CN109762142A - A kind of conjugate polymer material based on photo-thermal effect regulation carbon dioxide adsorption - Google Patents
A kind of conjugate polymer material based on photo-thermal effect regulation carbon dioxide adsorption Download PDFInfo
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Abstract
The present invention provides a kind of conjugate polymer materials based on photo-thermal effect regulation carbon dioxide adsorption.The structural formula of the conjugate polymer material is as shown in Equation 1.Wherein R is the functional group containing guanidine radicals, azido and polyethyleneimine (PEI), and A is the hexa-atomic aromatic ring containing 0-3 N atom, and structural unit number n is 4-60.This conjugated polymer, which possesses high surface, to reach 0.8mmol/g to the adsorption capacity of carbon dioxide with biggish specific surface area.Polymer has strong absorption near 808nm, and photothermal conversion ability is stronger, transfer efficiency 15%-35%.Polymer possesses gas absorption and photothermal conversion dual characteristics, and the absorption and release of carbon dioxide can be dynamically controlled by near infrared light, presents excellent application prospect of the pyrrolopyrrole type conjugated polymer in terms of gas absorption.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of conjugation high score based on photo-thermal effect regulation carbon dioxide adsorption
Sub- material.
Background technique
Carbon dioxide (CO2) closely bound up with vital movement, bear the acid-base balance for adjusting animal blood, cell liquid
Important task.CO2And plant vital activity is primarily involved in gas, CO2The variation of concentration directly affects the photosynthesis of plant and exhales
The intensity of suction effect.CO2It is the chief component of atmospheric greenhouse gas, with the improvement of people's environmental awareness, exploitation is cut
Real feasible CO2Biological activity, monitoring climate change and control agriculture in greenhouse production of the absorption/releasable material to life entity is adjusted
It is of great importance.
CO2Adsorption capacity be heavily dependent on the specific surface area of material, aperture and material surface can etc. factors.
Industrial widely used adsorbent material mainly has porous carbon materials, porous molecular screen, porous silica and metal bone at present
Frame porous material etc., these materials have the advantage of big specific surface area, but generally existing gas-selectively is lower, nothing is controllable
The shortcomings that releasability.People's material absorption property in order to further increase, people are often with organic amine compound to above-mentioned
Material is chemically treated, but reduces the stability of material.Porous conjugated polymer be developed in recent years one kind it is novel
Adsorbent material is the 3 D stereo macromolecule with the structural unit being continuously conjugated and pi-electron delocalization structure.Has stability
It is good, specific surface area is high, selection performance is good and the advantages such as large amount of adsorption, cause people's extensive concern.It is a large amount of inside conjugated polymer
Phenyl ring, pyrroles's equiconjugate structure enhance again material surface can, impart conjugated polymer to CO2Strong adsorption energy
Power.But people often only lay particular emphasis on the conjugated polymer of exploitation high absorption property at present, for having controlled release capability
Conjugated polymer is seldom interesting.CO is controlled using photo-thermal effect2Absorption release is one main research side, current scientific and technological circle
To.Polyethyleneimine and graphite alkenes adsorbent material have gas absorption and the characteristics of photo-thermal effect controlled releases, but photo-thermal
Transformation efficiency is low, limits extensive use.
Summary of the invention
An object of the present invention is to provide a kind of DPP type conjugated polymer.
DPP type conjugated polymer provided by the present invention, structural formula are as shown in Equation 1:
In above-mentioned formula 1, R is any one in following group:
In above-mentioned formula 1, A is with flowering structure, and wherein X is C or N atom；
Specifically, A is any one in following four:
Wherein,It indicates to replace position；
In above-mentioned formula 1, n is structural unit number, concretely 4-60.
DPP type conjugated polymer shown in above-mentioned formula 1 passes through the method included the following steps and is prepared:
Under the action of catalyst and ligand, by compound 2 shown in formula 2, bis- (the 5- bromine thiophenes of bis- (6-R base hexyl) -3, the 6- of 5-
Pheno -2- base) coupling reaction occurs for compound shown in pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone and formula 3, obtain formula 1
Shown DPP type conjugated polymer, wherein R beN3 is indicated with PDPP-Az.
R is in above-mentioned formula 2N3；
X is C or N atom in above-mentioned formula 3.
In the above method, the catalyst can are as follows: tris(dibenzylideneacetone) dipalladium (Pd2(dba)3) or four triphenylphosphines
Palladium (Pd (PPh3)4)；
The ligand can are as follows: triphenylphosphine (P (o-tol)3) or three (o-methyl-phenyl) phosphorus；
The molar ratio of compound shown in compound shown in formula 2 and formula 3 can be 3:2；
The molar ratio of compound shown in formula 2 and the catalyst, ligand successively may be used are as follows: 3:0.08-0.2:0.08-0.2, tool
Body can be 3:0.1:0.1.
The temperature of the coupling reaction can be 90-110 DEG C, and the time can be 12-24 hours.
The coupling reaction carries out in organic solvent, the organic solvent concretely toluene or chlorobenzene, benzene, tetrahydro furan
It mutters, chloroform.
The method can also further comprise that the PEI of PDPP-Az and 3- guanidine radicals -1- propine or alkynyl is carried out Click
Reaction, obtains R and is followed successively by DPP type conjugated polymer shown in the formula 1 of R1 or R3.
Wherein, the PEI of alkynyl carries out processing to PEI using the method in document and is made
(DOI:10.1016/j.carres.2006.04.028), the alkynyl specific method of PEI: be by 1g PEI,
0.4g propargylic acid and 1.5g EEDQ catalyst are dissolved in 25ml chloroform, and nitrogen protection stirring at normal temperature is for 24 hours.
In the Click reaction, the molar ratio of PDPP-Az and 3- guanidine radicals -1- propine or the PEI of alkynyl can are as follows: and 1:2~
5；
Dual catalyst used is made of cuprous bromide (CuBr) and pentamethyl-diethylenetriamine (PMDETA).
The molar ratio of the PDPP-Az and cuprous bromide, pentamethyl-diethylenetriamine successively may be used are as follows: 1:2~6:5~10.
The reaction temperature of the Click reaction can be room temperature, and the time can be 30-40 hours.
Click reaction carries out in organic solvent, the organic solvent concretely N, N '-dimethyl formamide
(DMF)。
DPP type conjugated polymer is in CO shown in above-mentioned formula 12Application in absorption/release also belongs to protection model of the invention
It encloses.
Further, DPP type conjugated polymer shown in above-mentioned formula 1 can be used for regulating and controlling CO in organism2Absorption and release.
It is a further object of the present invention to provide a kind of CO2Adsorbent material.
CO provided by the present invention2Adsorbent material contains DPP type conjugated polymer shown in formula 1.
CO is adjusted using DPP type conjugated polymer shown in formula 1 the present invention also provides a kind of2Absorption and release method.
The method, are as follows: the illumination power by controlling NIR makes polymer be raised to different temperature, to adjust polymerization
Object is to CO2Adsorption capacity.
That is, making DPP type conjugated polymer CO absorption shown in formula 12；Then NIR irradiation is carried out, so that the CO of absorption2Gradually
Release.
Concretely: polymer P DPP-Gu is in CO215min is adsorbed under atmosphere, is then irradiated using NIR, and the function of light is adjusted
Rate is 1W/cm2, illumination 5min or so, temperature rises to 80 DEG C or more, gradually releases CO2。
The DPP type that present invention design has synthesized a kind of three-dimensional netted absorption carbon dioxide with photothermal conversion ability is total
Conjugated polymer material can effectively adjust CO under the irradiation of NIR2Absorption and release process.
The present invention has the advantages that
1. synthetic method is simple and easy, synthetic route is shorter, and reaction yield is higher, and raw material is cheap, can promote and apply work
Synthesis in industry.
2. this conjugated polymer surface can be higher, while having higher specific surface area and pore structure, to CO2Have very strong
Selective adsorption capacity, to develop DPP type CO2Adsorbent material explores road.
3. this conjugated polymer absorbance near 808nm, has very strong photothermal conversion ability (15%-35%), due to
The stronger penetration capacity of infrared light, the material can regulate and control CO in vivo2Absorption and release.
4. introducing energy and CO inside polymer molecule2The functional group of reaction upgrades to object by single physisorption material
The shared material of reason/chemisorption.
Present invention design has synthesized a kind of near-infrared area (NIR) absorption CO2DPP type conjugated polymer, in the photograph of NIR light
It penetrates down, polymer can show strong photothermal conversion ability.In addition introducing and CO on polymer side chain2The guanidine radicals official of effect
It can roll into a ball, common physical absorption is upgraded into the shared structure of physical/chemical adsorption.This polymer combination photothermal conversion and
CO2The double dominant of absorption can effectively adjust CO under the irradiation of NIR2Absorption and release process.
Detailed description of the invention
Fig. 1 is the synthetic route chart of polymer shown in Chinese style 1 of the present invention.
Fig. 2 is the polymer P DPP-Az that the prepares and PDPP-Gu prepared in the embodiment of the present invention 2 in the embodiment of the present invention 1
Infrared spectrogram.
Fig. 3 is the SEM and molecular structure of polymer P DPP-Gu.The SEM that Fig. 3 a is PDPP-Gu schemes, upper right corner insertion
Picture is polymer P DPP-Gu sample drawing；Fig. 3 b illustrates the 3D structure for the propeller that PDPP-Gu molecule has.
Fig. 4 is polymer P DPP-Gu absorbance and light thermal property figure.Fig. 4 a is the absorbance figure of polymer P DPP-Gu；Figure
4b concentration is the infrared thermal imaging figure before and after the polymer P DPP-Gu aqueous solution illumination of 80 μ g/mL；Fig. 4 c is polymer P DPP-
The photo-thermal effect test chart of Gu；Fig. 4 d is the specific temperature lift-down curve of PDPP-Gu.
Fig. 5 is pore-size distribution, the CO of polymer P DPP-Gu2Absorption, release and selective phenogram.Fig. 5 a Fig. 5 b is 77K
At a temperature of, N2Adsorption/desorption curve and polymer P DPP-Gu graph of pore diameter distribution；Fig. 5 c is PDPP-Gu to CO2273K,
The absorption figure of 298K and to N2In the gas absorption figure of 273K；Fig. 5 d is PDPP-Gu CO absorption2When heat of adsorption.
The thermogravimetric that Fig. 6 is polymer P DPP-Gu adsorbs De contamination CO2Performance map and BTB solution testing CO absorption2Performance map；
Absorption/desorption CO of Fig. 6 a polymer P DPP-Gu2Thermogravimetric curve；Fig. 6 b is gas release before and after polymer P DPP-Gu illumination
Figure.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
In following embodiments, the monomer of A used is 1,3,5- tri- (boric acid pinacol ester) benzene, and R is R1 group.
The synthesis of embodiment 1, polymer P DPP-Gu
(1) bis- (6- bromine hexyl) -3,6- bis- (thiophene -2- base) pyrroles [3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, the 5H)-diketone of 2.5-
Synthesis
Under nitrogen protection, the compound DPP, 0.1g (2.2eq) of 0.25g (1eq) are sequentially added into the bottle with two necks of 100mL
The DMF of sodium hydride, 1.05g (5eq) 1,6- dibromo-hexane and 7mL.It is warming up to 115 DEG C the reaction was continued for 24 hours.Methylene chloride extraction,
Anhydrous sodium sulfate is dry.Residue is to produce with silica gel chromatograph post separation (methylene chloride: petroleum ether=5:1), first point of contact plate
Object point, yield 58.4%.
Structural characterization data are as follows:
1H-NMR(400MHz,CDCl3): δ (ppm) 8.93 (d, J=3.6Hz, 2H), 7.66 (d, J=5.2Hz, 2H),
7.31 (d, J=4.8Hz, 2H), 4.11 (t, J=5.2Hz, 4H), 3.42 (t, J=5.2Hz, 4H), 1.25-1.88 (m, 16H).
(2) bis- (6- AzidoheXyl) -3,6- bis- (thiophene -2- base) pyrroles [3, the 4-c] pyrroles-Isosorbide-5-Nitraes (2H, 5H)-of 2.5-
The synthesis of diketone
Under nitrogen protection, bis- (6- bromine hexyl) -3, the 6- bis- of 1.6g (1eq) 2.5- are sequentially added into the single port bottle of 25mL
(thiophene -2- base) pyrroles [3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, 1.44mL (4eq) TMSN3, 10.23mL (4eq) TBAF
With 12mL THF.Reaction mixture is stirred 3 hours at 65 DEG C.Methylene chloride extraction, anhydrous sodium sulfate are dry.Residue silicon
Glue chromatography post separation (THF: petroleum ether=5:1), contact plate third point are product point, yield 84.5%.
Structural characterization data are as follows:
1H-NMR(400MHz,CDCl3): δ (ppm) 8.93 (d, J=3.6Hz, 2H), 7.65 (d, J=8.8Hz, 2H),
7.30 (d, J=7.8Hz, 2H), 4.10 (t, J=5.2Hz, 4H), 3.28 (t, J=7Hz, 4H), 1.25-1.78 (m, 16H).
(3) bis- (6- the AzidoheXyl) -3,6- two of monomer 2.5- (5- bromothiophene -2- base) pyrroles [3,4-c] pyrroles -1,4
The synthesis of (2H, 5H)-diketone
Bis- (6- the AzidoheXyl) -3,6- two (thiophene -2- of 0.5g (1eq) 2.5- are sequentially added into the single port bottle of 10mL
Base) pyrroles [3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone and 5mL CHCl3.0.32g (2eq) is added after stirring 10min under ice bath
6h is stirred at room temperature after adding in NBS.Reaction product is poured into 100mL water, is extracted with dichloromethane, and filtering is clear with acetone after being spin-dried for
Wash remaining succinimide, filtration drying.Yield 95.0%.
Structural characterization data are as follows:
1H-NMR(400MHz,CDCl3): δ (ppm) 8.68 (d, J=4Hz, 2H), 7.24 (d, J=4.4Hz, 2H), 4.01
(t, J=7.6Hz, 4H), 3.29 (t, J=6.8Hz, 4H), 1.25-1.77 (m, 16H).
(4) synthesis of monomer 1,3,5- tri- (boric acid pinacol ester) benzene
Under nitrogen protection, it is double that 1,3,5- tribromo-benzene of 1.00g (2eq), 2.54g (3eq) are sequentially added to the bottle with two necks of 100mL
(pinacol combined) two boron, 1.87g (6eq) potassium acetate, 0.087g (0.04eq) PdCl2(dppf) and 10mL DMF.At 90 DEG C
Heating 24 hours.After being cooled to room temperature, 120mL deionized water is added.Black precipitate is collected by filtration, and is washed with deionized three
It is secondary, vacuum drying.Yield 98.0%.
Structural characterization data are as follows:
1H-NMR(400MHz,CDCl3): δ (ppm) 8.37 (s, 3H), 1.33 (s, 36H).
(5) synthesis of 3- guanidine radicals -1- propine
0.36g (1eq) propargylamine, 0.87g (1eq) 1H- pyrazoles -1- carbonamidine hydrochloric acid are sequentially added to the bottle with two necks of 100mL
Salt, 0.78g (1eq) triethylamine and 3mL DMF.Room temperature persistently stirs 16 hours.It is different that 100mL is poured this solution into after reaction
In propyl ether, the supernatant containing DMF and other impurities is discarded.Oil product is dried under vacuum, and obtains the product of oily.Yield
88.0%.
Structural characterization data are as follows:
1H-NMR (400MHz, DMSO): δ (ppm) 7.50 (br, 4H), 4.06 (d, J=6Hz, 2H), 2.51 (s, 1H)；1H-
NMR(400MHz,D2O): 4.01 (d, J=6.8Hz, 2H), 2.74 (s, 1H).
(5) synthesis of polymer P DPP-Az
Bis- (6- AzidoheXyl) (the 5- bromothiophenes-of -3,6- two of 100mg (3eq) 2.5- are sequentially added to the bottle with two necks of 25mL
2- yl) pyrroles [3,4-c] pyrroles-Isosorbide-5-Nitrae (2H, 5H)-diketone, 43mg (2eq) 1,3,5- tri- (boric acid pinacol ester) benzene, 4.3mg
(0.1eq) catalyst Pd2(dba)3, 1.2mg (0.1eq) ligand P (o-tol)3, one drop phase transfer catalyst Aliquat 336 plus
Enter into reaction flask, 0.8mL 2M K2CO3Aqueous solution and 10mL toluene.It is freezed three times in the case where argon gas protection, liquid nitrogen are cooling
Then reaction mixture is heated to 100 DEG C of reflux for 24 hours by deoxygenation.It is successively cleaned after reaction with methylene chloride, ethyl alcohol, water
Final product is obtained by filtration in polymer.Yield 71.4%.
Structural characterization data are as follows: infrared spectroscopy (cm-1): 2927.5,2852.2,2092.4,1662.3,1560.1,
1380.8,1083.8,804.2,732.8.
Infrared spectrogram is Fig. 2.
(6) synthesis of polymer P DPP-Gu
312mg polymer P DPP-Az, 140mg 3- guanidine radicals -1- propine, 500 μ L are sequentially added to the bottle with two necks of 25mL
PMDETA, 220mg CuBr and 15mL DMF, alkine compounds/azide ratio are set as 2:1.Mixture is existed first
Ultrasound 30 minutes, are then stirred at room temperature 36 hours under the power of 300W.After reaction successively with methylene chloride, ethyl alcohol,
Water cleaning cleaning polyalcohol, 6000rpm are centrifuged to obtain final product.Yield 70%.
Structural characterization data are as follows: infrared spectroscopy (cm-1): 3453.9,2927.5,2852.2,1662.3,1560.1,
1380.8,1083.8,804.2,732.8.
Infrared spectrogram is Fig. 2.
Structure, photo-thermal and the CO of the resulting conjugated polymer PDPP-Gu of 2 embodiment of embodiment 12Absorption property
(1) infrared spectrum characterization of conjugated polymer PDPP-Gu
Fig. 2 is the infrared spectrogram of PDPP-Gu, and compared with PDPP-Az, PDPP-Gu is in 2097cm-1Neighbouring-N3Group
Guanidine radicals peak near peak disappearance instead 3300.
(2) the microcosmic and molecular structure of conjugated polymer PDPP-Gu
The SEM that Fig. 3 a is PDPP-Gu schemes, and polymer has a large amount of pore structure on a microscopic scale as seen from the figure, tool
There is biggish specific surface area.Fig. 3 b illustrates the 3D structure for the propeller that PDPP-Gu molecule has, this is polymer P DPP-Gu
Possess biggish specific surface area and provides structure basis.
(3) absorbance of conjugated polymer PDPP-Gu and photothermal conversion performance
Fig. 4 a is the absorbance figure of polymer P DPP-Gu.As seen from the figure, polymer has very within the scope of 700-820nm
Strong absorbability, this shows that PDPP-Gu can be used as a kind of potential NIR absorbing material.Polymer concentration is 80 μ g/mL,
Water is solvent, is tested using 250 work station of analytikjena SPECORD.
Fig. 4 b concentration is the infrared thermal imaging figure before and after the polymer P DPP-Gu aqueous solution illumination of 80 μ g/mL.
Fig. 4 c is the photo-thermal effect test chart of polymer P DPP-Gu.
As seen from the figure, polymer P DPP-Gu is in 2W/cm2Light intensity under irradiate 5min, temperature reaches 60 DEG C, be higher than it is identical
The temperature of graphene oxide solution under warm concentration is compared with pure water blank group, and temperature improves 26 DEG C.
Fig. 4 d is the specific temperature lift-down curve of PDPP-Gu, this, which sufficiently illustrates polymer P DPP-Gu, has excellent photo-thermal to turn
Transducing power.According to the calculation method of document (DOI:10.1021/jp064341w), transfer efficiency reaches 21.4%.PDPP-Gu,
Graphene oxide (GO), reproducibility graphene oxide (rGO) concentration are that 80 μ g/mL, 808nm laser powers are 2W/cm2, shine
Penetrate time 5min.
(4) pore-size distribution of polymer P DPP-Gu, CO2Absorption, release and selection performance characterization
At a temperature of Fig. 5 a Fig. 5 b is 77K, N2Adsorption/desorption curve and polymer P DPP-Gu graph of pore diameter distribution, by scheming
Know that mesoporous inside PDPP-Gu and macropore accounts for the overwhelming majority, material possesses higher specific surface area, specific surface area 81.72m2/
g.Adsorption instrument is mostly used using the tri- station full function of 3Flex of micromeritics company to be tested.
Fig. 5 c is PDPP-Gu to CO2In the absorption figure of 273K, 298K and to N2In the gas absorption figure of 273K, You Tuke
Know, PDPP-Gu is to CO2Adsorption capacity be N2More than 100 times, in the case where 0 DEG C of 1bar, to CO2Absorption reach
0.8mmol/g.Caused by this mainly following three kinds of reason: (1) since a large amount of N, S, O etc. are heteroatomic higher in the presence of causing
Surface can, enhance the Van der Waals force of material；(2) cyclic structure energy and CO are conjugated2Stronger π-π interaction occurs；(3)
Guanidine radicals also can be with CO2Certain chemical reaction occurs.
Fig. 5 d is PDPP-Gu CO absorption2When heat of adsorption, as seen from the figure, for heat of adsorption near 30KJ/mol, surface can be compared with
It is high.
(5) photo-thermal effect of polymer P DPP-Gu controls CO2Adsorb releasability
Absorption/desorption CO of Fig. 6 a polymer P DPP-Gu2Thermogravimetric curve (25-85 DEG C of temperature, 101.3KPa), 25
DEG C, CO absorption under conditions of 1bar2Quality increases about 1.6% afterwards, and quality is almost restored after illumination.It uses
The STA2500Regulus synchronous solving work station of NETZSCH company is tested.
Fig. 6 b is gas release figure (the 0.25%BTB solution of pH=7, optical wavelength before and after polymer P DPP-Gu illumination
808nm, light intensity 2W/cm2), it is released with 0.25% bromothymol blue (BTB) solution of pH=7 detection polymer P DPP-Gu in figure
The CO put2.In the BTB solution for being passed through 1mL of the gas slowly of release, the experimental group BTB solution of illumination becomes obvious from blue
Brown color, the control group color without illumination but changes seldom.
Claims (10)
1. DPP type conjugated polymer shown in formula 1:
In above-mentioned formula 1, R is any one in following group:
In above-mentioned formula 1, A is with flowering structure, and wherein X is C or N atom；
It indicates to replace position；
In above-mentioned formula 1, n is structural unit number, is 4-60.
2. preparing the method that R in claim 1 is DPP type conjugated polymer shown in azido up-to-date style 1, comprising:
Under the action of catalyst and ligand, coupling reaction is occurred into for compound shown in compound shown in formula 2 and formula 3, obtains formula 1
Shown DPP type conjugated polymer, wherein R be
R is in formula 2
X is C or N atom in formula 3.
3. according to the method described in claim 2, it is characterized by: the catalyst are as follows: tris(dibenzylideneacetone) dipalladium or
Tetra-triphenylphosphine palladium；
The ligand are as follows: triphenylphosphine or three (o-methyl-phenyl) phosphorus；
The molar ratio of compound shown in compound shown in formula 2 and formula 3 is 3:2；
Compound shown in formula 2 and the catalyst, ligand molar ratio successively are as follows: 3:0.08-0.2:0.08-0.2；
The temperature of the coupling reaction is 90-110 DEG C, and the time is 12-24 hours；
The coupling reaction carries out in organic solvent, the organic solvent concretely toluene or chlorobenzene, benzene, tetrahydrofuran,
Chloroform.
4. according to the method in claim 2 or 3, it is characterised in that: it is azido that the method, which is still further comprised R,
DPP type conjugated polymer shown in formula 1 carries out Click with the PEI of 3- guanidine radicals -1- propine or alkynyl and reacts, and obtains R and is followed successively by R1
Or DPP type conjugated polymer shown in the formula 1 of R3.
5. according to the method described in claim 4, it is characterized by: R is shown in the formula 1 of azido in Click reaction
The molar ratio of the PEI of DPP type conjugated polymer and 3- guanidine radicals -1- propine or alkynyl are as follows: 1:2~5；
Dual catalyst used is made of cuprous bromide and pentamethyl-diethylenetriamine；
R be DPP type conjugated polymer and cuprous bromide shown in the formula 1 of azido, pentamethyl-diethylenetriamine molar ratio successively
Are as follows: 1:2~6:5~10；
The reaction temperature of the Click reaction is room temperature, and the time is 30-40 hours.
Click reaction carries out in organic solvent, the organic solvent concretely N, N '-dimethyl formamide.
6. DPP type conjugated polymer shown in claim 1 Chinese style 1 is in CO2Application in absorption/release.
7. DPP type conjugated polymer shown in claim 1 Chinese style 1 regulates and controls CO in vivo2Absorption and release in application.
8. a kind of CO2Adsorbent material contains DPP type conjugated polymer shown in claim 1 Chinese style 1.
9. a kind of adjust CO using DPP type conjugated polymer shown in claim 1 Chinese style 12Absorption and release method, are as follows: it is logical
It crosses DPP type conjugated polymer shown in the illumination power formula 1 of control NIR and is raised to different temperature, to adjust the polymer
To CO2Adsorption capacity.
10. according to the method described in claim 9, it is characterized by: the method are as follows: so that shown in claim 1 Chinese style 1
DPP type conjugated polymer CO absorption2；Then NIR irradiation is carried out, so that the CO of absorption2Gradually discharge.
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| CN114479020A (en) * | 2022-02-22 | 2022-05-13 | 中国科学院化学研究所 | Polymer semiconductor photoresist with side chain containing azide group, and preparation method and application thereof |
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