CN105435652A - MOF (metal-organic framework) and polyurethane crosslinked membrane as well as preparation method and application thereof - Google Patents
MOF (metal-organic framework) and polyurethane crosslinked membrane as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105435652A CN105435652A CN201510824149.6A CN201510824149A CN105435652A CN 105435652 A CN105435652 A CN 105435652A CN 201510824149 A CN201510824149 A CN 201510824149A CN 105435652 A CN105435652 A CN 105435652A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- organic framework
- metal organic
- diisocyanate
- mofs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 62
- 239000004814 polyurethane Substances 0.000 title claims abstract description 62
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 60
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 4
- 239000013177 MIL-101 Substances 0.000 claims description 4
- 239000013208 UiO-67 Substances 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 claims description 2
- 239000013206 MIL-53 Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000013207 UiO-66 Substances 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 239000002159 nanocrystal Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 39
- 239000013078 crystal Substances 0.000 description 23
- NKLPQNGYXWVELD-UHFFFAOYSA-M coomassie brilliant blue Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=C1 NKLPQNGYXWVELD-UHFFFAOYSA-M 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 239000000975 dye Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- -1 2, 2' -dihydroxybiphenyldicarboxylic acid Chemical compound 0.000 description 11
- 239000013110 organic ligand Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 5
- 239000013179 MIL-101(Fe) Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- AYLRODJJLADBOB-UHFFFAOYSA-N methyl 2,6-diisocyanatohexanoate Chemical compound COC(=O)C(N=C=O)CCCCN=C=O AYLRODJJLADBOB-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- BJZPWWQVDPTONA-UHFFFAOYSA-N 1-amino-6-phenylcyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound NC1(C(=CC=CC1C(=O)O)C1=CC=CC=C1)C(=O)O BJZPWWQVDPTONA-UHFFFAOYSA-N 0.000 description 1
- BPHCOQMSPAZRMX-UHFFFAOYSA-N 1-hydroxy-6-phenylcyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound OC1(C(C(=O)O)C=CC=C1C1=CC=CC=C1)C(=O)O BPHCOQMSPAZRMX-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 239000012923 MOF film Substances 0.000 description 1
- 239000012920 MOF membrane Substances 0.000 description 1
- SPTUBPSDCZNVSI-UHFFFAOYSA-N N=C=O.N=C=O.COC1=CC=CC=C1C1=CC=CC=C1OC Chemical compound N=C=O.N=C=O.COC1=CC=CC=C1C1=CC=CC=C1OC SPTUBPSDCZNVSI-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention discloses a MOF (metal-organic framework) and polyurethane crosslinked membrane as well as a preparation method and an application thereof. Post-synthesis modification is performed on active amino or hydroxyl on MOFs through a polyurethane prepolymer, nanocrystals of the MOFs are linked under the covalent bond function of active amino or hydroxyl and polyurethane prepolymer, so that the compatibility and the acting force between the MOFs particles and a polymer chain are improved, modified MOFs derivatives are endowed with excellent flexibility and a film-forming property, and a new method for preparing MOFs membrane devices is established. The synthesized MOFs membrane material has good selective separation effect on dye molecules in water and has great application prospects in the membrane separation field.
Description
Technical Field
The invention relates to a metal organic framework-polyurethane cross-linked membrane and a preparation method and application thereof, belonging to the technical field of polymer separation membranes.
Background
Metal Organic Frameworks (MOFs) are porous polymeric materials formed by covalently linking metal ions or clusters through organic ligands, exhibit the characteristics of both organic and inorganic materials, and have the advantages of high porosity, adjustable and controllable pore channels, structural diversity, high functionality, simple preparation and the like, and the unique advantages make them a hotspot of recent research. The MOFs have specific open pore channels and active sites, so that the MOFs have the property of selective permeation to certain molecules and have great potential in the separation field.
The MOFs is similar to inorganic crystal materials, and most of the MOFs are crystal powder or particles in physical state, and under the condition that the structure is not damaged, the brittle framework presents the characteristic of insolubility, so that although the MOFs has many incomparable advantages, the simple MOFs material is difficult to be formed into devices and is difficult to be popularized to practical application. In order to meet the requirements of further application and on the premise of not changing the original topological structure, how to improve the toughness and the processability of the alloy is a great challenge facing the field of MOFs.
In recent years, in order to realize the device of MOFs, studies on MOF film materials are sequentially reported, and the MOF-related film materials include: the MOFs film is characterized by comprising a supporting MOFs film and a composite substrate MOFs film, wherein the two films are endowed with dual properties of a substrate and the MOFs, but still have defects of different degrees, the supporting MOFs film is difficult to peel from the substrate and independently forms a film, and the strength of the supporting MOFs film is low; the problems of poor compatibility and particle agglomeration present in composite matrix membranes must be addressed in order to obtain satisfactory performance. Thus, although recent years have seen good performance and development in MOFs-related membrane materials, most still lack homogeneity at the molecular level. To further understand the underlying science and the role of MOF crystals, the present invention focuses on the development of individual MOF membrane materials.
The concept of post-synthesis modification of MOFs was first proposed by Kim, and this method has gained a great deal of application since then, and has resulted in a series of novel structures and properties, providing a wider space for the development of MOFs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel metal organic framework-polyurethane crosslinked film and a preparation method thereof.
Another object of the present invention is to provide the use of the crosslinked membrane material for the separation and purification of dye-containing wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
the metal organic framework-polyurethane composite material is prepared by reacting a metal organic framework material with a polyurethane substance, wherein the mass ratio of the metal organic framework material to the polyurethane substance is 0.01-75: 25-100.
The metal organic framework material is an organic-inorganic hybrid material, is constructed by organic ligands and inorganic metal units, and can be prepared conventionally by the technical personnel in the field according to the prior art.
In order to provide flexibility and film-forming property to the metal organic framework-polyurethane composite material, the metal organic framework material comprises: IRMOF-3, NH2-MIL-53、NH2-MIL-101、NH2-UiO66、HO-UiO-66、(HO)2-UiO66、NH2-UiO67、(NH2)2-UiO67、HO-UiO67、(HO)2-UiO67。
Wherein,
IRMOF-3 structural formula is Zn4O(NH2-BDC)3，NH2BDC is 2-amino-1, 4-terephthalic acid, made up of zinc nitrate hexahydrate and of a rigid materialLigand 2-amino-1, 4-terephthalic acid.
NH2-MIL-101 has the formula M3OX (NH2-BDC)3, M ═ Cr, Fe or Al, X ═ F or OH, NH2-BDC is 2-aminoterephthalic acid, and is a three-dimensional crystal obtained from the above and the rigid ligand 2-amino-1, 4-terephthalic acid.
NH2-UiO66, HO-UiO66, (HO)2-UiO66, NH2-UiO67, (NH2)2-UiO67, (HO) -UiO-67, (HO)2-UiO-67, the general structural formula of which is Zr6O4(OH)4L6, is a three-dimensional crystal obtained by using zirconium tetrachloride as a metal salt and a corresponding ligand L, wherein L in the 7 kinds of crystals is 2-amino-1, 4-terephthalic acid, 2-hydroxy-1, 4-terephthalic acid, 2, 5-dihydroxy-1, 4-terephthalic acid, 2-aminobiphenyldicarboxylic acid, 2 '-diaminobiphenyldicarboxylic acid, 2-hydroxybiphenyldicarboxylic acid, and 2, 2' -dihydroxybiphenyldicarboxylic acid in sequence. Preferably, the metal-organic framework material is a metal-organic framework crystal composed of metal ions Mn+And the organic ligand is prepared by solvothermal reaction, and the crystal structure of the organic ligand contains active amino or hydroxyl groups which can be post-modified.
The preparation method of IRMOF-3 crystals is as follows: CrystalGrowth & Design,2010,2, 1283-1288.
NH2The preparation method of the MIL-101 crystal is as follows: RSC Advances,2012,2,6417 and 6419.
The preparation method of the UiO series crystals is as follows: chem. Commun.,2013,49, 9449-.
Preferably, the metal ion Mn+Is one of Zr (IV), Fe (III), Al (III), Zn (II), etc. Through a large number of experimental verifications and analyses, the film device prepared by the metal organic framework material with the metal ions has better performances.
Preferably, the organic ligand is one of 2-amino-1, 4-terephthalic acid, 2' -diaminodiphenyl dicarboxylic acid, 2-hydroxy-1, 4-terephthalic acid, 2-dihydroxybiphenyl dicarboxylic acid, and the like. Through a large number of experimental verifications and analyses, the film device prepared by the metal organic framework material with the organic ligand has better performances.
The polyurethane substance in the invention is a plurality of polyurethane prepolymers in the prior art, and is an adduct of-NCO groups at two ends generated by reacting dihydric alcohol and excessive diisocyanate, wherein the dihydric alcohol comprises aliphatic polyether (commonly obtained by ring-opening polymerization of ethylene oxide, propylene oxide or tetrahydrofuran) with end hydroxyl groups with the molecular weight of hundreds to thousands, polyester polyol (commonly obtained by reacting dibasic acid with excessive dihydric alcohol and also obtained by ring-opening polymerization of lactone), polyolefin resin (such as butylated hydroxytoluene) or small molecular dihydroxy compounds, and the diisocyanate is more various, but not limited to the types of the polyurethane provided by the invention. Preferably, the polyurethane substance is an isocyanate group-terminated polyurethane prepolymer, and the structural formula is as follows:
wherein n is a natural number, OCN-R1the-NCO is aliphatic and aromatic diisocyanate and can be one of p-phenylene diisocyanate, 2, 4-toluene diisocyanate, 65/35-toluene diisocyanate, 80/20-toluene diisocyanate, 4, 4-diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, 3,3 '-dimethoxy-4, 4' -biphenyl diisocyanate, m-phenylene diisocyanate and methyl 2, 6-diisocyanatohexanoate.
HO-R2-OH is a diol compound. Can be small molecular dihydroxy compound, i.e. one of ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, diethylene glycol, hydroquinone dihydroxyethyl ether and N, N-bis-hydroxyethyl aniline, or polyether diol, i.e. polyethylene glycol [ HO (CH2CH2O) nH, N ≧ 1](PEG), polypropylene oxide [ HO (CH)2CH(CH3O)nH)，n≧1](PPO) may also be a polyester diol, i.e. a polycondensate of adipic acid and hexanediol, a polycondensate of adipic acid and diethylene glycol, a caprolactone ring-opening polymer, a polycondensate of terephthalic acid and hexanediol, a polycondensate of terephthalic acid and ethylene glycol, a polycondensate of terephthalic acid and diethylene glycol, or a hydroxyl-terminated polyolefin, such as a butylated hydroxyl gum prepolymer.
Through a large number of experimental verifications and analyses, when the polyether diol and the excessive diisocyanate are used for preparing the polyurethane prepolymer, the formed film device has better performances.
The preparation method of the isocyanate-terminated polyurethane prepolymer comprises the following steps:
adding 30-70 parts by weight of diisocyanate compound and 20-80 parts by weight of diol compound into a reaction container, stirring, reacting at 30-100 ℃ for 1-20 hours, stopping heating, removing unreacted micromolecules through reduced pressure distillation to obtain isocyanate group-terminated polyurethane prepolymer, determining NCO value through titration, and determining viscosity to be 1000-5000 mPa.s.
Preferably, the diol compound is one of PEG400, PEG600, PEG800, PEG2000, PPO1000 and PPO 2000.
Preferably, the diisocyanate compound is one of 2, 4-toluene diisocyanate, 4-diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, 3 '-dimethoxy-4, 4' -biphenyl diisocyanate, m-xylylene diisocyanate, and methyl 2, 6-diisocyanatohexanoate.
A metal framework-polyurethane cross-linked membrane is prepared from the metal framework-polyurethane composite material.
A preparation method of a metal framework-polyurethane composite material comprises the following steps:
adding 25-100 parts by weight of polyurethane substance and 30-80 parts by weight of solvent into a reaction vessel, stirring, dissolving, adding 0.01-75 parts by weight of metal organic framework material, reacting at 30-100 ℃ for 1-48 hours, stopping heating, and cooling to obtain the metal framework-polyurethane composite material.
The solvent is one or a mixture of more of dichloromethane, trichloromethane, tetrahydrofuran, N-dimethylformamide, acetone, ethyl acetate and dioxane.
The preparation method of the metal framework-polyurethane crosslinked film comprises the steps of coating the obtained metal framework-polyurethane composite material by a film forming method, and drying to obtain the metal organic framework-polyurethane crosslinked film.
The reaction is briefly as follows:
the film forming method includes a casting method, a spin coating method, a casting method, or the like.
The invention provides an application of a metal organic framework-polyurethane composite material in preparation of a dye-containing sewage separation membrane.
The invention also provides an application of the metal organic framework-polyurethane cross-linked membrane in separation of dye-containing sewage.
The invention has the beneficial effects that:
(1) the invention carries out post-synthesis modification on active amino or hydroxyl on MOFs by using an isocyanate-terminated polyurethane prepolymer, connects MOFsF nanocrystals by virtue of the covalent bond action of the two, enhances the compatibility and acting force between MOFs particles and a polymer chain, endows the modified MOFs derivatives with excellent flexibility and film-forming property, and establishes a novel method for preparing MOFs film devices. The synthesized MOFs membrane material has good selective separation effect on dye molecules in water, and has great application prospect in the field of membrane separation.
Compared with the traditional physical doping, the method enhances the acting force between the MOF particles and the polymer chains, and the independent MOFs membrane with flat and smooth surface and excellent toughness can be obtained by casting the reacted solution to form the membrane, and the MOF content and the thickness of the membrane can be adjusted according to the needs. Experimental results show that the synthesized MOFs film material has good selective separation effect on dye molecules in water.
(2) As a novel MOFs membrane material, the novel metal organic framework-polyurethane cross-linked membrane has a huge application prospect in the field of separation of printing and dyeing wastewater membranes, and the adsorption and separation experiments of the cross-linked membrane with 70 wt% of MOF content on Coomassie brilliant blue dye show that the maximum static adsorption quantity of the cross-linked membrane on Coomassie brilliant blue is 1.45 × 10-3mg/g. Membrane separation experiments showed that 5mL of a Coomassie brilliant blue solution at a concentration of 1cm was passed through 1 × 1cm2The filtration membrane with the diameter can achieve the interception of the Coomassie brilliant blue by 100 percent, the filtration membrane after filtration can achieve the desorption of the Coomassie brilliant blue by soaking the filtration membrane in methanol for 2 hours, the filtration membrane after soaking can be repeatedly used according to the conditions, the secondary interception rate of the Coomassie brilliant blue aqueous solution can achieve 90 percent, and the filtration membrane can achieve good separation effect on the Coomassie brilliant blue and direct yellow double-component mixed dye.
(3) NH to be used in the invention2The raw materials of-UiO, polyurethane prepolymer and the like are cheap and easily available, the preparation conditions of the cross-linked membrane are simple, rapid and mild, and the MOFs separation membrane material which has high performance, low cost and can be produced in batch is expected to be realized.
Drawings
FIG. 1 is NH2SEM pictures of UiO66 nanocrystals;
FIG. 2 is NH2SEM pictures of UiO67 nanocrystals;
FIG. 3 is NH2-XRD spectrum of UiO67 nanocrystals;
FIG. 4 is NH2-XRD spectrum of MIL-101(Fe) nanocrystals;
FIG. 5 is an XRD spectrum of IRMOF-3 crystals;
FIG. 6 is a photograph of a metal organic framework-polyurethane crosslinked film;
FIG. 7a is a standard curve of Coomassie Brilliant blue aqueous solution;
FIG. 7b is a UV-Vis spectrum of Coomassie Brilliant blue aqueous solution before and after adsorption;
FIG. 8 is a photograph showing the separation effect of a metal organic framework-polyurethane crosslinked film on Coomassie brilliant blue;
FIG. 9 is a photograph showing the separation effect of a metal organic framework-polyurethane crosslinked film on rhodamine;
FIG. 10 is a photograph showing the separation effect of a metal organic framework-polyurethane crosslinked film on a mixed dye;
FIG. 11 shows the comparison of metal organic framework-polyurethane crosslinked membrane to CO under 273K condition2The adsorption condition of (1);
FIG. 12 shows a metal organic framework-polyurethane crosslinked film and NH2-XRD powder diffraction pattern of UiO 66;
FIG. 13 shows a metal organic framework-polyurethane crosslinked film and NH2-FTIR spectrum of UiO 66.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1 Metal organic framework NH2Synthesis of-UiO 66
Dissolving organic ligand 2-amino terephthalic acid, zirconium tetrachloride and acetic acid in N, N-dimethylformamide solvent, keeping the temperature at 120 ℃ for 24h, cooling to room temperature to obtain light yellow nano-scale crystals, centrifuging and drying; wherein the ratio of the added amounts of the organic ligand 2-aminoterephthalic acid, zirconium tetrachloride, acetic acid and N, N-dimethylformamide solvent is 0.04 mmol: 0.04 mmol: 2 mmol: 1.6ml, the morphology of the crystals obtained is shown in FIG. 1.
Example 2 Metal organic framework NH2Synthesis of-UiO 67
Dissolving organic ligand 2, 2-diaminodiphenyl dicarboxylic acid, zirconium tetrachloride and acetic acid in an N, N-dimethylformamide solvent, keeping the temperature at 120 ℃ for 24 hours, cooling to room temperature to obtain yellow nanoscale crystals, centrifuging and drying; wherein the adding amount ratio of the organic ligand 2, 2-diaminodiphenyl dicarboxylic acid, zirconium tetrachloride, acetic acid and N, N-dimethylformamide solvent is 0.26 mmol: 0.26 mmol: 447 ul: 15ml, the morphology of the crystals obtained is shown in FIG. 2.
Example 3 Metal organic framework NH2Synthesis of-MIL-101 (Fe)
Dissolving organic ligand 2-amino terephthalic acid (1.09g,6mmol) and ferric trichloride hexahydrate (1.08g, 4mmol) in 20mLDMF, placing in a crystallization kettle, keeping the temperature at 110 ℃ for 16h, cooling to room temperature to obtain gray nano-scale crystals, centrifuging, washing with DMF and ethanol in sequence, and drying at 120 ℃ for 24h to obtain NH2MIL-101(Fe) crystalline powder, XRD results are shown in FIG. 4.
Example 4 Synthesis of Metal organic framework IRMOF-3
Dissolving 0.29mol of zinc nitrate hexahydrate in 10mL of DMF, dissolving 0.096mol of 2-amino terephthalic acid in 10mL of DMF, stirring the two solutions at room temperature for 1h respectively, mixing the two solutions, carrying out ultrasonic treatment for 5 min, then placing the mixture in a crystallization kettle, keeping the temperature at 90 ℃ for 36h, cooling to room temperature to obtain colorless crystals, centrifuging, washing with DMF, and drying to obtain IRMOF-3 crystal powder, wherein XRD results are shown in figure 5.
Example 5 Synthesis of polyether diol type polyurethane prepolymer
Adding 37g of 4, 4-diphenylmethane diisocyanate (MDI) and 63g of PPO (polypropylene oxide) with the molecular weight of 2000 into a reaction vessel in sequence, stirring at 80 ℃, reacting at constant temperature for 4 hours, stopping heating, and removing unreacted micromolecules through reduced pressure distillation to obtain a prepolymer with NCO being 10-11 and the viscosity being 2000-3000 mPa.s.
Example 6 Synthesis of polyester diol type polyurethane prepolymer
Adding 10g of 1, 6-Hexamethylene Diisocyanate (HDI) and 50g of terminal hydroxyl poly (hexamethylene adipate) with the molecular weight of about 1600 into a reaction vessel in sequence, stirring at 60 ℃, reacting at constant temperature for 6 hours, stopping heating, and removing unreacted micromolecules through reduced pressure distillation to obtain a prepolymer with NCO being 5-7 and viscosity being 2200-2500 mPa.s.
EXAMPLE 7 preparation of Metal organic framework-polyurethane Cross-Linked film
Reacting NH2Putting the crystal powder of UiO66 in chloroform, stirring and soaking for 3d at room temperature, and centrifugally drying; taking treated NH270 parts by weight of the-UiO 66 crystal powder was reacted with 30 parts by weight of the polyurethane prepolymer (OCN-R-NCO, NCO value: 10.2) synthesized in example 5 in 35 parts by weight of chloroform at 35 ℃ for 24 hours, and then poured into a polytetrafluoroethylene mold, and the solvent was evaporated at room temperature to obtain a pale yellow metal organic framework-polyurethane crosslinked film (see FIG. 6 for a film photograph).
EXAMPLE 8 preparation of Metal organic framework-polyurethane Cross-Linked film
NH in example 32-MIL-101(Fe) crystalline powder in acetone, chamberStirring and soaking for 2 days, and centrifugally drying; taking treated NH250 parts by weight of-MIL-101 (Fe) crystal powder and 30 parts by weight of polyurethane prepolymer (OCN-R-NCO, NCO value 6) synthesized in example 6 were reacted in 40 parts by weight of acetone at 50 ℃ for 12 hours, and then poured into a polytetrafluoroethylene mold, and the solvent was evaporated at room temperature to obtain a yellow metal organic framework-polyurethane crosslinked film.
EXAMPLE 9 preparation of Metal organic framework-polyurethane Cross-Linked film
Putting the metal organic framework IRMOF-3 crystal powder in the embodiment 4 into tetrahydrofuran, stirring and soaking at room temperature for 2d, centrifuging and drying, taking 70 parts by weight of the treated IRMOF-3 crystal powder and 50 parts by weight of polyurethane prepolymer (OCN-R-NCO, NCO value is 6) synthesized in the embodiment 6 into 60 parts by weight of tetrahydrofuran, reacting at 60 ℃ for 8h, pouring into a polytetrafluoroethylene mold, and volatilizing the solvent at room temperature to obtain the metal organic framework-polyurethane crosslinked film.
Example 10 adsorption of a Metal organic framework-polyurethane Cross-Linked film to Coomassie Brilliant blue
The metal organic framework-polyurethane crosslinked film of example 7 was soaked in 10mL of 2.13 × 10-6In mol/L Coomassie brilliant blue solution, after 24 hours, the dye adsorption result is quantitatively analyzed by an ultraviolet absorption spectrometry, and the result shows that the saturated adsorption quantity of the film to Coomassie brilliant blue is 1.45 × 10-3mg/mg, FIG. 7 shows a standard curve of Coomassie brilliant blue and the concentration change before and after adsorption.
Example 11 separation experiment of a Metal organic framework-polyurethane crosslinked Membrane on Coomassie Brilliant blue
The Φ 13mm metal-organic framework-polyurethane crosslinked film of example 7 (about 20mg) was taken, and 5ml of a 2.13 × 10 concentration solution was taken-6A mol/L Coomassie brilliant blue solution,slowly passing through the metal organic frame-polyurethane cross-linked membrane at the speed of 2.5mL/h by using a micro-volume sample injection pump, detecting the concentration of the solution before and after filtration by ultraviolet, and calculating the retention rate, wherein the result shows that the concentration of 5mL is 2.13 × 10-6When the mol/L Coomassie brilliant blue water solution passes through a membrane with the diameter of 13mm, the retention efficiency of dye molecules can reach 100 percent. FIG. 8 shows the experimental apparatus and effect of separation of Coomassie brilliant blue water solution by using metal organic frame-polyurethane cross-linked membrane as filter membrane.
Example 12 separation experiment of a Metal organic framework-polyurethane crosslinked Membrane on rhodamine
The Φ 13mm metal-organic framework-polyurethane crosslinked film of example 8 (about 20mg) was taken and 5mL of the concentration thereof was 1.24 × 10-6The mol/L rhodamine solution slowly passes through the metal organic framework-polyurethane cross-linked membrane at the speed of 2.5mL/h by a micro-volume sample injection pump, the concentration of the solution before and after filtration is detected by ultraviolet, and the retention rate is calculated, and the result shows that the concentration of 5mL is 1.24 × 10-6When the mol/L Coomassie brilliant blue water solution passes through a membrane with the diameter of 13mm, the retention efficiency of dye molecules can reach 92 percent. FIG. 9 shows an experimental device for separating rhodamine water solution by using a metal organic framework-polyurethane cross-linked membrane as a filter membrane and the separation effect.
Example 13 separation experiment of Metal organic framework-polyurethane crosslinked Membrane on Mixed dyes
The Φ 13mm metal-organic framework-polyurethane crosslinked film of example 7 (about 20mg) was taken, and 5mL Coomassie Brilliant blue (concentration 3.0 × 10)-6) And direct yellow (concentration of 2.0 × 10)-5mol/L) solution slowly passes through a metal organic framework-polyurethane cross-linked membrane at the speed of 2.5ml/h by using a micro-volume sample injection pump, the concentration of the solution before and after filtration is detected by ultraviolet, and the retention rate is calculated, and the result shows that when the mixed solution passes through a membrane with the diameter of 13mm, the retention efficiency of Coomassie brilliant blue dye molecules can reach 100 percent, and the transmittance of direct yellow can reach 92 percent, which indicates that the mixed solution passes through the membrane with the diameter of 13mm, and the mixed solution has the advantages of high solubility, high stabilityThe membrane has good selective adsorption effect on different dye molecules, and realizes effective separation of mixed dye aqueous solution. FIG. 10 shows the separation effect of a metal organic framework-polyurethane crosslinked membrane on a mixed aqueous solution of Coomassie Brilliant blue and direct yellow.
NH2-UiO66 and CO corresponding to the crosslinked membrane2The adsorption curve is shown in FIG. 11, which shows that the crosslinked material has a certain pore structure and can adsorb CO2There is still some adsorption.
NH2The XRD powder diffraction pattern of-UiO 66 and the corresponding crosslinked film is shown in FIG. 12, from which NH can be seen2The UiO66 retains the original framework structure without destroying its topology.
The reaction degree of FTIR study is shown in FIG. 13, and it can be seen that 2200cm-1Corresponding to the characteristic peak of isocyanate group in polyurethane prepolymer, disappearance of characteristic absorption peak of isocyanate group after film forming and 3300cm-1The weakening of the strong double peak corresponding to the primary amine indicates that the reaction has been completed.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. A metal organic framework-polyurethane composite material is characterized in that: the material is prepared by reacting a metal organic framework material with a polyurethane substance, wherein the mass ratio of the metal organic framework material to the polyurethane substance is 0.01-75: 25-100.
2. The composite material of claim 1, wherein: the metal organic framework material is IRMOF-3 and NH2-MIL-53、NH2-MIL-101、NH2-UiO66、OH-UiO-66、(OH)2-UiO66、NH2-UiO67、(NH2)2-UiO67、OH-UiO-67、(OH)2-UiO-67.
3. The composite material of claim 1, wherein: the polyurethane material is an addition product which is formed by the reaction of dihydric alcohol and diisocyanate and has-NCO groups at two ends.
4. The composite material of claim 3, wherein: the dihydric alcohol is one of polyether dihydric alcohol, polyester dihydric alcohol, hydroxyl-terminated polyolefin resin or micromolecular dihydroxy compound;
the diisocyanate is one of p-phenyl diisocyanate, 2, 4-toluene diisocyanate, 65/35-toluene diisocyanate, 80/20-toluene diisocyanate, 4-diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, 3 '-dimethoxy-4, 4' -biphenyl diisocyanate, m-xylylene diisocyanate and 2, 6-diisocyanate methyl caproate;
the polyether diol is polyethylene glycol [ HO (CH)2CH2O)nH，n≧1]Or polypropylene oxide [ HO (CH)2CH(CH3O)nH)，n≧1]；
The polyester diol is one of polycondensates of adipic acid and hexanediol, polycondensates of adipic acid and diethylene glycol, caprolactone ring-opening polymers, polycondensates of terephthalic acid and hexanediol, polycondensates of terephthalic acid and ethylene glycol and polycondensates of terephthalic acid and diethylene glycol;
the hydroxyl-terminated polyolefin resin is a hydroxyl-terminated adhesive;
the micromolecular dihydroxy compound is one of ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, hexanediol, diethylene glycol, hydroquinone dihydroxyethyl ether and N, N-dihydroxyethylaniline.
5. The method for preparing the metal organic framework-polyurethane composite material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
adding 25-100 parts by weight of polyurethane substance and 30-80 parts by weight of solvent into a reaction vessel, stirring, dissolving, adding 0.01-75 parts by weight of metal organic framework material, reacting at 30-100 ℃ for 1-48 hours, stopping heating, and cooling to obtain the metal framework-polyurethane composite material.
6. The method of claim 5, wherein: the solvent is one or a mixture of more of dichloromethane, trichloromethane, tetrahydrofuran, N-dimethylformamide, acetone, ethyl acetate and dioxane.
7. Use of the metal organic framework-polyurethane composite material of any one of claims 1 to 4 for preparing a dye-containing sewage separation membrane.
8. A metal organic framework-polyurethane crosslinked film is characterized in that: is prepared from the composite material of any one of claims 1 to 4.
9. The method for preparing a metal organic framework-polyurethane crosslinked film according to claim 8, wherein: coating the composite material according to any one of claims 1 to 4 by a film forming method, and drying to obtain a metal organic framework-polyurethane crosslinked film.
10. Use of the metal organic framework-polyurethane crosslinked membrane of claim 8 in dye-containing wastewater separation.
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