CN107936261A - A kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth - Google Patents
A kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth Download PDFInfo
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- CN107936261A CN107936261A CN201711254871.6A CN201711254871A CN107936261A CN 107936261 A CN107936261 A CN 107936261A CN 201711254871 A CN201711254871 A CN 201711254871A CN 107936261 A CN107936261 A CN 107936261A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The present invention provides a kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth.The two-dimentional stannous chloride nano crystal material for playing template and catalytic action is directly prepared in copper foil substrate using solid liquid interface fast preparation method, select 1,3,5 tribromo-benzenes and p-phenylenediamine are monomer molecule, polymerisation directly occurs in the two-dimentional stannous chloride nanocrystal surface as catalyst, grows two-dimentional organic polymer.The method disclosed in the present prepares two-dimentional organic polymer using surface-catalyzed reactions by specific monomer, has widened two-dimentional organic polymer reaction type.
Description
Technical field
The present invention relates to two-dimentional organic polymer material preparation field, more particularly to a kind of two dimensional crystal surface catalysis two dimension
The method of organic polymer growth.
Background technology
Two-dimentional organic polymer refers to be covalently attached by Orqanics Monomer and all has in 2 orthogonal directions periodically
Network structure.Due to its special structure, two-dimentional organic polymer has in gas absorption, material screening and device etc.
It is widely applied prospect.Polymerization for monomer molecule in solution, the monomer being related at present mainly include machine boric acid, organic
Boric acid/catechol, aniline/benzaldehyde and benzene cyanogen etc., while the reaction being related to is three polycondensation of boric acid, boron ester condensation, aldehyde amine
Condensation and cyano group trimerization reaction etc..2005,Report is anti-using boric acid trimerization and boron ester condensation first with Yaghi et al.
Two kinds of porous two-dimentional organic polymers should be constructed, they are can obtain aperture in 120 DEG C of reactions as raw material to benzene hypoboric acid
The two-dimentional organic polymer aggregation of 1.5nm, aperture has been obtained further through to benzene hypoboric acid and hexahydroxy triphenylene reactive polymeric
For the two-dimentional organic polymer aggregation of 2.7nm, the sample being prepared also has very high specific surface area, it is measured flat
Equal aperture and the aperture designed are very close.2008, Kuhn and Thomas etc. utilize cyano group trimerization reaction, with to benzene dicyan,
4,4 '-biphenyl dicyan and three benzonitrile base benzene etc. have obtained a variety of two-dimentional organic polymers for raw material.2011, the king of Lanzhou University
It is raw material to utilize 1,3,5- tri- aldehyde radical benzene and p-phenylenediamine for teacher etc., obtains the two-dimentional organic polymer that design radial is 1.8nm
Thing, but palladium is compound with obtained two-dimentional organic polymer, the catalyst of supported palladium is obtained, to Suzuki-Miyaura
Catalyzed coupling reaction has extraordinary catalytic performance.
The preparation of two-dimentional organic polymer can also be completed in the surface of solids.The surface of solids not only provides two-dimentional organic polymer
The template of thing polymerization, and promote monomer that stratiform, i.e. single or multiple lift two dimension organic polymer are more readily formed in the course of the polymerization process
Thing, rather than there is irregular pattern as the two-dimentional organic polymer aggregation being prepared in the solution.2008,
Abel etc. make use of on Ag (111) face reports that identical boric acid condensation and boron ester condensation reaction are obtained with Yaghi first
Two-dimentional organic polymer, the results showed that the two-dimentional organic polymer that this method obtains has very regular surface texture.2009,
For the sub- benzene of the ring six between hexaiodo such as Bieri and Fasel as raw material, silver be used as coupling agent, and has obtained with some defects but micro-
The two-dimentional organic polymer of compound with regular structure in sight, which make use of the response function of substrate, but substrate is not used as being catalyzed
Agent, but it is used as reactant to participate in coupling reaction.2011, Dichtel etc. utilized boron ester condensation reaction on single-layer graphene
The two-dimentional organic polymer thin film with ordered structure is obtained.Similar with the work of Yaghi etc., they have used boric acid and six
Hydroxyl triphenylene is raw material, is ultrasonically treated in organic solvent together with the substrate containing graphene, can obtain having regular
Surface texture.They further assemble hexagonal bore using pyrrole hypoboric acid and hexahydroxy triphenylene in graphene surface
The two-dimentional organic polymer of 3.2nm, and square aperture is constructed as the two of 2.3nm using phthalocyanine derivates and benzene hypoboric acid
Tie up organic polymer.The film thickness that this method obtains is 20-400nm.2013, chemistry institute of Chinese Academy of Sciences teacher Wan Lijun etc.
Using three aminophenyl benzene and terephthalaldehyde, and 1,3,5- benzene trioxins carry out certainly with p-phenylenediamine on high starch breeding surface
Assembling, has obtained having two-dimentional organic polymer of a small amount of defect area more than 200nm × 200nm.
More than preparation of the achievement being operated in terms of two-dimentional organic polymer for two-dimentional organic polymer and further
Using having established very good basis.Two-dimentional organic polymer is limited however, there is also some problems for current work
Species, growth and the application of thing.First, the chemical reaction occurred at present is limited to be easy to the reaction carried out, and is urged for needs
The reaction that agent auxiliary carries out seldom is related to；Second, for current substrate, it is limited primarily to gold, silver, copper or graphene
Deng these substrates primarily serve template action for the chemical reaction between monomer, without playing catalytic action, it is impossible to promote single
Polymerization between body；3rd, the two-dimentional organic polymer obtained at present is particularly the two-dimentional organic polymer ruler obtained in substrate
It is very little still smaller for practical applications, it is necessary to develop the method for more readily promoting monomer polymerization.In view of the above problems, need
Develop the approach that two-dimentional organic polymer is prepared in the substrate with catalysis.This is because first, catalyst can urge
The reaction of change is more extensive than monomer system used in report now, so as to provide more selections, its functional group's system is richer
Richness, it is highly beneficial for widening its application range；Second, monomer can be rapidly promoted in table in the reaction that catalyst surface carries out
The polymerization in face, is conducive to grow the two-dimentional organic polymer thin film of large area.Two-dimentional copper-based nano crystal is that growth two dimension has
The most suitable candidate's substrate of machine polymer, because copper-based nano crystal, including metallic copper, cupric oxide, cuprous oxide, copper chloride
There is catalytic action to a variety of chemical reactions with stannous chloride etc..Wherein stannous chloride catalyzed organic chemical reaction is very extensive, bag
It is azo compounds to include Henry reactions (aldehyde is coupled with nitroparaffins), alkene and azo molecules cyclisation coupling, amine compound coupling
Thing and amino-compound and halogenated compound coupling equimolecular between coupling reaction, these it has been reported that catalytic reaction for design
Two-dimentional organic polymer monomer has directive significance, and can widen two-dimentional organic polymer reaction type significantly.
The content of the invention
The method for proposing a kind of growth of two dimensional crystal surface catalysis two dimension organic polymer, using surface-catalyzed reactions by
Monomer prepares two-dimentional organic polymer, has widened two-dimentional organic polymer reaction type.
The present invention adopts the following technical scheme that：
A kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth, includes the following steps：
(1) directly prepared in copper foil substrate using solid liquid interface fast preparation method and play the two of template and catalytic action
Stannous chloride nano crystal material is tieed up, is easy to the solvent as copper chloride solution such as ethanol of volatilization, ferric trichloride is as regulation and control
Agent, is coated on copper foil surface by copper chloride (containing iron ion) solution, controls the additive amount of copper chloride solution, be placed in a certain range of
At a temperature of make rapid reaction, generate two-dimentional stannous chloride nano crystal material；
(2) it be monomer molecule to select 1,3,5- tribromo-benzenes and p-phenylenediamine, at a certain temperature, in certain time, necessarily
In solvent, under inert gas shielding, polymerisation directly occurs in the two-dimentional stannous chloride nanocrystal surface as catalyst,
The two-dimentional organic polymer of growth.
The scope of ferric trichloride additive amount is dense for copper chloride solution mole in solid liquid interface fast preparation method in step (1)
The 0.01%-10% of degree.
Copper chloride solution is a variety of suitable for drop coating, bar coating method, spraying etc. coated on copper foil surface method in step (1)
Method for solution coating, preferably bar coating method.
Make rapid reaction in step (1) at a temperature of a certain range, preferable temperature is 0~80 DEG C, when preferable
Between be 0.1~600s.
Reaction temperature is 50~380 DEG C in step (2).
The reaction time is 3h~72h in step (2).
Solvent for use is the organic solvent such as DMF and DMSO in step (2).
Inert gas is the inert gas such as nitrogen and argon gas in step (2).
The present invention has following advantage：
(1) the stannous chloride nano-sheet crystals material prepared by the present invention has the advantages that thickness is homogeneous, morphology controllable,
It is the most suitable candidate's substrate of the two-dimentional organic polymer of growth, possesses that preparation is simple, cost is low, is easy to industrialized mass production
The characteristics of.
(2) reaction carried out in catalyst surface can rapidly promote polymerization of the monomer on surface, be conducive to grow big
The two-dimentional organic polymer thin film of area.
Brief description of the drawings
Fig. 1 is the TEM details in a play not acted out on stage, but told through dialogues figure and transmission electron diffraction (TED) that the method for the present invention prepares stannous chloride nano-sheet crystals material
Figure.
Fig. 2 is that 1,3,5- tribromo-benzenes used in the method for the present invention and p-phenylenediamine are poly- in the case where stannous chloride is catalysts conditions
Close reaction schematic diagram.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
(1) copper foil of 25um thickness is selected, the one side of copper foil or two sides are the planes by polishing treatment, use deionization
It is dried for standby for 60 DEG C after water cleaning copper foil surface.
(2) 134.45mg Copper dichloride dihydrates powder is added in 10ml deionized waters, stirred 2 minutes, configuration~
The copper chloride solution of 0.1mol/L.1.63mg anhydrous ferric trichlorides powder is added into copper chloride solution.
(3) by 10mL~copper chloride solution of 0.1mol/L is added drop-wise to the burnishing surface of copper foil, by bar coating method
Liquid is uniformly dispersed in copper foil surface, forms the film of uniformly continuous.
(4) copper foil for carrying copper chloride solution is placed in drying process 5min in the baking oven that temperature is 60 DEG C.
(5) the cuprous chloride crystal film of copper foil surface is cleaned with absolute ethyl alcohol, drying for standby.
(6) 1,3,5- tribromo-benzene and p-phenylenediamine are dissolved in DMF, stirred evenly.
(7) by the straight DMF solution for adding 1,3,5- tribromo-benzenes and p-phenylenediamine of cuprous chloride crystal film, nitrogen is added
Form protective atmosphere.
(8) temperature is maintained 80 DEG C, flow back 12h.
(9) crystal film is collected, solvent and accessory substance, kept dry are removed with absolute ethyl alcohol.
Fig. 1 includes the TEM figures of stannous chloride flat crystal obtained by the present embodiment, shows the structure of stannous chloride flat crystal
Feature.
Fig. 2 illustrates the polymerization of 1,3,5- tribromo-benzene of the present embodiment and p-phenylenediamine in the case where stannous chloride is catalysts conditions anti-
Should.
Embodiment 2
(1) copper foil of 25um thickness is selected, the one side of copper foil or two sides are the planes by polishing treatment, use deionization
It is dried for standby for 60 DEG C after water cleaning copper foil surface.
(2) 134.45mg Copper dichloride dihydrates powder is added in 10ml deionized waters, stirred 2 minutes, configuration~
The copper chloride solution of 0.1mol/L.1.63mg anhydrous ferric trichlorides powder is added into copper chloride solution.
(3) by 10mL~copper chloride solution of 0.1mol/L is added drop-wise to the burnishing surface of copper foil, by bar coating method
Liquid is uniformly dispersed in copper foil surface, forms the film of uniformly continuous.
(4) copper foil for carrying copper chloride solution is placed in drying process 5min in the baking oven that temperature is 60 DEG C.
(5) the cuprous chloride crystal film of copper foil surface is cleaned with absolute ethyl alcohol, drying for standby.
(6) 1,3,5- tribromo-benzene and p-phenylenediamine are dissolved in DMF, stirred evenly.
(7) by the straight DMSOI solution for adding 1,3,5- tribromo-benzenes and p-phenylenediamine of cuprous chloride crystal film, nitrogen is added
Gas forms protective atmosphere.
(8) temperature is maintained 120 DEG C, flow back 10h.
(9) crystal film is collected, solvent and accessory substance, kept dry are removed with absolute ethyl alcohol.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within protection domain and the open scope.
Claims (8)
1. a kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth, includes the following steps：
(1) the two-dimentional chlorine for playing template and catalytic action is directly prepared in copper foil substrate using solid liquid interface fast preparation method
Change cuprous nano crystal material, be easy to the solvent as copper chloride solution such as ethanol of volatilization, ferric trichloride, will as adjusting control agent
Copper chloride (containing iron ion), solution was coated on copper foil surface, controls the additive amount of copper chloride solution, is placed in a certain range of temperature
Under make rapid reaction, generate two-dimentional stannous chloride nano crystal material；
(2) it be monomer molecule to select 1,3,5- tribromo-benzenes and p-phenylenediamine, and at a certain temperature, certain time is interior, certain solvent
In, under inert gas shielding, directly as catalyst two-dimentional stannous chloride nanocrystal surface occur polymerisation, growth
Two-dimentional organic polymer.
2. preparation method according to claim 1, it is characterised in that in step (1) in solid liquid interface fast preparation method
The scope of ferric trichloride additive amount is the 0.01%-10% of copper chloride solution molar concentration.
3. preparation method according to claim 1, it is characterised in that copper chloride solution is coated on copper described in step (1)
Paper tinsel surface method is suitable for a variety of method for solution coating, preferably bar coating method such as drop coating, bar coating method, spraying.
4. preparation method according to claim 1, it is characterised in that make described in step (1) at a temperature of a certain range
Rapid reaction occurs, and preferable temperature is 0~80 DEG C, and the preferable time is 0.1~600s.
5. preparation method according to claim 1, it is characterised in that certain temperature described in step (2) is 50~380
℃。
6. preparation method according to claim 1, it is characterised in that certain time described in step (2) is 3h~72h.
7. preparation method according to claim 1, it is characterised in that certain solvent is DMF and DMSO described in step (2)
Deng organic solvent.
8. preparation method according to claim 1, it is characterised in that inert gas described in step (2) is nitrogen and argon
The inert gases such as gas.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108751163A (en) * | 2018-07-07 | 2018-11-06 | 盐城师范学院 | A kind of preparation method of nitrogen-doped porous carbon material |
| CN108807939A (en) * | 2018-07-07 | 2018-11-13 | 盐城师范学院 | Preparation method of azo porous material/carbon nano tube composite electrode material |
| CN108794743A (en) * | 2018-07-07 | 2018-11-13 | 盐城师范学院 | A kind of preparation method of the organic covalent frame material in large aperture |
| CN108841009A (en) * | 2018-07-07 | 2018-11-20 | 盐城师范学院 | A kind of preparation method of different hole covalent organic frame material |
| CN108976411A (en) * | 2018-07-07 | 2018-12-11 | 盐城师范学院 | A kind of preparation method of cage covalent organic framework material |
| CN109134854A (en) * | 2018-07-07 | 2019-01-04 | 盐城师范学院 | A kind of preparation method of the adjustable two-dimentional organic material in aperture |
| CN109134853A (en) * | 2018-07-07 | 2019-01-04 | 盐城师范学院 | A kind of preparation method of two dimension organic material |
| CN109232884A (en) * | 2018-07-07 | 2019-01-18 | 盐城师范学院 | A kind of interface preparation method of two dimension organic framework materials |
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|---|---|---|---|---|
| CN108751163A (en) * | 2018-07-07 | 2018-11-06 | 盐城师范学院 | A kind of preparation method of nitrogen-doped porous carbon material |
| CN108807939A (en) * | 2018-07-07 | 2018-11-13 | 盐城师范学院 | Preparation method of azo porous material/carbon nano tube composite electrode material |
| CN108794743A (en) * | 2018-07-07 | 2018-11-13 | 盐城师范学院 | A kind of preparation method of the organic covalent frame material in large aperture |
| CN108841009A (en) * | 2018-07-07 | 2018-11-20 | 盐城师范学院 | A kind of preparation method of different hole covalent organic frame material |
| CN108976411A (en) * | 2018-07-07 | 2018-12-11 | 盐城师范学院 | A kind of preparation method of cage covalent organic framework material |
| CN109134854A (en) * | 2018-07-07 | 2019-01-04 | 盐城师范学院 | A kind of preparation method of the adjustable two-dimentional organic material in aperture |
| CN109134853A (en) * | 2018-07-07 | 2019-01-04 | 盐城师范学院 | A kind of preparation method of two dimension organic material |
| CN109232884A (en) * | 2018-07-07 | 2019-01-18 | 盐城师范学院 | A kind of interface preparation method of two dimension organic framework materials |
| CN108807939B (en) * | 2018-07-07 | 2021-01-29 | 盐城师范学院 | Preparation method of azo porous material/carbon nano tube composite electrode material |
| CN108976411B (en) * | 2018-07-07 | 2021-08-03 | 盐城师范学院 | Preparation method of cage type covalent organic framework material |
| CN108751163B (en) * | 2018-07-07 | 2021-09-14 | 盐城师范学院 | Preparation method of nitrogen-doped porous carbon material |
| CN108841009B (en) * | 2018-07-07 | 2021-09-14 | 盐城师范学院 | Preparation method of hetero-pore covalent organic framework material |
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Effective date of registration: 20210512 Address after: 224300 phase III Industrial Park, Lingang Industrial Zone, Sheyang County, Yancheng City, Jiangsu Province Patentee after: Sheyang Xingang sewage treatment plant Address before: New energy college, Xinchang campus, Yancheng Normal University, No.2, South hope Avenue, Yancheng City, Jiangsu Province, 224000 Patentee before: YANCHENG TEACHERS University |