CN100348649C - Polymer membrane preparation method - Google Patents
Polymer membrane preparation method Download PDFInfo
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- CN100348649C CN100348649C CNB2005100286264A CN200510028626A CN100348649C CN 100348649 C CN100348649 C CN 100348649C CN B2005100286264 A CNB2005100286264 A CN B2005100286264A CN 200510028626 A CN200510028626 A CN 200510028626A CN 100348649 C CN100348649 C CN 100348649C
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Abstract
The present invention relates to a method for preparing a polymer membrane, more specifically to a method for preparing a modified polymer membrane through a thermally induced phase separating method. In high-temperature digestion at an earlier stage of the membrane preparing procedures of the thermally induced phase-separating method, the chemical modification reaction of polymer is carried out. A base group with hydrophilicity and pollution resistance performance is combined with a polymer chain by covalent bonds so as to obtain modified polymer solution. Moreover, the solution is cooled for preparing a microporous membrane or a hollow-fiber membrane through the thermally induced phase separating preparation. The solid base material of the prepared microporous membrane or the hollow-fiber comprises mixture formed from unreacted polymer and the modified polymer. In addition, the hydrophilicity and the pollution resistance performance of the polymer membrane are raised, and the polymer membrane can be favorably used in the field of water treatment.
Description
Technical field
The invention belongs to the preparing technical field of polymeric film, be specifically related to the method that thermally induced phase separation prepares microporous membrane.
Background technology
Polymer microporous film is the micropore with countless intercommunications, and the aperture is the polymeric film of 0.01-10 μ m.The microporous membrane base material has polyolefine, polyvinylidene dichloride, polyvinylidene difluoride (PVDF), polyvinyl acetate (PVA), polymethacrylate, polymeric amide, polysulfones, derivatived cellulose, chitosan and derivative thereof, polybenzimidazole, polyvinyl alcohol and organosilicon etc.Industrialized at present microporous membrane majority is made by materials such as polypropylene, polyethylene, tetrafluoroethylene, polysulfones, and the preparation method mainly contains fusion drawn, solution precipitation, the thermic methods such as (TIPS) that is separated.Wherein thermally induced phase separation is meant that at high temperature (fusing point that generally is higher than crystalline polymer) is dissolved in polymkeric substance in the solvent of high boiling point, low volatility, form homogeneous phase solution, the cooling cooling causes solution to be separated then, select for use volatile reagent that solvent extraction is come out again, thereby obtain the high molecule micropore film of certain structural shape.This method can be applicable to many because poor solubility and can not be with the crystalline polymer of traditional solution legal system film.Its advantage is can be by adjusting cooling conditions and selecting suitable diluent to control the aperture, and aperture control is easier to.And fusion drawn method technology is relatively easy, but aperture control is difficult.
The microporous membrane of being made by polyolefine materials such as polypropylene, polyethylene and tetrafluoroethylene has excellent chemical stability and thermostability, but its surface hydrophilicity is poor, easily makes separating effect decline because of solute absorption and fenestra stop up in the process of membrane sepn.And because its hydrophobicity needs higher pressure gradient just can make water infiltrate fenestra when water treatment.On the other hand, traditional hydrophilic material such as polyvinyl alcohol, cellulose acetate etc., physical strength, thermostability and chemical resistance are then relatively poor.Therefore the hydrophobic film material being carried out hydrophilic modifying will make its application and use field widen.
People have paid many effort for the hole surface of modification forming film.When using polymer substance,, will cause the particularly reduction of flow of hole changes of properties especially for film with little average cell size.When using the heterogeneous phase chemistry modification, need to formulate the reaction scheme of a complexity, this will change membrane structure and performances such as physical strength and solvability, increase the complicacy of preparation process.For example, there are a lot of reports hydrophilic radical to be attached to matrix surface by treatment technologies such as radiation grafting, plasma graftings, can make material obtain hydrophilic effect preferably, but this method surface grafting at the fenestra wall, other parts of the solid substrate of film are not modified.The film of this surface modification can not be wetted again after doing, and in case dried uply just lose considerable perviousness, need keep the moistening of film surface before use.Therefore, need provide a kind of whole solid substrate that makes film all to obtain the preparation method of modification.
Summary of the invention
The objective of the invention is to propose a kind of simple to operation, conserve energy, can make the preparation method of the polymeric film that the product wetting ability is improved.
The method that the present invention proposes, it is the opportunity of utilizing the thermally induced phase separation film-forming process high-temperature digestion stage in early stage, carry out the polymer chemistry reaction, group (reactant that will contain this group is called properties-correcting agent) with possess hydrophilic property and resistance to crocking, be covalently bound on the main polymer chain, obtain containing polymer-modified solution, this solution is lowered the temperature again, being separated by thermic is prepared into microporous membrane or hollow-fibre membrane.The microporous membrane that makes or the solid substrate of hollow-fibre membrane comprise the blend of unreacted polymkeric substance and polymer-modified formation, have good hydrophilicity and resistance to crocking, can be used widely in the membrane sepn field.
In the method for the present invention, unreacted polymkeric substance, polymer-modified, unreacted properties-correcting agent, solvent do not need to separate after reaction, directly film forming.
The preparation method of a kind of polymeric film that the present invention proposes, be with polymkeric substance and solvent in reactor, lead to N
2And be heated with stirring to 120 ℃ of-250 ℃ of backflows, after treating complete melt into homogeneous phase, properties-correcting agent is added in the above-mentioned solution, after reacting 1-15 hour under 120 ℃-250 ℃, product cooling cooling is made microporous membrane, and wherein, the control of the feed ratio of polymkeric substance, solvent, properties-correcting agent is as follows: polymkeric substance is 1 with weight of solvent than scope: 1-1: 30, functional group's mol ratio of reacting in polymkeric substance and the properties-correcting agent is 1: 8-2: 1, and wherein polymkeric substance is ethene or the propylene copolymer with polar functional group; Properties-correcting agent is to have hydroxyl, carboxyl or amino polyoxyethylene glycol or derivatives thereof, has hydroxyl, carboxyl or amino natural polysaccharide or derivatives thereof, perhaps organic acid salt; Solvent is two, trivalent alcohol, C
12-C
18Alkane or aromatic hydrocarbons, saturated or unsaturated fatty acids acid glyceride, phthalic ester, aromatic oxide, dimethyl sulfoxide (DMSO) or dimethyl formamide.
Among the present invention, feeding method is that first mixed polymer and solvent add properties-correcting agent again.
Among the present invention, feeding method is that polymkeric substance, properties-correcting agent, solvent are added simultaneously.
Among the present invention, reaction finishes the product cooling and makes microporous membrane by watering membrane method.
Among the present invention, reaction finishes product cooling reaction and makes hollow-fibre membrane by the spinning of thermic phase disengagement method.
Among the present invention, polymkeric substance is to have hydroxyl, carboxyl or amino ethene or propylene copolymer.
Among the present invention, properties-correcting agent be polyoxyethylene glycol, poly glycol monomethyl ether, natural polysaccharide or derivatives thereof any.
Among the present invention, the natural polysaccharide or derivatives thereof be chitosan, chitin, hyaluronic acid, Mierocrystalline cellulose any.
Among the present invention, solvent is one or more a mixed solvent of dinoctyl phthalate, dibutyl phthalate, methyl-phenoxide, phenyl ether, whiteruss or vegetables oil.
The present invention is by condensation reaction, the group of possess hydrophilic property and resistance to crocking is covalently bound on the polymer chain, will contains the cooling of polymkeric substance and polymer-modified solution and be separated by thermic and make microporous membrane or hollow-fibre membrane with excellent hydrophilic and resistance to crocking.The inventive method is simple and convenient, and cost is low, and the film properties that makes is good.
Description of drawings
Fig. 1 is the SEM figure of mixture product film under 30 ℃ of air coolings (* 2000) of example 1.
Fig. 2 is the SEM figure of mixture product film under 30 ℃ of water coolings (* 5000) of example 1.
Embodiment
Following embodiment illustrates the present invention, but does not limit the present invention.
Embodiment 1
Take by weighing ethylene-acrylic acid copolymer (EAA ,-COOH content 9.7wt%) resin 10g and solvent dinoctyl phthalate (DOP) 150g in three-necked bottle, logical N
2And be heated with stirring to 180 ℃ of backflows, treat complete melt into homogeneous phase after.Accurately take by weighing the polyoxyethylene glycol MPEG (M of 9.4g methyl blocking
w350) add rapidly in the above-mentioned solution, under 180 ℃, carried out graft reaction 8 hours.Part reaction solution precipitates in methyl alcohol, obtains product through repeated multiple times washing suction filtration, then in 50 ℃ of following vacuum-drying 24h, gets faint yellow solid.Calculate percentage of grafting according to the weight that increases and be about 27.21%.
Another part product quenching in liquid nitrogen is solidified, getting a little sample is placed between a pair of cover glass, on 200 ℃ hot platform, heat 5min, rate of cooling with 2 ℃/min is lowered the temperature on hot platform then, utilize the temporal resolution laser light scattering instrument, determine its cloud point temperature (T by the variation of observing scattered light
Cloud).Measure its Tc (Tc) result with differential scanning calorimeter (DSC) and show that cloud point reduces after the grafting, ctystallizing point changes little, illustrates that the consistency of system is improved.
Other gets a little high temperature press mold of quenching solidified sample, cooling curing under different condition, quench disconnected and the extraction back with its section micropore form (seeing accompanying drawing) of scanning electron microscopic observation, show that system has obtained cellular microporous membrane by liquid-liquid phase separation.
With the faint yellow product press mold of first part's exsiccant, measure its contact angle and protein adsorption performance.With high density polyethylene(HDPE) (HDPE) film, ethylene-acrylic acid copolymer (EAA) film in contrast, contact angle test result following (unit: spend):
| Sample | Maximum value | Minimum value | Mean value |
| HDPE EAA EAA-g-MPEG | 106.0 90.6 85 | 102.5 85.8 78.5 | 104.8 88.8 81.6 |
Bovine serum albumin (BSA) absorption test result following (temperature: 30 ℃, the mg/cm of unit
2):
| BSA concentration (mg/ml) | HDPE | EAA | EAA-g-MPEG |
| 0.65 1.13 | 0.1412 0.2350 | 0.0916 0.1485 | 0.0494 0.0831 |
Be not difficult to find out that the wetting ability of film improves, and the absorption of proteins ability is reduced.
Embodiment 2
Take by weighing polypropylene maleic anhydride graft copolymer 5g (DG=1.03wt%) and solvent dibutyl phthalate (DBP) 200g in three-necked bottle, logical N
2And be heated with stirring to 200 ℃ of backflows, treat complete melt into homogeneous phase after, accurately take by weighing 1.2g polyoxyethylene glycol PEG400 and add in the above-mentioned solution rapidly, under 200 ℃, carried out graft reaction 4 hours.Part reaction solution precipitates in ethanol, obtains product through repeated multiple times washing suction filtration, then in 60 ℃ of following vacuum-drying 36h, gets white solid.Calculate percentage of grafting according to the weight that increases and be about 4.24%.Another part reaction solution makes film by the thermic phase disengagement method.With the contact angle that records with quadrat method is 80, and the adsorptive capacity of bovine serum albumin is 0.082.
All can obtain to implement according to the described scope of above-mentioned example content of the present invention, make the good polymeric film of modified effect.Therefore content of the present invention not only is confined to above-mentioned example.
Claims (7)
1, a kind of preparation method of polymeric film is characterized in that with polymkeric substance and solvent in reactor logical N
2And be heated with stirring to 120 ℃ of-250 ℃ of backflows, after treating complete melt into homogeneous phase, properties-correcting agent is added in the above-mentioned solution, after reacting 1-15 hour under 120 ℃-250 ℃, product cooling cooling is made microporous membrane, wherein, the control of the feed ratio of polymkeric substance, solvent, properties-correcting agent is as follows: polymkeric substance is 1 with weight of solvent than scope: 1-1: 30, and functional group's mol ratio of reacting in polymkeric substance and the properties-correcting agent is 1: 8-2: 1; Polymkeric substance is ethene or the propylene copolymer with polar functional group; Properties-correcting agent is to have hydroxyl, carboxyl or amino polyoxyethylene glycol or derivatives thereof, has hydroxyl, carboxyl or amino natural polysaccharide or derivatives thereof, perhaps organic acid salt; Solvent is two, trivalent alcohol, C
12-C
18Alkane or aromatic hydrocarbons, saturated or unsaturated fatty acids acid glyceride, phthalic ester, aromatic oxide, dimethyl sulfoxide (DMSO) or dimethyl formamide.
2, preparation method as claimed in claim 1 is characterized in that reaction finishes the product cooling and makes microporous membrane by watering membrane method.
3, preparation method as claimed in claim 1 is characterized in that reaction finishes the product cooling and makes hollow-fibre membrane by the spinning of thermic phase disengagement method.
4, preparation method as claimed in claim 1 is characterized in that polymkeric substance is to have hydroxyl, carboxyl or amino ethene or propylene copolymer.
5, preparation method as claimed in claim 1, it is characterized in that properties-correcting agent be polyoxyethylene glycol, poly glycol monomethyl ether, natural polysaccharide or derivatives thereof any.
6, preparation method as claimed in claim 5, it is characterized in that the natural polysaccharide or derivatives thereof be chitosan, chitin, hyaluronic acid, Mierocrystalline cellulose any.
7, preparation method as claimed in claim 1 is characterized in that solvent is one or more a mixed solvent of dinoctyl phthalate, dibutyl phthalate, methyl-phenoxide, phenyl ether, whiteruss or vegetables oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100286264A CN100348649C (en) | 2005-08-09 | 2005-08-09 | Polymer membrane preparation method |
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| CNB2005100286264A CN100348649C (en) | 2005-08-09 | 2005-08-09 | Polymer membrane preparation method |
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| CN1730520A CN1730520A (en) | 2006-02-08 |
| CN100348649C true CN100348649C (en) | 2007-11-14 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5277471B2 (en) * | 2007-10-19 | 2013-08-28 | 川崎重工業株式会社 | Separation membrane comprising polyethersulfone, process for producing the same, and membrane-forming stock solution |
| CN101618295B (en) * | 2009-07-31 | 2011-08-10 | 山东爱地高分子材料有限公司 | Method for continuously producing jelly of ultra-high molecular weight polyethylene porous membrane |
| CN101961611B (en) * | 2010-10-27 | 2012-11-07 | 江南大学 | Hollow polyester fiber microporous membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190355A (en) * | 1995-06-07 | 1998-08-12 | 美国梅姆特克公司 | Microfiltration membrane having high pore density and mixed isotropic and anisotropic structure |
| CN1254308A (en) * | 1996-12-12 | 2000-05-24 | 美国梅姆特克公司 | Highly asymmetric, hydrophilic, microfiltration membranes having large pore |
| CN1633329A (en) * | 2000-11-13 | 2005-06-29 | 美国污水过滤器集团公司 | Modified membranes |
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2005
- 2005-08-09 CN CNB2005100286264A patent/CN100348649C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1190355A (en) * | 1995-06-07 | 1998-08-12 | 美国梅姆特克公司 | Microfiltration membrane having high pore density and mixed isotropic and anisotropic structure |
| CN1254308A (en) * | 1996-12-12 | 2000-05-24 | 美国梅姆特克公司 | Highly asymmetric, hydrophilic, microfiltration membranes having large pore |
| CN1633329A (en) * | 2000-11-13 | 2005-06-29 | 美国污水过滤器集团公司 | Modified membranes |
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