CN105435652B - A kind of metal organic frame urethane crosslinks film and preparation method and application - Google Patents

A kind of metal organic frame urethane crosslinks film and preparation method and application Download PDF

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CN105435652B
CN105435652B CN201510824149.6A CN201510824149A CN105435652B CN 105435652 B CN105435652 B CN 105435652B CN 201510824149 A CN201510824149 A CN 201510824149A CN 105435652 B CN105435652 B CN 105435652B
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metal
film
metal organic
organic frame
mofs
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CN105435652A (en
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董育斌
姚丙建
姜卫玲
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Shandong Normal University
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Shandong Normal University
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    • 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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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/44—Materials comprising a mixture of organic materials
    • B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
    • 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
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention discloses a kind of metal organic frame urethane crosslinks film and preparation method and application, synthetic modification after being carried out with base polyurethane prepolymer for use as to the active amino on MOFs or hydroxyl, MOFs nanocrystals are linked up by both covalent bond effects, so that the compatibility and active force between MOFs particulates and polymer chain are strengthened, the MOFs derivatives after modification are assigned with excellent pliability and film forming, establish a kind of new method for preparing MOFs membrane modules.Synthesized MOFs membrane materials have good Selective Separation effect to dye molecule in water, there is huge application prospect in UF membrane field.

Description

A kind of metal organic frame-urethane crosslinks film and preparation method and application
Technical field
The present invention relates to a kind of metal organic frame-urethane crosslinks film and preparation method and application, belong to macromolecule Separate technical field of membrane.
Background technology
Metal organic frame (MOFs) is to be covalently attached the porous polymeric formed by organic ligand by metal ion or cluster Material, the characteristics of it shows organic and inorganic materials simultaneously, there is controllable high porosity, duct, structure diversity, rich Feature, the advantages that simple is prepared, the advantages of these are unique becomes the focus of Recent study.Specifically opened in MOFs Duct and avtive spot, make it that there is the property selectively passed through to some molecules, huge potential is shown in separation field.
MOFs is similar with inorganic crystal material, and physical state is mostly crystal powder or particle, in the feelings that structure is not destroyed Under condition, the characteristics of insoluble is presented in brittle framework, therefore, although MOFs possesses incomparable plurality of advantages, simple MOFs materials are difficult device, it is difficult to are generalized in practical application.In order to meet further application and it is original not changing its Topological structure on the premise of, how to improve its toughness and processability and already huge chosen as one of MOFs field faces War.
In recent years, in order to realize MOFs device, the research about MOF membrane materials is seen in report successively, MOF correlations Membrane material includes：Support type MOFs films and composite interstitial substance MOFs films, both the above film have been assigned matrix and MOFs pair Principal characteristic matter, but still the defects of various degrees, wherein support type MOFs films be mostly difficult peeled off from matrix and it is independent into Film, and its intensity is relatively low；In order to obtain satisfied performance, poor compatibility present in composite base plasma membrane and particle agglomeration problem are then Have to be resolved.Therefore, although having been achieved for good achievement and hair in terms of the related membrane materials of MOFs in recent years Exhibition, but most of homogeney for still lacking molecular level.For a further understanding of the effect of basic science and MOF crystal, sheet Independent MOF membrane materials are given priority in invention.
The concept of synthetic modification is proposed by Kim earliest after MOFs materials are carried out, and this method obtains thereafter largely should With, and a series of novel structure and property are generated, provide more wide space for MOFs development.
The content of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of novel metal organic frame-poly- ammonia Ester cross linking membrane and preparation method thereof.
It is a further object of the present invention to provide application of the crosslinking membrane material in separating and purifying waste water containing dye.
To achieve the above object, the present invention uses following technical proposals：
A kind of metal organic frame-compound polyurethane material, it is anti-by metal-organic framework material and polyurethanes material It should be made, wherein the mass ratio of the metal-organic framework material and polyurethanes material is 0.01~75:25~100.
The metal-organic framework material is class I organic-inorganic hybridized material, by organic ligand and inorganic metal unit Built-up, those skilled in the art can routinely prepare according to prior art.
To make metal organic frame-compound polyurethane material that there is pliability and film forming, the metal organic frame material Material includes：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 formulas are Zn4O(NH2-BDC)3, NH2- BDC is 2- amino-Isosorbide-5-Nitrae-terephthalic acid (TPA), is by six water Close the three-dimensional crystal that zinc nitrate and rigid ligand 2- amino -1,4- terephthalic acid (TPA)s obtain.
NH2-MIL-101 structural formulas are M3OX (NH2-BDC) 3, M=Cr, Fe or Al, and X=F or OH, NH2-BDC are 2- ammonia Base terephthalic acid (TPA), it is the three-dimensional crystal obtained by above-mentioned and rigid ligand 2- amino-Isosorbide-5-Nitrae-terephthalic acid (TPA).
NH2-UiO66、HO-UiO66、(HO)2-UiO66、NH2-UiO67、(NH2)2-UiO67、(HO)-UiO-67、 (HO) 2-UiO-67 general structures are Zr6O4 (OH) 4L6, are the three-dimensionals obtained by metal salt for zirconium chloride and corresponding ligand L Crystal, in 7 kinds of crystal of the above, L is followed successively by 2- amino-Isosorbide-5-Nitrae-terephthalic acid (TPA), 2- hydroxyls-Isosorbide-5-Nitrae-terephthalic acid (TPA), 2,5- bis- Hydroxyl -1,4- terephthalic acid (TPA)s, 2- aminobphenyls dioctyl phthalate, 2,2 '-diaminodiphenic acid, 2- xenols dioctyl phthalate, 2,2 '-dihydroxybiphenyl dioctyl phthalate.Preferably, the metal-organic framework material is metal organic frame crystal, and the metal has Machine frame crystal is by metal ions Mn+And organic ligand is made by solvent thermal reaction, containing after can carrying out in its crystal structure The active amino or oh group of modification.
The preparation method of IRMOF-3 crystal such as document：In Crystal Growth＆Design, 2010,2,1283-1288 It is described.
NH2The preparation method of-MIL-101 crystal such as document：RSC Advances, described in 2012,2,6417-6419.
The preparation method of UiO serial crystals such as document：Chem.Commun., 2013,49,9449-9451, Chem.Eur.J., described in 2015,21,314-323 and Chem.Eur.J., 2011,17,6643-6651.
Preferably, the metal ions Mn+For one kind in Zr (IV), Fe (III), Al (III), Zn (II) etc..Through excessive Experimental verification and analysis are measured, the properties for the membrane module that the metal-organic framework material with above-mentioned metal ion is prepared Preferably.
Preferably, the organic ligand be 2- amino-Isosorbide-5-Nitrae-terephthalic acid (TPA), 2,2 '-diaminodiphenic acid, 2- hydroxyls One kind in base 1,4- terephthalic acid (TPA)s and 2,2- dihydroxybiphenyl dioctyl phthalate etc..By lot of experiment validation and analysis, have The properties for the membrane module that the metal-organic framework material of above-mentioned organic ligand is prepared are preferable.
Polyurethanes material is a variety of base polyurethane prepolymer for use as of the prior art in the present invention, is by dihydric alcohol and excess Binary isocyanates reacts, and the both ends generated are all-the addition product of NCO group, wherein, dihydric alcohol includes molecular weight to be hundreds of To aliphatic polyether (conventional oxirane, expoxy propane or tetrahydrofuran ring opening polymerization form), the polyester of thousands of terminal hydroxy groups Polyalcohol (conventional binary acid forms with excess glycol reaction, can also be obtained by lactone ring opening polymerization), vistanex are (such as Fourth hydroxyl glue) or small molecule dihydroxy compounds, binary isocyanates be even more that species is various, but be not limited only to institute of the present invention The species of the polyurethane of offer.Preferably, the polyurethanes material is with isocyanate-terminated base polyurethane prepolymer for use as, knot Structure formula is as follows：
Wherein, n is natural number, OCN-R1- NCO is aliphatic and aromatic dicarboxylic isocyanates, can be to phenyl two Isocyanates, 2,4- toluene di-isocyanate(TDI)s, 65/35- toluene di-isocyanate(TDI)s, 80/20- toluene di-isocyanate(TDI)s, 4,4- bis- Methylenebis phenyl isocyanate, 1, hexamethylene-diisocyanate, 1,5- naphthalene diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenyl Diisocyanate, m-xylylene diisocyanate, one kind in 2,6- diisocyanate base methyl caproates.
HO-R2- OH is diatomic alcohol compounds.Can be small molecule dihydroxy compounds, i.e. ethylene glycol, propane diols, 1,3- Butanediol, 1,4- butanediols, hexylene glycol, diglycol, hydroquinones dihydroxy ethyl ether, N, in N- double hydroxyethyl aniline One kind or polyether Glycols, i.e. polyethylene glycol [HO (CH2CH2O) nH, n≤1] (PEG), PPOX [HO (CH2CH(CH3O)nH), n≤1] one kind or polyester diol in (PPO), i.e., adipic acid and hexylene glycol condensation polymer, Adipic acid and diglycol condensation polymer, caprolactone ring-opening polymerization polymer, terephthalic acid (TPA) and hexylene glycol condensation polymer, terephthaldehyde One kind in acid and ethylene glycol condensation polymer, terephthalic acid (TPA) and diglycol condensation polymer, can also be terminal hydroxy group polyolefin, Such as one kind in fourth hydroxyl glue prepolymer.
By lot of experiment validation and analysis, when preparing polyurethane prepolymer with polyether Glycols and excessive binary isocyanates During body, the membrane module properties of formation are preferable.
The preparation method of isocyanate-terminated base polyurethane prepolymer for use as, comprises the following steps：
By 20~80 parts of 30~70 parts of binary isocyanate compound, the diatomic alcohol compounds of parts by weight, it is added to this In reaction vessel, stirring, at 30~100 DEG C, react 1~20 hour, stop heating, it is unreacted small by being evaporated under reduced pressure removing Molecule, obtain isocyanate-terminated base polyurethane prepolymer for use as, nco value determined by titrating, and determine viscosity 1000~ 5000mPa.s。
Preferably, the diatomic alcohol compounds are PEG400, PEG600, PEG800, PEG2000, PPO1000, PPO2000 In one kind.
Preferably, described diisocyanate cpd is that 2,4- toluene di-isocyanate(TDI)s, 4,4- diphenyl methanes two are different Cyanate, hexamethylene diisocyanate, 1,5- naphthalene diisocyanates, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, One kind in XDI, 2,6- diisocyanate base methyl caproates.
A kind of metal framework-urethane crosslinks film, it is prepared by the metal framework-compound polyurethane material.
A kind of preparation method of metal framework-compound polyurethane material, comprises the following steps：
By 25~100 parts of the polyurethanes material of parts by weight, 30~80 parts of solvent is added in reaction vessel, stirring, molten Solution, adds 0.01~75 part of metal-organic framework material, at 30~100 DEG C, reacts 1~48 hour, stops heating, cools down, Produce metal framework-compound polyurethane material.
Described solvent is dichloromethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetone, acetic acid second One or more mixing in ester, dioxane.
The preparation method of a kind of metal framework-urethane crosslinks film, by metal framework-polyurethane composite obtained above Material come film, is dried by film build method, obtains metal organic frame-urethane crosslinks film.
The skeleton symbol of the reaction is as follows：
Wherein film build method includes the tape casting, spin-coating method or casting etc..
The present invention provides a kind of metal organic frame-compound polyurethane material answering in seperation film containing dye wastewater is prepared With.
The present invention also provides a kind of metal organic frame-application of the urethane crosslinks film in being separated containing dye wastewater.
The beneficial effects of the invention are as follows：
(1) after the present invention is carried out with isocyanate-terminated base polyurethane prepolymer for use as to the active amino on MOFs or hydroxyl Synthetic modification, MOFsF nanocrystals are linked up by both covalent bond effects so that MOFs particulates and polymer chain it Between compatibility and active force strengthened, assign modification after MOFs derivatives with excellent pliability and film forming, build A kind of new method for preparing MOFs membrane modules is found.Synthesized MOFs membrane materials have good selection to dye molecule in water Property separating effect, there is huge application prospect in UF membrane field.
Relatively conventional physical doping, this method make it that the active force between MOF particulates and polymer chain is strengthened, By carrying out cast film forming to solution after reaction, can obtain surfacing it is smooth, have excellent toughness independent MOFs films, And the thickness of MOF contents and film can be adjusted as needed.Test result indicates that synthesized MOFs membrane materials pair and examining Having examined has good Selective Separation effect to dye molecule in water.
(2) new MOFs membrane materials are used as, novel metal organic frame-urethane crosslinks film is led in dyeing waste water UF membrane There is huge application prospect in domain.MOF contents are absorption and separating experiment of the 70wt% cross linking membrane to Coomassie Brilliant Blue dye Show, the film is 1.45 × 10 to the maximum static adsorbance of Coomassie brilliant blue-3mg/g.UF membrane experiment shows 5mL concentration For the Coomassie brilliant blue aqueous solution pass through 1 × 1cm2The filter membrane of diameter, 100% can be reached to the interception of Coomassie brilliant blue, Filter membrane after filtering is soaked into 2h in methyl alcohol, the desorption of Coomassie brilliant blue can be reached, by the filter membrane after immersion according to above-mentioned Condition is reused, and can reach 90% to the second interception rate of the above-mentioned Coomassie brilliant blue aqueous solution, the film is to examining horse This light blue and direct yellow two-component mixed dye realize good separating effect.
(3) NH that the present invention uses2The raw material such as-UiO and base polyurethane prepolymer for use as is cheap and easy to get, the preparation condition letter of cross linking membrane It is single, quick, gentle, be expected to realize high-performance, low cost, can mass production MOFs separation membrane materials.
Brief description of the drawings
Fig. 1 is NH2The SEM pictures of-UiO66 nanocrystals；
Fig. 2 is NH2The SEM pictures of-UiO67 nanocrystals；
Fig. 3 is NH2The XRD spectra of-UiO67 nanocrystals；
Fig. 4 is NH2The XRD spectra of-MIL-101 (Fe) nanocrystal；
Fig. 5 is the XRD spectra of IRMOF-3 crystal；
Fig. 6 is the photo of metal organic frame-urethane crosslinks film；
The standard curve of Fig. 7 a Coomassie brilliant blue aqueous solution；
Fig. 7 b are the UV-Vis spectrograms before and after Coomassie brilliant blue adsorption from aqueous solution；
Fig. 8 is separating effect photo of the metal organic frame-urethane crosslinks film to Coomassie brilliant blue；
Fig. 9 is separating effect photo of the metal organic frame-urethane crosslinks film to rhodamine；
Figure 10 is separating effect photo of the metal organic frame-urethane crosslinks film to mixed dye；
Figure 11 be metal organic frame-urethane crosslinks film under the conditions of 273K, to CO2Absorption situation；
Figure 12 is metal organic frame-urethane crosslinks film and NH2- UiO66 XRD powder diffractograms；
Figure 13 is metal organic frame-urethane crosslinks film and NH2- UiO66 FTIR spectrograms.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
The metal organic frame NH of embodiment 12- UiO66 synthesis
Organic ligand 2- amino terephthalic acid (TPA)s, zirconium chloride, acetic acid are dissolved in DMF solvent, 120 DEG C of constant temperature 24h, are cooled to room temperature, obtain faint yellow nano crystals, centrifuge, and dry；Wherein organic ligand 2- amino is to benzene two Formic acid, zirconium chloride, the ratio of acetic acid and N,N-dimethylformamide solvent adding amount are 0.04mmol：0.04mmol：2mmol： 1.6ml, obtained crystal morphology are shown in Fig. 1.
The metal organic frame NH of embodiment 22- UiO67 synthesis
Organic ligand 2,2- diaminodiphenic acids, zirconium chloride, acetic acid are dissolved in DMF solvent In, 120 DEG C of constant temperature 24h, room temperature is cooled to, obtains Yellow nanometer level crystal, centrifuged, dried；Wherein organic ligand 2,2- diaminourea Biphenyl dicarboxylic acid, zirconium chloride, the ratio of acetic acid and N,N-dimethylformamide solvent adding amount are 0.26mmol：0.26mmol： 447ul：15ml, obtained crystal morphology are shown in Fig. 2.
The metal organic frame NH of embodiment 32- MIL-101 (Fe) synthesis
By organic ligand 2- amino terephthalic acid (TPA) (1.09g, 6mmol), Iron(III) chloride hexahydrate (1.08g, 4mmol), It is dissolved in 20mL DMF, is placed in crystallization axe, in 110 DEG C of constant temperature 16h, be down to room temperature, obtain grey nano crystals, centrifuges, according to It is secondary to be washed with DMF and ethanol, 24h is dried at one hundred and twenty degrees centigrade, obtains NH2- MIL-101 (Fe) crystal powder, XRD As a result Fig. 4 is seen.
The metal organic frame IRMOF-3 of embodiment 4 synthesis
0.29mol zinc nitrate hexahydrate is dissolved in 10mL DMF, 0.096mol 2- amino terephthalic acid (TPA)s are dissolved in In 10mL DMF, after 1h each is stirred at room temperature, two solution are mixed, ultrasound 5 minutes, are subsequently placed in crystallization axe, 90 DEG C constant temperature 36h, is down to room temperature, obtains clear crystal, centrifuges, is washed with DMF, dries, and obtains IRMOF-3 crystal powders, XRD knots Fruit sees Fig. 5.
The synthesis of the polyether Glycols Type Polyurethane Prepolymer of embodiment 5
By 4,4- methyl diphenylene diisocyanates (MDI) 37g, molecular weight is 2000 PPO (PPOX) 63g, It is added sequentially in reaction vessel, under the conditions of 80 DEG C, stirring, isothermal reaction 4 hours, stops heating, it is de- by being evaporated under reduced pressure Except unreacted small molecule, the prepolymer of NCO=10~11,2000~3000mPa.s of viscosity are obtained.
The synthesis of the polyester diol Type Polyurethane Prepolymer of embodiment 6
By 1, hexamethylene-diisocyanate (HDI) 10g, molecular weight is 1600 or so terminal hydroxy group polyadipate hexylene glycol ester 50g, it is added sequentially in reaction vessel, under the conditions of 60 DEG C, stirring, isothermal reaction 6 hours, stops heating, steamed by depressurizing The unreacted small molecule of removing is evaporated, obtains the performed polymer of NCO=5~7,2200~2500mPa.s of viscosity.
The preparation of 7 metal organic frames of embodiment-urethane crosslinks film
By NH2- UiO66 crystal powders are placed in chloroform, and immersion 3d, centrifugal drying is stirred at room temperature；Take the NH after treating2- Base polyurethane prepolymer for use as (OCN-R-NCO, nco value 10.2) 30 weight that the parts by weight of UiO66 crystal powders 70 synthesize with embodiment 5 Part in the chloroform of 35 parts by weight, react 24h under the conditions of 35 DEG C, after pour into Teflon mould, room temperature volatilization solvent to the greatest extent, Obtain lurid metal organic frame-urethane crosslinks film (film photo is shown in Fig. 6).
The preparation of 8 metal organic frames of embodiment-urethane crosslinks film
By the NH in embodiment 32- MIL-101 (Fe) crystal powder is placed in acetone, and immersion 2d is stirred at room temperature, and centrifugation is dry It is dry；Take the NH after treating2The base polyurethane prepolymer for use as that the parts by weight of-MIL-101 (Fe) crystal powder 50 synthesize with embodiment 6 (OCN-R-NCO, nco value 6) 30 parts by weight in the acetone of 40 parts by weight, react 12h under the conditions of 50 DEG C, after pour into polytetrafluoro In ethene mould, room temperature volatilization solvent to the greatest extent, metal organic frame-urethane crosslinks film of yellow is obtained.
The preparation of 9 metal organic frames of embodiment-urethane crosslinks film
Metal organic frame IRMOF-3 crystal powders in embodiment 4 are placed in tetrahydrofuran, immersion is stirred at room temperature 2d, centrifugal drying, the base polyurethane prepolymer for use as taking the parts by weight of IRMOF-3 crystal powders 70 after treating to be synthesized with embodiment 6 (OCN-R-NCO, nco value 6) 50 parts by weight in the tetrahydrofuran of 60 parts by weight, react 8h under the conditions of 60 DEG C, after pour into it is poly- In Teflon mold, room temperature volatilization solvent to the greatest extent, metal organic frame-urethane crosslinks film is obtained.
Adsorption experiment of 10 metal organic frames of the embodiment-urethane crosslinks film to Coomassie brilliant blue
The metal organic frame of Example 7-urethane crosslinks film, 10mL concentration is soaked in as 2.13 × 10-6Mol/L's In Coomassie Brillant Blue solution, quantitative analysis is carried out to Dye Adsorption result by ultraviolet absorption spectroscopy after 24h, as a result shown, The film is 1.45 × 10 to the saturated extent of adsorption of Coomassie brilliant blue-3Mg/mg, Fig. 7 give Coomassie brilliant blue standard curve and The front and rear change in concentration of absorption.
Separating experiment of 11 metal organic frames of the embodiment-urethane crosslinks film to Coomassie brilliant blue
The Φ 13mm metal organic frames of Example 7-urethane crosslinks film (about 20mg), 5ml concentration is taken as 2.13 ×10-6Mol/L Coomassie Brillant Blue solution, with micro- capacity sampling pump with 2.5ml/h speed slow transit through metal organic frame- Urethane crosslinks film, front and rear solution concentration is filtered by ultraviolet detection, and calculate rejection, as a result shown, 5mL concentration is 2.13 ×10-6When the mol/L Coomassie brilliant blue aqueous solution is by Φ 13mm film, the retention efficiency to dye molecule can reach 100%.Fig. 8 shows separating experiment of the metal organic frame-urethane crosslinks film as filter membrane to the Coomassie brilliant blue aqueous solution Device and separating effect.
Separating experiment of 12 metal organic frames of the embodiment-urethane crosslinks film to rhodamine
The Φ 13mm metal organic frames of Example 8-urethane crosslinks film (about 20mg), take 5mL concentration for 1.24 × 10-6Mol/L rhodamine liquor, metal organic frame-polyurethane is slow transitted through with 2.5ml/h speed with micro- capacity sampling pump Cross linking membrane, front and rear solution concentration is filtered by ultraviolet detection, and calculate rejection, as a result shown, 5mL concentration is 1.24 × 10- 6When the mol/L Coomassie brilliant blue aqueous solution is by Φ 13mm film, the retention efficiency to dye molecule can reach 92%.Fig. 9 Show that metal organic frame-urethane crosslinks film is imitated as filter membrane to the separating experiment device of the rhodamine aqueous solution and separation Fruit.
Separating experiment of 13 metal organic frames of the embodiment-urethane crosslinks film to mixed dye
The Φ 13mm metal organic frames of Example 7-urethane crosslinks film (about 20mg), take 5mL Coomassie brilliant blues (dense Spend for 3.0 × 10-6) and directly (concentration is 2.0 × 10 to Huang-5Mol/L mixed solution), with micro- capacity sampling pump with 2.5ml/h Speed slow transit through metal organic frame-urethane crosslinks film, front and rear solution concentration is filtered by ultraviolet detection, and calculate and cut Rate is stayed, is as a result shown, when the mixed solution is by Φ 13mm film, the retention efficiency to Coomassie Brilliant Blue dye molecule can reach To 100%, and directly yellow transmitance can reach 92%, show that there is the film good selectivity to inhale to different dyes molecule Attached effect, realize and the mixed dye aqueous solution is efficiently separated.Figure 10 shows metal organic frame-urethane crosslinks film pair The separating effect of Coomassie brilliant blue and direct yellow mixed aqueous solution.
NH2- UiO66 and corresponding cross linking membrane CO2Adsorption curve is as shown in figure 11, and display possesses certain opening structure, and To CO after crosslinking2Still there is certain absorption.
NH2The XRD powder diffractograms of-UiO66 and corresponding cross linking membrane are as shown in figure 12, as can be seen from the figure NH2- UiO66 remains original frame structure, does not destroy its topological structure.
It is as shown in figure 13 that FTIR have studied the extent of reaction, it can be seen that 2200cm-1It correspond to isocyanide in base polyurethane prepolymer for use as The characteristic peak of acid esters group, the disappearance of NCO characteristic absorption peak and 3300cm after film forming-1Locate strong bimodal corresponding to primary amine Decrease explanation reaction completed.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, model not is protected to the present invention The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not Need to pay various modifications or deformation that creative work can make still within protection scope of the present invention.

Claims (9)

1. a kind of metal organic frame-compound polyurethane material, it is characterized in that：It is by metal-organic framework material and polyurethanes Substance reaction is made, wherein the mass ratio of the metal-organic framework material and polyurethanes material is 0.01 ~ 75:25~100； The metal-organic framework material is IRMOF-3, NH2-MIL-53、NH2-MIL-101、NH2-UiO66、OH-UiO-66、 (OH)2-UiO66、NH2-UiO67、(NH2)2-UiO67、OH-UiO-67、(OH)2One kind in-UiO-67；
Metal organic frame-the compound polyurethane material is to be prepared by the following method to obtain：
By 25~100 parts of the polyurethanes material of parts by weight, 30~80 parts of solvent is added in reaction vessel, is stirred, dissolving, then 0.01~75 part of metal-organic framework material is added, at 30~100 DEG C, is reacted 1~48 hour, stops heating, cooling, produces Metal framework-compound polyurethane material.
2. composite as claimed in claim 1, it is characterized in that：Polyurethanes material is by dihydric alcohol and binary isocyanates Reaction, and the both ends generated are all-the addition product of NCO group.
3. composite as claimed in claim 2, it is characterized in that：The dihydric alcohol is polyether Glycols, polyester diol, end One kind in hydroxyl vistanex or small molecule dihydroxy compounds；
The binary isocyanates is to phenyl diisocyanate, 2,4 toluene diisocyanate, 65/35- toluene diisocynates Ester, 80/20- toluene di-isocyanate(TDI)s, 4,4- methyl diphenylene diisocyanates, hexamethylene diisocyanate, 1,5- naphthalenes two are different Cyanate, 3,3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, m-xylylene diisocyanate, the isocyanic acids of 2,6- bis- One kind in ester group methyl caproate；
The polyether Glycols are polyethylene glycol [HO (CH2CH2O)nH, n≤1] or PPOX [HO (CH2CH(CH3O)nH), n≧1]；
The polyester diol is adipic acid and hexylene glycol condensation polymer, adipic acid and diglycol condensation polymer, caprolactone are opened Cyclopolymer, terephthalic acid (TPA) and hexylene glycol condensation polymer, terephthalic acid (TPA) and ethylene glycol condensation polymer, terephthalic acid (TPA) and a contracting two One kind in ethylene glycol condensation polymer；
The terminal hydroxy group vistanex is fourth hydroxyl glue；
The small molecule dihydroxy compounds is ethylene glycol, propane diols, 1,3 butylene glycol, 1,4- butanediols, hexylene glycol, a contracting two Ethylene glycol, hydroquinones dihydroxy ethyl ether, N, one kind in N- double hydroxyethyl aniline.
4. the preparation method of metal organic frame-compound polyurethane material any one of claim 1 ~ 3, its feature It is to comprise the following steps：
By 25~100 parts of the polyurethanes material of parts by weight, 30~80 parts of solvent is added in reaction vessel, is stirred, dissolving, then 0.01~75 part of metal-organic framework material is added, at 30~100 DEG C, is reacted 1~48 hour, stops heating, cooling, produces Metal framework-compound polyurethane material.
5. preparation method as claimed in claim 4, it is characterized in that：Described solvent is dichloromethane, chloroform, tetrahydrochysene furan Mutter, one or more mixing in N,N-dimethylformamide, acetone, ethyl acetate, dioxane.
6. metal organic frame-compound polyurethane material any one of claim 1 ~ 3 is being prepared containing dye wastewater point From the application in film.
7. a kind of metal organic frame-urethane crosslinks film, it is characterized in that：It is as answering any one of claim 1 ~ 3 Condensation material is prepared.
8. the preparation method of metal organic frame-urethane crosslinks film described in claim 7, it is characterized in that：By claim 1 Composite any one of ~ 3 come film, is dried by film build method, obtains metal organic frame-urethane crosslinks Film.
9. metal organic frame-application of the urethane crosslinks film in being separated containing dye wastewater described in claim 7.
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