CN105219060A - Blend polymer containing ammonium root and sulfonate radical zwitter-ion group and preparation method thereof - Google Patents
Blend polymer containing ammonium root and sulfonate radical zwitter-ion group and preparation method thereof Download PDFInfo
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Abstract
The invention discloses skeleton and contain blend of two base polymers of ammonium root and sulfonate ion group and preparation method thereof respectively.To first be dissolved in aprotic polar solvent according to certain ratio containing two base polymers that are amino and sulfonic acid group respectively, then sedimentation in deionized water, obtains blend.These polymkeric substance, through acidifying, heat treated, obtain the poyblend material that skeleton contains zwitter-ion group, and these materials have nanofiltration/reverse osmosis desalination performance, can be applied to water treatment field.
Description
Application obtains the subsidy of Tianjin State Scientific and Technological Commission science and technology support main project (contract number is: 12ZCDZSF07000) and national " 863 " project (project number is: 2012AA03A601).
Technical field
The invention belongs to technical field of polymer materials, relate to the preparation field of nanofiltration, anti-penetration wastewater disposal mould material, in particular to the structure and preparation method thereof of the blend polymer containing ammonium root and sulfonate radical zwitter-ion group, be a kind of containing zwitter-ion membrane for water treatment material and high efficiency preparation method thereof in particular.
Background technology
In recent years, not only positively charged ion unit is contained but also become good resistant to pollution material containing anionic units in amphoteric ion polymer-polymkeric substance.Ultra-filtration membrane is coated the polymkeric substance of class phosphatide, the both sexes functional group units wherein contained can improve the flux of film and decreasing pollution (
polymerInternational, 2009,58 (12): 1350-1361).The existence of relative charge in material, makes zwitter-ion surface can form the hydration layer of " free water ", and makes material have good biocompatibility and contamination resistance.At first, Hawes etc. (
journalofMembraneScience, 1995,107 (3) 209-218,
journalofMembraneScience, 2010, 362 (1-2): 326-333) utilize plasma etching technology that zwitter-ion graftedzwitterionic2-methacryloyloxy-ethylphosphorylchol ine2-methacrylic acyloxy-Ethylphosphocholine is grafted to microfiltration membrane technique [19] .Afterthat of ontosurfacesofpoly (vinylidenefluoride) (PVDF) andcellulose polyvinylidene difluoride (PVDF) (PVDF) and cellulose acetate acetate (CA) microfiltrationmembraneswiththeplasmaetching (CA), the surface of Zhaoetal.tetheredthezwitterionic, improve the performance of water treatment microfiltration membrane.But because surface grafting preparation process is complicated, need specific instrument, be thus unsuitable for a large amount of preparation.Jiang etc. (
journalofMembraneScience2009,340 (1): 164-170) prepared the random polyacrylonitrile base polymer containing sulfonic acid and ammonium root by direct polymerization and prepared asymmetric ultra-filtration membrane with polyacrylonitrile (PAN) is blended, water flux and the contamination resistance of film all increase.2012, Cao
[deng (
journalofMembraneScience2012, adopted aqueous phase free radical reaction prepare novel amphoteric ion polymer PDHD 390-391 (3): 243-253.): and by preparing the nanofiltration membrane of compound after surface-coated is in polysulfone supporting layer again with glutaraldehyde cross-linking, obtain higher water flux and contamination resistance.But the preparation of these materials is difficult to control, and poor chemical stability, easily decompose.
Poly aromatic (sulphur) ether polymer due to its chemical stability high, mechanical property, resistance toheat are good, have a wide range of applications at film water process and proton or anion-exchange membrane fuel cells field.Functional groups amino in poly aromatic (sulphur) ether polymer of ammonification, not only directly can be cross-linked and obtain novel cross-linked polymer compound, and the novel high polymer material that the wetting ability that can be converted into skeleton cation is controlled.The application of poly aromatic (sulphur) ether in film water process at present containing ammonium radical ion rarely has report.Through finding prior art literature search, as far back as nineteen eighty-two Kesting, R.E. just prepared the complex reverse osmosis membrane of cellulose acetate and quaternised poly-piperazine phthalamide, there is good thermostability and chlorine resistance [Report (1982), 49pp]; Kovacs in 2011, JasonR utilizes the method for disperseing layer by layer, prepare the reverse osmosis composite membrane of diallyl dimethyl ammoniumchloride/4-sulfonate polystyrene/montmorillonite, improve the selectivity [PMSEPreprints (2011)] of reverse osmosis membrane.
Sulfonated poly aromatic (sulphur) ether is as the desirable selection of separation membrane, and in film water process such as reverse osmosis, nanofiltration, ultrafiltration, micro-filtration, osmotic distillation, ion-exchange, electrodialysis, and Proton Exchange Membrane Fuel Cells field has a wide range of applications.The sulfonated monomers polymerization adopted at present extensively, the sulfonated poly aromatic ether macromolecular material that after adopting than before, sulfonation method is obtained, there is lot of advantages, such as chemical stability be high, ionic group position and ratio control accurately, avoid the side reaction generations etc. such as chain rupture.Sulfonic acid group exists can not only optionally make some ion pass through, and improves the water permeability of separatory membrane, and makes it have strong resistance to chlorine and wider pH use range, simultaneously all greatly the strengthening through ability of its stain resistance and water.
Summary of the invention
The present invention be intended to prepare a series of chemical stability high, be cheaply easy to get, containing zwitterionic macromolecular material, be applied to reverse osmosis, in nanofiltration field.
The invention discloses a kind of novel structure containing zwitterionic blend polymer and composition and preparation method thereof that can be used as membrane for water treatment material.The structure of two base polymers of blend and composition blend is shown below:
N=0 or 1; 0<m, p≤1; Q=1 or 2;
Y=oxygen or sulphur;
X=F,Cl,Br,I,NO
3,HSO
3,HSO
4,NaSO
4；
M=H, first family basic metal, amine NR
1r
2r
3(R
1, R
2, R
3=H, C1-C6 alkyl or aryl).
Described in the present invention, skeleton contains the preparation method of the poyblend of ammonium root and sulfonate ion group respectively, it is characterized in that being undertaken by following step:
(1) by A-Poly and S-Poly two kinds respectively containing amino and sulfonic polymkeric substance according to certain ratio, be dissolved in high boiling non-protonic solvent, obtain certain density solution;
(2) by slow for above-mentioned solution impouring deionized water, obtain fibrous polymer, then under 60-80 DEG C of condition, soak 5-10 hour, 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 in deionized water, 5-10 hour is soaked under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum-drying, obtains containing zwitterionic poyblend A-blend-S(n=1);
(3) N-Methyl pyrrolidone solution (NMP) (w/v) of 20% of A-blend-S obtained from 1M hydrochloric acid is heated to backflow, and keep 1 hour, reduce temperature to 120 DEG C, then while hot in impouring deionized water, obtain fibrous polymer, then under 60-80 DEG C of condition, 5-10 hour is soaked, repeat 3-5 time, filter, dry, vacuum-drying, obtains containing zwitterionic poyblend A-blend-S(n=0).
Preparation method described in the present invention, the ratio of A-Poly and S-Poly is wherein the ratio containing amino and sulfonic mole number, and scope is 0.02:1 to 1:0.02.
Preparation method described in the present invention, high boiling point aprotic solvent is wherein methyl-sulphoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
Preparation method described in the present invention, the concentration of solution is wherein 10-60%.
Preparation method described in the present invention, wherein said 1M acid solution is hydrochloric acid, hydrofluoric acid, Hydrogen bromide, hydroiodic acid HI, nitric acid, sulfurous acid, sulfuric acid or sodium pyrosulfate.
After the present invention further discloses the blend polymer film forming containing ammonium root and sulfonate radical zwitter-ion group, there is nanofiltration and reverse osmosis performance, separating substances, water softening and pure water can be widely applied to and the field such as prepare.
Accompanying drawing illustrates:
Fig. 1 contains the structure of the blend polymer of ammonium root and sulfonate radical zwitter-ion group
embodiment:
In order to simple and clearly object, the hereafter appropriate description eliminating known technology, in order to avoid the description of those unnecessary details impact to the technical program.Below in conjunction with comparative example, the present invention is described further.Raw materials used as do not illustrated by commercially available especially.Such as A-poly-1 to A-poly-13, S-poly-7 etc. all have commercially available.
Intrinsic viscosity adopts Ubbelohde viscosimetry to measure, and probe temperature is 25 DEG C, and solvent is the nmp solution containing 0.05M lithiumbromide.
one, the preparation of blend polymer
1. containing amino alternating polymer:
2. containing amino unregulated polymer:
3. containing sulfonic unregulated polymer:
4. containing sulfonic alternating polymer:
S-poly-19(intrinsic viscosity: 0.65dL/g)
Embodiment 1-13
Get A-poly-1 to A-poly-13 to mix with S-poly-7 respectively, the mole number that the quality taken need meet the amino in A-Poly polymkeric substance is equal with the sulfonic mole number in S-Poly polymkeric substance.By above-mentioned dissolution of solid in NMP, total polymer concentration is made to be 25%(w/v), after abundant dissolving, by in slow for this solution impouring deionized water, obtain fibrous polymer, then under 60-80 DEG C of condition, 5-10 hour is soaked, repeat 3-5 time, filter, again in 1M aqueous hydrochloric acid, 5-10 hour is soaked under 60-80 DEG C of condition, repeat 2-3 time, and then in deionized water, 5-10 hour is soaked under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum-drying, obtain containing zwitterionic poyblend A-blend-S-1 ~ 13-1,
N-Methyl pyrrolidone solution (NMP) (w/v) of 20% of A-blend-S-1 ~ 13-1 obtained from 1M hydrochloric acid is heated to backflow, and keep 1 hour, reduce temperature to 120 DEG C, then while hot in impouring deionized water, obtain fibrous polymer, then under 60-80 DEG C of condition, 5-10 hour is soaked, repeat 3-5 time, filter, dry, vacuum-drying, obtains containing zwitterionic poyblend A-blend-S-1 ~ 13-0.
Adopt the structure of the blended two kinds of blend polymers obtained of A-poly-1 and S-poly-7 and conversion process to describe, other blend possesses identical preparation process and result:
Embodiment 14-22
With reference to the test method of embodiment 1, by random amino polymer A-poly-14 ~ 22 and random sulfonic group polymkeric substance S-poly-10 ~ 18 blended, the mole number that the quality taken need meet the amino in A-Poly polymkeric substance is equal with the sulfonic mole number in S-Poly polymkeric substance.Obtain blend polymer A-blend-S-14 ~ 22-1 and A-blend-S-14 ~ 22-0.
Embodiment 23
With reference to the test method of embodiment 1, to replace amino polymer A-poly-13 and alternately sulfonic group polymkeric substance S-poly-19 is blended, the mole number that the quality taken need meet the amino in A-Poly polymkeric substance is equal with the sulfonic mole number in S-Poly polymkeric substance.Obtain blend polymer A-blend-S-23-1 and A-blend-S-23-0
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 the useful area of wherein membrane cisterna test is about 21.22cm
2
Embodiment 24
Get 0.750g blend polymer A-blend-S-20-0, be dissolved in 10.0mLDMAC, after the metre filter of 0.45 μm, by polymers soln at leisure curtain coating on level, clean sheet glass (10.0 × 10.0cm).Heat up gradually under vacuum and carry out drying, 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.After being cooled to room temperature, film glass plate being soaked and boils 24h in deionized water, after film stripped down from sheet glass obtain transparent, that snappiness is good diaphragm, desalination rate 93%, water flux 9.3mLd
-1.
three, nanofiltration performance test
Test condition: the water inlet of nanofiltration membrane evaluating apparatus is simulated seawater, with magnesium chloride and pure water configuration, concentration is 2000ppm (mgL
-1), surveying film pressure is that 70psi(is about 0.48MPa), discharge 40mLmin
-1, experimental temperature is 25 ° of C, and the time of test is 24h, and the useful area of wherein membrane cisterna test is about 21.22cm
2
Embodiment 25
With reference to the film-forming method of embodiment 24, adopt blend polymer A-blend-S-21-0 to obtain diaphragm, carry out the test of nanofiltration performance, test result: MgCl
2rejection: 87%, water flux 10.5mLd
-1.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.
Claims (7)
1. the blend polymer of skeleton respectively containing ammonium root and sulfonate ion group, and composition two base polymers (A-Poly) of blend and the structure of (S-Poly) are shown below:
N=0 or 1; 0<m, p≤1; Q=1 or 2;
Y=oxygen or sulphur;
X=F,Cl,Br,I,NO
3,HSO
3,HSO
4,NaSO
4；
M=H, first family basic metal, amine NR
1r
2r
3(R
1, R
2, R
3=H, C1-C6 alkyl or aryl).
2. skeleton described in claim 1 contains the preparation method of the poyblend of ammonium root and sulfonate ion group respectively, it is characterized in that being undertaken by following step:
(1) by A-poly and S-poly two kinds respectively containing amino and sulfonic polymkeric substance according to certain ratio, be dissolved in high boiling non-protonic solvent, obtain certain density solution;
(2) by slow for above-mentioned solution impouring deionized water, obtain fibrous polymer, then under 60-80 DEG C of condition, soak 5-10 hour, 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 in deionized water, 5-10 hour is soaked under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum-drying, obtains containing zwitterionic poyblend A-blend-S(n=1);
(3) N-Methyl pyrrolidone solution (NMP) (w/v) of 20% of A-blend-S obtained from 1M hydrochloric acid is heated to backflow, and keep 1 hour, reduce temperature to 120 DEG C, then while hot in impouring deionized water, obtain fibrous polymer, then under 60-80 DEG C of condition, 5-10 hour is soaked, repeat 3-5 time, filter, dry, vacuum-drying, obtains containing zwitterionic poyblend A-blend-S(n=0).
3. preparation method according to claim 2, the ratio of A-poly and S-poly is wherein the ratio containing amino and sulfonic mole number, and scope is 0.02:1 to 1:0.02.
4. preparation method according to claim 2, high boiling point aprotic solvent is wherein methyl-sulphoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
5. preparation method according to claim 2, the concentration of solution is wherein 10-60%.
6. preparation method according to claim 2, wherein said 1M acid solution is hydrochloric acid, hydrofluoric acid, Hydrogen bromide, hydroiodic acid HI, nitric acid, sulfurous acid, sulfuric acid or sodium pyrosulfate.
7. after containing the poyblend film forming of ammonium root and sulfonate radical zwitter-ion group described in claim 1, the application in nanofiltration, anti-penetration wastewater disposal film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664736A (en) * | 2016-01-11 | 2016-06-15 | 天津师范大学 | Polymer blend containing ammonium and phosphate radical zwitterionic groups and preparation method thereof |
| US20200381761A1 (en) * | 2017-12-13 | 2020-12-03 | Evoqua Water Technolgies LLLC | Anion Exchange Membranes for Redox Flow Batteries |
Citations (3)
| 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 |
| CN101712756A (en) * | 2009-11-25 | 2010-05-26 | 天津师范大学 | Sulfonated polyether and phosphine oxide and preparation method thereof |
| CN103497324A (en) * | 2013-09-29 | 2014-01-08 | 天津师范大学 | Cation-contained high-molecular polyaryl (thio) ether phosphine oxide polymers and preparation method thereof |
-
2015
- 2015-06-01 CN CN201510291705.8A patent/CN105219060A/en active Pending
Patent Citations (3)
| 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 |
| CN101712756A (en) * | 2009-11-25 | 2010-05-26 | 天津师范大学 | Sulfonated polyether and phosphine oxide and preparation method thereof |
| CN103497324A (en) * | 2013-09-29 | 2014-01-08 | 天津师范大学 | Cation-contained high-molecular polyaryl (thio) ether phosphine oxide polymers and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664736A (en) * | 2016-01-11 | 2016-06-15 | 天津师范大学 | Polymer blend containing ammonium and phosphate radical zwitterionic groups and preparation method thereof |
| US20200381761A1 (en) * | 2017-12-13 | 2020-12-03 | Evoqua Water Technolgies LLLC | Anion Exchange Membranes for Redox Flow Batteries |
| US11929533B2 (en) * | 2017-12-13 | 2024-03-12 | Evoqua Water Technologies Llc | Anion exchange membranes for redox flow batteries |
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Application publication date: 20160106 |