CN112979890B - Pervaporation membrane with specific function and preparation method and application thereof - Google Patents
Pervaporation membrane with specific function and preparation method and application thereof Download PDFInfo
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- CN112979890B CN112979890B CN202110294043.5A CN202110294043A CN112979890B CN 112979890 B CN112979890 B CN 112979890B CN 202110294043 A CN202110294043 A CN 202110294043A CN 112979890 B CN112979890 B CN 112979890B
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- polysiloxane
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 238000005373 pervaporation Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title description 11
- -1 polysiloxane Polymers 0.000 claims abstract description 206
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 155
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 238000010790 dilution Methods 0.000 claims abstract description 48
- 239000012895 dilution Substances 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 39
- 239000011737 fluorine Substances 0.000 claims abstract description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 28
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 28
- 244000005700 microbiome Species 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- 238000005266 casting Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 125000002091 cationic group Chemical group 0.000 claims description 20
- 150000003254 radicals Chemical class 0.000 claims description 20
- 238000000855 fermentation Methods 0.000 claims description 17
- 230000004151 fermentation Effects 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 125000005504 styryl group Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 5
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 5
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- NYCQTUHDRKXIMP-UHFFFAOYSA-N butoxy-dimethoxy-methylsilane Chemical compound CCCCO[Si](C)(OC)OC NYCQTUHDRKXIMP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract description 26
- 238000000926 separation method Methods 0.000 abstract description 25
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 5
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000004907 flux Effects 0.000 description 19
- 230000006870 function Effects 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 10
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 238000011160 research Methods 0.000 description 6
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- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 239000003999 initiator Substances 0.000 description 2
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- 229920006254 polymer film Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000193401 Clostridium acetobutylicum Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a pervaporation membrane material with a specific function, which is obtained by polymerizing photoresponse polysiloxane and photoresponse dilution monomer in the presence of a photoinitiator. The pervaporation membrane material contains a photoresponse polysiloxane unit and a photoresponse dilution monomer unit; the photoresponse type dilution monomer has both photoinitiation groups and fluoroalkyl chains, so that the prepared fluorine-containing pervaporation membrane has a stronger hydrophobic effect than an original PDMS membrane, and the fluorine-containing pervaporation membrane can reduce the surface free energy of the membrane, thereby enhancing the biological pollution resistance of the membrane (reducing the adhesion of microorganisms). The extremely strong hydrophobicity and stain resistance improve the separation performance and long-term stability of the membrane.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a pervaporation membrane with a specific function, and a preparation method and application thereof.
Background
In the traditional polymer film preparation process, an organic solvent is inevitably used for dissolving a high molecular polymer, and the volatilization of the solvent can increase the actual operation difficulty and cause environmental pollution; meanwhile, due to the limitation of the material characteristics of the traditional polymer membrane, the hydrophobicity of the traditional polymer membrane is difficult to meet the requirement of the pervaporation membrane on the efficient recovery of organic matters, and the high free energy of the membrane surface is easy to cause the adhesion of microorganisms (membrane pollution).
Therefore, the problem is that a high-efficiency pervaporation membrane with specific functions of resisting biological pollution and the like and a preparation technology thereof need to be researched and developed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a pervaporation membrane material with specific functions and a preparation method thereof, aiming at the defects of the prior art. According to the method, fluorine-containing micromolecules are used as photoresponse type dilution monomers to replace traditional organic solvents, so that the surface free energy of the membrane is effectively reduced, membrane pollution is effectively avoided, and the long-term stability of the membrane is improved.
To this end, the first aspect of the present invention provides a pervaporation membrane material having a specific function, which is obtained by polymerizing a photoresponsive polysiloxane and a photoresponsive diluent monomer in the presence of a photoinitiator.
In the present invention, the pervaporation membrane material contains a photoresponsive polysiloxane unit and a photoresponsive dilution monomer unit.
In some embodiments of the present invention, the photo-responsive dilution monomer is a fluorine-containing photo-responsive dilution monomer; specifically, the light-responsive dilution monomer is a fluorine-containing responsive dilution monomer with a photoinitiation group and a fluoroalkyl chain; more preferably, the photoinitiating group comprises a cationic photoinitiating group and a free radical photoinitiating group; the cationic photoinitiating group comprises one or more of epoxy group, vinyl ether group, styryl group and mercapto-vinyl group; the free radical photoinitiating group comprises one or more of an acrylate group, a methacrylate group and an acrylamide group; still further preferably, the light-responsive diluent monomer comprises dodecafluoroheptyl methacrylate and/or tridecyl octyl methacrylate.
In other embodiments of the present invention, the photo-responsive polysiloxane comprises a polysiloxane containing cationic photo-initiation groups and/or a polysiloxane containing free radical photo-initiation groups; preferably, the polysiloxane containing the cationic photo-initiation group comprises one or more of epoxy polysiloxane, vinyl ether polysiloxane, styrene polysiloxane and mercapto-vinyl polysiloxane; and/or the polysiloxane containing the free radical photo-initiation group comprises one or more of acrylate-based polysiloxane, methacrylate-based polysiloxane and acrylamide-based polysiloxane; further preferably, the photo-responsive polysiloxane is a photo-responsive polydimethylsiloxane.
In some particularly preferred embodiments of the present invention, the pervaporation membrane material is a fluorine-containing pervaporation membrane material, which is composed of fluorine-containing photoresponsive dilution monomer units, and has a molecular structure shown in formula (i):
in the formula (I), the compound is shown in the specification,
x and y are the number of repeating units of a silicon-oxygen chain in the photoresponse polysiloxane unit, and the value is a positive integer;
z is the number of repeating units of carbon chains in the photoresponse polysiloxane unit, and the value is a positive integer;
d is the number of repeating units of carbon chains in the photoresponse type dilution monomer unit, and the value is a positive integer.
In some further specific preferred embodiments of the present invention, the fluorine-containing pervaporation membrane material has a water contact angle of 110 ° or more, a thickness of 5 to 100 μm, a stability of being used in synchronization with the biomass-based fermentation broth of 100 hours or more, and no microorganism attached to the surface; wherein the biomass-based fermentation liquid comprises one or more of butanol fermentation liquid, ethanol fermentation liquid and furfural fermentation liquid.
In a second aspect, the present invention provides a pervaporation membrane having a specific function, comprising a pervaporation membrane material according to the first aspect of the present invention.
In a third aspect of the present invention, there is provided a method for producing a pervaporation membrane having a specific function, comprising:
step A, adding a light-responsive dilution monomer and a photoinitiator into light-responsive polysiloxane for mixing to obtain a membrane casting solution;
b, defoaming the casting solution, and coating the defoamed casting solution on a substrate to obtain a liquid film coated on the substrate;
and step C, irradiating and curing the liquid film under ultraviolet light to obtain the pervaporation film with the specific function.
According to the invention, in the casting solution, the dosage of the photoresponse type dilution monomer is 10-200% of that of the photoresponse type siloxane; preferably, the mass ratio of the photoresponsive polysiloxane to the photoresponsive dilution monomer is (1-2.5): 1.
In some embodiments of the present invention, the photoinitiator is used in an amount of 1 wt% to 3 wt% of the total amount of the light-responsive dilution monomer and the light-responsive polysiloxane; preferably, the photoinitiator comprises 2-hydroxy-2-methyl propiophenone and/or diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus.
In the present invention, the photo-responsive polysiloxane is prepared by introducing a photo-initiating group into a polysiloxane; preferably, the photoresponsive polysiloxane is prepared by introducing a photoinitiating group into a polysiloxane by reacting a modifying agent with the polysiloxane under the action of a catalyst.
In some embodiments of the present invention, the polysiloxane comprises one or more of a hydroxyl-terminated polysiloxane, a hydroxyalkyl-terminated polysiloxane, an amino-terminated polysiloxane, a hydrogen-terminated polysiloxane, a vinyl-terminated polysiloxane, and a chloro-terminated polysiloxane.
In other embodiments of the present invention, the modifier is used in an amount of 5 wt% to 200 wt% of the polysiloxane, preferably, the modifier is a silane coupling agent having a photoinitiating group; the photoinitiating group is a free radical polymerization photoinitiating group or a cationic polymerization photoinitiating group; further preferably, the modifier comprises one or more of 3-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- [ (2,3) -glycidoxy ] propylmethyltrimethoxysilane.
In still other embodiments of the present invention, the catalyst is present in an amount of 1 wt% to 10 wt% of the polysiloxane; preferably, the catalyst comprises dibutyltin dilaurate.
In some specific embodiments of the present invention, the photo-responsive polysiloxane comprises a polysiloxane containing a cationic photo-initiation group and/or a polysiloxane containing a free radical photo-initiation group; wherein, the polysiloxane containing the cationic photo-initiation group comprises one or more of epoxy polysiloxane, vinyl ether polysiloxane, styryl polysiloxane and mercapto-vinyl polysiloxane; and/or the polysiloxane containing the free radical photoinitiating group comprises one or more of acrylate-based polysiloxane, methacrylate-based polysiloxane and acrylamide-based polysiloxane.
In some particularly preferred embodiments of the present invention, the photo-responsive polysiloxane comprises a photo-responsive polydimethylsiloxane.
In the invention, the light-responsive dilution monomer is a fluorine-containing light-responsive dilution monomer; specifically, the light-responsive dilution monomer is a fluorine-containing responsive dilution monomer with a photoinitiation group and a fluoroalkyl chain; more preferably, the photoinitiating group comprises a cationic photoinitiating group and a free radical photoinitiating group; the cationic photoinitiating group comprises one or more of epoxy group, vinyl ether group, styryl group and mercapto-vinyl group; the free radical photoinitiating group comprises one or more of an acrylate group, a methacrylate group and an acrylamide group; still further preferably, the light-responsive diluent monomer comprises dodecafluoroheptyl methacrylate and/or tridecyl octyl methacrylate.
According to the invention, the thickness of the liquid film is 5 to 100 μm.
In some embodiments of the invention, the intensity used for illumination is from 5 to 100mW/cm 2 Preferably 30-100mW/cm 2 。
In other embodiments of the present invention, the curing time is from 0.5 to 5 minutes, preferably from 1 to 5 minutes.
According to the method of the present invention, the casting solution optionally further comprises a first solvent; the content of the solvent I is 0-300% of the dosage of the photoresponse type siloxane, and preferably 10-300%; and/or the first solvent comprises one or more of dichloromethane, normal hexane, normal heptane and deionized water.
In a fourth aspect, the present invention provides the use of a pervaporation membrane according to the second aspect of the present invention or a pervaporation membrane prepared by the method according to the third aspect of the present invention, in an organic solvent to be separated; preferably, the organic solvent comprises one or more of butanol, ethanol and furfural.
The invention has the following advantages:
(1) the active light response type dilution monomer utilizes the characteristics of self micromolecules to replace the traditional organic solvent, reduces the viscosity of viscous polysiloxane, improves the reaction activity, and is green and environment-friendly.
(2) The active light-responsive diluent monomer has specific groups that can impart certain desirable characteristics to the film, such as the reaction equation described above: after the fluorine-containing monomer is added to participate in the reaction, the prepared fluorine-containing pervaporation membrane has a stronger hydrophobic effect than the original PDMS membrane, and meanwhile, fluorine can reduce the free energy of the membrane surface, so that the biological pollution resistance of the membrane is enhanced (for example, the adhesion of microorganisms is reduced).
(3) The extremely strong hydrophobicity and stain resistance improve the separation performance and long-term stability of the membrane.
Drawings
The invention is described in further detail below with reference to the attached drawing figures:
FIG. 1 illustrates the reaction mechanism for making a particular function pervaporation membrane material.
FIG. 2 is a scanning electron micrograph of the surface of the film of example 1 after a long period of use.
FIG. 3 is a scanning electron micrograph of the surface of the film of example 2 after a long period of use.
FIG. 4 is a scanning electron micrograph of the surface of the film after a long period of use in a comparative example.
Detailed Description
In order that the invention may be readily understood, a more particular description thereof will be rendered by reference to the appended drawings. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
In the present invention, ranges of concentrations, temperatures, or other physical or chemical properties or characteristics are used to cover or include the upper and lower limits of the ranges unless otherwise specified.
Term (I)
The term "water" as used herein means deionized water, distilled water or ultrapure water unless otherwise specified or limited.
The term "optional" as used herein means that optional ingredients may or may not be added.
The term "specific function" as used herein refers to an extremely strong hydrophobic property and anti-biofouling property, wherein the organism includes bacteria, fungi, and proteins, cell debris, and the like.
The term "photo-responsive polysiloxane" as used herein refers to a polysiloxane having a photo-initiating group, and is also referred to as a photo-responsive polysiloxane herein.
The term "light-responsive diluent monomer" as used herein refers to a diluent monomer having a photoinitiating group, and is also referred to as a light-responsive diluent monomer in the present invention.
Embodiments II
As mentioned above, in the conventional polymer film preparation process, an organic solvent is inevitably used to dissolve the high molecular polymer, and volatilization of the solvent increases the difficulty of actual operation and causes environmental pollution; meanwhile, due to the limitation of the material characteristics of the traditional polymer membrane, the hydrophobicity of the traditional polymer membrane is difficult to meet the requirement of the pervaporation membrane on the efficient recovery of organic matters, and the high free energy of the membrane surface is easy to cause the adhesion of microorganisms (membrane pollution).
In view of the above, the inventors of the present invention have conducted a great deal of research on hydrophobic pervaporation membranes, and the research of the inventors of the present invention finds that, by using fluorine-containing small molecules as photoresponse dilution monomers, the traditional organic solvent is replaced, (1) the viscosity of the membrane liquid can be reduced, excessive packaging of polymer chains can be alleviated, the intermolecular collision rate can be increased, and the reactivity can be increased; (2) the adverse effects of the traditional volatile organic solvent on the safety of operators and the environment are avoided; (3) the fluoroalkyl chain effectively reduces the surface free energy, effectively avoids membrane pollution and improves the long-term stability of the membrane; the present invention was thus obtained.
Therefore, the pervaporation membrane material having a specific function according to the first aspect of the present invention is obtained by polymerizing the photo-responsive polysiloxane and the photo-responsive diluent monomer in the presence of the photoinitiator, and the obtained pervaporation membrane material contains the photo-responsive polysiloxane unit and the photo-responsive diluent monomer unit in the molecule.
The inventor previously studied that polysiloxane has photoresponse characteristics through modification of a modifier and forms a network structure through ultraviolet irradiation to obtain a pervaporation membrane.
On the basis of the research, the inventor further adds an active light-responsive dilution monomer into polysiloxane with light-responsive capability, and utilizes ultraviolet light irradiation to graft the monomer into a network structure, so as to prepare the pervaporation membrane with specific functions (extremely strong hydrophobic property and anti-biological pollution property).
In the present invention, the photo-responsive polysiloxane includes a polysiloxane containing a cationic photo-initiating group and/or a polysiloxane containing a radical photo-initiating group; preferably, the polysiloxane containing the cationic photo-initiation group comprises one or more of epoxy polysiloxane, vinyl ether polysiloxane, styrene polysiloxane and mercapto-vinyl polysiloxane; and/or the polysiloxane containing the free radical photoinitiating group comprises one or more of acrylate-based polysiloxane, methacrylate-based polysiloxane and acrylamide-based polysiloxane.
The inventor researches and discovers that the traditional organic solvent is replaced by a fluorine-containing monomer which simultaneously has a photoinitiating group and a fluoroalkyl chain as a photoresponsive dilution monomer, and on one hand, the photoinitiating group can improve the reaction activity; on the other hand, the fluorine-containing pervaporation membrane prepared by the fluoroalkyl chain has a stronger hydrophobic effect than the original PDMS membrane, and meanwhile, the fluorine-containing pervaporation membrane can reduce the free energy of the surface of the membrane, so that the biological pollution resistance of the membrane is enhanced (for example, the adhesion of microorganisms is reduced), and the pervaporation membrane material has extremely strong antimicrobial adhesion performance; and the extremely strong hydrophobicity and stain resistance improve the separation performance and long-term stability of the membrane.
Therefore, the light-responsive dilution monomer is a fluorine-containing responsive dilution monomer having a photoinitiation group and a fluoroalkyl chain; specifically, the photoinitiating group includes a cationic photoinitiating group and a free radical photoinitiating group; the cationic photo-initiation group comprises one or more of epoxy group, vinyl ether group, styryl group and mercapto-vinyl group; the free radical photoinitiating group comprises one or more of an acrylate group, a methacrylate group and an acrylamide group.
The inventor further researches and discovers that the pervaporation membrane material prepared by taking dodecafluoroheptyl methacrylate and/or tridecyl octyl methacrylate as photoresponse type dilution monomers has better hydrophobic property and anti-biological pollution effect.
The pervaporation membrane material with the specific function is a fluorine-containing pervaporation membrane material formed by participation of a fluorine-containing photoresponse type dilution monomer unit, the fluorine-containing pervaporation membrane material is prepared by taking a fluorine-containing monomer with a photoinitiating group and a fluoroalkyl chain as a photoresponse type dilution monomer and photoresponse type polysiloxane, the preparation reaction mechanism is shown in figure 1, and as can be seen from figure 1, the molecular structure of the fluorine-containing pervaporation membrane material is shown as a formula (I):
in the formula (I), the compound is shown in the specification,
x and y are the number of repeating units of a silicon-oxygen chain in a polysiloxane unit, and the value is a positive integer;
z is the number of repeating units of carbon chains in the photoresponse polysiloxane unit, and the value is a positive integer;
d is the number of repeating units of carbon chains in the photoresponse type dilution monomer unit, and the value is a positive integer.
In some particularly preferred embodiments of the present invention, the fluorine-containing pervaporation membrane material has a water contact angle of 110 ° or more, for example, 111 ° to 113 ° or more, a thickness of 5 to 100 μm, a stability of 100 hours or more in synchronization with a biomass-based fermentation broth including one or more of a butanol fermentation broth, an ethanol fermentation broth, and a furfural fermentation broth, and no microbial attachment on the surface.
A second aspect of the invention relates to a pervaporation membrane with specific functionality comprising a pervaporation membrane material according to the first aspect of the invention, in particular a fluorine-containing pervaporation membrane material. Researches show that the fluorine-containing pervaporation membrane provided by the invention has specific functions (extremely strong hydrophobic property and biological pollution resistance) and also has good separation performance.
In some embodiments of the inventionIn the embodiment, the pervaporation membrane separates 1.5 wt% butanol aqueous solution at the temperature of 30-90 ℃ with the separation factor of 20-60 and the flux of 600- -2 ·h -1 (ii) a The separation factor of the pervaporation membrane for separating 1 wt% butanol aqueous solution at the temperature of 30-90 ℃ is 25-65, and the flux is 480-one 2500 g.m -2 ·h -1 (ii) a The separation factor for separating 5 wt% ethanol aqueous solution at 35-85 deg.C is 7-22, and the flux is 700- -2 ·h -1 。
Specifically, for example, in some examples, the pervaporation membrane separates a 1.5 wt% aqueous butanol solution at 30 to 90 ℃ with a separation factor of 20 to 60 and a flux of 600- -2 ·h -1 (ii) a The separation factor for separating 5 wt% ethanol aqueous solution at 35-85 deg.C is 7-20, and the flux is 800- -2 ·h -1 。
As another example, in other examples, the pervaporation membrane separates a 1 wt% aqueous butanol solution at 30-90 ℃ with a separation factor of 25-65 and a flux of 480- -2 ·h -1 (ii) a The separation factor for separating 5 wt% ethanol water solution at 35-85 ℃ is 8-22, and the flux is 700-3000 g.m -2 ·h -1 。
In a third aspect of the present invention, there is provided a method for producing a pervaporation membrane having a specific function, comprising:
step A, adding a light-responsive dilution monomer and a photoinitiator into light-responsive polysiloxane, and uniformly mixing to obtain a membrane casting solution;
b, defoaming the casting solution, and coating the defoamed casting solution on a substrate to obtain a liquid film coated on the substrate, wherein the thickness of the liquid film is 5-100 μm;
and step C, carrying out irradiation curing on the liquid film for 0.5-5 minutes, preferably 1-5 minutes under ultraviolet light to obtain the pervaporation film with the specific function.
In the step A, the mixing is performed by stirring, which may be mechanical stirring or magnetic stirring, and the rotation speed is 600-.
The amounts of the respective reactants constituting the reaction system in step A were as follows:
(1) in the casting solution, the dosage (mass) of the light-responsive dilution monomer is 10-200% (including 10% and 200%) of the dosage (mass) of the light-responsive polysiloxane; preferably, the mass ratio of the photoresponsive polysiloxane to the photoresponsive dilution monomer is (1-2.5): 1;
(2) the photoinitiator is preferably used in an amount of 1 to 3 wt% based on the total amount of the light-responsive dilution monomer and the light-responsive polysiloxane.
In the invention, the light-responsive dilution monomer is a fluorine-containing light-responsive dilution monomer; specifically, the light-responsive dilution monomer is a fluorine-containing responsive dilution monomer with a photoinitiation group and a fluoroalkyl chain; more preferably, the photoinitiating group comprises a cationic photoinitiating group and a free radical photoinitiating group; the cationic photoinitiating group comprises one or more of epoxy group, vinyl ether group, styryl group and mercapto-vinyl group; the free radical photoinitiating group comprises one or more of an acrylate group, a methacrylate group and an acrylamide group; still further preferably, the light-responsive diluent monomer comprises dodecafluoroheptyl methacrylate and/or tridecyl octyl methacrylate.
The photoinitiator in the present invention is not particularly limited as long as it is matched with a photoinitiating group, that is, a radical polymerization type matched with an initiator for initiating radical polymerization, a cationic polymerization type matched with an initiator for initiating cationic polymerization; preferably, the photoinitiator includes, but is not limited to, 2-hydroxy-2-methyl propiophenone and/or diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus.
In the present invention, the photo-responsive polysiloxane is prepared by introducing a photo-initiating group into a polysiloxane; preferably, the photo-responsive polysiloxane is prepared by introducing a photo-initiation group into a polysiloxane by reacting a modifier with the polysiloxane under the action of a catalyst.
According to the invention, the modifier is used in an amount of 5-200 wt% of the polysiloxane; preferably, the modifier is a silane coupling agent having a photoinitiating group. The silane coupling agent having a photoinitiating group, which is a radical polymerization type photoinitiating group or a cationic polymerization type photoinitiating group, is not particularly limited in the present invention as long as it has a photoinitiating group; particularly preferably, the modifier comprises one or more of 3-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- [ (2,3) -glycidoxy ] propylmethyltrimethoxysilane.
In some embodiments of the invention, the catalyst is present in an amount of 1 wt% to 10 wt% of the polysiloxane; preferably, the catalyst includes, but is not limited to, dibutyltin dilaurate.
In other embodiments of the present invention, the polysiloxane comprises one or more of hydroxyl-terminated polysiloxane, hydroxyalkyl-terminated polysiloxane, amino-terminated polysiloxane, hydrogen-terminated polysiloxane, vinyl-terminated polysiloxane, and chloro-terminated polysiloxane; particularly preferably, the polysiloxane is hydroxyl-terminated polydimethylsiloxane. The molecular weight of the polysiloxane is not limited, and 1000-90000 can be used.
In the present invention, the photo-responsive polysiloxane comprises a polysiloxane containing a cationic photo-initiation group and/or a polysiloxane containing a radical photo-initiation group; wherein, the polysiloxane containing the cationic photoinitiating group comprises one or more of epoxy polysiloxane, vinyl ether polysiloxane, styryl polysiloxane and mercapto-vinyl polysiloxane; and/or the polysiloxane containing the free radical photo-initiation group comprises one or more of acrylate-based polysiloxane, methacrylate-based polysiloxane and acrylamide-based polysiloxane; preferably, the photo-responsive polysiloxane comprises a photo-responsive polydimethylsiloxane.
The substrate for coating is not particularly limited in the present invention, and for example, the substrate for coating may be a polyacrylonitrile ultrafiltration membrane substrate, a polysulfone substrate, or a nonwoven fabric.
The ultraviolet light source used for irradiation in the present invention is not particularly limited, and for example, the ultraviolet light source may be an LED light source or a mercury lamp light source; the intensity for illumination is 5-100mW/cm 2 Preferably 30-100mW/cm 2 。
According to the invention, the casting solution also optionally contains a solvent I, for example, in some cases, in the step A, adding a light-responsive dilution monomer, a photoinitiator and a solvent I into a light-responsive polysiloxane, and uniformly mixing to obtain the casting solution; the content of the solvent I is 0-300 percent of that of the photoresponse polysiloxane, preferably 10-300 percent (mass percentage, including 10 percent and 300 percent); and/or the first solvent comprises one or more of dichloromethane, normal hexane, normal heptane and deionized water.
It is easy to understand that the pervaporation membranes with different thicknesses can be obtained after the liquid membranes with different thicknesses are irradiated and cured in the preparation process of the pervaporation membranes, the separation factor of the pervaporation membranes for separating 1.5 wt% butanol aqueous solution at the temperature of 30-90 ℃ is 20-60, and the flux is 600- -2 ·h -1 (ii) a The separation factor of the pervaporation membrane for separating 1 wt% butanol aqueous solution at the temperature of 30-90 ℃ is 25-65, and the flux is 480- -2 ·h -1 (ii) a The separation factor for separating 5 wt% ethanol aqueous solution at 35-85 ℃ is 7-22, and the flux is 700-3500 g.m -2 ·h -1 。
In a fourth aspect, the present invention provides the use of a pervaporation membrane according to the second aspect of the present invention or a pervaporation membrane prepared by the method according to the third aspect of the present invention, in an organic solvent to be separated; preferably, the organic solvent comprises one or more of butanol, ethanol and furfural.
In the present invention, a JC2000D3 contact angle measuring instrument (Shanghai Mediterranean digital technology equipment, Inc.) is used to measure the film material or the film contact angle.
In the invention, an SU8000 type field emission scanning electron microscope (Hitachi high and New technology Co.) is adopted to observe the adhesion phenomenon of microorganisms on the surface of the film.
In the present invention, the feed side and permeate side component concentrations were measured by GC-2014C gas chromatography (Shimadzu, Japan).
Taking the separation of an aqueous butanol solution as an example:
w is the total mass (g) of feed liquid collected on the permeate side; t is the test time (h); a is the membrane area (m) 2 )；x b And y b Respectively, butanol feed side and permeate side concentrations (wt%)
The flux test method comprises the following steps: and (4) carrying out pervaporation test for a certain time t, collecting the feed liquid on the permeation side, weighing, recording W, and calculating the flux J according to the formula.
Separation factor test method: the feed liquids on the raw material side and the permeate side were collected respectively, the component contents thereof were analyzed by gas chromatography, and the separation factor β was calculated by the above formula.
Examples III
The present invention will be specifically described below with reference to specific examples. The experimental methods described below are, unless otherwise specified, all routine laboratory procedures. The experimental materials described below, unless otherwise specified, are commercially available.
Example 1:
(1) preparation of photoresponsive polydimethylsiloxane: 11g of hydroxyl-terminated polydimethylsiloxane (hydroxyl-terminated polydimethylsiloxane, molecular weight 50000), 2g of modifier gamma-methacryloxypropyltrimethoxysilane (corresponding to 18% by weight of the polysiloxane), 0.2g of catalyst dibutyltin dilaurate (corresponding to 1.8% by weight of the polysiloxane) were mixed and thoroughly mixed by mechanical stirring at 600 rpm; defoaming to obtain the polydimethylsiloxane with photoresponse.
(2) Preparing a casting solution: taking 5g of the photoresponse type polydimethylsiloxane, adding 2g of dodecafluoroheptyl methacrylate (the mass ratio of the photoresponse type polysiloxane to the photoresponse type diluting monomer is 2.5:1) and 1 wt% of photoinitiator 2-hydroxy-2-methyl propiophenone (which is equivalent to 1 wt% of the total amount of the photoresponse type diluting monomer and the photoresponse type polysiloxane), and mechanically stirring and fully mixing at 1000rpm to obtain the casting solution.
(3) Film scraping: and defoaming the casting solution, coating fluorine on a polyvinylidene fluoride substrate, and scraping the film to a thickness of 5-100 mu m to obtain a liquid film.
(4) And (3) curing: transfer the liquid film to 30mW/cm 2 Irradiating for 5min under an ultraviolet lamp to obtain the fluorine-containing polydimethylsiloxane membrane with the solid surface.
The water contact angle of the fluorine-containing polydimethylsiloxane membrane material prepared by the method is 111 degrees; the stability of synchronous use with fermentation liquor such as butanol, ethanol and the like is more than 100h, no microorganism surface adhesion phenomenon (shown in figure 2) occurs after the test, the performance is not reduced, and the biological pollution resistance is effective; the separation factor for separating 1.5 wt% butanol aqueous solution at 30-90 deg.C is 20-60, and the flux is 600-3000g/m 2 H; the separation factor for separating 5 wt% ethanol aqueous solution at 35-85 deg.C is 7-20, and the flux is 800- 2 /h。
Example 2:
(1) preparation of photoresponsive polydimethylsiloxane: 5g of a hydroxyl-terminated polydimethylsiloxane (molecular weight 20000), 1g of a modifier 3-methacryloxypropylmethyldimethoxysilane (corresponding to 20% by weight of the polysiloxane), 0.1g of a catalyst dibutyltin dilaurate (corresponding to 2% by weight of the polysiloxane) were mixed and thoroughly mixed by mechanical stirring at 600 rpm; defoaming to obtain the polydimethylsiloxane with photoresponse.
(2) Preparing a casting solution: 5g of the photoresponse polydimethylsiloxane is taken, 5g of dodecafluoromethacrylate (the mass ratio of the photoresponse polysiloxane to the photoresponse diluting monomer is 1:1) and 3 wt% of photoinitiator diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus methacrylate (which is equivalent to 3 wt% of the total amount of the photoresponse diluting monomer and the photoresponse polysiloxane) are added, and the mixture is mechanically stirred and fully mixed at 1000rpm to obtain the casting solution.
(3) Film scraping: and defoaming the casting solution, coating fluorine on a polyvinylidene fluoride substrate, and scraping the film to a thickness of 20-50 μm to obtain a liquid film.
(4) And (3) curing: the liquid film was transferred to 80mW/cm 2 Irradiating under ultraviolet lamp for 5min to obtain fluorine-containing material with solid surfaceA polydimethylsiloxane membrane.
The fluorine-containing polydimethylsiloxane membrane material prepared by the method has a water contact angle of more than 113 degrees; after the stability of the fermentation liquor used synchronously with butanol, ethanol and the like reaches over 400 hours, the microorganism surface adhesion phenomenon (shown in figure 3) is avoided, the performance is not reduced, and the biological pollution resistance is effective; the separation factor for separating 1 wt% butanol aqueous solution at 30-90 deg.C is 25-65, and the flux is 480-2500g/m 2 H; the separation factor for separating 5 wt% ethanol water solution at 35-85 deg.C is 8-22, and the flux is 700-3000g/m 2 H is used as the reference value. Comparative example:
(1) preparing the light-responsive polydimethylsiloxane: 5g of hydroxyl-terminated polydimethylsiloxane (molecular weight 20000), 1g of modifier 3-methacryloxypropylmethyldimethoxysilane and 0.1g of catalyst dibutyltin dilaurate are mixed and fully mixed by mechanical stirring at 600 revolutions; defoaming to obtain the polydimethylsiloxane with photoresponse.
(2) Preparing a casting solution: and (3) taking 5g of the photoresponse polydimethylsiloxane, adding 1% of photoinitiator 2-hydroxy-2-methyl propiophenone, and mechanically stirring and fully mixing by 1000 revolutions to obtain a casting solution.
(3) Film scraping: and defoaming the casting solution, coating fluorine on a polyvinylidene fluoride substrate, and scraping the film to a thickness of 20-50 μm to obtain a liquid film layer.
(4) And (3) curing: transferring the liquid film layer to 30mW/cm 2 Irradiating for 5min under an ultraviolet lamp to obtain the polydimethylsiloxane film with the solid surface.
The fluorine-containing polydimethylsiloxane membrane material prepared by the method has a water contact angle of 102 degrees; the separation factor for separating 1 wt% butanol aqueous solution at 30-90 deg.C is 15-50, and the flux is 1800g/m 2 H; the separation factor for separating 5 wt% ethanol water solution at 35-85 deg.C is 5-150, and the flux is 400-3000g/m 2 The separation test is carried out synchronously with fermentation liquor of butanol, ethanol and the like, when the test time exceeds 50h, the membrane flux and the separation factor begin to decrease, the decrease range can reach more than 30 percent, and after the test is finished, the surface attachment of microorganisms (clostridium acetobutylicum, proteins, cell debris and the like) occursPhenomenon (see fig. 4).
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the appended claims, and changes can be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (15)
1. A pervaporation membrane material is prepared by polymerizing photoresponse polysiloxane and photoresponse dilution monomer in the presence of a photoinitiator;
the pervaporation membrane material contains a photoresponse polysiloxane unit and a photoresponse dilution monomer unit;
wherein the light-responsive dilution monomer is dodecafluoroheptyl methacrylate or tridecafluoroctyl methacrylate;
and/or the photoresponsive polysiloxane comprises a polysiloxane containing a cationic photoinitiating group and/or a polysiloxane containing a free radical photoinitiating group; the polysiloxane containing the cationic photo-initiation group comprises one or more of epoxy polysiloxane, vinyl ether polysiloxane, styrene polysiloxane and mercapto-vinyl polysiloxane; and/or the polysiloxane containing the free radical photoinitiating group comprises one or more of acrylate-based polysiloxane, methacrylate-based polysiloxane and acrylamide-based polysiloxane.
2. The pervaporation membrane material according to claim 1, wherein said photo-responsive polysiloxane is a photo-responsive polydimethylsiloxane.
3. The pervaporation membrane material according to claim 1 or 2, wherein the pervaporation membrane material is a fluorine-containing pervaporation membrane material, which is composed of fluorine-containing photoresponse dilution monomer units, and has a molecular structure shown in formula (i):
in the formula (I), the compound is shown in the specification,
x and y are the number of repeating units of a silicon-oxygen chain in the photoresponse polysiloxane unit, and the value is a positive integer;
z is the number of repeating units of carbon chains in the photoresponse polysiloxane unit, and the value is a positive integer;
d is the number of repeating units of carbon chains in the photoresponse type dilution monomer unit, and the value is a positive integer; the fluorine-containing pervaporation membrane material has a water contact angle of more than 110 degrees, a thickness of 5-100 mu m, stability of synchronous use with biomass-based fermentation liquor of more than 100h and no microorganism adhesion on the surface; wherein the biomass-based fermentation liquid comprises one or more of butanol fermentation liquid, ethanol fermentation liquid and furfural fermentation liquid.
4. A pervaporation membrane comprising a pervaporation membrane material according to any of claims 1-3.
5. A method of making the pervaporation membrane of claim 4, comprising:
step A, adding a light-responsive dilution monomer and a photoinitiator into light-responsive polysiloxane, and uniformly mixing to obtain a membrane casting solution;
b, defoaming the casting solution, and coating the defoamed casting solution on a substrate to obtain a liquid film coated on the substrate;
step C, irradiating and curing the liquid film under ultraviolet light to obtain a pervaporation film;
in the casting solution, the dosage of the photoresponse type dilution monomer is 10-200 wt% of the dosage of the photoresponse type polysiloxane;
and/or, in the casting solution, the amount of the photoinitiator is 1 wt% -3 wt% of the total amount of the light-responsive dilution monomer and the light-responsive polysiloxane.
6. The method according to claim 5, wherein the mass ratio of the photo-responsive polysiloxane to the photo-responsive dilution monomer is (1-2.5): 1.
7. The method of claim 5,
the photoinitiator comprises 2-hydroxy-2-methyl propiophenone and/or diphenyl- (2,4, 6-trimethyl benzoyl) oxyphosphorus;
the photoresponse type dilution monomer is dodecafluoroheptyl methacrylate or tridecafluoroctyl methacrylate;
and/or the photoresponsive polysiloxane is prepared by introducing photoinitiating groups into a polysiloxane; the photoresponse polysiloxane is prepared by introducing a photoinitiation group into polysiloxane through the reaction of a modifier and the polysiloxane under the action of a catalyst.
8. The method of claim 7,
the polysiloxane comprises one or more of hydroxyl-terminated polysiloxane, hydroxyalkyl-terminated polysiloxane, amino-terminated polysiloxane, hydrogen-terminated polysiloxane, vinyl-terminated polysiloxane and chlorine-terminated polysiloxane;
and/or, the modifier is 5-200 wt% of polysiloxane; the modifier is a silane coupling agent with a photoinitiating group; the photoinitiating group is a free radical polymerization photoinitiating group or a cationic polymerization photoinitiating group; the modifier comprises one or more of 3-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- [ (2,3) -glycidoxy ] propylmethyltrimethoxysilane;
and/or the amount of the catalyst is 1-10 wt% of the polysiloxane; the catalyst comprises dibutyltin dilaurate.
9. The method according to claim 8, wherein the photo-responsive polysiloxane comprises a cationic photoinitiating group-containing polysiloxane and/or a free radical photoinitiating group-containing polysiloxane; wherein, the polysiloxane containing the cationic photoinitiating group comprises one or more of epoxy polysiloxane, vinyl ether polysiloxane, styryl polysiloxane and mercapto-vinyl polysiloxane; and/or the polysiloxane containing the free radical photoinitiating group comprises one or more of acrylate-based polysiloxane, methacrylate-based polysiloxane and acrylamide-based polysiloxane.
10. The method of claim 9, wherein the photo-responsive polysiloxane is a photo-responsive polydimethylsiloxane.
11. The method according to any one of claims 5 to 10, wherein the liquid film has a thickness of 5 to 100 μm; and/or the intensity for illumination is 5-100mW/cm 2 (ii) a And/or the curing time is 0.5-5 minutes.
12. The method according to claim 11, wherein the intensity for the illumination is 30-100mW/cm 2 (ii) a And/or the curing time is 1-5 minutes.
13. The method according to any one of claims 5 to 10, wherein the casting solution further optionally comprises a first solvent; the content of the first solvent is 0-300% of that of the photoresponse polysiloxane; and/or the first solvent comprises one or more of dichloromethane, normal hexane, normal heptane and deionized water.
14. The method as claimed in claim 13, wherein the first solvent is contained in an amount of 10% to 300% based on the photoresponsive polysiloxane.
15. Use of a pervaporation membrane according to claim 4 or a pervaporation membrane prepared according to the method of any of claims 5 to 14 in an organic solvent to be separated; the organic solvent comprises one or more of butanol, ethanol and furfural.
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