CN114685763B - Conjugated polymer based on triarylboron and preparation method and application thereof - Google Patents
Conjugated polymer based on triarylboron and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemical gas sensing, and particularly relates to a triarylboron-based conjugated polymer, and a preparation method and application thereof. According to the invention, the boron-nitrogen unit containing triarylboron is taken as an ammonia response unit, and a class of triarylboron conjugated polymer containing B-N covalent bonds is developed by regulating and controlling the copolymerization unit, and the ammonia response value of the triarylboron conjugated polymer breaks through 10000 for the first time, so that the triarylboron-nitrogen conjugated polymer can be used as a disposable ammonia sensor, can not only effectively sense gas molecules, and is convenient for disposable use in the future Internet of things society. The triarylboron conjugated polymer containing B-N covalent bonds is obtained by polymerizing triarylboron monomers and other comonomers through palladium catalysis cross-coupling reaction, and related polymer semiconductor materials are obtained through purification, and the triarylboron conjugated polymer is used as a novel sensing material with extremely high gas response and selectivity, and belongs to the blank in the research history of electrochemical gas sensing technology.
Description
Technical Field
The invention belongs to the technical field of electrochemical gas sensing, and particularly relates to a triarylboron-based conjugated polymer, and a preparation method and application thereof.
Background
The gas sensor has the advantages of good stability, high sensitivity, high response speed, simple structure and the like, has important development and application potential in the fields of environmental protection, medical treatment, food chemical industry and the like, and has recently received extensive attention from scientific researchers based on the important development and application potential. The rapid development of gas sensing technology has a close relation with the development of novel and efficient gas-sensitive materials. Therefore, developing a novel and excellent gas sensing unit and conjugated polymer will bring great commercial value and application potential to the improvement of high sensitivity and quick response performance of the device.
At present, semiconductor-based gas-sensitive materials are designed and developed as main sensing materials, and in particular, metal-based semiconductor gas-sensitive materials typified by zinc oxide thin films and nonmetallic organic semiconductor materials typified by polythiophene, dialkyltetrathiapentadiene, polypyrrole, and the like are being widely studied. But the ammonia response can only reach about 100 at most (gas sensitive response: ra/Rg, ra: response resistance of the gas sensor in air, rg: response resistance of the gas sensor in test gas). Therefore, development of a novel high-response gas-sensitive sensing unit has huge development space in the field of semiconductor-based gas-sensitive sensing.
Disclosure of Invention
According to the invention, the boron-nitrogen unit containing triarylboron is taken as an ammonia response unit, and a class of triarylboron conjugated polymer containing B-N covalent bonds is developed by regulating and controlling the copolymerization unit, and the ammonia response value of the triarylboron conjugated polymer breaks through 10000 for the first time, so that the triarylboron conjugated polymer can be used as a disposable ammonia sensor, can effectively sense gas molecules, and is convenient for disposable use in the future Internet of things society.
The triarylboron conjugated polymer containing B-N covalent bonds is obtained by polymerizing triarylboron monomers and other comonomers through palladium catalysis cross-coupling reaction, and related polymer semiconductor materials are obtained through purification, and the triarylboron conjugated polymer is used as a novel sensing material with extremely high gas response and selectivity, and belongs to the blank in the research history of electrochemical gas sensing technology.
In order to achieve the above object, the present invention adopts the following technical measures:
a triarylboron conjugated polymer containing B-N covalent bonds belongs to organic semiconductor conjugated polymers, and the structural formulas of the triarylboron conjugated polymer containing B-N covalent bonds are shown as the following formulas (1) and (II):
wherein the saidSelected from any one of the following structures:
the saidSelected from any one of the following structures: :
wherein n is a natural number of 1 to 10000, R and R 1 Each selected from H, C 1 ～C 40 Is any one of alkyl chain, alkylthio chain, alkoxy chain, cyano group, halogen atom and nitro substituent, and X is any one of O, S, se, te.
Further, the saidIs->
Further, the triarylboron conjugated polymer containing B-N covalent bonds is obtained by polymerizing triarylboron monomers and comonomer A through palladium-catalyzed cross-coupling reaction, wherein the triarylboron monomers have the structural formula ofR 1 And->As previously described; the comonomer A is a bis (trimethyltin) monomer or a bis (pinacolato) borate monomer;
further, the comonomer A is
Specifically, the triarylboron conjugated polymer containing the B-N covalent bond is prepared by the following method:
under the anhydrous and anaerobic conditions, triarylboron monomers, a comonomer A, tris (o-methylphenyl) phosphorus and a palladium catalyst (preferably tris (dibenzylideneacetone) dipalladium) are placed in an anhydrous solvent, stille polymerization reaction is carried out under the conditions of light shielding and heating reflux, and after the Stille polymerization reaction is finished, a blocking agent is added for blocking, and the B-N covalent bond triarylboron conjugated polymer is obtained by purification.
Further, the anhydrous solvent is anhydrous toluene.
Further, the molar ratio of the arylboron monomer, comonomer A, palladium catalyst to tris (o-methylphenyl) phosphorus is 1:1:0.02:0.16.
Further, the reaction temperature of the Stille polymerization reaction is 110-120 ℃ and the reaction time is 24-48 h.
The invention also provides application of the triarylboron conjugated polymer containing the B-N covalent bond in a gas sensor, and the triarylboron conjugated polymer containing the B-N covalent bond can be used as a gas sensitive material in the gas sensor.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention innovatively designs a class of triaryl boron-containing conjugated polymer sensing materials, and a gas sensor with excellent performance is obtained based on the sensing materials, so that an ammonia response value higher than 10000 is realized for the first time, and potential application of the triaryl boron-containing conjugated polymer sensing materials in the field of gas sensing is realized;
(2) The triarylboron polymer material based on the B-N covalent bond has the advantages of simple reaction route, green and the like, and can be applied to the aspect of actual production.
Drawings
FIG. 1 is a graph showing the response of polymer 7 after 40ppm ammonia treatment.
FIG. 2 shows the response of polymer 7 to various gases (all at 40ppm concentration) at 25 ℃.
FIG. 3 is a photograph of the alarm system of polymer 7 and the alarm lamp is turned on after 40ppm ammonia gas treatment.
FIG. 4 is a graph showing the current-voltage characteristics of polymer 7 before and after treatment with 40ppm ammonia.
FIG. 5 is a graph showing the response of polymer 9 after 40ppm ammonia treatment.
In each graph, ra/Rg in the ordinate is the gas-sensitive response, ra: response resistance of the gas sensor in air, rg: response resistance of the gas sensor in the test gas.
Detailed Description
The technical scheme of the invention is further explained below by combining specific embodiments.
Example 1 preparation of monomers containing B-N covalent bonds specific reaction steps and reaction conditions are as follows:
(1) Raw material 1 or intermediate reactants, sodium hydride, tetra (triphenylphosphine) palladium, tri (o-methylphenyl) phosphorus, dichlorobenzene borane, bromosuccinimide, 2, 5-di (trimethyltin) thiophene, triethylamine, tetrahydrofuran, toluene, o-dichlorobenzene, chloroform, are purchased from companies such as An Naiji, aletin, shanghai microphone, and the like. Wherein tetrahydrofuran, toluene, o-dichlorobenzene and chloroform are used after anhydrous treatment.
(2) Preparation of Compound 2
Carrying out Suzuki coupling reaction on the raw materials 1 and 2-thiophene pinacol borate, wherein the Suzuki coupling reaction specifically comprises the following steps: compound 1, namely 2-iodo-5-bromoaniline (287.8 mg,0.966 mmol), pinacol 2-thiopheneboronic acid ester (130.4 mg,2.2 mmol), tetrakis (triphenylphosphine) palladium (55.8 mg,0.048 mmol) and potassium carbonate solution (2.4 mL,4.82mmol,2 m) were taken as starting materials, put into a two-necked flask under argon protection, then argon was introduced to vent the system for several times, dry toluene (10 mL) was added in a dark state, the system was kept anhydrous and anaerobic, after stirring at 80 ℃ for 12h, the solvent was removed under reduced pressure to obtain an orange solid, which was purified by silica gel column chromatography (dichloromethane/n-hexane=1:5) to obtain compound 2 (223 mg,0.88 mmol) in 91% yield.
(3) Preparation of Compound 3
Compound 2 (144.8 mg,0.57 mmol), sodium hydride (34.46 mg,1.5 mmol) as a starting material, was placed in a two-necked flask under argon, then dried tetrahydrofuran (7 mL) was added, stirred at 70℃for 2h, then 5- (bromomethyl) undecane (161.8 mg,0.63 mmol) was added under argon and the resulting mixture was stirred at 70℃for a further 12 h. After removal of the solvent under reduced pressure, purification was performed by silica gel column chromatography (dichloromethane/n-hexane=1:8) to give compound 3 (207.1 mg,0.49 mmol) in 86% yield.
(4) Preparation of Compound 4
Compound 3 (200 mg,0.47 mmol) and 1.1 times the molar amount of N-bromosuccinimide (92.5 mg,0.52 mmol) were added to a reaction vessel using N, N-dimethylformamide as a solvent, stirred at room temperature under the protection of argon for 3 hours, and after removal of the solvent under reduced pressure, purification was performed by silica gel column chromatography (pure N-hexane) to give compound 4 (207.4 mg,0.41 mmol) in 88% yield.
(5) Preparation of monomer 5
Compound 4 (207 mg,0.41 mmol), phenyl boron dichloride (131.82 mg,0.83 mmol) and triethylamine (251.96 mg,2.79 mmol) were placed in a two-necked flask under argon protection, then dried o-dichlorobenzene (6 mL) was added, the resulting mixture was stirred at 180℃for 24h, the solvent was removed under reduced pressure, and purification was performed by silica gel column chromatography. Monomer 5 (209.5 mg,0.36 mmol) was obtained in 87% yield.
1 HNMR(400MHz,CDCl 3 ,25℃)δ7.94–7.88(d,J＝8.4Hz,1H),7.83–7.78(d,J＝1.9Hz,1H),7.58–7.51(m,2H),7.48–7.29(m,5H),4.15–4.09(d,J＝6.9Hz,2H),1.33–1.03(m,17H),0.91–0.79(dt,J＝13.5,7.0Hz,6H).
Example 2 preparation of conjugated polymers containing B-N covalent bonds the chemical reaction scheme is shown below:
the specific reaction steps and reaction conditions are as follows:
(1) Monomers 6 and 7, tetrakis (triphenylphosphine) palladium, tris (o-methylphenyl) phosphorus, 2, 5-bis (trimethyltin) thiophene, hexa-n-butylditin tetrahydrofuran, toluene were purchased from An Naiji, aletin, etc.
(2) Preparation of Polymer 7
Monomer 5 (84 mg,0.143 mmol) and monomer 6 (60.5 mg,0.143 mmol) prepared in example 1 were added to a reaction flask, respectively, tris (dibenzylideneande-acetone) dipalladium (2.7 mg, 0.003mmol) and tris (o-methylphenyl) phosphorus (7.1 mg,0.023 mmol) were accurately weighed into the flask, then the system was protected by argon, light-protected from tinfoil, an anhydrous toluene solution (5 mL) was added thereto, and after refluxing at 120℃for 48 hours, bromobenzene (200 mg,1.28 mmol) was added as a capping agent, and the reaction was continued for 5 hours. After the reaction, the system is cooled to room temperature, dissolved in 100 ml of chloroform, washed with water, dried, and most of solvent is removed to obtain polymer, the polymer is dripped into absolute ethyl alcohol to be separated out, the obtained polymer product is washed with small molecules and catalyst by a Soxhlet extractor through acetone and tetrahydrofuran in turn, finally the polymer is extracted by chloroform, and macromolecule 7 (127.2 mg) is obtained after drying, the yield is high: 88%.
1 HNMR(400MHz,CDCl 3 ,25℃):δ8.34–7.97(m,J＝8.7,3.7Hz,1H),7.95–7.30(m,7H),7.23–6.64(m,3H),4.49–3.81(s,2H),2.05–1.69(s,2H),1.44–0.66(m,21H). 11 B NMR(128MHz,CDCl 3 )δ32.5.
(3) Preparation of Polymer 9
Into a reaction flask were added monomer 5 (84 mg,0.143 mmol) and monomer 8 (82.9 mg,0.143 mmol) of example 1, respectively, tris (dibenzylideneande-acetone) dipalladium (2.7 mg, 0.003mmol) and tris (o-methylphenyl) phosphorus (7.1 mg,0.023 mmol) were accurately weighed into the reaction flask, the system was then protected by argon, a light-shielding sheet was placed therein, an anhydrous toluene solution (5 mL) was added thereto, and after refluxing at 120℃for 48 hours, bromobenzene (200 mg,1.28 mmol) was added as a capping agent, and the reaction was continued for 5 hours. After the reaction, the system is cooled to room temperature, dissolved in 100 ml of chloroform, washed with water, dried, and most of solvent is removed to obtain polymer, the polymer is dripped into absolute ethyl alcohol to be separated out, the obtained polymer product is washed with acetone and tetrahydrofuran in turn to remove small molecules and catalyst, finally the polymer is extracted with chloroform, and polymer 9 (145.3 mg) is obtained after drying, the yield is high: 87%.
1 HNMR(400MHz,CDCl 3 ,25℃)δ8.41–6.60(m,10H),4.36–3.78(s,2H),1.67–0.48(m,23H).
Example 3
The application of the conjugated polymer containing B-N covalent bond according to the present invention as a gas-sensitive material for an efficient room temperature ammonia electrochemical sensor is illustrated by taking the materials (polymers 7 and 9) obtained in example 2 as an example, but the present invention is not limited to the illustrated example.
The preparation process comprises the following steps:
simple room temperature ammonia sensor assembly:
the sensing material is coated on the interdigital electrode, then two ends are connected with leads and then externally connected with a 3V button cell, and an alarm bulb with the voltage of 0.3V is connected in series in the circuit. Two simple low-energy ammonia alarming systems (the alarming voltage is 0.3V and no current amplifier) are assembled, and the practical application of the system in an ammonia electrochemical sensor is researched.
Mixing proper amount of organic molecular powder and terpineol (as adhesive), fully grinding in agate mortar to obtain uniform paste, slowly and uniformly coating on silver interdigital electrode, rotating for 10 seconds at 1800 rpm, repeating for several times to obtain flat coating, drying, and aging at 200 ℃ for 12 hours to improve stability.
The specific detection steps are as follows:
the simple room temperature ammonia gas sensor is prepared by the monomer 7 and the monomer 9 respectively according to the method, then the room temperature ammonia gas sensor is placed in an air chamber, the air chamber is kept in a vacuum state (25 ℃), ammonia water with corresponding concentration is quickly injected into the vacuum air chamber for gasification by a miniature needle tube, and electric signals with different concentrations are detected in real time by a Keithley 2612 data acquisition system.
FIG. 1 is a graph showing the response of polymer 7 after 40ppm ammonia treatment.
FIG. 2 shows the response of polymer 7 to various gases (all at 40ppm concentration) at 25 ℃.
FIG. 3 is a photograph of the alarm system of polymer 7 and the alarm lamp is turned on after 40ppm ammonia gas treatment.
FIG. 4 is a graph showing the current-voltage characteristics of polymer 7 before and after treatment with 40ppm ammonia.
FIG. 5 is a graph showing the response of polymer 9 after 40ppm ammonia treatment.
In each graph, ra/Rg in the ordinate is the gas-sensitive response, ra: response resistance of the gas sensor in air, rg: response resistance of the gas sensor in the test gas.
The results of fig. 1-5 show that: the novel copolymer prepared by the invention has a very high response value, has high selectivity to ammonia, and can light an LED lamp after the polymer acts with the ammonia, so that the ammonia can obviously improve the conductivity of the polymer.
The above examples of the present invention are only examples for clearly illustrating the present invention, and are not limiting of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (7)
1. A triarylboron conjugated polymer containing B-N covalent bonds has the structural formula shown in the following formula (1) and formula (II):
wherein the saidSelected from any one of the following structures:
the saidSelected from any one of the following structures:
wherein n is a natural number of 1 to 10000, R and R 1 Each selected from H, C 1 ～C 40 Is any one of alkyl chain, alkylthio chain, alkoxy chain, cyano group, halogen atom and nitro substituent, and X is any one of O, S, se, te.
2. The method for producing a B-N covalent bond-containing triarylboron conjugated polymer as described in claim 1, wherein said B-N covalent bond-containing triarylboron conjugated polymer is produced by triarylboronThe monomer and the comonomer A are obtained by palladium catalysis cross coupling reaction polymerization, and the structural formula of the triarylboron monomer isThe comonomer A is a ditrimethyltin monomer or a bis-pinacolato borate monomer.
3. The preparation method according to claim 2, wherein the triarylboron conjugated polymer having a B-N covalent bond is prepared by the following method:
under the anhydrous and anaerobic conditions, triarylboron monomers, a comonomer A, tri (o-methylphenyl) phosphorus and a palladium catalyst are placed in an anhydrous solvent, a Stille polymerization reaction is carried out under the conditions of light shielding and heating reflux, after the Stille polymerization reaction is finished, a blocking agent is added for blocking, and the B-N covalent bond triarylboron conjugated polymer is obtained after purification.
4. A process according to claim 3, wherein the comonomer a is
5. A process according to claim 3, wherein the molar ratio of aryl boron monomer, comonomer a, palladium catalyst to tris (o-methylphenyl) phosphorus is 1:1:0.02:0.16.
6. A process according to claim 3, wherein the Stille polymerization is carried out at a reaction temperature of 110 to 120 ℃ for a reaction time of 24 to 48 hours.
7. The use of the triarylboron conjugated polymer containing a B-N covalent bond as defined in claim 1 in a gas sensor gas-sensitive material.
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