CN107722289A - A kind of seperation film and preparation method thereof of organic ligand for MOF and preparation method thereof, a kind of MOF containing organic ligand - Google Patents
A kind of seperation film and preparation method thereof of organic ligand for MOF and preparation method thereof, a kind of MOF containing organic ligand Download PDFInfo
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- CN107722289A CN107722289A CN201711062637.3A CN201711062637A CN107722289A CN 107722289 A CN107722289 A CN 107722289A CN 201711062637 A CN201711062637 A CN 201711062637A CN 107722289 A CN107722289 A CN 107722289A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a kind of organic ligand for MOF, the organic ligand has the structure as shown in formula (I), wherein, x is that 7~10, n is 20~30.The invention provides a kind of organic ligand MOF, the coordinating metal in the organic ligand MOF is iron.Present invention also offers the seperation film of MOF containing organic ligand a kind of, including basement membrane and the organic ligand MOF for being compounded in membrane surface.Regulation and control of the present invention from MOF aperture sizes, it have selected the chemical constitution of specific organic ligand, with reference to specific coordinating metal, in conjunction with the influence of MOF growing environments and matrix structure, ion selectivity separation is studied, accurate regulation and control MOF frame sizes, are allocated as realizing the Selective Separation to ion based on aperture sieve, so as to preferably realize being selectively adsorbing and separating in multivalent state solion system.
Description
Technical field
The present invention relates to metal-organic framework compound nano-material technical field, it is related to a kind of organic ligand and its system
Preparation Method, organic ligand MOF, a kind of seperation film and preparation method thereof, more particularly to a kind of organic ligand and its system for MOF
Preparation Method, organic ligand MOF, the seperation film and preparation method thereof of MOF containing organic ligand a kind of.
Background technology
Metal-organic framework complex (Metal-Organic Frameworks), abbreviation MOFs, is often referred to metal ion
Or metal cluster forms the crystalline material with periodicity infinite network structure with organic ligand by self assembling process, it has both
The order and controllability of hybrid inorganic-organic characteristic and crystal structure, microporosity, special light, electricity, magnetic property and industrial
Potential application, become one of hot research field of new function material instantly.
MOF materials have the characteristics of porous and big specific surface area, and these are with dividing applied to catalysis, gas absorption
From critical nature, thus constantly change one of main purpose of MOFs material metals center and linking arm in existing research and be exactly
Make material that there is bigger specific surface area.MOF materials also have a diversity of structure and function, its variable metal center and have
Machine part result in the diversity of its structure and function, and the selection of metal center almost covers all metals, including main group member
Element, transition elements, lanthanide series metal etc., wherein using more for Zn, Cu, Zr etc..Valence state, the coordination ability of different metal are different
The appearance of different materials is also resulted in, the application of MOFs materials has been widened in the combination of different functional groups significantly.Equally, MOF
Also there is undersaturated metallic site, due to the presence of small solvent molecule in preparation process, unsaturated metal center enters with it
Row is combined to meet coordination demand, and these solvent molecules can be removed after heating or application of vacuum, so that unsaturated gold
Belong to site exposure.These exposure unsatuated metal sites can have the function that gas absorption and separate, can also with
The material of amino or carboxyl is coordinated, so that MOFs materials are as pharmaceutical carrier or the effective tool of peptides separation.In addition,
The catalyst that MOFs materials containing unsatuated metal site can act also as catalytic reaction accelerates the progress reacted.Just because of
There is MOF materials crystal framework opening, duct controllability, superhigh specific surface area, skeleton Diversity, composition can design
Behind property, excellent surface modified and can Post functionalization the advantages that, make it that there is huge application prospect in numerous areas, especially
In adsorbing domain.
But the adsorbing separation of admixture of gas is concentrated mainly on to concern of the MOF materials in terms of adsorbing separation, and it is right
The concern of liquid phase adsorption and separation is relatively fewer.It is but particularly stable to some solution systems with the continuous development of MOF materials
MOF materials report, also gradually begin to focus on the adsorbing separation in solution system in the industry.But existing MOF materials from
Application in son separation also only exists in the desk study stage, larger difficulty in application not only be present, the characteristic of itself, such as
The size controls of MOF frameworks, chargedization, stability and MOF layer thickness controllabilities and recycling etc. are both needed to further investigate,
Important ion selectivity separation function particularly in practical process, still needs to be explored.
Therefore, a kind of MOF materials with ion selectivity separation function how are obtained, widen MOF in ion selectivity
Application in separation field, it has also become many forward-looking researchers widely one of focus of attention in the industry.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of organic ligand for MOF and its preparation
Method, organic ligand MOF, the seperation film and preparation method thereof of MOF containing organic ligand a kind of, organic ligand prepared by the present invention
MOF, specific chemical constitution and coordinating metal are employed, be capable of accuracy controlling MOF frame size, realize the selection to ion
Property separation, and then can apply to seawater concentration salt manufacturing in realize ion selectivity separate.
The invention provides a kind of organic ligand for MOF, the organic ligand has the structure as shown in formula (I)；
Wherein, x is that 7~10, n is 20~30.
The invention provides a kind of preparation method of the organic ligand for MOF, comprise the following steps：
1) by bis- terephthalate, after bromo -1- alkene, acid binding agent and the mixing of the first solvent, condensation reaction is carried out, is obtained
To double bond containing monomer；
2) in the presence of catalyst, the double bond containing intermediate that above-mentioned steps are obtained is polymerize in the second solvent
After reaction, the polymer of the structure containing bis- terephthalate is obtained；
3) polymer for the structure containing bis- terephthalate for obtaining above-mentioned steps and alkali enter water-filling in the 3rd solvent
Solve after reacting, then reacted with acidic materials, obtain the organic ligand for MOF.
Preferably, the ester includes diethyl terephthalate, terephthalic acid (TPA) dipropyl and to benzene two
One or more in formic acid dibutyl ester；
Bromo -1- the alkene includes the bromo- 1- heptene of 7-, the bromo- 1- octenes of 8-, the bromo- 1- nonenes of 9- and the bromo- 1- decene of 10-
In one or more；
The acid binding agent includes the one or more in potassium carbonate, triethylamine, pyridine and diisopropylethylamine；
First solvent includes DMF, N, N- diethylformamides, DMA, N,
One or more in N- diethyl acetamides and 1-METHYLPYRROLIDONE；
The bis- terephthalate and the mol ratio of bromo -1- alkene are (3.0~3.4)：(12.0~13.6)；
The mol ratio of the bis- terephthalate and acid binding agent is (0.1~0.5)：1；
The mol ratio of first solvent and bis- terephthalate are (90~100)：1；
The temperature of the condensation reaction is 70~90 DEG C；The time of the condensation reaction is 20~24h.
Preferably, the catalyst is urged including generation Grubbs catalyst, two generation Grubbs catalyst and three generations Grubbs
One or more in agent；
Second solvent includes the one or more in dichloromethane, chloroform, dichloroethanes and chloroethanes；
The mol ratio of the double bond containing monomer and the catalyst is (3.0~3.4)：(0.03~0.034)；
The mol ratio of second solvent and double bond containing monomer is (300~350)：1；
The temperature of the polymerisation is 30~50 DEG C；The time of the polymerisation is 6~8h.
Preferably, the alkali includes the one or more in potassium hydroxide, sodium hydroxide, ammonium hydroxide and triethylamine；
The acidic materials include hydrochloric acid and/or sulfuric acid；
3rd solvent includes DMF, N, N- diethylformamides, dimethyl sulfoxide (DMSO), N, N- diformazans
One or more in yl acetamide and N, N- diethyl acetamide；
The mol ratio of the alkali and the polymer of the structure containing bis- terephthalate is (1.0~2.0)：1；
PH value when described and acidic materials are reacted is 1~2；
The mol ratio of 3rd solvent and the polymer of the structure containing bis- terephthalate is (450~500)：1；
The temperature of the hydrolysis is 80~100 DEG C；The time of the hydrolysis is 10~12h.
The invention provides a kind of organic ligand MOF, the coordinating metal in the organic ligand MOF is iron；
Organic ligand in the organic ligand MOF is the organic ligand or above-mentioned technical proposal described in above-mentioned technical proposal
Organic ligand prepared by the preparation method described in any one.
The invention provides the seperation film of MOF containing organic ligand a kind of, including basement membrane and it is compounded in the organic of membrane surface
Part MOF；
The organic ligand MOF is the organic ligand MOF described in above-mentioned technical proposal.
Preferably, the fine and close growth of the separation membrane surface has organic ligand MOF；
The thickness of the seperation film is 150~200 μm；
The material of the basement membrane include brominated polyphenylether, polybenzimidazoles, polyethersulfone ketone and polyether-ether-ketone in one kind or
It is a variety of；
The basement membrane is finger-like pore basement membrane or spongy hole basement membrane；
The thickness of the basement membrane is 90~150 μm.
The invention provides a kind of preparation method of the seperation film of MOF containing organic ligand, comprise the following steps：
A) basement membrane is put into, organic ligand, mineralizer, soluble ferric iron salt and organic solvent mixed liquor in, reacted,
Obtain the seperation film of the MOF containing organic ligand；
The organic ligand is described in organic ligand or above-mentioned technical proposal any one described in above-mentioned technical proposal
Organic ligand prepared by preparation method.
Preferably, the mineralizer includes the one or more in formic acid, hydrochloric acid and benzoic acid；
The soluble ferric iron salt includes the one or more in ferric trichloride, ferric sulfate and ferric nitrate；
The organic solvent includes N, N- diethylformamides, DMF, DMA, N,
One or more in N- diethyl acetamides and 1-METHYLPYRROLIDONE；
The mass ratio of the mineralizer and the organic ligand is (70~90)：1；
The organic ligand and the mol ratio of the soluble ferric iron salt are (0.02~0.04)：(0.02~0.04)；
The mass ratio of the organic solvent and the organic ligand is (110~130)：1；
The temperature of the reaction is 110~130 DEG C；The time of the reaction is 36~48h.
The invention provides a kind of organic ligand for MOF, the organic ligand has the structure as shown in formula (I).
The invention provides a kind of organic ligand MOF, the coordinating metal in the organic ligand MOF is iron.Present invention also offers one
Kind MOF containing organic ligand seperation film, including basement membrane and the organic ligand MOF for being compounded in membrane surface.Compared with prior art,
The present invention is only built upon the basis of the pore size and framework chemical modification using MOF for existing MOF action oriented research
The Selective Separation of upper realization, there is limitation in it.The regulation and control from MOF aperture sizes of the invention, have selected specific
Organic ligand chemical constitution, it is right in conjunction with the influence of MOF growing environments and matrix structure with reference to specific coordinating metal
Ion selectivity separation is studied, and accurate regulation and control MOF frame sizes, is allocated as based on aperture sieve for realizing the choosing to ion
Selecting property separates, and so as to preferably realize in multivalent state solion system, is selectively adsorbing and separating.
The seperation film of the MOF provided by the invention containing organic ligand, using organic porous polymer base material as supporting layer, utilize
What the functional group of polymer surfaces and additional macromolecule organic ligand participated in MOF densification tunics constructs growth.Porous polymeric
The design of nitride layer reduces transport resistance of the ion in film, can not only offset the surface resistance caused by the MOF compacted zones of surface
The adverse effect that increase and ionic flux reduce, while the presence of the loose structure of polymer matrix and top layer functional group is also more
Be advantageous to the growth of MOF structures, improve the adhesive force of MOF layers and porous basement membrane.The invention uses macromolecule organic
Part replaces organic micromolecule ligand, can strengthen the ability to MOF framework aperture structure precision controls, beneficial to the sieve of multivalent ion
Point, the transmission of monovalention is lifted, and the introducing of macromolecular chain improves the chemical stability of MOF layers again.
Test result indicates that the MOF base seperation films of pbz polymer organic ligand provided by the invention, this film utilizes MOF's
Aperture sieve is allocated as being used in progress one in solution system system/bivalent ions separation, its Na+With Mg2+Separation rate is 19.12, and
Na+Flux be 100.57*10-10mol/cm2/s。
Brief description of the drawings
Fig. 1 is the iron-based MOF of pbz polymer organic ligand provided by the invention preparation process schematic flow sheet；
Fig. 2 is the surface scan electricity of the iron-based MOF separating layer membranes of pbz polymer organic ligand prepared by the embodiment of the present invention 1
Mirror figure.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply for further explanation the features and advantages of the present invention rather than to patent requirements of the present invention
Limitation.
All raw materials of the present invention, its source is not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, its purity is not particularly limited, and present invention preferably employs analyze pure or MOF nano materials
The conventional purity in field.
The invention provides a kind of organic ligand for MOF, it is characterised in that the organic ligand has such as formula (I)
Shown structure；
Wherein, x is that 7~10, n is 20~30.
Implication represented by group in structure shown in formula (I) is not particularly limited the present invention, with people in the art
Member known to group represent conventional sense, those skilled in the art can according to practical situations, raw material condition and
Product requirement is selected and adjusted,
In structure shown in formula (I) of the present invention, x is preferably 7~10, and more preferably 8~9, it is specifically as follows 7,8,9 or 10
In any one.N of the present invention is preferably 20~30, more preferably 22~28, more preferably 24~26.
It is a kind of macromolecule provided by the present invention for MOF (Metal Organic Frameworks) organic ligand
Organic ligand, each repeat unit therein contain terephthalic acid (TPA) structure, are easy in follow-up MOF preparations and metal ion shape
Into coordination structure, meanwhile, the double bond of end can carry out further reaction to improve its separating property.
The invention provides a kind of preparation method of the organic ligand for MOF, comprise the following steps：
1) by bis- terephthalate, after bromo -1- alkene, acid binding agent and the mixing of the first solvent, condensation reaction is carried out, is obtained
To double bond containing monomer；
2) in the presence of catalyst, the double bond containing intermediate that above-mentioned steps are obtained is polymerize in the second solvent
After reaction, the polymer of the structure containing bis- terephthalate is obtained；
3) polymer for the structure containing bis- terephthalate for obtaining above-mentioned steps and alkali enter water-filling in the 3rd solvent
Solve after reacting, then reacted with acidic materials, obtain the organic ligand for MOF.
The present invention by bis- terephthalate, after bromo -1- alkene, acid binding agent and the mixing of the first solvent, is contracted first
Reaction is closed, obtains double bond containing monomer.
Selection of the present invention to the ester is not particularly limited, with routine well known to those skilled in the art
Ester, those skilled in the art can be carried out according to practical situations, raw material condition and product requirement
Selection and adjustment, the present invention further improve final products performance, being advantageous to production should to ensure the effect of Selective Separation
With the ester preferably includes diethyl terephthalate, terephthalic acid (TPA) dipropyl and the fourth of terephthalic acid (TPA) two
One or more in ester, more preferably diethyl phthalate, terephthalic acid (TPA) dipropyl or dibutyl terephthalate.
Selection of the present invention to the bromo -1- alkene is not particularly limited, with routine well known to those skilled in the art
Bromo -1- alkene, those skilled in the art can be selected according to practical situations, raw material condition and product requirement
Selecting and adjust, the present invention is ensures the effect of Selective Separation, and further raising final products performance, is advantageous to production application,
Bromo -1- the alkene is preferably included in the bromo- 1- heptene of 7-, the bromo- 1- octenes of 8-, the bromo- 1- nonenes of 9- and the bromo- 1- decene of 10-
The bromo- 1- heptene of one or more, more preferably 7-, the bromo- 1- octenes of 8-, the bromo- 1- nonenes of 9- or the bromo- 1- decene of 10-.
Selection of the present invention to the acid binding agent is not particularly limited, with conventional acid binding agent well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to practical situations, raw material condition and product requirement, this
Invent to ensure reaction effect, further improve final products performance, the acid binding agent preferably includes potassium carbonate, triethylamine, pyrrole
One or more in pyridine and diisopropylethylamine, more preferably potassium carbonate, triethylamine, pyridine or diisopropylethylamine, it is more excellent
Elect potassium carbonate as.
Selection of the present invention to first solvent is not particularly limited, organic with routine well known to those skilled in the art
Solvent, those skilled in the art can be selected and adjusted according to practical situations, raw material condition and product requirement
Whole, the first solvent of the present invention preferably includes DMF, N, N- diethylformamides, N, N- dimethylacetamides
Amine, N, the one or more in N- diethyl acetamides and 1-METHYLPYRROLIDONE, more preferably DMF, N,
N- diethylformamides, DMA, N, N- diethyl acetamides or 1-METHYLPYRROLIDONE, more preferably N, N-
Dimethylformamide.
The addition of above-mentioned raw materials is not particularly limited the present invention, with the amount of being routinely added to well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to practical condition, raw material condition and product requirement, this
Invent further to improve final products performance, improve and optimize course of reaction, the bis- terephthalate and bromo -1- alkene
The mol ratio of hydrocarbon is (3.0~3.4)：(12.0~13.6), more preferably (3.05~3.35)：(12.0~13.6), more preferably
For (3.1~3.3)：(12.0~13.6), or be (3.0~3.4)：(12.2~13.4), or be (3.0~3.4)：
(12.5~13.1), or be (3.0~3.4)：(12.7~12.9), most preferably 3.2：12.8.The terephthalic acid (TPA) two
The mol ratio of ester and acid binding agent is preferably (0.1~0.5)：1, more preferably (0.15~0.45)：1, more preferably (0.2~
0.4)：1, more preferably (0.25~0.35)：1.The mol ratio of first solvent and bis- terephthalate be preferably (90~
100)：1, more preferably (92~98)：1, more preferably (94~96)：1.
The parameter of the condensation reaction is not particularly limited the present invention, with conventional condensation well known to those skilled in the art
The parameter of reaction, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, the present invention is further raising final products performance, perfect and optimization course of reaction, the temperature of the condensation reaction
Preferably 70~90 DEG C, more preferably 72~88 DEG C, more preferably 75~85 DEG C.The time of the condensation reaction is preferably 20~
24h, more preferably 20.5~23.5h, more preferably 21~23h.
The present invention is further improves the effect of reaction, complete and optimization course of reaction, and above-mentioned preparation process specifically can be with
For：
By bis- terephthalate, bromo -1- alkene and acid binding agent are dissolved in the first solvent, then by this solution certain
At a temperature of carry out condensation reaction for a period of time after, filter off acid binding agent, double bond monomer must be contained by being evaporated liquid phase,
The present invention is then in the presence of catalyst, and the double bond containing intermediate that above-mentioned steps are obtained is in the second solvent
After carrying out polymerisation, the polymer of the structure containing bis- terephthalate is obtained.
Selection of the present invention to the catalyst is not particularly limited, with well known to those skilled in the art conventionally used for this
The catalyst of class reaction, those skilled in the art can enter according to practical situations, raw material condition and product requirement
Row selection and adjustment, the present invention further improve final products performance, being advantageous to production should to ensure the effect of Selective Separation
With the catalyst is preferably included in generation Grubbs catalyst, two generation Grubbs catalyst and three generations's Grubbs catalyst
One or more, more preferably including generation Grubbs catalyst, two generation Grubbs catalyst or three generations's Grubbs catalyst, more
Preferably two generation Grubbs catalyst or three generations's Grubbs catalyst.
Selection of the present invention to second solvent is not particularly limited, organic with routine well known to those skilled in the art
Solvent, those skilled in the art can be selected and adjusted according to practical situations, raw material condition and product requirement
Whole, the second solvent of the present invention preferably includes the one or more in dichloromethane, chloroform, dichloroethanes and chloroethanes, more
Preferably dichloromethane, chloroform, dichloroethanes or chloroethanes, more preferably dichloromethane.
The addition of above-mentioned raw materials is not particularly limited the present invention, with the amount of being routinely added to well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to practical condition, raw material condition and product requirement, this
Invent further to improve final products performance, improve and optimize course of reaction, the double bond containing monomer and the catalyst
Mol ratio be preferably (3.0~3.4)：(0.03~0.034), more preferably (3.05~3.35)：(0.03~0.034), more
Preferably (3.1~3.3)：(0.03~0.034), or be (3.0~3.4)：(0.0305~0.0335), or for (3.0~
3.4)：(0.031~0.033), most preferably 3.2：0.032.Mole of second solvent of the present invention and double bond containing monomer
Than being preferably (300~350)：1, more preferably (310~340)：1, more preferably (320~330)：1.
The parameter of the polymerisation is not particularly limited the present invention, with typical polymerization well known to those skilled in the art
The parameter of reaction, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, the present invention is further raising final products performance, perfect and optimization course of reaction, the temperature of the polymerisation
Preferably 30~50 DEG C, more preferably 32~48 DEG C, more preferably 35~45 DEG C.The time of the polymerisation is preferably 6~
8h, more preferably 6.3~7.8h, more preferably 6.5~7.5h.
The present invention is further improves the effect of reaction, complete and optimization course of reaction, and above-mentioned preparation process specifically can be with
For：
The double bond containing monomer that the present invention obtains above-mentioned steps, is dissolved in the second solvent, using catalyst certain
At a temperature of carry out polymerisation, obtain the polymer (height of the structure containing bis- terephthalate of the structure containing bis- terephthalate
Strand), then be precipitated out in methyl alcohol, the high polymer material after drying.
The polymer and alkali for the structure containing bis- terephthalate that the present invention finally obtains above-mentioned steps are in the 3rd solvent
In reaction is hydrolyzed after, then reacted with acidic materials, obtain the organic ligand for MOF.
Selection of the present invention to the alkali is not particularly limited, with well known to those skilled in the art anti-conventionally used for hydrolyzing
The alkali answered, those skilled in the art can be selected according to practical situations, raw material condition and product requirement and
Adjustment, alkali of the present invention preferably include the one or more in potassium hydroxide, sodium hydroxide, ammonium hydroxide and triethylamine, more
Preferably potassium hydroxide, sodium hydroxide, ammonium hydroxide or triethylamine, more preferably potassium hydroxide.
Selection of the present invention to the acidic materials is not particularly limited, with it is well known to those skilled in the art conventionally used for
The acidic materials of hydrolysis, those skilled in the art can want according to practical situations, raw material condition and product
Ask and selected and adjusted, alkali of the present invention preferably includes hydrochloric acid and/or sulfuric acid, more preferably hydrochloric acid or sulfuric acid, more preferably
For hydrochloric acid.
Selection of the present invention to the 3rd solvent is not particularly limited, organic with routine well known to those skilled in the art
Solvent, those skilled in the art can be selected and adjusted according to practical situations, raw material condition and product requirement
Whole, the 3rd solvent of the present invention preferably includes DMF, N, N- diethylformamides, dimethyl sulfoxide (DMSO), N,
One or more in N- dimethyl acetamides and N, N- diethyl acetamide, more preferably DMF, N, N-
Diethylformamide, dimethyl sulfoxide (DMSO), DMA or N, N- diethyl acetamide, more preferably dimethyl are sub-
Sulfone.
The addition of above-mentioned raw materials is not particularly limited the present invention, with the amount of being routinely added to well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to practical condition, raw material condition and product requirement, this
Invent further to improve final products performance, improve and optimization course of reaction, the alkali contain bis- terephthalate with described
The mol ratio of the polymer of structure is preferably (1.0~2.0)：1, more preferably (1.2~1.8)：1, more preferably (1.4~
1.6)：1.The mol ratio of the polymer of 3rd solvent and the structure containing bis- terephthalate be preferably (450~
500)：1, more preferably (460~490)：1, more preferably (470~480)：1.
The parameter of the hydrolysis is not particularly limited the present invention, with routine hydrolysis well known to those skilled in the art
The parameter of reaction, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, the present invention is further raising final products performance, perfect and optimization course of reaction, the temperature of the hydrolysis
Preferably 80~100 DEG C, more preferably 83~98 DEG C, more preferably 85~95 DEG C.The time of the hydrolysis is preferably 10
~12h, more preferably 10.3~11.8h, more preferably 10.5~11.5h.
The addition of the acidic materials is not particularly limited the present invention, anti-with hydrolysis well known to those skilled in the art
Conventional sour addition after answering, those skilled in the art can want according to practical condition, raw material condition and product
Ask and selected and adjusted, the pH value during addition, the i.e. reaction of the acidic materials of the present invention (and acidic materials
PH value when being reacted) it is preferably 1~2, more preferably 1,1.5 or 2.
The parameter of the reaction (reaction for adding acidic materials progress) is not particularly limited the present invention, art technology
Personnel can be selected and adjusted according to practical condition, raw material condition and product requirement.
The present invention is further improves the effect of reaction, complete and optimization course of reaction, and above-mentioned preparation process specifically can be with
For：
The present invention polymer that obtains above-mentioned steps and alkali are dissolved in the 3rd solvent, and hydrolysis is extremely under certain temperature
Untill solution is clarified, then it is acidity that this solution, which is adjusted to pH value, that is, has solid generation, then this solid is passed through into methanol and acetone
Washing repeatedly after, obtain the organic ligand for MOF, i.e., the high polymer material of double bond containing terephthalic acid (TPA) structure.
Specifically, when ester is diethyl terephthalate, the above-mentioned preparation of the present invention is for the organic of MOF
The reaction equation of part, as shown in following formula (1)~formula (3)：
Above-mentioned steps of the present invention provide a kind of organic ligand for MOF and preparation method thereof, and the present invention passes through selection
The organic ligand of specified chemical structure, pass through the agent structure of organic ligand, the length and functional group of side chain so that high score
Sub- organic ligand is independently synthesized, and its aperture can flexibly be adjusted according to its applicable cases after being coordinated as MOF structures
Control, MOF structures are grown by base material of inorganic material compared to traditional, MOF structure growths of the invention are in Porous-Organic base table
Face, and one layer of fine and close MOF crystal film can be formed.
The invention provides a kind of organic ligand MOF, the coordinating metal in the organic ligand MOF is iron；
Organic ligand in the organic ligand MOF is the organic ligand or above-mentioned technical proposal described in above-mentioned technical proposal
Organic ligand prepared by the preparation method described in any one.
The present invention is to the MOF, i.e. the definition of metal-organic framework materials is not particularly limited, with people in the art
Common metal-organic framework materials or MOFs concept known to member.Organic ligand is upper in MOF materials of the present invention
The organic ligand described in technical scheme or the organic ligand of the preparation method preparation described in above-mentioned technical proposal any one are stated, is matched somebody with somebody
Position metal is iron.
The present invention is to the material or the range of choice and optimum principle of structure in the organic ligand MOF, with being previously used for
The range of choice of material or structure in MOF organic ligand and preparation method thereof is consistent with optimum principle, not another herein
One repeats.
The invention provides the seperation film of MOF containing organic ligand a kind of, including basement membrane and it is compounded in the organic of basement membrane side
Part MOF；
The organic ligand MOF is the organic ligand MOF described in above-mentioned technical proposal.
The present invention is and preceding to organic ligand MOF material in the seperation film or the range of choice of structure and optimum principle
State that the range of choice of material in organic ligand MOF or structure is consistent with optimum principle, and this is no longer going to repeat them.
Selection of the present invention to the basement membrane is not particularly limited, and is used with conventional seperation film well known to those skilled in the art
Base film, those skilled in the art can be selected according to practical condition, raw material condition and product requirement and
Adjustment, basement membrane of the present invention is preferably that finger-like pore basement membrane or spongy hole basement membrane, the material of the basement membrane preferably include bromination
One or more in polyphenylene oxide, polybenzimidazoles, polyethersulfone ketone and polyether-ether-ketone, more preferably brominated polyphenylether, polyphenyl are simultaneously
Imidazoles, polyethersulfone ketone or polyether-ether-ketone.The parameter of the basement membrane is not particularly limited the present invention, ripe with those skilled in the art
The parameter for the conventional seperation film base film known, those skilled in the art can be according to practical condition, raw material conditions
And product requirement is selected and adjusted, the thickness of basement membrane of the present invention is preferably 90~150 μm, more preferably 100~
140 μm, more preferably 110~130 μm, more preferably 115~125 μm.
The compound definition is not particularly limited the present invention, determines so that routine well known to those skilled in the art is compound
Justice, those skilled in the art can be selected and adjusted according to practical condition, raw material condition and product requirement,
It is of the present invention it is compound be preferably growth, key connect, grafting, deposition, cladding and half coat in one or more, more preferably make a living
Long, key connects or grafting, more preferably grows, is specifically as follows fine and close growth, i.e., the described fine and close growth of separation membrane surface is organic
Part MOF.
The seperation film of the MOF of the present invention containing organic ligand can consider with multi-lamellar Rotating fields, including base membrane layer
With the organic ligand MOF layers for being compounded in the side surface of base membrane layer one.Organic ligand MOF layers (MOF separating layers) of the present invention
The preferably fine and close MOF layers of pbz polymer organic ligand.
The performance parameter of the seperation film of the MOF containing organic ligand is not particularly limited the present invention, people in the art
After member is prepared according to before-mentioned products, method or subsequent processes, you can specific performance parameter is obtained, but can be according to reality
Applicable cases, raw material condition and product requirement are selected and adjusted, and the present invention enters one to ensure the effect of Selective Separation
Step improves separation film properties, is advantageous to production application, and the thickness of the seperation film is 150~200 μm, and more preferably 160~190
μm, more preferably 170~180 μm.
The aperture sieve of MOF layers is made full use of in the seperation film of the MOF layers of implication macromolecule organic ligand provided by the invention
It is allocated as carrying out ion isolation, because its organic ligand is chained up by macromolecular chain, thus MOF ducts is served into one
The effect of step control, it is that this film provides extensively in ion isolation, the particularly application in the separation of liquid phase multivalent state ion selectivity
Wealthy prospect.
Present invention also offers a kind of preparation method of the seperation film of MOF containing organic ligand, comprise the following steps：
A) basement membrane is put into, organic ligand, mineralizer, soluble ferric iron salt and organic solvent mixed liquor in, reacted,
Obtain the seperation film of the MOF containing organic ligand；
The organic ligand is described in organic ligand or above-mentioned technical proposal any one described in above-mentioned technical proposal
Organic ligand prepared by preparation method.
The present invention contains to the range of choice and optimum principle of material or structure in the preparation method of the seperation film with foregoing
The range of choice of material or structure in organic ligand MOF seperation film is consistent with optimum principle, and this is no longer going to repeat them.
Selection of the present invention to the basement membrane is not particularly limited, and is used with conventional seperation film well known to those skilled in the art
Base film, those skilled in the art can be selected according to practical condition, raw material condition and product requirement and
Adjustment, basement membrane of the present invention is preferably porous basement membrane, more preferably finger-like pore basement membrane or spongy hole basement membrane；The basement membrane
Material preferably includes the one or more in brominated polyphenylether, polybenzimidazoles, polyethersulfone ketone and polyether-ether-ketone, more preferably bromine
Change polyphenylene oxide, polybenzimidazoles, polyethersulfone ketone or polyether-ether-ketone.
Selection of the present invention to the mineralizer is not particularly limited, with preparation MOF materials well known to those skilled in the art
The mineralizer of material, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, mineralizer of the present invention preferably includes the one or more in formic acid, hydrochloric acid and benzoic acid, more preferably first
Acid, hydrochloric acid or benzoic acid, most preferably formic acid.
Selection of the present invention to the soluble ferric iron salt is not particularly limited, with solubility well known to those skilled in the art
Molysite, those skilled in the art can be selected and adjusted according to practical condition, raw material condition and product requirement
Whole, soluble ferric iron salt of the present invention preferably includes the one or more in ferric trichloride, ferric sulfate and ferric nitrate, more preferably
Ferric trichloride, ferric sulfate or ferric nitrate, most preferably ferric trichloride.
Selection of the present invention to the organic solvent is not particularly limited, with such reaction well known to those skilled in the art
Organic solvent, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, organic solvent of the present invention preferably includes N, N- diethylformamides, DMF, N, N- diformazans
Yl acetamide, N, the one or more in N- diethyl acetamides and 1-METHYLPYRROLIDONE, more preferably N, N- diethyl first
Acid amides, DMF, DMA, N, N- diethyl acetamides or 1-METHYLPYRROLIDONE, it is more excellent
Elect N, N- diethylformamides as.
The addition of the mineralizer is not particularly limited the present invention, with such reaction well known to those skilled in the art
Mineralizer addition, those skilled in the art can be according to practical condition, raw material condition and product requirement
Selected and adjusted, the mass ratio of mineralizer of the present invention and the organic ligand is preferably (70~90)：1, more preferably
For (73~88)：1, more preferably (75~85)：1.
The addition of the soluble ferric iron salt is not particularly limited the present invention, with well known to those skilled in the art such
The addition of the soluble ferric iron salt of reaction, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and adjusted, and the mol ratio of organic ligand of the present invention and the soluble ferric iron salt is preferably (0.02
~0.04)：(0.02~0.04), more preferably (0.024~0.036)：(0.02~0.04), more preferably (0.028~
0.032)：(0.02~0.04), or be (0.022~0.038)：(0.02~0.04), or be (0.024~0.036)：
(0.02~0.04), or be (0.026~0.034)：(0.02~0.04).
The addition of the organic solvent is not particularly limited the present invention, with well known to those skilled in the art such anti-
The addition for the organic solvent answered, those skilled in the art can be according to practical condition, raw material condition and products
It is required that being selected and being adjusted, the mass ratio of organic solvent of the present invention and the organic ligand is (110~130)：1, more
Preferably (113~127)：1, more preferably (115~125)：1.
The parameter of the reaction is not particularly limited the present invention, with the ginseng of such reaction well known to those skilled in the art
Number, those skilled in the art can be selected and adjusted according to practical condition, raw material condition and product requirement,
The temperature of reaction of the present invention is preferably 110~130 DEG C, more preferably 117~127 DEG C, more preferably 115~125 DEG C；Institute
The time for stating reaction is preferably 36~48h, more preferably 38~46h, more preferably 40~44h.Reaction of the present invention is preferred
For solvent thermal reaction.
The present invention is further improves the effect of reaction, complete and optimization course of reaction, and above-mentioned preparation process specifically can be with
For：
Double bond containing terephthalic acid (TPA) structuring polymer obtained above, soluble trivalent iron salt and mineralizer ultrasound is molten
Solution obtains mixed liquor in the 4th solvent, is put into reactor, then porous basement membrane is placed in reactor, at a certain temperature,
Solvent thermal reaction is carried out, obtains the iron-based MOF separating layer membranes of the seperation film of the MOF containing organic ligand, i.e. pbz polymer organic ligand.
Specifically, when ester is diethyl terephthalate, the above-mentioned MOF of iron-based containing organic ligand of the present invention
Seperation film in, prepare organic ligand iron-based MOF reaction equation, be shown below：
Above-mentioned steps of the present invention provide a kind of organic ligand for MOF and preparation method thereof, organic ligand MOF, one
Kind MOF containing organic ligand seperation film and preparation method thereof.From the regulation and control of MOF aperture sizes, have selected specifically has the present invention
The chemical constitution of machine part, with reference to specific coordinating metal, in conjunction with the influence of MOF growing environments and matrix structure, to ion
Selective Separation is studied, and accurate regulation and control MOF frame sizes, is allocated as based on aperture sieve for realizing the selectivity to ion
Separation, so as to preferably realize in multivalent state solion system, it is selectively adsorbing and separating.
MOF ion selectivity seperation films based on macromolecule organic ligand prepared by the present invention, it is creative with macromolecule
Chain substitution organic molecule is introduced into MOF frame structures as organic ligand, regulates and controls the configuration of skeleton, so as to complete aperture screening
Purpose, and by self-growing method by MOF introduce Porous-Organic base table layer, can not only lift the selectivity of film but also can increase
Add ionic flux.The present invention is to be leading from new MOF materials are grown, by MOF in porous organic polymer material surface
The accuracy controlling of framework pore size, and then obtain the MOF tunic materials for Anion separation process more efficiently, stable
Material, has not only expanded the species of MOF materials, is the selectivity that MOF materials can be from application realization to solution system intermediate ion
Separation, it can more complete it and provide theory and technology support to efficiently separating for different valence state anion, and there is important science
Meaning and it is widely applied prospect.The present invention for MOF select seperation film precision construct and its applied to seawater concentrate salt manufacturing and
Nitration mixture is reclaimed with separating, and single multi- valency anion selectivity separation field provides theoretical foundation and practical basis.
Test result indicates that the MOF base seperation films of pbz polymer organic ligand provided by the invention, this film utilizes MOF's
Aperture sieve is allocated as being used in progress one in solution system system/bivalent ions separation, its Na+With Mg2+Separation rate is 19.12, and
Na+Flux be 100.57*10-10mol/cm2/s。
In order to further illustrate the present invention, with reference to embodiments to a kind of organic ligand provided by the invention and its preparation
Method, organic ligand MOF, a kind of seperation film and preparation method thereof are described in detail, but it is to be understood that these embodiments are
Implemented under premised on technical solution of the present invention, give detailed embodiment and specific operating process, simply
To further illustrate the features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention
It is also not necessarily limited to following embodiments.
Embodiment 1
The preparation of the macromolecule organic ligand of 1.1 structures containing terephthalic acid (TPA)
By 3.2mmol diethyl terephthalate, the 12.0mmol bromo- 1- alkene of 7- and 16.0mmol potassium carbonate dissolve
In 24ml DMFs, then potassium carbonate is filtered off after this solution is reacted into 24h at 90 DEG C, be evaporated N, N- bis-
NMF obtains monomer (1).
By 0.3mmol monomer (1) and 0.032mmol two generation Grubbs catalyst dissolutions in 6ml dichloromethane, this
Solution reacts 8h at 40 DEG C, and it is precipitated out in 30ml methanol, and drying solid obtains polymer (2).
0.3mmol polymer (2) and 4.5mmol potassium hydroxide are dissolved in 10ml dimethyl sulfoxides, it is anti-at 90 DEG C
12h is answered untill solution is clarified, then it is 1 that 2MHCl, which is added dropwise, to solution ph, then the solid of generation is passed through into 30ml methanol and 30ml
The washing repeatedly of acetone obtains the polymer (3) of double bond containing terephthalic acid (TPA), i.e. organic ligand.
The preparation of the iron-based MOF separating layer membranes of 1.2 macromolecule organic ligands
By 0.136mmol polymer (3) and 0.111mmol ferric trichlorides and 2ml formic acid ultrasonic dissolution in 4ml N, N- bis-
In ethyl-formamide, then finger-like pore basement membrane is placed in one, reacts 48h at 130 DEG C, obtain the iron-based of pbz polymer organic ligand
MOF separating layer membranes.
Referring to Fig. 1, the preparation process flow that Fig. 1 is the iron-based MOF of pbz polymer organic ligand provided by the invention is illustrated
Figure.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 1 characterize.
Referring to Fig. 2, Fig. 2 is the table of the iron-based MOF separating layer membranes of pbz polymer organic ligand prepared by the embodiment of the present invention 1
Surface scan electron microscope.
As shown in Figure 2, due to using the functional group of membrane surface linked iron ion again be coordinated link macromolecule it is organic
Part, therefore one layer of fine and close MOF layer is grown in membrane surface, and due to also show this MOF's in MOF crystallographic figure
Regular octahedron structure.As can be seen here, one layer of fine and close MOF crystal film can be grown in Porous-Organic primary surface.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 1 carry out performance detection.
Using macromolecule organic ligand manufactured in the present embodiment iron-based MOF separating layer membranes using electrodialysis plant to it is single,
Polyvalent cation is separated, and sodium ion and magnesium ion are contained in separation system, and separating experiment result is the flux of sodium ion
For 80.51*10-10mol/cm2/ s, the flux of magnesium ion is 4.56*10-10mol/cm2/ s, then separation is 17.63, so
Film shows preferable list, polyvalent cation separating property.
Embodiment 2
The preparation of the macromolecule organic ligand of 2.1 structures containing terephthalic acid (TPA)
By 3.2mmol diethyl terephthalate, the 12.8mmol bromo- 1- alkene of 8- and 16.0mmol potassium carbonate dissolve
In 24ml DMFs, then potassium carbonate is filtered off after this solution is reacted into 26h at 80 DEG C, be evaporated N, N- bis-
NMF obtains monomer (1).
By 0.3mmol monomer (1) and 0.034mmol generation Grubbs catalyst dissolutions in 6ml dichloromethane, this
Solution reacts 7h at 35 DEG C, and it is precipitated out in 30ml methanol, and drying solid obtains polymer (2).
0.3mmol polymer (2) and 4.5mmol potassium hydroxide are dissolved in 10ml dimethyl sulfoxides, it is anti-at 100 DEG C
10h is answered untill solution is clarified, then be added dropwise 2M HCl to solution ph be 1, then by the solid of generation by 30ml methanol and
The washing repeatedly of 30ml acetone obtains the polymer (3) of double bond containing terephthalic acid (TPA).
The preparation of the iron-based MOF separating layer membranes of 2.2 macromolecule organic ligands
By 0.101mmol polymer (3) and 0.093mmol ferric trichlorides and 2ml formic acid ultrasonic dissolution in 4ml N, N- bis-
In ethyl-formamide, then finger-like pore basement membrane is placed in one, reacts 48h at 120 DEG C, obtain the iron-based of pbz polymer organic ligand
MOF separating layer membranes.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 2 carry out performance detection.
Using macromolecule organic ligand manufactured in the present embodiment iron-based MOF separating layer membranes using electrodialysis plant to it is single,
Polyvalent cation is separated, and sodium ion and magnesium ion are contained in separation system, and separating experiment result is the flux of sodium ion
For 80.61*10-10mol/cm2/ s, the flux of magnesium ion is 4.51*10-10mol/cm2/ s, then separation is 17.86, so
Film shows preferable list, polyvalent cation separating property.
Embodiment 3
The preparation of the macromolecule organic ligand of 3.1 structures containing terephthalic acid (TPA)
By 3.4mmol terephthalic acid (TPA) dipropyl, the 13.0mmol bromo- 1- alkene of 9- and 16.0mmol potassium carbonate dissolve
In 24ml DMFs, then potassium carbonate is filtered off after this solution is reacted into 20h at 70 DEG C, be evaporated N, N- bis-
NMF obtains monomer (1).
By 0.3mmol monomer (1) and 0.034mmol two generation Grubbs catalyst dissolutions in 6ml dichloromethane, this
Solution reacts 6h at 30 DEG C, and it is precipitated out in 30ml methanol, and drying solid obtains polymer (2).
0.3mmol polymer (2) and 4.5mmol potassium hydroxide are dissolved in 10ml dimethyl sulfoxides, it is anti-at 80 DEG C
11h is answered untill solution is clarified, then be added dropwise 2M HCl to solution ph be 1, then by the solid of generation by 30ml methanol and
The washing repeatedly of 30ml acetone obtains the polymer (3) of double bond containing terephthalic acid (TPA).
The preparation of the iron-based MOF separating layer membranes of 3.2 macromolecule organic ligands
By 0.145mmol polymer (3) and 0.074mmol ferric trichlorides and 2ml formic acid ultrasonic dissolution in 4ml N, N- bis-
In ethyl-formamide, then finger-like pore basement membrane is placed in one, reacts 40h at 110 DEG C, obtain the iron-based of pbz polymer organic ligand
MOF separating layer membranes.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 3 carry out performance detection.
Using macromolecule organic ligand manufactured in the present embodiment iron-based MOF separating layer membranes using electrodialysis plant to it is single,
Polyvalent cation is separated, and sodium ion and magnesium ion are contained in separation system, and separating experiment result is the flux of sodium ion
For 88.75*10-10mol/cm2/ s, the flux of magnesium ion is 4.78*10-10mol/cm2/ s, then separation is 18.56, so
Film shows preferable list, polyvalent cation separating property.
Embodiment 4
The preparation of the macromolecule organic ligand of 4.1 structures containing terephthalic acid (TPA)
By 3.2mmol terephthalic acid (TPA) dipropyl, the 12.8mmol bromo- 1- alkene of 9- and 16.0mmol potassium carbonate dissolve
In 24ml DMFs, then potassium carbonate is filtered off after this solution is reacted into 24h at 90 DEG C, be evaporated N, N- bis-
NMF obtains monomer (1).
By 0.3mmol monomer (1) and 0.032mmol two generation Grubbs catalyst dissolutions in 6ml dichloromethane, this
Solution reacts 8h at 45 DEG C, and it is precipitated out in 30ml methanol, and drying solid obtains polymer (2).
0.3mmol polymer (2) and 4.5mmol potassium hydroxide are dissolved in 10ml dimethyl sulfoxides, it is anti-at 90 DEG C
10h is answered untill solution is clarified, then it is 1 that 2MHCl, which is added dropwise, to solution ph, then the solid of generation is passed through into 30ml methanol and 30ml
The washing repeatedly of acetone obtains the polymer (3) of double bond containing terephthalic acid (TPA).
The preparation of the iron-based MOF separating layer membranes of 4.2 macromolecule organic ligands
By 0.109mmol polymer (3) and 0.111mmol ferric trichlorides and 2ml formic acid ultrasonic dissolution in 4ml N, N- bis-
In ethyl-formamide, then finger-like pore basement membrane is placed in one, reacts 48h at 130 DEG C, obtain the iron-based of pbz polymer organic ligand
MOF separating layer membranes.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 4 carry out performance detection.
Using macromolecule organic ligand manufactured in the present embodiment iron-based MOF separating layer membranes using electrodialysis plant to it is single,
Polyvalent cation is separated, and sodium ion and magnesium ion are contained in separation system, and separating experiment result is the flux of sodium ion
For 90.68*10-10mol/cm2/ s, the flux of magnesium ion is 4.84*10-10mol/cm2/ s, then separation is 18.72, so
Film shows preferable list, polyvalent cation separating property.
Embodiment 5
The preparation of the macromolecule organic ligand of 5.1 structures containing terephthalic acid (TPA)
By 3.3mmol diethyl terephthalate, the 12.6mmol bromo- 1- alkene of 7- and 16.0mmol potassium carbonate dissolve
In 24ml DMFs, then potassium carbonate is filtered off after this solution is reacted into 22h at 80 DEG C, be evaporated N, N- bis-
NMF obtains monomer (1).
By 0.3mmol monomer (1) and 0.03mmol generation Grubbs catalyst dissolutions in 6ml dichloromethane, this
Solution reacts 8h at 35 DEG C, and it is precipitated out in 30ml methanol, and drying solid obtains polymer (2).
0.3mmol polymer (2) and 4.5mmol potassium hydroxide are dissolved in 10ml dimethyl sulfoxides, it is anti-at 80 DEG C
12h is answered untill solution is clarified, then it is 1 that 2MHCl, which is added dropwise, to solution ph, then the solid of generation is passed through into 30ml methanol and 30ml
The washing repeatedly of acetone obtains the polymer (3) of double bond containing terephthalic acid (TPA).
The preparation of the iron-based MOF separating layer membranes of 5.2 macromolecule organic ligands
By 0.091mmol polymer (3) and 0.148mmol ferric trichlorides and 2ml formic acid ultrasonic dissolution in 4ml N, N- bis-
In ethyl-formamide, then finger-like pore basement membrane is placed in one, reacts 36h at 115 DEG C, obtain the iron-based of pbz polymer organic ligand
MOF separating layer membranes.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 5 carry out performance detection.
Using macromolecule organic ligand manufactured in the present embodiment iron-based MOF separating layer membranes using electrodialysis plant to it is single,
Polyvalent cation is separated, and sodium ion and magnesium ion are contained in separation system, and separating experiment result is the flux of sodium ion
For 100.57*10-10mol/cm2/ s, the flux of magnesium ion is 5.26*10-10mol/cm2/ s, then separation is 19.12, so
Film shows preferable list, polyvalent cation separating property.
Embodiment 6
The preparation of the macromolecule organic ligand of 6.1 structures containing terephthalic acid (TPA)
By 3.2mmol diethyl terephthalate, the 12.8mmol bromo- 1- alkene of 8- and 16.0mmol potassium carbonate dissolve
In 24ml DMFs, then potassium carbonate is filtered off after this solution is reacted into 24h at 70 DEG C, be evaporated N, N- bis-
NMF obtains monomer (1).
By 0.3mmol monomer (1) and 0.032mmol two generation Grubbs catalyst dissolutions in 6ml dichloromethane, this
Solution reacts 6h at 50 DEG C, and it is precipitated out in 30ml methanol, and drying solid obtains polymer (2).
0.3mmol polymer (2) and 4.5mmol potassium hydroxide are dissolved in 10ml dimethyl sulfoxides, it is anti-at 100 DEG C
10h is answered untill solution is clarified, then be added dropwise 2M HCl to solution ph be 1, then by the solid of generation by 30ml methanol and
The washing repeatedly of 30ml acetone obtains the polymer (3) of double bond containing terephthalic acid (TPA).
The preparation of the iron-based MOF separating layer membranes of 6.2 macromolecule organic ligands
By 0.121mmol polymer (3) and 0.148mmol ferric trichlorides and 2ml formic acid ultrasonic dissolution in 4ml N, N- bis-
In ethyl-formamide, then finger-like pore basement membrane is placed in one, reacts 36h at 130 DEG C, obtain the iron-based of pbz polymer organic ligand
MOF separating layer membranes.
The iron-based MOF separating layer membranes of the pbz polymer organic ligand prepared to the embodiment of the present invention 6 carry out performance detection.
Using macromolecule organic ligand manufactured in the present embodiment iron-based MOF separating layer membranes using electrodialysis plant to it is single,
Polyvalent cation is separated, and sodium ion and magnesium ion are contained in separation system, and separating experiment result is the flux of sodium ion
For 82.08*10-10mol/cm2/ s, the flux of magnesium ion is 4.53*10-10mol/cm2/ s, then separation is 18.12, so
Film shows preferable list, polyvalent cation separating property.
Above to a kind of organic ligand for MOF provided by the invention and preparation method thereof, organic ligand MOF, one kind
Seperation film of the MOF containing organic ligand and preparation method thereof is described in detail, and specific case used herein is to this hair
Bright principle and embodiment is set forth, the explanation of above example be only intended to help the method for understanding the present invention and its
Core concept, including best mode, and also cause any person skilled in the art to put into practice the present invention, including manufacture
With use any device or system, and the method for any combination of implementation.It should be pointed out that the ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and
Modification is also fallen into the protection domain of the claims in the present invention.The scope of patent protection of the present invention is defined by the claims,
And may include those skilled in the art it is conceivable that other embodiment.It is not different from weighing if these other embodiments have
Profit requires the structural element of character express, or if they include character express being equal without essence difference with claim
Structural element, then these other embodiments should also include within the scope of the claims.
Claims (10)
1. a kind of organic ligand for MOF, it is characterised in that the organic ligand has the structure as shown in formula (I)；
Wherein, x is that 7~10, n is 20~30.
2. the preparation method of a kind of organic ligand for MOF, it is characterised in that comprise the following steps：
1) by bis- terephthalate, after bromo -1- alkene, acid binding agent and the mixing of the first solvent, condensation reaction is carried out, is contained
The monomer of double bond；
2) in the presence of catalyst, the double bond containing intermediate that above-mentioned steps are obtained carries out polymerisation in the second solvent
Afterwards, the polymer of the structure containing bis- terephthalate is obtained；
3) polymer for the structure containing bis- terephthalate for obtaining above-mentioned steps and alkali are hydrolyzed instead in the 3rd solvent
Ying Hou, then reacted with acidic materials, obtain the organic ligand for MOF.
3. preparation method according to claim 2, it is characterised in that the ester includes terephthalic acid (TPA) two
One or more in ethyl ester, terephthalic acid (TPA) dipropyl and dibutyl terephthalate；
Bromo -1- the alkene is included in the bromo- 1- heptene of 7-, the bromo- 1- octenes of 8-, the bromo- 1- nonenes of 9- and the bromo- 1- decene of 10-
It is one or more；
The acid binding agent includes the one or more in potassium carbonate, triethylamine, pyridine and diisopropylethylamine；
First solvent includes DMF, N, N- diethylformamides, DMA, N, N- bis-
One or more in ethyl acetamide and 1-METHYLPYRROLIDONE；
The bis- terephthalate and the mol ratio of bromo -1- alkene are (3.0~3.4)：(12.0~13.6)；
The mol ratio of the bis- terephthalate and acid binding agent is (0.1~0.5)：1；
The mol ratio of first solvent and bis- terephthalate are (90~100)：1；
The temperature of the condensation reaction is 70~90 DEG C；The time of the condensation reaction is 20~24h.
4. preparation method according to claim 2, it is characterised in that the catalyst include generation Grubbs catalyst,
One or more in two generation Grubbs catalyst and three generations's Grubbs catalyst；
Second solvent includes the one or more in dichloromethane, chloroform, dichloroethanes and chloroethanes；
The mol ratio of the double bond containing monomer and the catalyst is (3.0~3.4)：(0.03~0.034)；
The mol ratio of second solvent and double bond containing monomer is (300~350)：1；
The temperature of the polymerisation is 30~50 DEG C；The time of the polymerisation is 6~8h.
5. preparation method according to claim 2, it is characterised in that the alkali includes potassium hydroxide, sodium hydroxide, hydrogen-oxygen
Change the one or more in ammonium and triethylamine；
The acidic materials include hydrochloric acid and/or sulfuric acid；
3rd solvent includes DMF, N, N- diethylformamides, dimethyl sulfoxide (DMSO), N, N- dimethyl second
One or more in acid amides and N, N- diethyl acetamide；
The mol ratio of the alkali and the polymer of the structure containing bis- terephthalate is (1.0~2.0)：1；
PH value when described and acidic materials are reacted is 1~2；
The mol ratio of 3rd solvent and the polymer of the structure containing bis- terephthalate is (450~500)：1；
The temperature of the hydrolysis is 80~100 DEG C；The time of the hydrolysis is 10~12h.
6. a kind of organic ligand MOF, it is characterised in that the coordinating metal in the organic ligand MOF is iron；
Organic ligand in the organic ligand MOF is any one for the organic ligand described in claim 1 or claim 2~5
Organic ligand prepared by the preparation method described in.
7. a kind of MOF containing organic ligand seperation film, it is characterised in that including basement membrane and the organic ligand for being compounded in basement membrane side
MOF；
The organic ligand MOF is the organic ligand MOF described in claim 6.
8. seperation film according to claim 7, it is characterised in that the fine and close growth of the separation membrane surface has organic ligand
MOF；
The thickness of the seperation film is 150~200 μm；
The material of the basement membrane includes the one or more in brominated polyphenylether, polybenzimidazoles, polyethersulfone ketone and polyether-ether-ketone；
The basement membrane is finger-like pore basement membrane or spongy hole basement membrane；
The thickness of the basement membrane is 90~150 μm.
9. the preparation method of a kind of MOF containing organic ligand seperation film, it is characterised in that comprise the following steps：
A) basement membrane is put into, organic ligand, mineralizer, soluble ferric iron salt and organic solvent mixed liquor in, reacted, obtained
The seperation film of the MOF containing organic ligand；
The organic ligand is the organic ligand described in claim 1 or the preparation method described in claim 2~5 any one
The organic ligand of preparation.
10. preparation method according to claim 9, it is characterised in that the mineralizer includes formic acid, hydrochloric acid and benzoic acid
In one or more；
The soluble ferric iron salt includes the one or more in ferric trichloride, ferric sulfate and ferric nitrate；
The organic solvent includes N, N- diethylformamides, DMF, DMA, N, N- bis-
One or more in ethyl acetamide and 1-METHYLPYRROLIDONE；
The mass ratio of the mineralizer and the organic ligand is (70~90)：1；
The organic ligand and the mol ratio of the soluble ferric iron salt are (0.02~0.04)：(0.02~0.04)；
The mass ratio of the organic solvent and the organic ligand is (110~130)：1；
The temperature of the reaction is 110~130 DEG C；The time of the reaction is 36~48h.
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