CN107353242B - Two-dimentional supermolecule porous polymer, monomer compound and preparation method - Google Patents
Two-dimentional supermolecule porous polymer, monomer compound and preparation method Download PDFInfo
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a kind of two-dimentional supermolecule porous polymer, monomer compound and preparation methods.Amphipathic group is introduced in monomer molecule used in two-dimentional supermolecule porous polymer of the invention, is obtained by the method for self assembly, and internal structure high-sequential and there is long-range periodicity.
Description
Technical field
The present invention relates to a kind of two-dimentional supermolecule porous polymer, monomer compound and preparation methods.
Background technique
Ultra-thin perforated membrane is due to its permeability, selective transport capacity and can be used as nano molecular sieve etc. in chemical work
The fields such as journey, biological medicine, environmental protection, food, health care and the energy tool have been widely used (Y.Peng, Y.Li, Y.Ban,
H.Jin,W.Jiao,X.Liu,W.Yang,Science 2014,346,1356-1359.).Two-dimentional polymeric material has relatively solid
Fixed porosity, therefore be a kind of ideal ultra-thin porous film, however its design and synthesis is complex and difficulty is big, makes
The acquisition for obtaining this kind of material is also extremely difficult.In two-dimentional polymeric material, monomer primitive can take covalent bond and non-covalent bond
Two ways connection, the former is commonly referred to as two-dimensional polymer, and the latter is commonly defined as two-dimentional supermolecule polymer.Two dimension polymerization
Object can be removed by lamellar precursor or monomer polymerize under given conditions to obtain, and two-dimentional supermolecule polymer mainly utilizes
It is prepared by the monomer primitive self assembly under noncovalent interaction driving.It is reported to there is solution phase self assembly to construct soluble single layer
Two-dimentional supermolecule porous polymer: two-dimentional supermolecule organic frame (K.-D.Zhang, J.Tian, D.Hanifi, Y.Zhang,
A.C.-H.Sue,T.-Y.Zhou,L.Zhang,X.Zhao,Y.Liu,Z.-T.Li,J.Am.Chem.Soc.2013,135,
17913-17918).Preparation method (the S.- of some other two-dimentional supermolecule organic frame is developed again in subsequent research
Q.Xu,X.Zhang,C.-B.Nie,Z.-F.Pang,X.-N.Xu,X.Zhao,Chem.Commun.2015,51,16417-
16420;T.-Y.Zhou,Q.-Y.Qi,Q.-L.Zhao,J.Fu,Y.Liu,Z.Ma,X.Zhao,Polym.Chem.,2015,6,
3018-3023.), but the two-dimentional supermolecule porous polymer of internal structure high-sequential and long-range periodicity is obtained still
It is very difficult.And the degree of order of internal structure is to directly affect the key factor of porous film quality, low structurally ordered degree meaning
Defect is more to reduce its performance in film, the only high degree of order just can guarantee the homogeneity of film inner hole structure, to obtain
Obtain high-performance.Therefore, how self assembly obtains the two-dimentional supermolecule porous polymeric of internal structure high-sequential and long-range periodicity
Object is one of the critical issue in this field.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome existing internal structure high-sequential and long-range periodic
Property the poromeric acquisition of two-dimentional supermolecule it is difficult, and provide a kind of two-dimentional supermolecule porous polymer, monomer
Close object and preparation method.Amphipathic group is introduced in monomer molecule used in two-dimentional supermolecule porous polymer of the invention,
It is obtained by the method for self assembly, and internal structure high-sequential and there is long-range periodicity, had in separation field and answer well
With prospect, the specifically separation of nanoparticle, pollutant, drug, biomolecule and chemical products;Preparation method is simple simultaneously,
Realization easy to operate is conducive to industrialized production and application.
The present invention mainly solves above-mentioned technical problem by the following technical programs.
The present invention provides the poromeric monomeric compounds of two dimension supermolecule shown in a kind of general formula I:
In general formula I, R1、R1aAnd R1bIt independently is hydrophobic grouping, R2、R2aAnd R2bIt independently is hydrophilic radical, Y, YaAnd Yb
It independently is C or N, as Y, YaAnd YbWhen independently being N, R3、R3aAnd R3bIt is not present, as Y, YaAnd YbWhen independently being C, R3、R3a
And R3bIt independently is hydrogen, amino, nitro, C1-C4Alkoxy, C1-C4Alkyl thiol or halogen;
M1、M1aAnd M1bIt independently is Cl、Br、I、ClO4、CH3COO、CH3(C6H4)SO3、PF6、AsF6、
BF4Or NO3。
In general formula I, R1、R1aAnd R1bIn, the hydrophobic grouping is conventional hydrophobic grouping, preferably substituted or unsubstituted
C1-C20Alkyl, the substituted C1-C20Substituent group in alkyl is selected from one or more of following groups (preferably 1-6
It is a, more preferable 1-3): halogen (preferably F, Cl, Br or I) or C1-C4Alkyl (preferably methyl, ethyl, n-propyl, isopropyl, just
Butyl, isobutyl group or tert-butyl).The substituted or unsubstituted C1-C20The preferably substituted or unsubstituted C of alkyl1-C10Alkane
Base, the substituted or unsubstituted C1-C10C described in alkyl1-C10The preferred methyl of alkyl, ethyl, n-propyl, isopropyl,
Normal-butyl, isobutyl group, tert-butyl, n-pentyl or its isomer, n-hexyl or its isomer, n-heptyl or its same point
Isomers, n-octyl or its isomer, n-nonyl or its isomer, or, positive decyl or its isomer.
In general formula I, R2、R2aAnd R2bIn, the hydrophilic radical is conventional hydrophilic radical, preferably oligomeric ethylene glycol base,
The oligomeric ethylene glycol base is preferredThe wherein positive integer that n is 1~10, more preferably
R3、R3aAnd R3bIn, the C1-C4The preferred methoxyl group of alkoxy, ethyoxyl, positive propoxy, isopropoxy, positive fourth
Oxygroup, isobutoxy or tert-butoxy.
R3、R3aAnd R3bIn, the C1-C4The preferred first sulfydryl of alkyl thiol, second sulfydryl, positive third sulfydryl, isopropyl sulfydryl, just
Fourth sulfydryl, isobutyl sulfydryl or tertiary fourth sulfydryl.
R3、R3aAnd R3bIn, the halogen preferred F, Cl, Br or I.
In a preferred embodiment of the invention, R1、R1aAnd R1bIt is preferred that identical, R2、R2aAnd R2bIt is preferred that identical, Y, YaAnd Yb
It is preferred that identical, R3、R3aAnd R3bIt is preferred that identical.
The present invention provides the systems of the poromeric monomeric compound of two dimension supermolecule shown in the general formula I described in one kind
Preparation Method comprising the following steps: in solvent, compound 12, compound 11, compound 11a and compound 11b are carried out as follows
Shown in react;
Wherein, R1、R1a、R1b、R2、R2a、R2b、Y、Ya、Yb、R3、R3aAnd R3bDefinition as described above.
In the preparation method, the condition of the reaction is the conventional condition of the such reaction in this field.For example, institute
The preferred alcohols solvent of the solvent stated, more preferable ethyl alcohol.The dosage of the solvent can be the dosage of the such reaction routine in this field,
As long as not influencing the progress of reaction.The dosage of the compound 12, compound 11, compound 11a and compound 11b
It can be the dosage of the such reaction routine in this field.Solvent reflux temperature~120 DEG C under the preferred normal pressure of the temperature of the reaction, example
Such as 70-120 DEG C.Detection method (such as TLC, HPLC, GC or HNMR of this field routine can be used in the process of the reaction
Deng) be monitored, as reaction when preferably being disappeared using any compound 12, compound 11, compound 11a or compound 11b
Terminal.
The reaction can also carry out under gas (preferably nitrogen or argon gas) protection.
The present invention also provides a kind of poromeric preparation methods of two-dimentional supermolecule comprising the following steps: by institute
The poromeric monomeric compound of two dimension supermolecule and CB [8] shown in the general formula I stated carry out self assembly in a solvent, i.e.,
It can.
The solvent can be solvent conventional in the poromeric preparation method of two-dimentional supermolecule, preferably water.It is described
Solvent dosage can be conventional for the such reaction in this field dosage, two dimension supermolecule shown in the preferably general formula I is porous
The molar concentration of the monomeric compound of polymer in a solvent is 0.00005mol/L-1mol/L, more preferable 0.0005mol/L.
The dosage of the poromeric monomeric compound of two dimension supermolecule and CB [8] shown in the general formula I can be such for this field
React conventional dosage, the two molar ratio preferred 8:3-4:9, more preferable 2:3.
The time independently filled can be the time of the such reaction routine in this field, preferably -24 hours 1 minute, more excellent
It selects 10 minutes.
During the autonomous dress, the method that concussion or ultrasound can be used, to guarantee two dimension shown in the general formula I
The poromeric monomeric compound of supermolecule and CB [8] are sufficiently mixed.
The present invention also provides two dimension oversubscription made from the poromeric preparation method of two-dimentional supermolecule described in one kind
Sub- porous polymer.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
In the present invention, entitled cucurbit [8] uril of CB [8] English, Chinese name are as follows: cucurbit [8] urea.
The positive effect of the present invention is that:
(1) two-dimentional supermolecule porous polymer preparation method of the invention is simple, realization easy to operate.
(2) the poromeric small-angle scattering peak of two-dimentional supermolecule of the invention is very sharp, and has multiple scattering peaks to be seen
It observes;TEM observes directly the hole of high-sequential, and therefore, two-dimentional supermolecule porous polymer of the invention has high-sequential
Internal structure;Its as ultra-thin porous film, with ultra-thin porous film in the prior art (such as J.Am.Chem.Soc.2013,
135,17913-17918 and Polym.Chem., the two-dimentional supermolecule porous polymer in 2015,6,3018-3023) it compares, matter
It measures, performance is high.
(3) two-dimentional supermolecule porous polymer of the invention has good application prospect in separation field.
Detailed description of the invention
Fig. 1 be embodiment 1 made from monomeric compound I-1 and CB [8] nuclear-magnetism titrate spectrogram, wherein a, b, c, d, e and
F refers respectively to monomeric compound I-1 and 0, proton of 0.375,0.75,1.125, the 1.5 and 1.875 equivalent CB [8] in heavy water
Magnetic resonance spectrogram.
Fig. 2 is Job ' the s plot working curve diagram of monomeric compound I-1 and CB [8] made from embodiment 1.
Fig. 3 is monomeric compound I-1 made from the embodiment 1 of various concentration, is dissipated with the dynamic optical of solution after CB [8] assembling
Penetrate figure.
The two-dimentional supermolecule that Fig. 4 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close transmission electron microscope (TEM) figure (scale bar 200nm) of object.
The two-dimentional supermolecule that Fig. 5 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close transmission electron microscope (TEM) figure (scale bar 50nm) of object.
The two-dimentional supermolecule that Fig. 6 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close transmission electron microscope (TEM) figure (scale bar 20nm) of object.
The two-dimentional supermolecule that Fig. 7 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close the AFM spectrogram of object.
The two-dimentional supermolecule that Fig. 8 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close the corresponding cross-sectional analysis figure of AFM spectrogram of object.
The two-dimentional supermolecule that Fig. 9 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
The solution for closing object is synchronised radiation X-ray small-angle scattering spectrogram.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments, Calcd for refers to that calculated value, Found refer to measured value.
The preparation of 1 monomeric compound I-1 of embodiment
The preparation of compound 4
The addition bromo- Isosorbide-5-Nitrae-dimethoxy benzene (1.0g, 4.6mmol) of 2- in the single port bottle of 25mL, AcOH (5mL), then slowly
HNO is added dropwise3(0.4mL) has in solution a large amount of yellow solids to be precipitated, and after 0.5h, filtering rinses filter residue with a large amount of water, finally
It dries in a vacuum drying oven, obtains bright yellow solid powder compounds 4 (1.1g, 92%).1H NMR(400MHz,CDCl3):δ
3.90(s,3H),3.93(s,3H),7.32(s,1H),7.45(s,1H)。
The preparation of compound 5
Compound 4 (1.5g, 5.72mmol) is added in the single port bottle of 250mL, AcOH (25mL), 48%HBr (100mL) are molten
Liquid, flow back 4h.It is extracted after cooling with ethyl acetate (4 × 20mL), organic phase is washed with water, then dry with anhydrous magnesium sulfate.Filtering,
It is spin-dried for solvent, obtains orange/yellow solid compound 5 (1.19g, 89%).1H NMR(400MHz,CDCl3):δ5.53(s,1H),
7.38(s,1H),7.72(s,1H),10.15(s,1H)。
The preparation of compound 6
5 (5.0g, 21.4mmol) are added in the there-necked flask of 250mL, vacuumizes to lead to and changes argon gas three times, inject anhydrous DMF
(95mL) is rapidly added NaH (1.7g, 42.7mmol).After 0.5h, bromohexane (1.52mL, 10.7mmol) is dissolved in anhydrous DMF
It slowly is added dropwise in (5mL).Mixture stirs 4h after being heated to reflux, is then quenched with the aqueous ammonium chloride solution of saturation, then
It is extracted with DCM (400mL).Organic phase is dry with anhydrous magnesium sulfate after being washed with salt.Solvent is evaporated off in filtering back spin.Column chromatography point
From petroleum ether: the isolated yellow solid compound 6 (5.9g, 87%) of ethyl acetate (1:10).1H NMR(400MHz,
CDCl3): δ 10.30 (s, 1H), 7.49 (s, 1H), 7.44 (s, 1H), 4.01 (t, J=6.4Hz, 2H), 1.85 (dt, J=
14.3,6.5Hz, 2H), 1.58-1.45 (m, 2H), 1.42-1.30 (m, 4H), 0.91 (t, J=7.1Hz, 3H)13C NMR
(500MHz,CDCl3):δ149.37,149.09,124.57,124.26,106.16,70.16,31.41,28.77,25.58,
22.53,13.97.MS(ESI):m/z316.0[M-H]-.HRMS(ESI):Calcd for C12H16BrNO4:
317.0257.Found:317.0256。
The preparation of compound 8
Compound 6 (2.1g, 6.6mmol) is added in the there-necked flask of 250mL, compound 7 (3.45g, 9.9mmol), K2CO3
(2.74g, 19.8mmol), anhydrous DMF (30mL).Flow back 48h under the conditions of argon gas.It is spin-dried for solvent, methylene chloride and 10% is added
Dilute hydrochloric acid.Organic layer is washed with water three times, and it is dry to add anhydrous magnesium sulfate.Solvent is spin-dried for after filtering.Column chromatography for separation, acetic acid second
The isolated brown oil liquid 8 (1.6g, 48%) of ester.1H NMR(400MHz,DMSO-d6):δ7.71(s,1H),7.62(s,
1H), 4.57 (t, J=4.8Hz, 1H), 4.37-4.18 (m, 2H), 4.06 (t, J=6.4Hz, 2H), 3.80-3.67 (m, 2H),
3.80-3.54 (m, 2H), 3.54-3.44 (m, 8H), 3.39 (dd, J=7.8,3.0Hz, 2H), 1.78-1.63 (m, 2H),
1.52-1.37 (m, 2H), 1.38-1.22 (m, 4H), 0.88 (t, J=7.1Hz, 3H)13C NMR(500MHz,DMSO-d6):δ
149.06,145.79,139.36,121.16,117.57,109.72,72.79,70.61,70.45,70.28,70.24,
70.20,70.12,69.20,31.27,28.77,25.49,22.50,14.32.MS(ESI):m/z 494.3[M+H]+.HRMS
(ESI):Calcd forC20H33BrNO8[M+H]+:494.1384.Found:494.1383。
The preparation of compound 10
Compound 8 (524mg, 1.06mmol) is added in the there-necked flask of 100mL, compound 9 (200mg, 0.32mmol), Pd
[P(Ph3)]4(37mg, 0.03mmol), toluene (30mL), ethyl alcohol (10mL), 2M wet chemical (5mL).It is risen after substituting gas
Temperature is to reacting for 24 hours at 85 DEG C.Then methylene chloride extraction is added, organic phase is dry with anhydrous magnesium sulfate again after being washed with water.Filtering
After be spin-dried for solvent.Column chromatography for separation, ethyl acetate: the isolated orange/yellow solid 10 (320mg, 21%) of methanol (8:1).1H
NMR(400MHz,DMSO-d6):δ7.62(s,3H),7.60(s,6H),7.33(s,3H),7.16(s,3H),7.14(s,3H),
4.41-4.25 (m, 6H), 4.01 (t, J=6.2Hz, 6H), 3.82-3.69 (m, 6H), 3.59 (dd, J=5.8,3.5Hz, 6H),
3.49 (ddd, J=16.6,8.1,4.0Hz, 24H), 3.42-3.33 (m, 6H), 1.74-1.56 (m, 6H), 1.42-1.29 (m,
6H), 1.29-1.16 (m, 12H), 0.80 (t, J=7.0Hz, 9H)13C NMR(500MHz,DMSO-d6):δ149.35,
146.89,146.12,138.58,135.92,131.42,131.24,123.60,117.97,109.85,72,78,70.48,
70.26,70.20,69.52,69.30,60.64,31.22,28.82,25.54,22.45,14.23.MS(MALDI-TOF):m/
z1507.7[M+Na]+.HRMS(MALDI-TOF):Calcd for C73H108N6O26Na[M+Na]+:1507.7205.Found:
1507.7245。
The preparation of monomeric compound I-1
In the high-pressure hydrogenation bottle of 100mL, be added 10 (320mg, 0.22mmol), 10%Pd/C (32mg), methanol (30mL),
Methylene chloride (10mL).It is reacted for 24 hours under the conditions of 30atm, 40 DEG C.Stop heating later, using dicalite speed plus, obtains
Brown solution is spin-dried for obtaining brown solid --- and compound 12-1 (i.e. in compound 12, R1、R1aAnd R1bN-hexyl independently is,
R2、R2aAnd R2bIt independently is tetraethylene-glycol base).Compound 12-1 is added in 50mL tube sealing, compound 11 is added
(395mg, 1.10mmol), ethyl alcohol (20mL).It substitutes and flows back 5d (5 days) under the conditions of 120 DEG C after gas.Stop reaction, is spin-dried for solvent.
Column chromatography for separation, methanol: nitromethane: the isolated black solid I-1 of saturated ammonium chloride (9:1:0.4) (124mg, 30%).1H NMR(400MHz,Methanol-d4): δ 9.31 (d, J=6.1Hz, 6H), 8.87 (d, J=4.7Hz, 6H), 8.68 (d, J=
6.1Hz, 6H), 8.09 (d, J=4.5Hz, 6H), 7.62 (d, J=8.1Hz, 6H), 7.53 (s, 3H), 7.43 (s, 3H), 7.25
(d, J=8.2Hz, 6H), 4.35 (s, 6H), 4.09 (t, J=5.5Hz, 6H), 3.71 (s, 6H), 3.55 (d, J=16.8Hz,
30H), 3.44 (d, J=4.4Hz, 6H), 1.93-1.66 (m, 6H), 1.56-1.39 (m, 6H), 1.32 (d, J=2.6Hz,
12H),0.88(s,9H).13C NMR(500MHz,DMSO-d6):δ154.33,150.85,147.14,142.17,135.00,
134.99,130.40,122.29,117.05,111.02,72.21,70.18,70.11,70.05,69.95,69.66,69.65,
69.53,68.92,68,90,68.87,31.18,28.81,25.56,22.32,13.12.MS(MALDI-TOF):m/z 605.3
[M/3-Cl]+.HRMS(MALDI-TOF):Calcd for C108H132N7O18[M/3-Cl]+:604.9871.Found:
604.9858。
2 monomeric compound I-2 of embodiment
The preparation method of monomeric compound I-2 is similar with the above method, wherein compound 12-1 replaces with compound 12-2
(i.e. in compound 12, R1、R1aAnd R1bIt independently is n-hexyl, R2、R2aAnd R2bIt independently is triethylene-glycol base).1H NMR
(400MHz,Methanol-d4) δ: 9.32 (d, J=6.7Hz, 6H), 8.89 (d, J=6.0Hz, 6H), 8.70 (d, J=
6.8Hz, 6H), 8.11 (d, J=6.0Hz, 6H), 7.64 (d, J=8.5Hz, 6H), 7.52 (s, 3H), 7.44 (s, 3H), 7.27
(d, J=8.6Hz, 6H), 4.45-4.28 (m, 6H), 4.10 (t, J=6.0Hz, 6H), 3.83-3.69 (m, 6H), 3.60 (s,
12H), 3.53-3.46 (m, 6H), 1.88-1.72 (m, 6H), 1.45 (dd, J=14.4,7.3Hz, 6H), 1.32 (dd, J=
14.4,10.7Hz, 12H), 0.89 (t, J=6.9Hz, 9H)13C NMR(125MHz,Methanol-d4)δ:154.48,
150.86,150.54,147.16,145.05,142.14,135.07,131.64,130.53,130.29,125.17,123.45,
122.27,116.90,111.03,72.33,70.12,70.03,69.53,69.48,68.91,60.68,31.18,28.81,
25.56,22.32,13.10.
Embodiment 3
The two-dimentional poromeric self assembly preparation of supermolecule
Monomeric compound I-1 (1.9mg, 0.001mmol), CB [8] (3.83mg, 0.0015mmol) are added in vial
With pure water (1mL).The two-dimentional supermolecule porous polymer solution can be obtained in ultrasound after ten minutes after system concussion.It is tied
Structure can pass through the technologies such as nuclear magnetic resonance, dynamic light scattering, transmission electron microscope, atomic force microscope, X-ray small-angle scattering
Means are observed identification.
Fig. 1 be embodiment 1 made from monomeric compound I-1 and CB [8] nuclear-magnetism titrate spectrogram, wherein a, b, c, d, e and
F refers respectively to monomeric compound I-1 and 0, proton of 0.375,0.75,1.125, the 1.5 and 1.875 equivalent CB [8] in heavy water
Magnetic resonance spectrogram.
The combination ratio that Fig. 1 demonstrates monomeric compound I-1 and CB [8] is 2:3.
Fig. 2 is Job ' the s plot working curve diagram of monomeric compound I-1 and CB [8] made from embodiment 1, wherein horizontal
Coordinate is monomeric compound I-1, molar content in the mixture of monomeric compound I-1 and CB [8], 0.0 is 100%CB
[8], 1.0 be 100% monomeric compound I-1).
The combination ratio (molar ratio) that Fig. 2 further demonstrates monomeric compound I-1 and CB [8] is 2:3.
It is molten after monomeric compound I-1 made from embodiment 1 of the Fig. 3 for various concentration, with CB [8] 2:3 assembling in molar ratio
The dynamic light scattering diagram of liquid.Obtained two dimension supermolecule porous polymer solution is directly carried out with dynamic light scattering after assembling
Characterization.
Fig. 3 illustrates to form the poromeric size of two-dimentional supermolecule in various concentration solution with the increasing of concentration
Increase greatly.
I-1 concentration (mM) | 0.015625 | 0.03125 | 0.0625 | 0.125 | 0.25 |
Partial size (nm) | 61.6 | 61.6 | 67.5 | 74.0 | 88.9 |
The two-dimentional supermolecule that Fig. 4 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close the TEM figure of object.Two dimension supermolecule porous polymer solution obtained after assembling is carefully dripped on TEM copper mesh, it is molten
It is characterized after agent volatilization with transmission electron microscope.
Fig. 4, Fig. 5 and Fig. 6 transmission electron microscope under 200nm, 50nm and 20nm scale bar (TEM) figure respectively, by
Fig. 5 and Fig. 6 can be clearly seen that long-range periodicity, regular, high-sequential network, and the grid knot of the long-range order
Structure never had been reported that in the related to two-dimentional poromeric document of supermolecule.Therefore, Fig. 4 demonstrates internal structure
The poromeric formation of two-dimentional supermolecule of high-sequential.
The two-dimentional supermolecule that Fig. 7 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
Close the AFM spectrogram of object;Fig. 8 is the cross-sectional analysis figure of Fig. 7.Obtained two-dimentional supermolecule porous polymer solution after assembling
It carefully drips on AFM silicon wafer, is characterized after solvent volatilization with atomic force microscope.
Large scale can be observed in Fig. 7 and Fig. 8 and very smooth, thickness (vertical range --- verticaldistance) is
5.1 the laminated structure of nanometer, corresponding two-dimensional polymer demonstrates the presence of ultra-thin two-dimentional paradigmatic structure.
The two-dimentional supermolecule that Fig. 9 is formed after being monomeric compound I-1 made from embodiment 1 and CB [8] self assembly is porous poly-
The solution for closing object is synchronised radiation X-ray small-angle scattering spectrogram, wherein abscissa (q (nm)-1) indicate Scattering of Vector, ordinate
INT indicates scattering strength.
Clear, sharp (100), (110) and (200) scattered signal can be observed in Fig. 9, it was demonstrated that gained two dimension is super
The high-sequential degree and long-range periodicity of molecular porous polymeric inner.
Claims (11)
1. the poromeric monomeric compound of two dimension supermolecule shown in a kind of general formula I:
In general formula I, R1、R1aAnd R1bIt independently is C1-C10Alkyl, R2、R2aAnd R2bIt independently isWherein n
For 1~10 positive integer, Y, YaAnd YbIt independently is C or N, as Y, YaAnd YbWhen independently being N, R3、R3aAnd R3bIt is not present, when
Y、YaAnd YbWhen independently being C, R3、R3aAnd R3bIt independently is hydrogen, amino, nitro, C1-C4Alkoxy, C1-C4Alkyl thiol or halogen
Element;
M1、M1aAnd M1bIt independently is Cl、Br、I、ClO4、CH3COO、CH3(C6H4)SO3、PF6、AsF6、BF4
Or NO3。
2. the poromeric monomeric compound of two dimension supermolecule, feature shown in general formula I as described in claim 1 exist
In,
In general formula I, R2、R2aAnd R2bIn, it is describedFor
3. the poromeric monomeric compound of two dimension supermolecule, feature shown in general formula I as claimed in claim 2 exist
In the C1-C10Alkyl be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl,Neopentyl, n-hexyl or its isomerism, n-heptyl
Or its isomerism, n-octyl or its isomerism, n-nonyl or its isomerism, or, positive decyl or its isomerism.
4. the poromeric monomeric compound of two dimension supermolecule shown in general formula I as described in any one of claims 1-3,
It is characterized in that, is
5. the poromeric monomer chemical combination of two dimension supermolecule shown in a kind of general formula I according to any one of claims 1-4
The preparation method of object, which is characterized in that it includes the following steps: in solvent, by compound 12, compound 11, compound 11a and
Compound 11b carries out reaction as follows;
Wherein, R1、R1a、R1b、R2、R2a、R2b、Y、Ya、Yb、R3、R3aAnd R3bDefinition with described in claim any one of 1-4.
6. preparation method as claimed in claim 5, which is characterized in that
The solvent is alcohols solvent;
And/or the temperature of the reaction is solvent reflux temperature~120 DEG C under normal pressure;
And/or the reaction also carries out under gas shield.
7. preparation method as claimed in claim 6, which is characterized in that the solvent is ethyl alcohol.
8. a kind of two dimension supermolecule porous polymer, which is characterized in that it is made by following method, and the method includes following
Step: by the poromeric monomeric compound of two dimension supermolecule shown in general formula I according to any one of claims 1-4 and
CB [8] carries out self assembly in a solvent.
9. two dimension supermolecule porous polymer as claimed in claim 8, which is characterized in that described in the preparation method
Solvent be water;And/or the poromeric monomeric compound of two dimension supermolecule shown in the general formula I is in a solvent
Molar concentration is 0.00005mol/L-1mol/L;And/or the poromeric list of two dimension supermolecule shown in the general formula I
The molar ratio of body compound and CB [8] are 8:3-4:9;And/or the time independently filled is -24 hours 1 minute.
10. two dimension supermolecule porous polymer as claimed in claim 9, which is characterized in that described in the preparation method
General formula I shown in the molar ratio of the poromeric monomeric compound of two dimension supermolecule and CB [8] be 2:3;And/or it is described
The time independently filled be 10 minutes.
11. a kind of such as the poromeric preparation method of the described in any item two-dimentional supermolecules of claim 8-10 comprising under
Column step: by the poromeric monomeric compound of two dimension supermolecule shown in general formula I according to any one of claims 1-4
Self assembly is carried out in a solvent with CB [8], the condition of the method independently filled is such as any one of claim 8-10
It is described.
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