CN1623639A - Process for modifying reaction at surface of separating film of polymer - Google Patents
Process for modifying reaction at surface of separating film of polymer Download PDFInfo
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- CN1623639A CN1623639A CN 200410066750 CN200410066750A CN1623639A CN 1623639 A CN1623639 A CN 1623639A CN 200410066750 CN200410066750 CN 200410066750 CN 200410066750 A CN200410066750 A CN 200410066750A CN 1623639 A CN1623639 A CN 1623639A
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- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
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- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical group C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 claims description 3
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
A process for modifying the surface of polymer separating membrane by graft reaction includes such steps as immersing the membrane to be modified in supercritical CO2, triggering by free radical trigger or peroxide radical generated by high-energy radiation, diffusing various functional free-radical monomers onto the external and internal surfaces of said membrane by supercritical CO2 fluid, and graft reaction at proper temp and under proper pressure.
Description
Technical field
The present invention relates to the polymer separation film material is carried out the graft reaction technology of surface modification, is exactly the method for introducing functional molecular at surface of separating film of polymer by graft reaction specifically.
Background technology
In recent decades, membrane separation technique as a kind of high efficiency, high selectivity, low energy consumption with oligosaprobicly separate, purifying, concentrate and purification techniques, not only its technology itself has obtained development rapidly, and the also expansion significantly of its application, particularly demonstrated powerful growth momentum in fields such as sewage disposal and reuse, food, biotechnology and clinical medicine.In the membrane separation technique research, core problem is the diffusion barrier of processability excellence.Because synthetic polymer good processing properties and Modulatory character, organic polymer becomes most important separation membrane material.Up to now, common synthetic polymer separation membrane has polysulfones, polyether sulfone, polyester, polyimides and TPO (polyethylene, polypropylene, polyacrylonitrile, Kynoar and polytetrafluoroethylene (PTFE) etc.).Regrettably, these polymer great majority are hydrophobic materials, are used for sewage disposal, and serious membrane pollution problem can be brought in fields such as biotechnology and medical science, shortens the service life of diffusion barrier greatly, increase use cost.In addition, be applied to the diffusion barrier of different occasions, different separation systems, should have different separation selectivities, different parent/hydrophobicitys, different surface naturies.For example, when diffusion barrier is used for bioactivator such as enzyme immobilization, cell, antibody, antigen and biotin, not only require responding property of separation membrane surface group, and need certain biocompatibility.This means needs the method and the technology of convenience, easy row that diffusion barrier is carried out surface modification.
The separation membrane surface modification is the importance of membrane separation technique research, also is one of current active research the most field.The method of separation membrane surface modification mainly contains physics coating, surface oxidation or etching, chemical coupling and glycerol polymerization etc.Surface reactive material can be adsorbed onto the film surface though physics applies, very easily run off; Surface oxidation or etching can cause damage to polymer separation film; Chemical coupling requires the film surface to have reactive group in advance; Therefore above-mentioned three kinds of methods are used and are very limited.Graft reaction is attached to separation membrane surface to monomer molecule with the form of chemical bond, has both kept the characteristic of grafting molecule, does not destroy the character of diffusion barrier again.Carry out glycerol polymerization at separation membrane surface and need satisfy two primary conditions, the one, its surperficial generation can trigger monomer the free radical of reaction, the 2nd, the separation membrane surface abundant monomer that distributes.Traditional radical reaction is difficult to satisfy above-mentioned condition, and application limitation is bigger.The simple irradiation that relies on UV, plasma or other high-energy ray, though can produce free radical and carry out graft reaction on the film surface, this method be confined to the outer surface of diffusion barrier, the degree of depth and the degree of grafting are restricted.Adopt suitable method and technology, promote that initator and monomer are the keys of diffusion barrier being carried out the graft reaction modification to separation membrane surface (comprising outer surface and inner surface) diffusion.
Supercritical CO
2Temperature 〉=31.1 ℃ pressure 〉=7.38MPa, state is between gas-liquid.Have the high density that is similar to liquid, be similar to gas like lower viscosity, zero surface tension, low-k, high volatile volatile, low vaporization energy and chemical inertness.
Nearly critical CO
2Be meant the CO 2 fluid (see Figure of description) of temperature and pressure near the carbon dioxide critical line, character is near supercritical CO
2Fluid, and the minor variations of temperature and pressure can cause its character to change significantly, therefore nearly critical CO
2Fluid has good control.
Supercritical CO
2Nonpolar and have extremely low dielectric constant, as a kind of solvent of excellent combination property, but replace organic solvent dissolving and disperse most free yl polymerizating monomers.Excellent in chemical inertia and environmental friendliness etc. make supercritical CO
2Become suitable polymerization reaction medium.
Supercritical CO
2Extremely low viscosity not only makes it have good flowability and scattering and permeating performance, and greatly reduces cage effect, has improved the free radical efficient of initator; Zero surface tension makes it have good wetting and plasticity to polymer, can promote outer surface and the inner surface diffusion to diffusion barrier of initator and polymerization single polymerization monomer.Utilize temperature and pressure can change supercritical CO easily
2Solubility property, can adjust monomer at polymer phase and supercritical CO with this
2Distribution mutually, and then the graft reaction on controlling diaphragm surface.Supercritical CO
2This unusual controllability, the drying property of excellent comprehensive performance and cleaning, and also the source is abundant, with low cost, pollution-free.Make it be suitable for the surface grafting reaction of diffusion barrier.
Summary of the invention
The purpose of this invention is to provide a kind of easy, eco-friendly method of carrying out the graft reaction modification, to realize regulation and control to separation membrane surface character at surface of separating film of polymer.
The step of method is as follows:
1) polymer separation film that will treat modification is fixed on the supporter, places supercritical CO
2In the reactor, temperature is 31.1～70 ℃, and pressure is 7.38～32Mpa, uses supercritical CO
2Fluid is pre-to be soaked into 0.5～1 hour;
2) at CO
2Under the atmosphere, in aforesaid reaction vessel, add the radical reaction monomer, with supercritical CO
2Or nearly critical CO
2Fluid is exposed to the peroxidating group initiation that produces in the air as decentralized medium with initator or through the polymer separation film behind the high-energy radiation irradiation, carries out graft reaction at separation membrane surface, 40～80 ℃ of reaction temperatures, 1～36 hour reaction time;
3) reaction is finished, slowly emptying CO
2, be decompressed to zero, stop heating simultaneously, take out the graft reaction Modified Membrane, and use solvent clean, with polymer segment, use supercritical CO then except that the not grafting of striping surface adhesion
2Extraction, drying.
Advantage of the present invention is:
1, uses supercritical CO
2Make reaction medium, simple to operate, good reproducibility, environmental friendliness, and CO
2Can repetitive cycling use, with low cost;
2, supercritical CO
2The diffuse fluid penetrating power is strong, and graft reaction can be deeply to the diffusion barrier inner surface, the percent grafting height; Regulate supercritical CO
2Density can be controlled the grafting degree of depth and degree;
3, the face graft ratio is more even, and grafting degree is controlled easily;
4, because supercritical CO
2The zero interfacial tension of reaction medium has reduced glycerol polymerization process solvent and has caused the influence of internal stress to the diffusion barrier structure;
5, the simple and cleaning of the last handling processes such as drying of graft modification diffusion barrier.
Description of drawings
Accompanying drawing is the density-pressure thermoisopleth schematic diagram of liquid and supercritical carbon dioxide.
The specific embodiment
The present invention uses supercritical CO
2Decentralized medium as graft reaction, utilize the dissolving, diffusion, penetrating power of its excellence and to the wetting of most polymer and plasticising performance, promoted the diffusion of monomer and initator effectively to surface of separating film of polymer and endoporus, improve the grafting degree of separation membrane surface monomer, improved the uniformity of face grafting.
The decentralized medium of graft polymerization reaction of the present invention is: supercritical CO
2Fluid (temperature 〉=31.1 ℃, pressure 〉=7.38MPa; Be lower than the ruined temperature and pressure of polymer film body) or nearly critical CO
2Fluid (temperature and pressure is seen accompanying drawing near the critical line of carbon dioxide).
The polymer separation film material is: Kynoar, polyacrylonitrile, polypropylene, polyethylene, polysulfones, polyether sulfone, poly (aryl ether sulfone ketone), polytetrafluoroethylene (PTFE), polyester or polyimides; The diffusion barrier structure comprises perforated membrane or non-porous film; That the diffusion barrier form comprises is flat, tubular type or doughnut formula.The radical reaction monomer comprises styrene, maleic anhydride, itaconic anhydride, acrylate, acrylic acid, methacrylate, GMA, hydroxyethyl methacrylate, methacrylic acid, acrylamide, vinylpyridine or vinyl pyrrolidone.Initator is: azo isobutyronitrile, benzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate or di-cyclohexylperoxy di-carbonate.High-energy radiation is: plasma, electron beam,
60Co and gamma-rays.Graft modification film post processing cleaning solvent is: water, ethanol, acetone or oxolane.
It is 5～15 minutes that polymer separation film behind the present invention's process high-energy radiation irradiation is exposed to the airborne time.
Be described in further detail below in conjunction with application example, but these examples are not used for limiting the present invention.
Embodiment 1
PVDF microporous barrier (flat sheet membrane, 20 centimetres of 10 cm x) is fixed in one has on the supporter of definite shape, place 1000ml column type supercritical CO
2Airtight in the reactor (φ 68mm/400mm), be warming up to 35 ℃ again, be forced into 9MPa, the slow emptying CO of pressure-reducing valve is opened in molten 0.5 hour of preimpregnation
2, so that next step graft reaction.Then at CO
2Under the atmosphere, in reactor, add the mix monomer (mol ratio 1: 1) of 50g styrene (St) and maleic anhydride (MAH) successively, and 0.28g azo isobutyronitrile (AIBN), closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (60 ℃ of temperature, pressure 7.38MPa) simultaneously, constant temperature, constant voltage reaction 1 hour.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, soaks 24h with acetone, removes not grafting polymer segment of surface.ATR-IR, XPS and elementary analysis show that the copolymer of styrene and maleic anhydride is grafted to PDVF microporous barrier surface, and the face grafting is even, and percent grafting is 3.0%, and microcellular structure did not have significant change before and after electron microscope photo scanning showed grafting.
Embodiment 2
Operation treats that with example 1 the modification counterdie changes the PAN microporous barrier into, and the graft copolymerization monomer changes 1.6g itaconic anhydride (ITA) into, and initator changes 0.03g benzoyl peroxide (BPO), closed reactor into.Open CO
2The intake valve pressurization is warming up to supercriticality (80 ℃ of temperature, pressure 20MPa) simultaneously, constant temperature, constant voltage reaction 10 hours.The graft modification film characterizes with ATR-IR, XPS, elementary analysis and ESEM, and percent grafting is 6.8%.
Embodiment 3
PP dense non-porous film (flat sheet membrane, 20 centimetres of 10 cm x) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 1 hour in the reactor, and operation is with example 1; Take out the PP microporous barrier, put into plasma generator rapidly, regulate vacuum under the argon atmospher to 20Pa, 100W plasma irradiation 10～20 minutes, the film behind the plasma irradiation exposed to the open air in air 15 minutes, moved into supercritical CO rapidly
2In the reactor; At CO
2Under the atmosphere, in reactor, add 3.4g hydroxyethyl methacrylate monomer (HEMA) successively, closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (60 ℃ of temperature, pressure 30MPa) simultaneously, constant temperature, constant voltage reaction 4 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, removes the polymer segment of not grafting with ethanol and acetone soaking and washing.With the PP film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 12.4%.
Embodiment 4
PE microporous barrier (flat sheet membrane, 20 centimetres of 10 cm x) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 0.7 hour in the reactor, and operation is with example 1; Take out the PE microporous barrier, put into pre-irradiation under the high-energy electron accelerator of 2MeV rapidly, irradiation dose is controlled at 90KGy, and the film behind the electron beam irradiation exposed to the open air in air 10 minutes, moved into supercritical CO rapidly
2In the reactor; At CO
2Under the atmosphere, in reactor, add 6.2g GMA (GMA) successively, closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (60 ℃ of temperature, pressure 30MPa) simultaneously, constant temperature, constant voltage reaction 12 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, removes not grafting polymer segment with ethanol and acetone soaking and washing.With the PE film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 7.5%.
Embodiment 5
PES hollow-fibre membrane (φ 0.08mm/200mm) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 0.5 hour in the reactor, and operation is with example 1; Then at CO
2Under the atmosphere, in reactor, add 4.8g vinyl pyrrolidone (VP) successively, and the 0.12g dilauroyl peroxide, closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (80 ℃ of temperature, pressure 30MPa) simultaneously, constant temperature, constant voltage reaction 36 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, removes the polymer segment of not grafting with the deionized water soaking and washing.With the PE film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 17.5%.
Embodiment 6
PS tube-type micropore film (φ 0.8mm/200mm) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 0.5 hour in the reactor, and operation is with example 5; Then at CO
2Under the atmosphere, in reactor, add the 4.8g vinylpyridine successively, and the 0.12g di-cyclohexylperoxy di-carbonate, closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (40 ℃ of temperature, pressure 25MPa) simultaneously, constant temperature, constant voltage reaction 20 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, removes the polymer segment of not grafting with the deionized water soaking and washing.With the PS film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 20.9%.
Embodiment 7
PTFE microporous barrier (flat sheet membrane, 20 centimetres of 10 cm x) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 0.7 hour in the reactor, and operation is with example 1; Take out the PTFE microporous barrier, used the gamma-radiation pre-irradiation rapidly 10 minutes, the film behind the irradiation exposed to the open air in air 5 minutes, moved into supercritical CO rapidly
2In the reactor; At CO
2Under the atmosphere, in reactor, add 5.2g acrylic acid (AA) successively, closed reactor.Open CO
2The intake valve pressurization is warming up to nearly critical condition (30 ℃ of temperature, pressure 30MPa) simultaneously,
Constant temperature, constant voltage reaction 16 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, removes not grafting polymer segment with the deionized water soaking and washing.With the PTFE film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 8.5%.
Embodiment 8
Poly (aryl ether sulfone ketone) (PPESK) microporous barrier (flat sheet membrane, 20 centimetres of 10 cm x) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 0.7 hour in the reactor, and operation is with example 6; Take out the PPESK microporous barrier, use rapidly
60Co pre-irradiation 10 minutes, the film behind the irradiation exposed to the open air in air 5 minutes, moved into supercritical CO rapidly
2In the reactor; At CO
2Under the atmosphere, in reactor, add 3.5g acrylamide (AAM) successively, closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (31.1 ℃ of temperature, pressure 32MPa) simultaneously, constant temperature, constant voltage reaction 6 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, removes not grafting polymer segment with the deionized water soaking and washing.With the PPESK film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 5.5%.
Embodiment 9
Polyimides (PEI) microporous barrier (flat sheet membrane, 20 centimetres of 10 cm x) is fixed in one has on the supporter of definite shape, place supercritical CO
2Preimpregnation is molten 1 hour in the reactor, and operation is with example 1; Then at CO
2Under the atmosphere, in reactor, add the 4.8g methyl methacrylate successively, and the 0.12g di-isopropyl peroxydicarbonate, closed reactor.Open CO
2The intake valve pressurization is warming up to supercriticality (50 ℃ of temperature, pressure 25MPa) simultaneously, constant temperature, constant voltage reaction 10 hours.Opening the slow exhaust of pressure-reducing valve is zero until reactor pressure, takes out the graft modification film, spends the polymer segment that the oxolane soaking and washing is removed not grafting.With the PEI film of ATR-IR, XPS, elementary analysis and the graft modification of scanning electron microscope analysis sign, the face grafting is even, and percent grafting is 8.9%.
Claims (8)
1. method of carrying out the graft reaction modification at surface of separating film of polymer, the step of method is as follows:
1) polymer separation film that will treat modification is fixed on the supporter, places supercritical CO
2In the reactor, temperature is 31.1～70 ℃, and pressure is 7.38～32Mpa, uses supercritical CO
2Fluid is pre-to be soaked into 0.5～1 hour;
2) at CO
2Under the atmosphere, in aforesaid reaction vessel, add the radical reaction monomer, with supercritical CO
2Or nearly critical CO
2Fluid is exposed to the peroxidating group initiation that produces in the air as decentralized medium with initator or through the polymer separation film behind the high-energy radiation irradiation, carries out graft reaction at separation membrane surface, 40～80 ℃ of reaction temperatures, 1～36 hour reaction time;
3) reaction is finished, slowly emptying CO
2, be decompressed to zero, stop heating simultaneously, take out the graft reaction Modified Membrane, and use solvent clean, use supercritical CO then
2Extraction, drying.
2. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that the decentralized medium of said graft polymerization reaction is: supercritical CO
2Fluid or nearly critical CO
2Fluid.
3. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that said polymer separation film material is: Kynoar, polyacrylonitrile, polypropylene, polyethylene, polysulfones, polyether sulfone, poly (aryl ether sulfone ketone), polytetrafluoroethylene (PTFE), polyester or polyimides; The diffusion barrier structure comprises perforated membrane or non-porous film; That the diffusion barrier form comprises is flat, tubular type or doughnut formula.
4. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that said radical reaction monomer comprises styrene, maleic anhydride, itaconic anhydride, acrylate, acrylic acid, methacrylate, GMA, hydroxyethyl methacrylate, methacrylic acid, acrylamide, vinylpyridine or vinyl pyrrolidone.
5. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that said initator is: azo isobutyronitrile, benzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate or di-cyclohexylperoxy di-carbonate.
6. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that said high-energy radiation is: plasma, electron beam,
60Co and gamma-rays.
7. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that said to be exposed to the airborne time through the polymer separation film behind the high-energy radiation irradiation be 5～15 minutes.
8. a kind of method of carrying out the graft reaction modification at surface of separating film of polymer according to claim 1 is characterized in that said graft modification film post processing cleaning solvent is: water, ethanol, acetone or oxolane.
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