CN1602995A - Method for preparing aromatic polyurea porous membrane - Google Patents
Method for preparing aromatic polyurea porous membrane Download PDFInfo
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- CN1602995A CN1602995A CN 200410054328 CN200410054328A CN1602995A CN 1602995 A CN1602995 A CN 1602995A CN 200410054328 CN200410054328 CN 200410054328 CN 200410054328 A CN200410054328 A CN 200410054328A CN 1602995 A CN1602995 A CN 1602995A
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Abstract
The invention disclosesone aromatic polyuria porous membrane preparing method, including following steps: Carries on the solution polymerization to aromatic two ammonium and the aromatic two isocyanogens diethylene glycol dinitrate in organic solvent under inert atmosphere, spreads the polymer solution blows on the plate, plunges peptizer the bath or drying, coagulates it to the thin film, takes out the remaining solvent, obtains the aromatic polyuria porous membrane.the aromatic polyuria porous membrane preparated by using this invention method, the machine capability and the heat-stable performance is extremely outstanding, can be widely applied to preparate the industry pure water and the ultra pure water, the water desalinization, and softens the pharmaceutical industry and the medical industry, the food industry, the metallurgical industry,sewage treatment in the environment projects and recircling so on domains.
Description
Technical field
The present invention relates to the preparation method of aromatic polyureas perforated membrane.
Background technology
Since last century the seventies, the functional membrane development is very rapid, and principal item has regenerated cellulose, cellulose esters, polyamide, Kynoar, polytetrafluoroethylene (PTFE), polypropylene, polyvinyl chloride or the like.In recent years, the functional membrane technology has obtained further development again, is widely used in the numerous areas such as wastewater treatment and reuse in industrial pure water and PREPARATION OF ULTRA-PURE WATER, water demineralizing and softening, medical industry and health care industry, food industry, metallurgical industry, the environmental project.
The perforated membrane that is used for various filtrations or dialysis at present mainly contains five series products.The one, the cellulose acetate perforated membrane, its resistance to acids and bases, poor solvent resistance, also gamma ray resistant irradiation not, application surface is narrower.The 2nd, polypropylene porous film, owing to adopt fusion drawn method spinning membrane system, the porosity of film is low, is no more than 60% usually, water flux is low.The 3rd, the polysulfones perforated membrane, its anti-aromatic solvent, halogenated hydrocarbon solvent poor performance can not be used to handle the liquid that contains these solvents, and when being used to contain the treatment fluid of surfactant for a long time, easily cause problems such as film-strength decline and distortion.The 4th, polyvinylidene fluoride porous film, though its resistance to acids and bases is strong, gamma ray resistant, organic solvent-resistant (as strong oxidizer, halogenated hydrocarbons, aliphatic hydrocarbon etc.), it is relatively more difficult to make high-quality Kynoar doughnut perforated membrane.The 5th, polytetrafluoroethylporous porous membrane, it has excellent heat-resisting and chemical-resistance, but this film needs multilayer superimposition to be unlikely to damage in long-term the use, and multilayer superimposition makes the processing technology complexity.Aromatic polyureas can pass through solution polymerization at normal temperatures, and the macromolecular chain structure of its rigidity makes it have high-strength, Gao Mo, heat-resisting characteristic, uses damage and the distortion that is not easy to cause material for a long time.Aromatic polyureas can be by the wet-formed perforated membrane of making, and its preparation method has not yet to see any report.
Summary of the invention
The technical issues that need to address of the present invention are the preparation methods that disclose a kind of aromatic polyureas perforated membrane, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
Aromatic diamine and aromatic diisocyanate are carried out polymerisation in solution under the inert atmosphere in organic solvent, the chemical constitution of resulting polymers has following repetitive:
Wherein: R is
Or
Vulcabond: aromatic diamine=1～1.3: 1 mol ratio, more suitably mol ratio is 1.02～1.15: 1, and polymerization temperature is 10-80 ℃, and more suitably temperature is 20-50 ℃, and polymerization time is 1-6 hour, more suitably polymerization time is 2-4 hour;
According to optimized technical scheme of the present invention, add appropriate amount of catalysts when being preferably in reaction, as triethylamine or dibutyltin dilaurate, can improve reaction speed;
Polymer solution is coated with scrapes on flat board, the preferred glass plate forms the liquid film of 50～100 μ m thickness;
The flat board that scribbles liquid film is immersed coagulating agent bathe or under 40～60 ℃ temperature, dry, be frozen into film, use hot wash, remove residual solvent, obtain the aromatic polyureas perforated membrane;
It is 25～40% the dimethylacetylamide aqueous solution that said coagulating agent is selected from water or weight concentration
According to the preferred scheme of the present invention, can in the polymer solution of gained, add inorganic pore-foaming agent, stir, said inorganic pore-foaming agent is selected from a kind of in sodium chloride, potassium chloride or the sodium acid carbonate etc.;
Said organic solvent is selected from dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or N, the N-dimethyl pyrrolidone;
Said aromatic diamine is selected from p-phenylenediamine (PPD), m-phenylene diamine (MPD), o-phenylenediamine, 4, a kind of in 4 ' two amido diphenyl-methanes or 4,4 ' the diamines yl diphenyl ether;
Said aromatic diisocyanate is selected from 4,4 '-vulcabond diphenyl-methane, 2,4-toluene di-isocyanate(TDI) (TDI) or 2, a kind of or its mixture in the 6-toluene di-isocyanate(TDI) (TDI).
Adopt the aromatic polyureas perforated membrane of method preparation of the present invention, mechanical performance and thermal stability are all very excellent, can be widely used in the numerous areas such as wastewater treatment and reuse in industrial pure water and PREPARATION OF ULTRA-PURE WATER, water demineralizing and softening, medical industry and health care industry, food industry, metallurgical industry, the environmental project.
Description of drawings
Fig. 1 is the cross-section photograph (10 of the perforated membrane of embodiment 8
3Doubly).
Fig. 2 is the cellular micropore (10 of the perforated membrane of embodiment 8
4Doubly).
Fig. 3 is the cross-section photograph (10 of the perforated membrane of embodiment 9
3Doubly).
Fig. 4 is the cellular micropore (10 of the perforated membrane of embodiment 9
4Doubly).
Fig. 5 is the cross-section photograph (10 of the perforated membrane of embodiment 10
3Doubly).
Fig. 6 is the cellular micropore (10 of the perforated membrane of embodiment 10
4Doubly).
Fig. 7 is the cross-section photograph (10 of the perforated membrane of embodiment 11
3Doubly).
Fig. 8 is the cellular micropore (10 of the perforated membrane of embodiment 11
4Doubly).
The specific embodiment
Embodiment 14,4 '-vulcabond diphenyl-methane (MDI)
With 5.0 grams 4,4 '-vulcabond diphenyl-methane (0.02mol) and be dissolved with 28 of 1.08 gram m-phenylene diamine (MPD)s (0.01mol) and restrain dimethylacetamide solutions and successively add in the 250ml three-neck flask is at logical N
2With carry out prepolymerization under the mechanical agitation.The pre-polymerization temperature is controlled at about 55 ℃, and pre-polymerization 30 minutes obtains the performed polymer of molecule two ends band NCO group.
The 12 gram dimethylacetamide solutions that will be dissolved with 1.08 gram m-phenylene diamine (MPD)s (0.01mol) then progressively add and carry out chain extending reaction in the three-neck flask.This moment system in NCO/NH
2Mol ratio is 1: 1.Continue down to stir 2 hours at 55 ℃, obtain faint yellow transparent thick polyureas solution, the total solid content of solution is about 16%.Add the NCO of diethylamine sealing macromolecular chain end, and to regulate pH with acetic anhydride be 7.
Gained solution is coated with scrapes film forming, baking is 4 hours in 60 ℃ of baking ovens, just obtains water white polyurea film.
Adopting Ubbelohde viscometer to record product performance viscosity under 30 ℃ is 0.36dL/g, and the fracture strength that the applying electronic strength tester records polyurea film is 27MPa, and extension at break is 13%, and elastic modelling quantity is 1200MPa; Adopt heat to vow that weight analysis records about 190 ℃ of the thermal degradation temperature of polyurea film.
Embodiment 2
Operating procedure is identical with embodiment one.Change NCO/NH in the reaction system
2Mol ratio is 1.075: 1.The inherent viscosity of products therefrom is 0.56dL/g, and fracture strength is 44MPa, and extension at break is 7%, and elastic modelling quantity is 1262MPa; Thermal degradation temperature approximately is 220 ℃.
Embodiment 3
Operating procedure is identical with embodiment 1.Change NCO/NH in the reaction system
2Mol ratio is 1.2: 1, and polymerization temperature is 60 ℃.The inherent viscosity of products therefrom is 0.42dL/g, and fracture strength is 68MPa, and extension at break is 17%, and elastic modelling quantity is 1077MPa.
Embodiment 4
Operating procedure is identical with embodiment 1.Change NCO/NH in the reaction system
2Mol ratio is 1.022: 1, and polymerization temperature is 72 ℃, 7 hours time, and in system, add 2 triethylamines as catalyst.The inherent viscosity of products therefrom is 0.84dL/g, and fracture strength is 74MPa, and extension at break is 25%, and elastic modelling quantity is 2191MPa.
Embodiment 5
Operating procedure is identical with embodiment 4.Change NCO/NH in the reaction system
2Mol ratio is 1.1: 1.Polymerization time 5 hours.The inherent viscosity of products therefrom is 0.85dL/g, and fracture strength is 66MPa, and extension at break is 135%, elastic modelling quantity 1437MPa.
Embodiment 6
Operating procedure is identical with embodiment 5.Changing polymerization temperature is 28 ℃.The inherent viscosity of products therefrom is 0.73dL/g, and fracture strength is 114MPa, and extension at break is 159%, and elastic modelling quantity is 2320MPa.
Embodiment 7
Operating procedure is identical with embodiment 6.The change catalyst is a dibutyltin dilaurate.The inherent viscosity of products therefrom is 0.52dL/g, and fracture strength is 60.9MPa, and extension at break is 95%, and elastic modelling quantity is 1203MPa.
Embodiment 8
Make polyureas solution by embodiment 6 and be coated with and scrape on glass plate, form the liquid film of about 0.1mm thickness.The glass plate that scribbles liquid film is immersed in the pure water coagulating bath, behind the solidification forming, use hot wash, remove residual solvent, obtain the aromatic polyureas perforated membrane.The microcellular structure of perforated membrane is shown in the electron scanning micrograph of Fig. 1 and Fig. 2.
Embodiment 9
The interpolation weight concentration is 2% common salt particle in the polyureas solution of embodiment 8, and about 300 orders of particle size stir.Operating procedure by embodiment 8 prepares perforated membrane then.The bubble that records the perforated membrane sample presses (referring to that gas blow is full of the required pressure of film of liquid) to be 0.11Mpa, and the microcellular structure of perforated membrane is shown in the electron scanning micrograph of Fig. 3 and Fig. 4.
Embodiment 10
Operating procedure is identical with embodiment 9.Changing coagulation bath composition, is that 36% the dimethylacetylamide aqueous solution replaces pure water as setting medium with weight concentration, and the microcellular structure that obtains perforated membrane is shown in the electron scanning micrograph of Fig. 5 and Fig. 6, and the bubble of perforated membrane sample is pressed and is 0.02Mpa.
Embodiment 11
Operating procedure is identical with embodiment 9.Changing coagulation bath composition, is that 27% the dimethyl formamide aqueous solution replaces pure water as setting medium with weight concentration, and the microcellular structure that obtains perforated membrane is shown in the electron scanning micrograph of Fig. 7 and Fig. 8, and the bubble of perforated membrane sample is pressed and is 0.02Mpa.
Claims (8)
1. the preparation method of an aromatic polyureas perforated membrane is characterized in that, comprises the steps:
Aromatic diamine and aromatic diisocyanate are carried out polymerisation in solution under the inert atmosphere in organic solvent, the chemical constitution of resulting polymers has following repetitive:
Wherein: R, R ' representative contains the alkyl of phenyl ring;
Polymerization temperature is 10-80 ℃, and polymerization time is 1-6 hour;
Polymer solution is coated with scrapes on flat board, form liquid film;
The flat board that scribbles liquid film is immersed coagulating agent bathe or dry, be frozen into film, remove residual solvent, obtain the aromatic polyureas perforated membrane;
It is 25～40% the dimethylacetylamide aqueous solution that said coagulating agent is selected from water or weight concentration;
Said organic solvent is selected from dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or N, the N-dimethyl pyrrolidone;
2. method according to claim 1 is characterized in that R is
Or
R ' is
Or
3. method according to claim 1 is characterized in that vulcabond: aromatic diamine=1～1.3: 1 mol ratio.
4. method according to claim 1 is characterized in that, polymerization temperature is 20-50 ℃, and polymerization time is 2-4 hour.
5. method according to claim 1 is characterized in that, said aromatic diamine is selected from p-phenylenediamine (PPD), m-phenylene diamine (MPD), o-phenylenediamine, 4, a kind of in 4 ' two amido diphenyl-methanes or 4,4 ' the diamines yl diphenyl ether; Said aromatic diisocyanate is selected from 4,4 '-vulcabond diphenyl-methane, 2,4-toluene di-isocyanate(TDI) or 2, a kind of or its mixture in the 6-toluene di-isocyanate(TDI).
6. according to each described method of claim 1～5, it is characterized in that add appropriate amount of catalysts during reaction, catalyst is selected from triethylamine or dibutyltin dilaurate.
7. according to each described method of claim 1～5, it is characterized in that, add inorganic pore-foaming agent in the polymer solution of gained, said inorganic pore-foaming agent is selected from a kind of in sodium chloride, potassium chloride or the sodium acid carbonate etc.
8. method according to claim 6 is characterized in that, adds inorganic pore-foaming agent in the polymer solution of gained, and said inorganic pore-foaming agent is selected from a kind of in sodium chloride, potassium chloride or the sodium acid carbonate.
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| CN 200410054328 CN1602995A (en) | 2004-09-07 | 2004-09-07 | Method for preparing aromatic polyurea porous membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096765B (en) * | 2006-06-30 | 2012-01-04 | 株式会社荏原制作所 | Fluid mechanical part resistant to slurry erosiveness and fluid machinery having same |
| CN102762285A (en) * | 2009-08-03 | 2012-10-31 | 索尔维特殊聚合物意大利有限公司 | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
-
2004
- 2004-09-07 CN CN 200410054328 patent/CN1602995A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101096765B (en) * | 2006-06-30 | 2012-01-04 | 株式会社荏原制作所 | Fluid mechanical part resistant to slurry erosiveness and fluid machinery having same |
| CN102762285A (en) * | 2009-08-03 | 2012-10-31 | 索尔维特殊聚合物意大利有限公司 | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
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