CN1640533A - Method for hydrophilic modification of ultrahigh molecular weight polyethylene microporous membrane surface - Google Patents
Method for hydrophilic modification of ultrahigh molecular weight polyethylene microporous membrane surface Download PDFInfo
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- CN1640533A CN1640533A CN 200410062258 CN200410062258A CN1640533A CN 1640533 A CN1640533 A CN 1640533A CN 200410062258 CN200410062258 CN 200410062258 CN 200410062258 A CN200410062258 A CN 200410062258A CN 1640533 A CN1640533 A CN 1640533A
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 40
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 40
- 239000012982 microporous membrane Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title description 17
- 238000012986 modification Methods 0.000 title description 4
- 230000004048 modification Effects 0.000 title description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000007127 saponification reaction Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000002715 modification method Methods 0.000 claims abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229920000578 graft copolymer Polymers 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 4
- 230000004888 barrier function Effects 0.000 description 15
- 230000004907 flux Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 230000010148 water-pollination Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The hydrophilic modification method of surface of ultrahigh molecular weight polyethylene microporous filtering membrane belongs to the field of ozone grafted ultrahigh molecular weight polyethylene microporous filtering membrane preparation technology. It is characterized by that it utilizes ozone to initiate graft reaction on the surface of microporous filtering membrane, it selects vinyl-acetic ester (VAc) as graft monomer, after graft reaction makes saponification hydrolysis to form polyvinyl alcohol (PVA) hydrophilic group. The obtained microporous filtering membrane has good hydrophilic property and moisture absorbability.
Description
Technical field
The present invention relates to a kind of hydrophilic microporous filter membrane preparation method who is used for sewage disposal and blood purifying field, more specifically be meant a kind of ozone grafting ultrahigh molecular weight polyethylene microporous membrane preparation method.
Background technology
Ultra-high molecular weight polyethylene (UHMWPE) miillpore filter has the porosity height, mechanical strength is big, good chemically-resistant solvent corrosion, the erosion performance of anti-bacterium the and better biocompatibility are arranged, stable in the medium-term and long-term serviceability of sewage disposal, as to be difficult for excellences such as degraded performance again.But because UHMWPE is a non-polar material, the surface can be low, presents inertia and hydrophobicity, as sewage treating material, has shortcomings such as poor, the easy static electrification of water imbibition, antifouling property difference with it, therefore must carry out hydrophilic modifying to it.
Graft copolymerization is a kind ofly can give the polymer surfaces superior function and do not influence the method for its bulk properties.What application was more at present is gamma-rays radiation and plasma initiation grafting, its Modified Membrane mostly is polypropylene (PP), polyethersulfone ketone (PES), polysiloxanes etc., as: J.membrane Science, 2000, the 190:215-226 report is grafted to HEMA on the PP film with gamma-emitting method; J.membrane Science, 2002, the 209:255-269 report is grafted to polyacrylic acid (MAA) on the polyethersulfone ketone (PES) with low temperature plasma, makes its surface hydrophilic.Ultraviolet and ozone grafting method are the polymer surface modifying methods that adopts in recent years, as: J.membrane Science, 2000, the 169:269-276 report is grafted to HEMA on polypropylene (PP) miillpore filter with the method for ozone grafting.
The ultra-high molecular weight polyethylene main chain is the methylene of line style long-chain, symmetrical configuration, and also molecular weight is big, and the entanglement point between the strand is more, and the surface is difficult for handling.Both at home and abroad research is more is surface modification to the UHMWPE fiber, fiberglass/composite, and 1998 (5), 9 have mainly reported the progress of this respect.J.Biomedical Materials Research, 1997,38 (4): 361-369 report adopts first plasma treatment, and ultra-violet radiation or direct gamma-emitting method are to the UHMWPE fibre modification then, and grafted monomers mostly is hydrophobicity methyl methacrylate (MMA) monomer.Usefulness liquid oxidatively method, plasmon uv photo initiated graftings such as the domestic Yuan Shao court of a feudal ruler, Hu Fu increase are handled the UHMWPE fiber, with design interface layer structure, change its interlaminar shear strength, and these method equipment are had relatively high expectations, and are difficult to serialization production, and the industrialization difficulty is bigger.
The ozone activation crosslinking technology is a strong oxidizing property of utilizing ozone, produces active group on UHMWPE microporous barrier surface, carries out monomer-graftedly then, and this method is simple to operate, be easy to control.Utilize the ozone activation crosslinking technology that the hydrophilic modifying of UHMWPE microporous barrier be yet there are no report.
Summary of the invention
The objective of the invention is to propose a kind of ozone activation grafting method, preparation hydrophilic microporous filter membrane makes film have excellent hydrophilic and resistance tocrocking.
The present invention is achieved in that a kind of method for making of ozone activation grafting hydrophilic microporous filter membrane, and its basic principle is seen accompanying drawing 2.
This method mainly comprises the following steps: 1) preliminary treatment of UHMWPE microporous barrier; 2) grafted monomers is purified; 3) ozone treatment on film surface; 4) graft reaction of vinyl acetate monomer; 5) saponification of graft copolymer membrane; 6) post processing of film is characterized in that: select the UHMWPE miillpore filter as the hydrophilic modification material; Select vinyl acetate (VAc) monomer-grafted, the polyvinyl acetate saponification hydrolysis of grafting produces polyvinyl alcohol (PVA) hydrophilic radical then; Select the surface of ozone treatment UHMWPE microporous barrier, ozone concentration is 10~50mg/L.Described ozone generating condition is operating voltage 180~220V, and discharge current is 0.2~0.8A, 20~50 ℃ of temperature, and oxygen flow is 0.2~1.0L/min.The condition of described monomer-grafted reaction is: monomer concentration 1.0~20.0%, ferrous salt catalyst concn 1.0 * 10
-6~5.0 * 10
-3Mol/L, 10~80 ℃ of monomer reaction temperature; Reaction time 1~10h.
The invention is characterized in: it may further comprise the steps successively:
(1) preliminary treatment of UHMWPE miillpore filter: film is put into absolute ethyl alcohol, and ultrasonic cleaning 4~5 hours is standby;
(2) select vinyl acetate (VAc) monomer-grafted, under the vacuum of 30~100 ℃ and 0.01~0.08MPa, decompression distillation is purified, and places refrigerator and cooled to hide, and is standby to this monomer;
(3) to above-mentioned film surface ozone treatment.
Being placed in the oxidation reactor 4 through pretreated UHMWPE miillpore filter in the step (1), regulate the temperature of water-bath, making the gas temperature that enters water-bath 2 from oxidation tank is 5~50 ℃; Open the cooling water switch of ozone generator 3, regulate discharge, make it be slightly larger than the regulation discharge of ozone generator; Start ozone generator 3 then, at discharge current is that 0.2~0.8A, voltage are that 180~220V, temperature are under 5~50 ℃, making the oxygen gas flow rate that enters ozone generator from water-bath is 0.2~1.0L/min, when oxygen concentration is 10~50mg/L, behind ultrahigh molecular weight polyethylene microporous membrane activation processing 10~90min, the powered-down switch, continue to purge whole system and film surface with oxygen, after two minutes, close oxygen valve, take out miillpore filter;
(4) the ozone activation grafting is handled
UHMWPE miillpore filter behind the ozone activation is put into polymerization pipe, is under 10~80 ℃ in reaction temperature, adds concentration and is 1.0~20.0% vinyl acetate solution and adds 1.0 * 10
-6~5.0 * 10
-3Behind the mol/L ferrous salt catalyst, reaction 1~10h;
(5) the saponification hydrolysis of graft copolymer membrane
UHMWPE miillpore filter behind the graft reaction is taken out, and extracting 24h in the Soxhlet withdrawal device places the NaOH of 0.2~10.0mol/L or the alcoholic solution of potassium hydroxide then, at 10~50 ℃ of saponification 2~10h.
(6) post processing of film
Film after the saponification cleans up with deionized water, dries.
The invention has the beneficial effects as follows: use the inventive method and can control the UHMWPE miillpore filter of the saponification degree of grafted monomers, and the hydrophily of miillpore filter is lasting with acquisition different hydrophilic performance.Method of the present invention is to utilize ozone at microporous barrier surface initiation grafting, is a kind of effective ways of preparation hydrophilic porous film.This method is to utilize ozone that high molecule micropore filter membrane surface is handled, make the film surface produce active group, utilize the characteristic that free radical that this active group produces can addition functional group, certain monomers is introduced the microporous barrier surface carry out grafting, and make grafted monomers produce hydrophilic radical through the saponification hydrolysis, obtain the lasting and controlled microporous barrier of hydrophily.Its contact angle is not 106 ° before the grafting, after grafting VAc and the saponification hydrolysis, is 78% o'clock at saponification degree, and its contact angle is 65 °, when the saponification degree of grafted monomers is 99%, contact angle be 49 ° not the water flux of grafting cephacoria under 0.5MPa, be 150L/m
2H, after grafting VAc and the 99% saponification hydrolysis, water flux increases to 553L/m under the same terms
2H.
Ozone activation and the stable performance of initiation grafting UHMWPE microporous barrier, the weakness that its hydrophilic effect can decay in time when not only having overcome simple ozone treatment, and the hydrophilic porous film that can obtain having the different hydrophilic performance by the saponification degree of control grafted monomers.
Description of drawings
Fig. 1 is the ozone activation device schematic diagram that the present invention uses.
Among the figure: 1, oxygen is irritated; 2, water-bath; 3, ozone generator; 4, oxidation reactor.
Fig. 2 ozone activation grafting vinyl acetate, and hydrolysis produces polyvinyl alcohol hydrophilic radical schematic diagram.
The specific embodiment
The method of the ozone activation grafting super high molecular weight hydrophilic microporous filter membrane of the present invention's preparation comprises the following steps:
(1) preliminary treatment of UHMWPE miillpore filter: film is put into absolute ethyl alcohol, and ultrasonic cleaning 4~5 hours is standby;
(2) select vinyl acetate (VAc) monomer-grafted, under the vacuum of 30~100 ℃ and 0.01~0.08MPa, decompression distillation is purified, and places refrigerator and cooled to hide, and is standby to this monomer;
(3) to above-mentioned film surface ozone treatment.
Being placed in the oxidation reactor 4 through pretreated UHMWPE miillpore filter in the step (1), regulate the temperature of water-bath, making the gas temperature that enters water-bath 2 from oxidation tank is 5~50 ℃; Open the cooling water switch of ozone generator 3, regulate discharge, make it be slightly larger than the regulation discharge of ozone generator; Start ozone generator 3 then, at discharge current is that 0.2~0.8A, voltage are that 180~220V, temperature are under 5~50 ℃, making the oxygen gas flow rate that enters ozone generator from water-bath is 0.2~1.0L/min, when oxygen concentration is 10~50mg/L, behind ultrahigh molecular weight polyethylene microporous membrane activation processing 10~90min, the powered-down switch, continue to purge whole system and film surface with oxygen, after two minutes, close oxygen valve, take out miillpore filter;
(4) the ozone activation grafting is handled
UHMWPE miillpore filter behind the ozone activation is put into polymerization pipe, is under 10~80 ℃ in reaction temperature, adds concentration and is 1.0~20.0% vinyl acetate solution and adds 1.0 * 10
-6~5.0 * 10
-3Behind the mol/L ferrous salt catalyst, reaction 1~10h;
(5) the saponification hydrolysis of graft copolymer membrane
UHMWPE miillpore filter behind the graft reaction is taken out, with acetone extracting 24h in the Soxhlet withdrawal device, place the NaOH of 0.2~10.0mol/L or the alcoholic solution of potassium hydroxide then, at 10~50 ℃ of saponification 2~10h.
(6) post processing of film
Film after the saponification cleans up with deionized water, dries.
The hydrophily UHMWPE microporous barrier of the present invention's preparation can be used for sewage disposal and blood oxygenator etc.
The hydrophily UHMWPE microporous barrier that the present invention makes carries out the water flux test.
Embodiment 1: with the pretreated UHMWPE microporous barrier of 5 * 10cm size at 180V voltage, 0.8A under the oxygen gas flow rate of discharge current and 1.0L/min, ozone concentration with 40mg/L is handled 15min, place polymerization pipe then, add the ethanolic solution of 10.0% vinyl acetate of having purified (VAc), and add 1.0 * 10
-6The frerrous chloride aqueous catalyst solution of mol/L, seal polymerization pipe, place constant temperature oscillator,, take out in 20 ℃ of reaction 10h, film is cleaned up, in the NaOH of 0.5mol/L methanol solution, behind 25 ℃ of saponification hydrolysis 10h, clean film to neutral, prepared hydrophilic porous film is under 0.5MPa, and water flux is 246L/m
2H.
Embodiment 2: with the pretreated UHMWPE microporous barrier of 5 * 5cm size at 220V voltage, 0.2A under the oxygen gas flow rate of discharge current and 0.2L/min, ozone concentration with 10mg/L is handled 90min, place polymerization pipe then, add the acetone soln of 20% vinyl acetate of having purified (VAc), and add 5.0 * 10
-3The iron ammonium sulfate aqueous catalyst solution of mol/L, seal polymerization pipe, place constant temperature oscillator,, take out in 40 ℃ of reaction 5h, film is cleaned up, in the KOH of 1.0mol/L ethanolic solution, behind 10 ℃ of saponification hydrolysis 8h, clean film to neutral, prepared hydrophilic porous film is under 0.5MPa, and water flux is 156L/m
2H.
Embodiment 3: with the pretreated UHMWPE microporous barrier of 5 * 10cm size at 200V voltage, 0.4A under the oxygen gas flow rate of discharge current and 0.4L/min, ozone concentration with 30mg/L is handled 30min, place polymerization pipe then, add the ethyl acetate solution of 3% vinyl acetate of having purified (VAc), and add 2.6 * 10
-4The iron ammonium sulfate aqueous catalyst solution of mol/L, seal polymerization pipe, place constant temperature oscillator,, take out in 40 ℃ of reaction 3h, film is cleaned up, in the NaOH of 0.8mol/L aqueous isopropanol, behind 50 ℃ of saponification hydrolysis 2h, clean film to neutral, prepared hydrophilic porous film is under 0.5MPa, and water flux is 201L/m
2H.
Embodiment 4: with the pretreated UHMWPE microporous barrier of 10 * 10cm size at 200V voltage, 0.6A under the oxygen gas flow rate of discharge current and 1.0L/min, ozone concentration with 50mg/L is handled 10min, place polymerization pipe then, add the toluene solution of 1.0% vinyl acetate of having purified (VAc), and add 4.0 * 10
-4The frerrous chloride aqueous catalyst solution of mol/L, seal polymerization pipe, place constant temperature oscillator,, take out in 80 ℃ of reaction 1h, film is cleaned up, in the KOH of 1.0mol/L methanol solution, behind 30 ℃ of saponification hydrolysis 5h, clean film to neutral, prepared hydrophilic porous film is under 0.5MPa, and water flux is 276L/m
2H.
Embodiment 5: with the pretreated UHMWPE microporous barrier of 5 * 10cm size at 220V voltage, 0.8A under the oxygen gas flow rate of discharge current and 0.6L/min, ozone concentration with 50mg/L is handled 20min, place polymerization pipe then, add the ethyl acetate solution of 10.0% vinyl acetate of having purified (VAc), and add 7.8 * 10
-4The iron ammonium sulfate aqueous catalyst solution of mol/L, seal polymerization pipe, place constant temperature oscillator,, take out in 30 ℃ of reaction 5h, film is cleaned up, in the NaOH of 0.7mol/L aqueous isopropanol, behind 30 ℃ of saponification hydrolysis 3h, clean film to neutral, prepared hydrophilic porous film is under 0.5MPa, and water flux is 309L/m
2H.
Claims (1)
1. the hydrophilic modification method of ultrahigh molecular weight polyethylene microporous membrane surface, the invention is characterized in: it may further comprise the steps successively:
(1) preliminary treatment of UHMWPE miillpore filter: film is put into absolute ethyl alcohol, and ultrasonic cleaning 4~5 hours is standby;
(2) select vinyl acetate, promptly VAc is monomer-grafted, and under the vacuum of 30~100 ℃ and 0.01~0.08MPa, decompression distillation is purified, and places refrigerator and cooled to hide, and is standby to this monomer;
(3) to above-mentioned film surface ozone treatment:
Being placed in the oxidation reactor 4 through pretreated UHMWPE miillpore filter in the step (1), regulate the temperature of water-bath, make the gas temperature that enters water-bath 2 from oxidation tank be (5~50) ℃; Open the cooling water switch of ozone generator 3, regulate discharge, make it be slightly larger than the regulation discharge of ozone generator; Start ozone generator 3 then, at discharge current is under 0.2~0.8A, voltage are 180~220V, temperature for (5~50) ℃, making the oxygen gas flow rate that enters ozone generator from water-bath is 0.2~1.0L/min, when oxygen concentration is 10~50mg/L, behind ultrahigh molecular weight polyethylene microporous membrane activation processing 10~90min, the powered-down switch, continue to purge whole system and film surface with oxygen, after two minutes, close oxygen valve, take out miillpore filter;
(4) the ozone activation grafting is handled
UHMWPE miillpore filter behind the ozone activation is put into polymerization pipe, under reaction temperature is (10~80) ℃, adds concentration and be 1.0~20.0% vinyl acetate solution and add 1.0 * 10
-6~5.0 * 10
-3Behind the mol/L ferrous salt catalyst, reaction 1~10h;
(5) the saponification hydrolysis of graft copolymer membrane
UHMWPE miillpore filter behind the graft reaction is taken out, and extracting 24h in the Soxhlet withdrawal device places the NaOH of 0.2~10.0mol/L or the alcoholic solution of potassium hydroxide then, at (10~50) ℃ saponification 2~10h.
(6) post processing of film
Film after the saponification cleans up with deionized water, dries.
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CN102000517A (en) * | 2009-08-28 | 2011-04-06 | 中国科学院上海应用物理研究所 | Hydrophilic modification method for macromolecular filter membrane and obtained product |
CN102131567A (en) * | 2008-06-30 | 2011-07-20 | 3M创新有限公司 | Method of forming hydrophilic membrane |
CN101735474B (en) * | 2009-12-23 | 2011-09-07 | 中国石油天然气股份有限公司 | Hydrophilic polyethylene microporous membrane and preparation method thereof |
CN101612527B (en) * | 2009-07-21 | 2011-11-30 | 清华大学 | Method for modifying surfaces of polymer porous membranes and membrane pores |
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