethyl sulfoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
Heretofore described preparation method, the concentration of solution therein is 10-60%.
Heretofore described preparation method, wherein said 1M acid solution is hydrochloric acid, Fluohydric acid., hydrobromic acid, hydroiodic acid, nitric acid, sulfurous acid, sulphuric acid or sodium bisulfate.
After the present invention further discloses the blend polymer film forming containing ammonium root and phosphonate radical amphion group, there is nanofiltration and reverse osmosis performance, it is possible to be widely applied to separating substances, water softening and pure water and the field such as prepare.
Accompanying drawing illustrates:
Fig. 1 contains the structure of the blend polymer of ammonium root and phosphonate radical amphion group.
Detailed description of the invention:
For purposes of simplicity and clarity, the hereafter appropriate description eliminating known technology, in order to avoid those unnecessary details impact descriptions to the technical program. Below in conjunction with comparative example, the present invention is described further. Raw materials used as illustrated especially to be commercially available. Such as A-poly-1 to A-poly-13 etc. are commercially available.
Intrinsic viscosity adopts Ubbelohde viscosimetry to measure, and test temperature is 25 DEG C, and solvent is the nmp solution containing 0.05M lithium bromide.
One, the preparation of blend polymer
1. the alternating polymer containing amino:
2. the atactic polymer containing amino:
3. the atactic polymer containing phosphonate group:
4. the alternating polymer containing phosphonate group:
P-poly-28(intrinsic viscosity: 0.45dL/g)
Embodiment 1-13
Taking A-poly-1 to A-poly-13 to mix with P-poly-7 respectively, it is equal with the molal quantity of the phosphonate group in P-Poly polymer that the quality weighed need to meet the molal quantity of the amino in A-Poly polymer. Above-mentioned solid is dissolved in NMP, making total polymer concentration is 25%(w/v), after fully dissolving, this solution is slowly poured in deionized water, obtain fibrous polymer, then soak 10 hours under 60-80 DEG C of condition, repeat 5 times, filter, again in 1M aqueous hydrochloric acid solution, soak 10 hours under 60-80 DEG C of condition, repeat 3 times, and then soak 10 hours in deionized water under 60-80 DEG C of condition, repeat 5 times, filter, dry, vacuum drying, obtain containing zwitterionic polyblend A-blend-P-1～13-1;
N-Methyl pyrrolidone solution (NMP) (w/v) by the 20% of the A-blend-P-1～13-1 prepared from 1M hydrochloric acid is heated to backflow, and keep 1 hour, reduce temperature to 120 DEG C, be then poured into while hot in deionized water, obtain fibrous polymer, then soak 10 hours under 60-80 DEG C of condition, repeat 5 times, filter, dry, vacuum drying, obtains containing zwitterionic polyblend A-blend-P-1～13-0.
Structure and conversion process for adopting the blended two kinds of blend polymers obtained of A-poly-1 and P-poly-7 describe below, and other blend possesses identical preparation process and result:
Embodiment 14-22
Test method with reference to embodiment 1, by blended to random amino polymer A-poly-14～22 and random phosphonate group polymer P-poly-10～18, it is equal with the molal quantity of the phosphonate group in P-Poly polymer that the quality weighed need to meet the molal quantity of the amino in A-Poly polymer. Obtain blend polymer A-blend-P-14～22-1 and A-blend-S-14～22-0:
Embodiment 23-31
Test method with reference to embodiment 1, by blended to random amino polymer A-poly-14～22 and random phosphonate group polymer P-poly-19～27, it is equal with the molal quantity of the phosphonate group in P-Poly polymer that the quality weighed need to meet the molal quantity of the amino in A-Poly polymer. Obtain blend polymer A-blend-P-14～22-1 and A-blend-P-14～22-0:
Embodiment 32
Test method with reference to embodiment 1, to replace amino polymer A-poly-13 and alternately phosphonate group polymer P-poly-28 is blended, the molal quantity that the quality weighed need to meet the amino in A-Poly polymer is equal with the sulfonic molal quantity in P-Poly polymer. Obtain blend polymer A-blend-P-32-1 and A-blend-P-32-0:
Two, reverse osmosis membrane performance test:
Test condition: 25 DEG C, 2000ppm sodium chloride solution, flow velocity 40.0mLmin-1, pressure 400psi, the time of test is 24h, and wherein the effective area of membrane cisterna test is about 21.22cm2。
Embodiment 33
Take 0.750g blend polymer A-blend-P-20-0, be dissolved in 10.0mLDMAC, after the filter of 0.45 μm filters, by polymer solution curtain coating at leisure on level, clean glass plate (10.0 × 10.0cm). Heat up gradually under a nitrogen atmosphere and be dried, first rise to 60 DEG C of dry 12h, then rise to 90 DEG C of dry 12h, finally rise to 120 DEG C of dry 12h. Again under vacuum, dry 8h at 120 DEG C of temperature. After being cooled to room temperature, film glass plate is soaked and boils 24h in deionized water, after film is obtained diaphragm transparent, that pliability is good, desalination rate 92.5%, water flux 8.3mLd from stripping down glass plate-1。
Three, nanofiltration performance test
Test condition: density of magnesium chloride is 2000ppm (mgL-1), surveying film pressure is that 70psi(is about 0.48MPa), discharge 40mLmin-1, experimental temperature is 25 DEG C, and the time of test is 24h, and wherein the effective area of membrane cisterna test is about 21.22cm2。
Embodiment 34
With reference to the film-forming method of embodiment 33, adopt blend polymer A-blend-P-21-0 to prepare diaphragm, carry out the test of nanofiltration performance, test result: MgCl2Rejection: 85%, water flux 9.8mLd-1。
After the preferred embodiment described in detail, it is familiar with this skilled worker to be clearly understood that, various change and amendment can be carried out under without departing from above-mentioned claim and spirit, all any simple modification, equivalent variations and modifications above example made according to the technical spirit of the present invention, belong to the scope of technical solution of the present invention.
Claims (7)
1. skeleton contains the blend polymer (A-blend-P) of ammonium root and phosphonium acid ion group respectively, and the structure of two base polymers (A-Poly) of composition blend and (P-Poly) is shown below:
M=0 or 1;
N=1 or 2;
0 < p, q≤1; R, t=1 or 2;
Y=oxygen or sulfur;
X=F,Cl,Br,I,NO3,HSO3,HSO4Or NaSO4;
M=H, first family alkali metal, amine NR1R2R3(R1, R2, R3=H, C1-C6Alkyl or aryl).
2. the preparation method that skeleton described in claim 1 contains the polyblend of ammonium root and phosphonium acid ion group respectively, it is characterised in that undertaken by the steps:
(1) A-poly and P-poly two kinds is contained the polymer of amino and phosphonate group respectively according to certain ratio, be dissolved in high boiling non-protonic solvent, obtain certain density solution;
(2) above-mentioned solution is slowly poured in deionized water, obtains fibrous polymer, then soak 5-10 hour under 60-80 DEG C of condition, repeat 3-5 time, filter, then soak 5-10 hour in 1M aqueous acid, under 60-80 DEG C of condition, repeat 2-3 time, and then soak 5-10 hour in deionized water under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum drying, obtains containing zwitterionic polyblend A-blend-P(m=1, n=2);
(3) the N-Methyl pyrrolidone solution (NMP) (w/v) of the 20% of the A-blend-S prepared from 1M hydrochloric acid is heated to backflow, and keep 1 hour, reduce temperature to 120 DEG C, be then poured into while hot in deionized water, obtain fibrous polymer, then soak 5-10 hour under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum drying, obtains containing zwitterionic polyblend A-blend-P(m=0, n=1).
3. the preparation method described in claim 2, the ratio of A-poly and P-poly therein is the ratio of the molal quantity containing amino and phosphonate group, ranges for 0.02:1 to 1:0.02.
4. the preparation method described in claim 2, high boiling point aprotic solvent therein is dimethyl sulfoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
5. the preparation method described in claim 2, the concentration of solution therein is 10-60%.
6. the preparation method described in claim 2, wherein said 1M acid solution is hydrochloric acid, Fluohydric acid., hydrobromic acid, hydroiodic acid, nitric acid, sulfurous acid, sulphuric acid or sodium bisulfate.
7. containing application in preparation nanofiltration, anti-penetration wastewater disposal film after the polyblend film forming of ammonium root and phosphonate radical amphion group described in claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823824A (en) * | 2017-01-18 | 2017-06-13 | 燕山大学 | Carry the preparation method of the polyether sulfone functional membrane of polyamino phosphonic acid functional groups |
| CN106823841A (en) * | 2017-01-18 | 2017-06-13 | 燕山大学 | A kind of preparation method of polyether sulfone function and service seperation film |
| CN109316965A (en) * | 2018-10-22 | 2019-02-12 | 华中科技大学 | Organic phosphonate permeates the application for drawing solute and positive permeability apparatus as positive |
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| CN1364098A (en) * | 1999-04-30 | 2002-08-14 | 托马斯·翰翎 | Step-by-step alkyltion of polymeric amins |
| WO2011028541A2 (en) * | 2009-08-24 | 2011-03-10 | Oasys Water, Inc. | Forward osmosis membranes |
| US20110120941A1 (en) * | 2009-11-24 | 2011-05-26 | International Business Machines Corporation | Composite membranes with performance enhancing layers |
| CN102634010A (en) * | 2012-04-23 | 2012-08-15 | 天津师范大学 | Polymers containing phosphoric acid group and salts thereof, and preparation method and application thereof |
| CN105219060A (en) * | 2015-06-01 | 2016-01-06 | 天津师范大学 | Blend polymer containing ammonium root and sulfonate radical zwitter-ion group and preparation method thereof |
-
2016
- 2016-01-11 CN CN201610013279.6A patent/CN105664736A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364098A (en) * | 1999-04-30 | 2002-08-14 | 托马斯·翰翎 | Step-by-step alkyltion of polymeric amins |
| WO2011028541A2 (en) * | 2009-08-24 | 2011-03-10 | Oasys Water, Inc. | Forward osmosis membranes |
| US20110120941A1 (en) * | 2009-11-24 | 2011-05-26 | International Business Machines Corporation | Composite membranes with performance enhancing layers |
| CN102634010A (en) * | 2012-04-23 | 2012-08-15 | 天津师范大学 | Polymers containing phosphoric acid group and salts thereof, and preparation method and application thereof |
| CN105219060A (en) * | 2015-06-01 | 2016-01-06 | 天津师范大学 | Blend polymer containing ammonium root and sulfonate radical zwitter-ion group and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823824A (en) * | 2017-01-18 | 2017-06-13 | 燕山大学 | Carry the preparation method of the polyether sulfone functional membrane of polyamino phosphonic acid functional groups |
| CN106823841A (en) * | 2017-01-18 | 2017-06-13 | 燕山大学 | A kind of preparation method of polyether sulfone function and service seperation film |
| CN106823824B (en) * | 2017-01-18 | 2019-07-26 | 燕山大学 | Carry the preparation method of the polyether sulfone functional membrane of polyamino phosphonic acid functional groups |
| CN106823841B (en) * | 2017-01-18 | 2019-08-23 | 燕山大学 | A kind of preparation method of polyether sulfone function and service seperation film |
| CN109316965A (en) * | 2018-10-22 | 2019-02-12 | 华中科技大学 | Organic phosphonate permeates the application for drawing solute and positive permeability apparatus as positive |
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