CN108003345A - A kind of synthetic method of high nitrogen-containing conjugation microporous polymer - Google Patents
A kind of synthetic method of high nitrogen-containing conjugation microporous polymer Download PDFInfo
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- CN108003345A CN108003345A CN201711340714.7A CN201711340714A CN108003345A CN 108003345 A CN108003345 A CN 108003345A CN 201711340714 A CN201711340714 A CN 201711340714A CN 108003345 A CN108003345 A CN 108003345A
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Abstract
The present invention relates to a kind of synthetic method of high nitrogen-containing conjugation microporous polymer, including：Four (4 bromophenyl) methane are mixed with aryl diamine, add palladium catalyst, catalyst ligand, alkaline agent, then add in a nitrogen atmosphere at 105~115 DEG C of solvent and carry out 22~26h of coupling reaction, washed, vacuum drying obtains high nitrogen-containing conjugation microporous polymer；Wherein four (4 bromophenyl) methane, aryl diamine, palladium catalyst, catalyst ligand, the molar ratio of alkaline agent are 1：2：0.05~0.1：0.1~0.15：5~5.5.The present invention uses Buchwald Hartwig coupling reactions, so that in the presence of palladium chtalyst and alkali cross-coupling reaction occurs for fragrant bromine and arylamine, C N keys are generated, so as to synthesize high nitrogen-containing conjugation microporous polymer, there is important application prospect in fields such as gas absorption, catalyst carrier, energy storages.
Description
Technical field
The invention belongs to microporous polymer technical field, more particularly to a kind of synthesis of high nitrogen-containing conjugation microporous polymer
Method.
Background technology
Conjugation microporous polymer is made of lightweight elements such as carbon, hydrogen, oxygen, nitrogen, boron, comprising a large amount of apertures less than 2nm's
Micropore, has the characteristics that high surface area, three-dimensional conjugated backbone, stability is good, pore passage structure is controllable modifies, in various fields
Show great application value, such as gas absorption/separation, sensor, heterocatalysis, luminous energy catch and shifts, electrochemistry.
Conjugation microporous polymer is research hotspot in recent years.
The synthetic method of common conjugation microporous polymer includes Suzuki, Yamamoto, Sonogashira, Glaser
Deng metal coupling reaction, oxidation polymerization, cyclic trimerization reaction etc..These reaction generally with formed C-C coupling based on, gained polymerization
Thing has large specific surface area, but nitrogen element content is less.According to the literature, the introducing of nitrogen is conducive to be conjugated microporous polymer
Application of the thing in fields such as gas absorption, catalyst carrier, energy storages.Therefore, it is badly in need of finding new conjugation microporous polymer
The synthetic method of thing, makes to contain a large amount of nitrogens in its skeleton structure.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of synthetic method of high nitrogen-containing conjugation microporous polymer, adopt
With a kind of new coupling reaction Buchwald-Hartwig, high nitrogen-containing microporous polymer, wherein aryl bromide and fragrance are synthesized
Amine sloughs hydrogen bromide under the action of palladium catalyst, generates C-N keys, forms conjugation microporous polymer network structure.C-N keys
In the presence of, microporous polymer high nitrogen-containing and excellent oxidation-reduction quality can be assigned, be conducive to be conjugated microporous polymer gas inhale
The application in the fields such as attached, catalyst carrier, energy storage.
A kind of synthetic method of high nitrogen-containing conjugation microporous polymer of the present invention, including：
Four (4- bromophenyls) methane are mixed with aryl diamine, palladium catalyst, catalyst ligand, alkaline agent are added, then in nitrogen
Added under gas atmosphere at 105~115 DEG C of solvent and carry out 22~26h of coupling reaction, washed, vacuum drying obtains high nitrogen-containing and is total to
Yoke microporous polymer；Wherein four (4- bromophenyls) methane, aryl diamine, palladium catalyst, catalyst ligand, the molar ratio of alkaline agent are 1：
2：0.05~0.1：0.1~0.15：5~5.5.
The aryl diamine is the aromatic compounds containing two amidos, selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 2,
3- diamino-pyridines, 2,5- diamino-pyridines, 2,6- diamino-pyridines or 3,4- diamino-pyridines.
The palladium catalyst is double (dibenzalacetone) palladiums.
The catalyst ligand is 2- dicyclohexylphosphontetrafluoroborates -2', 4', 6'- tri isopropyl biphenyl.
The alkaline agent is sodium tert-butoxide.
The solvent is toluene, and the amount ratio of toluene and four (4- bromophenyls) methane is 150mL：1mmol.
The process conditions of the washing are：12h is first washed with deionized, is then washed with organic solvent surname extraction
24h。
The organic solvent is chloroform and methanol.
The vacuum drying technological parameter is：Vacuum drying temperature is 55~65 DEG C, vacuum drying time for 22~
26h。
The high nitrogen-containing conjugation microporous polymer is used for gas absorption, catalyst carrier or energy storage.
Beneficial effect
(1) present invention is carried using Buchwald-Hartwig coupling reactions synthesis high nitrogen-containing microporous polymer, this method
A kind of thinking of the conjugation microporous polymer of new synthesis high nitrogen-containing has been supplied, has utilized four (4- bromophenyls) methane and aryl diamine
Two kinds of monomers slough hydrogen bromide under the action of palladium catalyst, generate C-N keys, form conjugation microporous polymer network structure, its
Middle C-N keys can also assign polymer excellent oxidation-reduction quality.
(2) the high nitrogen-containing conjugation microporous polymer that the present invention synthesizes, in gas absorption, catalyst carrier, energy storage
There is important application prospect Deng field.
Brief description of the drawings
Fig. 1 is the ATR-IR figures that the high nitrogen-containing that embodiment 1 synthesizes is conjugated microporous polymer -1；
Fig. 2 is that the high nitrogen-containing that embodiment 1 synthesizes is conjugated microporous polymer -113C-NMR schemes；
Fig. 3 is that the high nitrogen-containing that embodiment 1 synthesizes is conjugated N of the microporous polymer -1 under 77.4K2Adsorption-desorption it is bent
Line chart；
Fig. 4 is the ATR-IR figures that the high nitrogen-containing that embodiment 2 synthesizes is conjugated microporous polymer -2；
Fig. 5 is that the high nitrogen-containing that embodiment 2 synthesizes is conjugated microporous polymer -213C-NMR schemes；
Fig. 6 is that the high nitrogen-containing that embodiment 2 synthesizes is conjugated N of the microporous polymer -2 under 77.4K2Adsorption-desorption it is bent
Line chart；
Fig. 7 is the ATR-IR figures that the high nitrogen-containing that embodiment 3 synthesizes is conjugated microporous polymer -3；
Fig. 8 is that the high nitrogen-containing that embodiment 3 synthesizes is conjugated microporous polymer -313C-NMR schemes；
Fig. 9 is that the high nitrogen-containing that embodiment 3 synthesizes is conjugated N of the microporous polymer -3 under 77.4K2Adsorption-desorption it is bent
Line chart；
Figure 10 is the ATR-IR figures that the high nitrogen-containing that embodiment 4 synthesizes is conjugated microporous polymer -4；
Figure 11 is that the high nitrogen-containing that embodiment 4 synthesizes is conjugated microporous polymer -413C-NMR schemes；
Figure 12 is that the high nitrogen-containing that embodiment 4 synthesizes is conjugated N of the microporous polymer -4 under 77.4K2Adsorption-desorption it is bent
Line chart；
Figure 13 is the ATR-IR figures that the high nitrogen-containing that embodiment 5 synthesizes is conjugated microporous polymer -5；
Figure 14 is that the high nitrogen-containing that embodiment 5 synthesizes is conjugated microporous polymer -513C-NMR schemes；
Figure 15 is that the high nitrogen-containing that embodiment 5 synthesizes is conjugated N of the microporous polymer -5 under 77.4K2Adsorption-desorption it is bent
Line chart；
Figure 16 is the ATR-IR figures that the high nitrogen-containing that embodiment 6 synthesizes is conjugated microporous polymer -6；
Figure 17 is that the high nitrogen-containing that embodiment 6 synthesizes is conjugated microporous polymer -613C-NMR schemes；
Figure 18 is that the high nitrogen-containing that embodiment 6 synthesizes is conjugated N of the microporous polymer -6 under 77.4K2Adsorption-desorption it is bent
Line chart；
Figure 19 is the ATR-IR figures that the high nitrogen-containing that embodiment 7 synthesizes is conjugated microporous polymer -7；
Figure 20 is that the high nitrogen-containing that embodiment 7 synthesizes is conjugated microporous polymer -713C-NMR schemes；
Figure 21 is that the high nitrogen-containing that embodiment 7 synthesizes is conjugated N of the microporous polymer -7 under 77.4K2Adsorption-desorption it is bent
Line chart.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Embodiment 1
By four (4- bromophenyls) methane (636.02mg, 1mmol) and two kinds of monomers of p-phenylenediamine (216.28mg, 2mmol)
It is placed in Schlenk pipes (200ml), double (dibenzalacetone) palladiums (46mg, 0.08mmol) of addition, 2- dicyclohexylphosphontetrafluoroborate -2',
4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in a nitrogen atmosphere
Add 150mL toluene, coupling reaction 24h in 110 DEG C of oil baths.After reaction, 12h is first washed with deionized, then in rope
24h is washed with chloroform and methanol respectively in family name's extractor, to remove unreacted raw material and oligomer.Finally it is placed in 60 DEG C
Under vacuum drying oven in dry 24h, obtain high nitrogen-containing conjugation microporous polymer, be denoted as polymer -1, its BET specific surface area is
94m2/g。
Polymer -1 and four (4- bromophenyls) methane that the present embodiment obtains, the ATR-IR test results of p-phenylenediamine are as schemed
Shown in 1, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1Place is right there are stretching vibration peak
- NH in phenylenediamine2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The flexural vibrations peak at place, these features
Peak disappears in the infrared spectrum of polymer -1, illustrates that there is no C-Br and-NH in polymer -12Functional group；While polymer-
813cm is clearly present in 1 spectrum-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that phenyl ring is not destroyed, so as to characterize
The successful synthesis of polymer -1.
The polymer -1 that the present embodiment obtains13C-NMR test results are as shown in Figure 2, it is known that have 5 kinds of different carbon in figure
Peak：Its chemical shift is respectively 140ppm, 134.5ppm, 130.5ppm, 115.5ppm and 62.5ppm, this five kinds of chemical shifts
To the carbon atom of 5 class difference chemical environments in emergencing copolymer -1.The result also further demonstrate the successful conjunction of polymer -1
Into.
N of the polymer -1 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in Figure 3, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -1；In middle high relative pressure region
(P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -1.Last desorption curve does not have
Have and closed completely with adsorption curve, this is because part N2Remain in the hole of sample polymer -1 and fail to be made by thorough desorption
Into.
Embodiment 2
By four (4- bromophenyls) methane (636.02mg, 1mmol) and two kinds of monomers of m-phenylene diamine (MPD) (216.28mg, 2mmol)
It is placed in Schlenk pipes (200ml), double (dibenzalacetone) palladiums (46mg, 0.08mmol) of addition, 2- dicyclohexylphosphontetrafluoroborate -2',
4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in a nitrogen atmosphere
Add 150mL toluene, coupling reaction 24h in 110 DEG C of oil baths.After reaction, 12h is first washed with deionized, then in rope
24h is washed with chloroform and methanol respectively in family name's extractor, to remove unreacted raw material and oligomer.Finally it is placed in 60 DEG C
Under vacuum drying oven in dry 24h, obtain high nitrogen-containing conjugation microporous polymer, be denoted as polymer -2, its BET specific surface area is
47m2/g。
Polymer -2 and four (4- bromophenyls) methane that the present embodiment obtains, the ATR-IR test results of m-phenylene diamine (MPD) are as schemed
Shown in 4, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1Place there are stretching vibration peak,
- NH in phenylenediamine2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The flexural vibrations peak at place, these features
Peak disappears in the spectrum of polymer -2, illustrates that there is no C-Br and-NH in polymer -22Functional group；While polymer -2
Bright in spectrum, video memory is in 813cm-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that phenyl ring is not destroyed, so as to characterize poly-
The successful synthesis of compound -2.
The polymer -2 that the present embodiment obtains13C-NMR test results are as shown in Figure 5, it is known that have 6 kinds of different carbon in figure
Peak：Its chemical shift is respectively 142ppm, 135ppm, 129.5ppm, 114ppm, 110.5ppm and 62.5ppm, this six kinds of chemistry
Carbon atom of the displacement to six class difference chemical environments in emergencing copolymer -2.The result also further demonstrate polymer -2 into
Work(synthesizes.
N of the polymer -2 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in Figure 6, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -2；In middle high relative pressure region
(P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -2.Last desorption curve does not have
Have and closed completely with adsorption curve, this is because part N2Remain in the hole of sample polymer -2 and fail to be made by thorough desorption
Into.
Embodiment 3
By four (4- bromophenyls) methane (636.02mg, 1mmol) and two kinds of monomers of o-phenylenediamine (216.28mg, 2mmol)
It is placed in Schlenk pipes (200ml), double (dibenzalacetone) palladiums (46mg, 0.08mmol) of addition, 2- dicyclohexylphosphontetrafluoroborate -2',
4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in a nitrogen atmosphere
Add 150mL toluene, coupling reaction 24h in 110 DEG C of oil baths.After reaction, 12h is first washed with deionized, then in rope
24h is washed with chloroform and methanol respectively in family name's extractor, to remove unreacted raw material and oligomer.Finally it is placed in 60 DEG C
Under vacuum drying oven in dry 24h, obtain high nitrogen-containing conjugation microporous polymer, be denoted as polymer -3, its BET specific surface area is
81m2/g。
Polymer -3 and four (4- bromophenyls) methane that the present embodiment obtains, the ATR-IR test results of o-phenylenediamine are as schemed
Shown in 7, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1Place is adjacent there are stretching vibration peak
- NH in phenylenediamine2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The flexural vibrations peak at place, these features
Peak disappears in the spectrum of polymer -3, illustrates that there is no C-Br and-NH in polymer -32Functional group；While polymer -3
813cm is clearly present in spectrum-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that phenyl ring is not destroyed, so as to characterize polymerization
The successful synthesis of thing -3.
The polymer -3 that the present embodiment obtains13C-NMR test results are as shown in Figure 8, it is known that have 5 kinds of different carbon in figure
Peak：Its chemical shift is respectively 140ppm, 133ppm, 128ppm, 114ppm and 62.5ppm, this five kinds of chemical shifts are just right
Answer the carbon atom of 5 class difference chemical environments in polymer -3.The result also further demonstrate the successful conjunction of polymer -3
Into.
N of the polymer -3 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in Figure 9, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -3；In middle high relative pressure region
(P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -3.Last desorption curve does not have
Have and closed completely with adsorption curve, this is because part N2Remain in the hole of sample polymer -3 and fail to be made by thorough desorption
Into.
Embodiment 4
By four (4- bromophenyls) methane (636.02mg, 1mmol) and 2,3- diamino-pyridine (218.26mg, 2mmol) two
Kind monomer is placed in Schlenk pipes (200ml), adds double (dibenzalacetone) palladiums (46mg, 0.08mmol), 2- dicyclohexyls
Phosphine -2', 4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in nitrogen
150mL toluene, coupling reaction 24h in 110 DEG C of oil baths are added under atmosphere.After reaction, 12h is first washed with deionized, so
24h is washed with chloroform and methanol respectively in apparatus,Soxhlet's afterwards, to remove unreacted raw material and oligomer.Most postposition
Dry 24h in vacuum drying oven at 60 DEG C, obtains high nitrogen-containing conjugation microporous polymer, is denoted as polymer -4, its BET compares table
Area is 54m2/g。
The ATR-IR tests of polymer -4 and four (4- bromophenyls) methane, 2,3- diamino-pyridines that the present embodiment obtains are tied
Fruit is as shown in Figure 10, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1There is flexible shake in place
Dynamic the peak ,-NH in 2,3- diamino-pyridines2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The bending at place is shaken
Dynamic peak, these characteristic peaks disappear in the spectrum of polymer -4, illustrate that there is no C-Br and-NH in polymer -42Functional group；Together
When polymer -4 spectrum in be clearly present 813cm-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that aromatic ring is not destroyed,
So as to characterize the successful synthesis of polymer -4.
The polymer -4 that the present embodiment obtains13C-NMR test results are as shown in figure 11, it is known that have 5 classes different in figure
Carbon peak：Its chemical shift is respectively 139ppm, 130ppm, 118.5ppm, 115ppm, 62.5ppm, this at five chemical shift correspond to
The carbon atom of 5 kinds of different chemical environments in polymer -4.The result also further demonstrate the successful synthesis of polymer -4.
N of the polymer -4 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in figure 12, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -4；In middle high relative pressure region
(P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -4.Last desorption curve does not have
Have and closed completely with adsorption curve, this is because part N2Remain in the hole of sample polymer -4 and fail to be made by thorough desorption
Into.
Embodiment 5
By four (4- bromophenyls) methane (636.02mg, 1mmol) and 2,5- diamino-pyridine (218.26mg, 2mmol) two
Kind monomer is placed in Schlenk pipes (200ml), adds double (dibenzalacetone) palladiums (46mg, 0.08mmol), 2- dicyclohexyls
Phosphine -2', 4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in nitrogen
150mL toluene, coupling reaction 24h in 110 DEG C of oil baths are added under atmosphere.After reaction, 12h is first washed with deionized, so
24h is washed with chloroform and methanol respectively in apparatus,Soxhlet's afterwards, to remove unreacted raw material and oligomer.Most postposition
Dry 24h in vacuum drying oven at 60 DEG C, obtains high nitrogen-containing conjugation microporous polymer, is denoted as polymer -5, its BET compares table
Area is 37m2/g。
The ATR-IR tests of polymer -5 and four (4- bromophenyls) methane, 2,5- diamino-pyridines that the present embodiment obtains are tied
Fruit is as shown in figure 13, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1There is flexible shake in place
Dynamic the peak ,-NH in 2,5- diamino-pyridines2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The bending at place is shaken
Dynamic peak, these characteristic peaks disappear in the spectrum of polymer -5, illustrate that there is no C-Br and-NH in polymer -52；It polymerize at the same time
The spectrum of thing -5, in be clearly present 813cm-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that aromatic ring is not destroyed, so that
Characterize the successful synthesis of polymer -5.
The polymer -5 that the present embodiment obtains13C-NMR test results are as shown in figure 14, it is known that have 6 classes different in figure
Carbon peak：Its chemical shift is respectively 146ppm, 139ppm, 130.5ppm, 119ppm, 115ppm and 62.5ppm, this chemistry at six
Carbon atom of the displacement to 6 kinds of different chemical environments in emergencing copolymer -5.The result also further demonstrate polymer -5 into
Work(synthesizes.
N of the polymer -5 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in figure 15, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -5；In middle high relative pressure region
(P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -5.Last desorption curve does not have
Have and closed completely with adsorption curve, this is because part N2Remain in the hole of sample polymer -5 and fail to be made by thorough desorption
Into.
Embodiment 6
By four (4- bromophenyls) methane (636.02mg, 1mmol) and 2,6-diaminopyridine (218.26mg, 2mmol) two
Kind monomer is placed in Schlenk pipes (200ml), adds double (dibenzalacetone) palladiums (46mg, 0.08mmol), 2- dicyclohexyls
Phosphine -2', 4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in nitrogen
150mL toluene, coupling reaction 24h in 110 DEG C of oil baths are added under atmosphere.After reaction, 12h is first washed with deionized, so
24h is washed with chloroform and methanol respectively in apparatus,Soxhlet's afterwards, to remove unreacted raw material and oligomer.Most postposition
Dry 24h in vacuum drying oven at 60 DEG C, obtains high nitrogen-containing conjugation microporous polymer, is denoted as polymer -6, its BET compares table
Area is 37m2/g。
The ATR-IR test knots of polymer -6 and four (4- bromophenyls) methane that the present embodiment obtains, 2,6-diaminopyridine
Fruit is as shown in figure 16, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1There is flexible shake in place
Dynamic the peak ,-NH in 2,6-diaminopyridine2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The bending at place is shaken
Dynamic peak, these characteristic peaks disappear in the spectrum of polymer -6, illustrate that there is no C-Br and-NH in polymer -62；It polymerize at the same time
813cm is clearly present in the spectrum of thing -6-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that aromatic ring is not destroyed, so that table
Levy the successful synthesis of polymer -6.
The polymer -6 that the present embodiment obtains13C-NMR test results are as shown in figure 17, it is known that have 6 in figure significantly
Carbon peak：Its chemical shift is respectively 154ppm, 139ppm, 130.5ppm, 119ppm, 100.5ppm, 62.5ppm, this changes at six
Displacement study just correspond to the carbon atom of 6 different chemical environments in polymer -6.The result also further demonstrate polymerization
The successful synthesis of thing -6.
N of the polymer -6 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in figure 18, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -6；In middle high relative pressure region
(P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -6.Last desorption curve does not have
Have and closed completely with adsorption curve, this is because part N2Remain in the hole of sample polymer -6 and fail to be made by thorough desorption
Into.
Embodiment 7
By four (4- bromophenyls) methane (636.02mg, 1mmol) and 3,4- diamino-pyridine (218.26mg, 2mmol) two
Kind monomer is placed in Schlenk pipes (200ml), adds double (dibenzalacetone) palladiums (46mg, 0.08mmol), 2- dicyclohexyls
Phosphine -2', 4', 6'- tri isopropyl biphenyl (57.21mg, 0.12mmol), sodium tert-butoxide (499.72mg, 5.2mmol), in nitrogen
150mL toluene, coupling reaction 24h in 110 DEG C of oil baths are added under atmosphere.After reaction, 12h is first washed with deionized, so
24h is washed with chloroform and methanol respectively in apparatus,Soxhlet's afterwards, to remove unreacted raw material and oligomer.Most postposition
Dry 24h in vacuum drying oven at 60 DEG C, obtains high nitrogen-containing conjugation microporous polymer, is denoted as polymer -7, its BET compares table
Area is 24m2/g。
The ATR-IR tests of polymer -7 and four (4- bromophenyls) methane, 3,4- diamino-pyridines that the present embodiment obtains are tied
Fruit is as shown in figure 19, it is known that the C-Br in four (4- bromophenyls) methane on aromatic ring is in 510,532 and 1079cm-1There is flexible shake in place
Dynamic the peak ,-NH in 3,4- diamino-pyridines2In 3421 and 3334cm-1There are stretching vibration peak and 1632cm at place-1The bending at place is shaken
Dynamic peak, these characteristic peaks disappear in the spectrum of polymer -7, illustrate that there is no C-Br and-NH in polymer -72；It polymerize at the same time
813cm is clearly present in the spectrum of thing -7-1The flexural vibrations peak of C-H on the aromatic ring at place, illustrates that aromatic ring is not destroyed, so that table
Levy the successful synthesis of polymer -7.
The polymer -7 that the present embodiment obtains13C-NMR test results are as shown in figure 20, it is known that have in figure 7 kinds it is different
Carbon peak：Its chemical shift be respectively 145ppm, 137ppm, 130.5ppm, 119.5ppm, 114.5ppm, 110ppm and
62.5ppm, carbon atom of this seven kinds of chemical shifts to 7 kinds of different chemical environments in emergencing copolymer -7.The result is also further
Confirm the successful synthesis of polymer -7.
N of the polymer -7 that the present embodiment obtains under 77.4K2Adsorption-desorption curve it is as shown in figure 21, it is known that absorption
Thermoisopleth is in low relative pressure region (P/P0<0.001) when, gas absorption has the stage of one section of rapid growth, and the slope of curve is very
Height, this is because the effect of micropore filling, shows that there are substantial amounts of microcellular structure in polymer -7；And in Zhong Gao relative pressures area
Domain (P/P0=0.1~1.0) when, curve has obvious rise to show eurypyloue presence in polymer -7.Last desorption curve
No and adsorption curve closes completely, this is because part N2Remain in the hole of sample polymer -7 and fail thoroughly to be desorbed
Caused by.
Claims (10)
1. a kind of synthetic method of high nitrogen-containing conjugation microporous polymer, including：
Four (4- bromophenyls) methane are mixed with aryl diamine, palladium catalyst, catalyst ligand, alkaline agent are added, then in nitrogen gas
Added under atmosphere at 105~115 DEG C of solvent and carry out 22~26h of coupling reaction, washed, it is micro- that vacuum drying obtains high nitrogen-containing conjugation
Pore polymer；Wherein four (4- bromophenyls) methane, aryl diamine, palladium catalyst, catalyst ligand, the molar ratio of alkaline agent are 1：2：
0.05~0.1：0.1~0.15：5~5.5.
A kind of 2. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
Aryl diamine is the aromatic compounds containing two amidos, selected from p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 2,3- diamino-pyridines,
2,5- diamino-pyridines, 2,6- diamino-pyridines or 3,4- diamino-pyridines.
A kind of 3. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
Palladium catalyst is double (dibenzalacetone) palladiums.
A kind of 4. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
Catalyst ligand is 2- dicyclohexylphosphontetrafluoroborates -2', 4', 6'- tri isopropyl biphenyl.
A kind of 5. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
Alkaline agent is sodium tert-butoxide.
A kind of 6. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
Solvent is toluene, and the amount ratio of toluene and four (4- bromophenyls) methane is 150mL：1mmol.
A kind of 7. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
The process conditions of washing are：12h is first washed with deionized, then washs 24h with organic solvent surname extraction.
A kind of 8. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 7, it is characterised in that：It is described
Organic solvent is chloroform and methanol.
A kind of 9. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：It is described
Vacuum drying technological parameter is：Vacuum drying temperature is 55~65 DEG C, and vacuum drying time is 22~26h.
A kind of 10. synthetic method of high nitrogen-containing conjugation microporous polymer according to claim 1, it is characterised in that：Institute
State high nitrogen-containing conjugation microporous polymer and be used for gas absorption, catalyst carrier or energy storage.
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| CN110305320A (en) * | 2019-07-05 | 2019-10-08 | 福建师范大学 | Micropore organic polymer containing abundant nitrogen site |
| CN110483769A (en) * | 2019-08-15 | 2019-11-22 | 东华大学 | Two fluorenes of spiral shell is conjugated microporous polymer/carbon nano-tube hybridization material and preparation method thereof |
| CN111484614A (en) * | 2020-03-20 | 2020-08-04 | 东华大学 | Preparation method of supercapacitor electrode material |
| CN114870652A (en) * | 2022-05-10 | 2022-08-09 | 镇江猎盾特种材料有限公司 | Porphyrin-based conjugated microporous polymer blended ultrafiltration membrane, preparation and application |
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| CN114870652B (en) * | 2022-05-10 | 2024-05-31 | 镇江猎盾特种材料有限公司 | Porphyrin-based conjugated microporous polymer blended ultrafiltration membrane, and preparation and application thereof |
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| CN110305319A (en) * | 2019-07-05 | 2019-10-08 | 福建师范大学 | The preparation method of microporous polymer |
| CN110305320A (en) * | 2019-07-05 | 2019-10-08 | 福建师范大学 | Micropore organic polymer containing abundant nitrogen site |
| CN110305319B (en) * | 2019-07-05 | 2021-08-10 | 福建师范大学 | Process for preparing microporous polymers |
| CN110305320B (en) * | 2019-07-05 | 2021-08-10 | 福建师范大学 | Microporous organic polymers containing rich nitrogen sites |
| CN110483769A (en) * | 2019-08-15 | 2019-11-22 | 东华大学 | Two fluorenes of spiral shell is conjugated microporous polymer/carbon nano-tube hybridization material and preparation method thereof |
| CN111484614A (en) * | 2020-03-20 | 2020-08-04 | 东华大学 | Preparation method of supercapacitor electrode material |
| CN114870652A (en) * | 2022-05-10 | 2022-08-09 | 镇江猎盾特种材料有限公司 | Porphyrin-based conjugated microporous polymer blended ultrafiltration membrane, preparation and application |
| CN114870652B (en) * | 2022-05-10 | 2024-05-31 | 镇江猎盾特种材料有限公司 | Porphyrin-based conjugated microporous polymer blended ultrafiltration membrane, and preparation and application thereof |
| WO2024053282A1 (en) * | 2022-09-09 | 2024-03-14 | Jsr株式会社 | Polymer, composition, cured product, laminate, and electronic component |
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