CN102274693A - Method for preparing organic pervaporation membrane - Google Patents
Method for preparing organic pervaporation membrane Download PDFInfo
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- CN102274693A CN102274693A CN2011101417935A CN201110141793A CN102274693A CN 102274693 A CN102274693 A CN 102274693A CN 2011101417935 A CN2011101417935 A CN 2011101417935A CN 201110141793 A CN201110141793 A CN 201110141793A CN 102274693 A CN102274693 A CN 102274693A
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- supporter
- difunctional
- polymer
- aminopropyl
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- 239000012528 membrane Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005373 pervaporation Methods 0.000 title abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 230000003750 conditioning effect Effects 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 28
- 230000008016 vaporization Effects 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 230000008595 infiltration Effects 0.000 claims description 12
- 238000001764 infiltration Methods 0.000 claims description 12
- 230000000640 hydroxylating effect Effects 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052863 mullite Inorganic materials 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 4
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 claims description 3
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 claims description 3
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 3
- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 claims description 3
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 claims description 3
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- UTEBVBBGZIBAGZ-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypentane-1,5-diamine Chemical compound NCCC[Si](OC)(OC)OC(CCN)CCN UTEBVBBGZIBAGZ-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical group CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 6
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 18
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 18
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 18
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 230000004907 flux Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 239000007888 film coating Substances 0.000 description 4
- 238000009501 film coating Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for preparing a composite pervaporation membrane. The method comprises the following steps of: dissolving an organic matter in a solvent to prepare a homogeneous phase membrane forming solution; adding a crosslinking agent and a difunctional conditioning agent into the membrane forming solution, uniformly mixing and adding a catalyst; coating the prepared membrane forming solution containing the difunctional conditioning agent on a supporting body; and finally performing aftertreatment on the composite membrane to prepare the composite pervaporation membrane. By the method, the permeability and selectivity of the pervaporation membrane can be improved simultaneously, and the stability of the composite membrane is also improved.
Description
Technical field
The present invention relates to a kind of the preparation and the technology of regulating and control organic infiltrating and vaporizing membrane, specifically be meant by utilizing " reaction inhibition and interface are wetting " synergy to regulate and control the micro chemical of organic infiltrating and vaporizing membrane and the interface bond strength between heterogeneous microstructure and organic separating layer and the supporting layer.
Background technology
The infiltration evaporation process is the method for good separating liquid mixture, comprises the dehydration of organic aqueous solution, organic separation in the water, the separation of binary organic mixture etc.Organic film material is widely used in the infiltration evaporation process.Organic infiltrating and vaporizing membrane is because its low price, and good film-forming property has become the preferred material of infiltration evaporation film preparation.Yet, still lack the controlled preparation that effective means realizes film micro chemical and heterogeneous microstructure at present.For infiltrating and vaporizing membrane, the interface marriage relation between separating layer and the supporting layer the long-time stability of film.In addition, for the film preparation of reality, key is how to improve permeability of the membrane and selectivity simultaneously.If have a kind of easy method, can realize above-mentioned purpose simultaneously, for the development of infiltrating and vaporizing membrane, be very favorable.
Traditional method is from the degree of cross linking of control coating solution or by introducing the optimization that the inorganic method for preparing mixed substrate membrane containing nano-grade molecular sieve mutually realizes film properties.The degree of cross linking is to control by changing crosslinking agent kind, content or crosslinking time.If mixed substrate membrane containing nano-grade molecular sieve is the realization by inorganic introducing thing, the optimization of matrix membrane material property.These methods, the space of optimized controllable is less, and final properties increases when can't realize permeation flux and separating property.These methods are difficult to realize the raising of separating layer and supporting layer interface binding power, must realize the raising of binding ability between separating layer and the supporting layer by introduce the method for reaction active groups or plasma treatment at the interface of separating layer and supporting layer.
Summary of the invention
Purpose of the present invention is exactly the problem that can be regulated and control when present infiltrating and vaporizing membrane can not be realized interface junction contract between micro chemical and heterogeneous microstructure and separating layer and the supporting layer in order to solve, has proposed a kind of method for preparing organic infiltrating and vaporizing membrane.
Technical scheme of the present invention is: propose to utilize the micro chemical of " it is wetting with the interface that reaction suppresses " organic infiltrating and vaporizing membrane that acts synergistically and heterogeneous microstructure and organic polymer separating layer to combine with interface between the supporting layer.Realize the synergy of " it is wetting with the interface that reaction suppresses " by in coating solution, adding " conditioning agent of bi-component ", thereby reach the purpose that the micro chemical of the organic infiltrating and vaporizing membrane of control and heterogeneous microstructure and organic polymer separating layer combine with interface between the supporting layer.Described osmosis vaporizing compound membrane of the present invention by porous supporting body (comprising inorganic supporting body and organic supporter) and preparation organic polymer separating layer on porous supporting body form.
Concrete technical scheme of the present invention is: a kind of method for preparing organic infiltrating and vaporizing membrane, and its concrete steps are as follows:
(1) supporter is carried out hydroxylating or surface grafting preliminary treatment;
(2) will prepare the used polymer of infiltration evaporation separating layer and be dissolved in the solvent, stir;
(3) add crosslinking agent and difunctional conditioning agent (two kinds of materials are composite), the back that stirs adds catalyst, and after stirring, standing and defoaming promptly gets the coating solution for preparing organic separating layer again;
(4) coating solution that step (3) is made is coated on the resulting supporter of step (1), optimised organic infiltrating and vaporizing membrane when promptly obtaining the interface junction contract between micro chemical and heterogeneous microstructure and separating layer and the supporting layer after the shaping.
It is benchmark with the quality for preparing the used polymer of infiltration evaporation separating layer that solvent in the above-mentioned steps (2) adds quality, is 1-20 times of polymer quality, is preferably 8-20 times of polymer quality.
The adding quality of crosslinking agent is benchmark with the polymer quality in the above-mentioned steps (3), is the 0.5%-20% of polymer quality; The adding quality of difunctional conditioning agent (two kinds of materials are composite) is benchmark with the polymer quality, is the 0.1%-20% of polymer quality, is preferably the 1%-18% of polymer quality; In the wherein difunctional conditioning agent, two kinds of composite ratios of material are 1/10-9/10.
Catalyst adding quality is the 0.05%-10% of polymer quality in the above-mentioned steps (3), is preferably the 0.5%-5% of polymer quality.
Mixing speed is 150-2000rpm in the preferred steps (2), and mixing time is 0.5-12 hour; Add crosslinking agent and difunctional conditioning agent in the step (3), and mixing speed is 150-1500rpm after adding catalyst, mixing time is 0.5-12 hour.
Supporter described in the step 1 is inorganic supporting body or organic supporter, and wherein said inorganic supporting body can be mullite, Al
2O
3, ZrO
2, TiO
2, SiO
2In a kind of material or the supporter of several composite, supporter be shaped as sheet, tubulose or doughnut supporter; Described organic supporter can be polyether sulfone, polysulfones, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), cellulose acetate, polyacrylonitrile or polyvinylidene fluoride, and it is shaped as porous chip supporter or doughnut supporter.
Used polymer is any one in dimethyl silicone polymer, poly-octyl group methylsiloxane, polyethylene glycol, polyvinyl alcohol or the shitosan in the described step 2.
Used solvent is any one in water, methyl alcohol, ethanol, n-hexane, normal heptane, normal octane, benzene,toluene,xylene, chloroform or the oxolane in the described step 2.
Difunctional conditioning agent is an octyltri-ethoxysilane in the described step 3, the n-octyl trimethoxy silane, the dodecyl triethoxysilane, the n-octyl trichlorosilane, the dodecyl trichlorosilane, hexadecyl trichlorosilane, the dodecyl trimethoxy silane, the cetyl trimethoxy silane, the cetyl triethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane, the phenylamino MTES, the phenylamino MTMS, two kinds of materials is composite between aminoethyl aminoethyl aminopropyl trimethoxysilane or the polyamino alkyltrialkoxysilaneand.
Used crosslinking agent is silester, VTES, vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, alkoxytitanium acid esters, maleic anhydride, oxalic acid, citric acid, trimellitic anhydride, phthalic anhydride or 1 in the described step 3, any one in the 6-adipic acid.
Used catalyst is any one in dibutyl tin dilaurate, platinum catalyst, oxalic acid or the concentrated sulfuric acid in the described step 3.
Used painting method can be a knifing in the described step 3, spin coating, and spraying is immersed-is lifted and The tape casting.
Beneficial effect:
The unique physico-chemical property that utilizes film forming solution microphase-separated self to produce, providing a kind of has pervasive, easy and need not the auxiliary film-forming method of special installation, this method can improve permeation flux and separation factor simultaneously, thereby simplified the preparation process of infiltrating and vaporizing membrane, and reduced the preparation cost of infiltrating and vaporizing membrane, play a part to seeing importantly for the development of infiltrating and vaporizing membrane, help in the industrial production of reality, applying.
The present invention relates to a kind of method of passing through microphase-separated behavior controlling diaphragm microstructure in the infiltrating and vaporizing membrane materials process for preparing, not only be suitable for the superior membrane material of solubility property, also be fit to the superior membrane material of diffusion.Relate to and a kind ofly simple in film forming solution, add difunctional conditioning agent and improve the absorption property of membrane material and supporting body surface binding ability and membrane material and the method for diffusion, realize the permeation flux of membrane material and optionally raising simultaneously.The precursor aqueous solution of whole infiltration evaporation membrane material all is to be configured in same reaction vessel, need not reduce the energy consumption of infiltrating and vaporizing membrane material preparation by the method for modifying of complexity, thereby reduces the preparation cost of infiltration evaporation membrane material.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further details, but the invention is not restricted to these embodiment.
Embodiment 1: utilize (v/v) 7: 3 concentrated sulfuric acid and hydrogen peroxide solution that mullite supporter soaked overnight is carried out the hydroxylating preliminary treatment, use washed with de-ionized water then.Get 4 gram dimethyl silicone polymer (PDMS) and 72g n-hexanes, add the vinyltrimethoxy silane of 0.75g as crosslinking agent after mixing 1h under the 800rpm rotating speed, 0.6g the n-octyl trichlorosilane and 0.1g phenylamino MTES as difunctional conditioning agent, the 800rpm rotating speed adds 0.08g dibutyl tin dilaurate catalyst after stirring 2h down, 400rpm stirs 8h down can obtain uniform PDMS film coating solution, adopt dipping-pulling method on tubular type mullite supporter, to film at last, can obtain the PDMS compounding permeation vaporizing film that permeability and selectivity improve simultaneously.
Comparative example 1: utilize (v/v) 7: 3 concentrated sulfuric acid and hydrogen peroxide solution that mullite supporter soaked overnight is carried out the hydroxylating preliminary treatment, use washed with de-ionized water then.Get 4 gram dimethyl silicone polymer (PDMS) and 72g n-hexanes, add the vinyltrimethoxy silane of 0.75g as crosslinking agent after mixing 1h under the 800rpm rotating speed, the 800rpm rotating speed adds 0.08g dibutyl tin dilaurate catalyst after stirring 4h down, 400rpm stirs 4h down can obtain uniform PDMS film coating solution, adopt dipping-pulling method on tubular type mullite supporter, to film at last, can obtain the PDMS compounding permeation vaporizing film that permeability and selectivity improve simultaneously.
By the infiltration evaporation result as can be known, the flux that adds the organic infiltrating and vaporizing membrane behind the difunctional conditioning agent has increased by 30%, and separation factor has increased by 60%.Utilize the adhesion between cut technical testing film separating layer and the support body layer, find that adhesion has improved 60%.
Embodiment 2: the polyether sulfone supporter is immersed in 12h carries out the hydroxylating preliminary treatment in the deionized water.Get poly-octyl group methylsiloxane (POMS) of 5 grams and 55g toluene, the 650rpm rotating speed stir down add 0.05g behind the 2h VTES as crosslinking agent, 0.03g gamma-aminopropyl-triethoxy-silane and 0.12g cetyl triethoxysilane as difunctional conditioning agent, the 650rpm rotating speed adds 0.1g oxalic acid catalyst after stirring 2h down, the 450rpm rotating speed stirs 4h down can obtain uniform PDMS film coating solution, adopt The tape casting on the polyether sulfone supporter, to film at last, can obtain the PDMS compounding permeation vaporizing film that permeability and selectivity improve simultaneously.
Comparative example 2: the polyether sulfone supporter is immersed in 12h carries out the hydroxylating preliminary treatment in the deionized water.Get poly-octyl group methylsiloxane (POMS) of 5 grams and 55g toluene, the 650rpm rotating speed adds the VTES of 0.05g as crosslinking agent after stirring 2h down, the 650rpm rotating speed adds 0.1g oxalic acid catalyst after stirring 4h down, the 450rpm rotating speed stirs 4h down can obtain uniform PDMS film coating solution, adopt The tape casting on the polyether sulfone supporter, to film at last, can obtain the PDMS compounding permeation vaporizing film that permeability and selectivity improve simultaneously.
By the infiltration evaporation result as can be known, flux and the separation factor that adds difunctional conditioning agent organic infiltrating and vaporizing membrane afterwards improved 50% respectively.Utilize the adhesion between cut technical testing film separating layer and the support body layer, find that adhesion has improved 100%.
Embodiment 3: the cellulose acetate supporter is immersed in to spend the night in the 5wt% dilution heat of sulfuric acid carries out the hydroxylating preliminary treatment.Getting 5 gram polyvinyl alcohol (PVA) and 75g dimethylbenzene mixes, the 300rpm rotating speed adds the silester of 0.04g as crosslinking agent after stirring 10h down, 0.03g hexadecyl trichlorosilane and 0.05g N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane as difunctional conditioning agent, the 300rpm rotating speed adds the 0.04g platinum catalyst after stirring 8h down, the 700rpm rotating speed stirs down that 10h can be uniformly dispersed and the precursor liquid of stable PDMS composite, adopt the striking coating method on the cellulose acetate supporter, to film at last, can obtain the PDMS composite membrane that microphase-separated reaches balance.
Comparative example 3: the cellulose acetate supporter is immersed in to spend the night in the 5wt% dilution heat of sulfuric acid carries out the hydroxylating preliminary treatment.Getting 5 gram polyvinyl alcohol (PVA) and 75g dimethylbenzene mixes, the 300rpm rotating speed adds the silester of 0.04g as crosslinking agent after stirring 10h down, the 300rpm rotating speed adds the 0.12g platinum catalyst after stirring 8h down, the 700rpm rotating speed stirs down that 10h can be uniformly dispersed and the precursor liquid of stable PDMS composite, adopt the striking coating method on the cellulose acetate supporter, to film at last, can obtain the PDMS composite membrane that microphase-separated reaches balance.
By the infiltration evaporation result as can be known, the flux that adds the organic infiltrating and vaporizing membrane behind the difunctional conditioning agent has increased by 40%, and separation factor has increased by 50%.Utilize the adhesion between cut technical testing film separating layer and the support body layer, find that adhesion has improved 55%.
Embodiment 4: with TiO
2Supporter is immersed in hydroxylating processing 14h in the 5wt% alkene sulfuric acid solution.Getting 3 gram shitosans (CS) and 30g normal heptane mixes, the 700rpm rotating speed stir down the 3-aminopropyl triethoxysilane that adds 0.02g behind the 1h as N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane of the dodecyl trimethoxy silane of crosslinking agent, 0.05g and 0.01g as difunctional conditioning agent, the 850rpm rotating speed adds 0.08g dibutyl tin dilaurate catalyst after stirring 4h down, the 750rpm rotating speed stirs down that 8h can be uniformly dispersed and the precursor liquid of stable PDMS composite, adopts dip-coating method at TiO at last
2Film on the supporter, can obtain the PDMS composite membrane that microphase-separated reaches balance.
Comparative example 4: with TiO
2Supporter is immersed in hydroxylating processing 14h in the 5wt% alkene sulfuric acid solution.Getting 3 gram shitosans (CS) and 30g normal heptane mixes, the 700rpm rotating speed adds the 3-aminopropyl triethoxysilane of 0.02g as crosslinking agent after stirring 5h down, the 850rpm rotating speed adds 0.08g dibutyl tin dilaurate catalyst after stirring 4h down, the 750rpm rotating speed stirs down that 8h can be uniformly dispersed and the precursor liquid of stable PDMS composite, adopts dip-coating method at TiO at last
2Film on the supporter, can obtain the PDMS composite membrane that microphase-separated reaches balance.
By the infiltration evaporation result as can be known, the flux that adds the organic infiltrating and vaporizing membrane behind the difunctional conditioning agent has increased by 60%, and separation factor has increased by 80%.Utilize the adhesion between cut technical testing film separating layer and the support body layer, find that adhesion has improved 120%.
Claims (8)
1. method for preparing organic infiltrating and vaporizing membrane, its concrete steps are as follows:
(1) supporter is carried out hydroxylating or surface grafting preliminary treatment;
(2) will prepare the used polymer of infiltration evaporation separating layer and be dissolved in the solvent, stir;
(3) add crosslinking agent and difunctional conditioning agent, the back that stirs adds catalyst, and after stirring, standing and defoaming promptly prepares the coating solution of organic separating layer again;
(4) coating solution that step (3) is made is coated in step (1) on pretreated supporter, obtains organic infiltrating and vaporizing membrane after the moulding.
2. method according to claim 1, the adding quality that it is characterized in that described solvent are 1-20 times of polymer quality; The adding quality of crosslinking agent is the 0.5%-20% of polymer quality; The adding quality of difunctional conditioning agent is the 0.1%-20% of polymer quality, and in the wherein difunctional conditioning agent, two kinds of composite mass ratioes of material are 1/10-9/10; It is the 0.05%-10% of polymer quality that catalyst adds quality.
3. method according to claim 2, the adding quality that it is characterized in that described solvent are 8-20 times of polymer quality; The adding quality of difunctional conditioning agent is the 1%-18% of polymer quality; It is the 0.5%-5% of polymer quality that catalyst adds quality.
4. method according to claim 1 is characterized in that the mixing speed in the step (2) is 150-2000rpm, and mixing time is 0.5-12 hour; Add crosslinking agent and difunctional conditioning agent in the step (3), and mixing speed is 150-1500rpm after adding catalyst, mixing time is 0.5-12 hour.
5. method according to claim 1 is characterized in that described supporter is inorganic supporting body or organic supporter, and wherein said inorganic supporting body is mullite, Al
2O
3, ZrO
2, TiO
2Or SiO
2In a kind of material or several composite material supporters; Described organic supporter is polyether sulfone, polysulfones, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), cellulose acetate, polyacrylonitrile or polyvinylidene fluoride supporter.
6. method according to claim 1 is characterized in that described polymer is any one in dimethyl silicone polymer, poly-octyl group methylsiloxane, polyethylene glycol, polyvinyl alcohol or the shitosan; Described solvent is any one in water, methyl alcohol, ethanol, n-hexane, normal heptane, normal octane, benzene,toluene,xylene, chloroform or the oxolane; Described crosslinking agent is silester, VTES, vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, alkoxytitanium acid esters, maleic anhydride, oxalic acid, citric acid, trimellitic anhydride, phthalic anhydride or 1, any one in the 6-adipic acid; Described catalyst is any one in dibutyl tin dilaurate, platinum catalyst, oxalic acid or the sulfuric acid.
7. method according to claim 1 is characterized in that described difunctional conditioning agent is an octyltri-ethoxysilane, the n-octyl trimethoxy silane, the dodecyl triethoxysilane, the n-octyl trichlorosilane, the dodecyl trichlorosilane, hexadecyl trichlorosilane, the dodecyl trimethoxy silane, the cetyl trimethoxy silane, the cetyl triethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyldiethoxysilane, the phenylamino MTES, the phenylamino MTMS, two kinds of materials is composite between aminoethyl aminoethyl aminopropyl trimethoxysilane or the polyamino alkyltrialkoxysilaneand.
8. method according to claim 1 is characterized in that described painting method is knifing, spin coating, spraying, immersion-lift or The tape casting.
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