A polymer receptor material based on n-type narrow bandgap and its preparation method and application

Abstract

The present invention relates to a polymer receptor material based on an n-type narrow band gap and a preparation method and application thereof, belonging to the technical field of functional materials. The structural formula of the polymer material is:. The n-type narrow band gap polymer receptor material based on the present invention, as a GC stationary phase, shows high selectivity for components with similar physicochemical properties, and can efficiently separate various mixtures of components with different polarities, especially various isomer mixtures that are difficult to separate. The n-type narrow band gap polymer receptor functional material of the present invention has a stable structure, good thermal stability, good solubility and film-forming properties in organic solvents, and provides advantages for the preparation of high-efficiency chromatographic columns. The n-type narrow band gap polymer receptor functional material of the present invention has low raw material cost, simple synthesis method and high product yield.

Description

Technical Field

[0001] The invention relates to a polymer receptor material based on an n-type narrow band gap and a preparation method and application thereof, belonging to the technical field of functional materials. Background Art

[0002] GC has high efficiency in separation, qualitative and quantitative analysis, and has been widely used in the analysis and determination of complex sample components in various fields. Among them, the core and key of chromatographic separation and analysis is the selectivity and separation performance of the chromatographic stationary phase.

[0003] At present, high-efficiency organic solar cells usually use conjugated polymers with n-type narrow bandgap structures. Such polymers exhibit good thermal stability and planarity, which promotes the stacking of molecules and effectively promotes the charge transfer between molecules. They can be used as excellent devices and are widely used in organic solar cells. From the characteristics of the molecules, it can be seen that TVT polymers have good chemical and thermal stability. At present, there are no reports on the use of n-type narrow bandgap polymers in chromatographic separation. Summary of the invention

[0004] In view of this, the present invention provides a polymer receptor material based on an n-type narrow band gap. When this type of functional material is used as a chromatographic stationary phase for gas chromatography analysis and determination, it exhibits high selectivity and separation ability for various components and isomers with similar properties. In addition, the chromatographic column prepared using this type of functional material has good thermal stability, repeatability and reproducibility, and has great application potential in gas chromatography separation.

[0005] The present invention also provides a method for preparing the polymer receptor material. The method has low raw material cost, simple synthesis method and high product yield.

[0006] Another object of the present invention is to provide the application of the above polymer receptor material.

[0007] The technical solution adopted by the present invention to achieve the above-mentioned purpose is:

[0008] The present invention provides a polymer receptor material based on an n-type narrow band gap, the structural formula of which is:

[0009] ;

[0010] Wherein, n is 1-20.

[0011] The present invention also provides a method for preparing the above-mentioned n-type narrow bandgap polymer receptor material, comprising the following steps:

[0012] (1) 2-bromothiophene-3-carboxylic acid hexyl ester, (E)-1,2-bis(tri-n-butyltin)ethylene, and tetrakistriphenylphosphine palladium were added to toluene to dissolve, and the mixture was evacuated with nitrogen and placed in an oil bath for reaction. After the reaction was completed, the solution was extracted and dried, filtered and concentrated, and then purified by silica gel chromatography using a mixture of petroleum ether and dichloromethane as an eluent, and concentrated by rotary evaporation to obtain compound 1;

[0013] (2) Dissolve compound 1 in anhydrous THF and stir at low temperature; add n-BuLi dropwise under nitrogen and continue stirring, add trimethyltin chloride solution, continue to keep warm and stir, and then move to room temperature and stir; after the reaction is completed, extract the solution, dry it, filter and concentrate it, and then recrystallize it from anhydrous ethanol to obtain compound 2;

[0014] (3) Add toluene to compound 2, bromide Y1-Br, tris(o-methylphenyl)acetone dipalladium) and tri(o-methylphenyl)phosphine to dissolve the mixture. After N2 is evacuated, the air is drained and the mixture is placed in an oil bath and stirred for reaction. After the reaction temperature is lowered, the prepared polymer is dropped into methanol for precipitation. The precipitated solid is then extracted with methanol, n-hexane and chloroform in sequence. After the solution is concentrated, the solution is dropped into methanol to obtain a blue-black solid.

[0015] Preferably, in step (1), the molar ratio of 2-bromothiophene-3-carboxylic acid hexyl ester and (E)-1,2-bis(tri-n-butyltin)ethylene is 2-3:1; the mass ratio of 2-bromothiophene-3-carboxylic acid hexyl ester and tetrakistriphenylphosphine palladium is 5-6:0.04; and the volume ratio of petroleum ether and dichloromethane is 3:1.

[0016] Preferably, in step (1), the reaction is carried out at 100-120°C for 22-25 h.

[0017] Preferably, in step (2), the molar ratio of the compound 1, n-BuLi and trimethyltin chloride is 4-5:15-16:17-18; and the concentration of the trimethyltin chloride solution is 1-1.5 mol / L.

[0018] Preferably, in step (2), the low-temperature stirring temperature is -78°C; after adding n-BuLi, stirring is continued for 1 hour; the heat preservation stirring is stirring at -78°C for 1 hour; and the room temperature stirring time is 3-4 hours.

[0019] Preferably, in step (3), the molar ratio of the compound 2 to the bromide Y1-Br is 1:1-1.5; the molar ratio of the compound 2, trisdibenzylideneacetone dipalladium and tri(o-methylphenyl)phosphine is 1:0.05:0.05.

[0020] Preferably, in step (3), the bromide Y1-Br has the structural formula:

[0021] .

[0022] Preferably, in step (3), the stirring reaction is carried out at 100-120°C for 46-48 hours; after the reaction temperature is reduced by 10-20°C, the prepared polymer is dropped into methanol for precipitation.

[0023] The present invention also provides the use of the above-mentioned polymer receptor material based on n-type narrow band gap as a stationary phase for gas chromatography separation in gas chromatography analysis.

[0024] The material molecules provided by the present invention have good planarity, and the special stacking mode allows TVT molecules to form effective regular stacking in the chromatographic column, and can effectively perform selective adsorption when the mixed gas passes through. In addition, TVT itself has strong electron-withdrawing properties, which should have obvious selectivity for some molecules with strong electron-withdrawing groups, thereby effectively separating and analyzing certain types of analytes.

[0025] The reaction route of the polymer receptor material provided by the present invention is:

[0026]

[0027] The beneficial effects of the present invention are:

[0028] (1) The n-type narrow bandgap polymer material described in the present invention, as a GC stationary phase, exhibits high selectivity for components with similar properties and can efficiently separate mixtures of various components with different polarities, especially mixtures of various isomers that are difficult to separate.

[0029] (2) The n-type narrow bandgap polymer material of the present invention has a stable structure, good thermal stability, good solubility and moldability in organic solvents, forms a regular stacking pattern, and is easy to prepare a chromatographic column with high column efficiency.

[0030] (3) The raw material cost used in the preparation of the n-type narrow bandgap polymer material of the present invention is low, the synthesis method is simple, and the product yield is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The NMR spectrum of the n-type narrow bandgap polymer receptor material TVT prepared in Example 1;

[0032] Figure 2 The chromatogram of the mixed sample of non-polar alkane mixture separated by the n-type narrow band gap polymer receptor material TVT prepared in Example 1 as the stationary phase; wherein the substances corresponding to the chromatographic peaks 1 to 8 are: heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane;

[0033] Figure 3 The separation chromatogram of the n-type narrow bandgap polymer receptor material prepared in Example 1 as a stationary phase to a mixture of polar alcohol isomers; wherein the substances corresponding to the chromatographic peaks 1 to 8 are, in order: n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, and n-undecanol;

[0034] Figure 4 The n-type narrow bandgap polymer receptor material prepared in Example 1 is a chromatogram of the stationary phase separation of diethylbenzene isomers; wherein the substances corresponding to the chromatographic peaks 1 to 3 in the figure are, in order: m-diethylbenzene, p-diethylbenzene and o-diethylbenzene;

[0035] Figure 5 The separation chromatogram of the n-type narrow bandgap polymer receptor material prepared in Example 1 as a stationary phase to a mixture of trichlorobenzene isomers; wherein the substances corresponding to the chromatographic peaks 1 to 3 are, in order: 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene and 1,2,3-trichlorobenzene;

[0036] Figure 6 The chromatogram of the n-type narrow bandgap polymer receptor material prepared in Example 1 as the stationary phase for separating chloronitrobenzene; wherein the substances corresponding to the chromatographic peaks 1 to 3 in the figure are, in order: m-chloronitrobenzene, p-chloronitrobenzene, and o-chloronitrobenzene. DETAILED DESCRIPTION

[0037] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments, wherein the methods are conventional methods unless otherwise specified, and the raw materials can be obtained from public commercial channels unless otherwise specified.

[0038] The bromide Y1-Br used in the present invention was purchased from Jiaxing Hepu Optoelectronics Technology Co., Ltd.

[0039] The steps of preparing a capillary chromatographic column using the n-type narrow bandgap polymer functional material prepared in the example as the stationary phase are as follows:

[0040] A quartz capillary column of a certain length (5 m to 30 m) and an inner diameter of 0.25 mm was taken, first rinsed with dichloromethane for 20 min, and then aged at 260 °C for 3 h under a nitrogen atmosphere; then, a saturated solution of sodium chloride methanol was continuously introduced into the capillary column under nitrogen pressure until the outflowing liquid became turbid, and the solution in the capillary column was discharged, and then maintained at 200 °C for 3 h under nitrogen; the TVT material (polymer receptor material) prepared by the present invention was dissolved in dichloromethane to prepare a suitable concentration (0.10 mg / mL to 0.50 mg / mL, w / v) is prepared by ultrasonic treatment for 5 min, and then the stationary phase solution is passed into a capillary column. One end of the capillary column is sealed and the other end is connected to a vacuum pump. The solvent is evaporated in a 40 °C water bath, and the stationary phase is deposited on the inner wall of the capillary column. The capillary column is then aged under the following aging conditions: first, it is kept at 40 °C for 30 min, and then the temperature is increased to 180 °C at a heating rate of 1 °C / min and kept for 6 h. The aged capillary column is a chromatographic column that can be used for GC analysis.

[0041] Example 1

[0042] The specific preparation steps of n-type narrow bandgap polymer acceptor material TVT are as follows:

[0043] (1) 2-Bromothiophene-3-carboxylic acid hexyl ester (5.80 g, 20.00 mmol), (E)-1,2-bis(tri-n-butyltin)ethylene (5.1 g, 8.33 mmol), and tetrakistriphenylphosphine palladium (40 mg) were added to a 100 mL two-necked flask, and 40 mL of toluene was added to dissolve the monomers. The mixture was purged with nitrogen for 10 minutes and placed in an oil bath at 110 °C for reaction for 24 h. After the reaction was completed, dichloromethane was added to extract the solution, and the solution was dried with anhydrous MgSO4, filtered, and concentrated using a rotary evaporator. Then, the mixture was purified by silica gel chromatography column (200-300 mesh) using a mixture of petroleum ether and dichloromethane in a ratio of 3:1 (v / v) as the eluent. After rotary evaporation and concentration, a yellow oily compound 1 was obtained.

[0044] (2) Compound 1 (2.00 g, 4.46 mmol) was dissolved in 40 mL of anhydrous THF and stirred at -78 °C. 6.50 mL of n-BuLi (2.4 M, 15.6 mmol) was added dropwise under nitrogen and stirred for 1 h. 17.84 mL of trimethyltin chloride (1.0 M, 17.84 mmol) solution was added and stirred for 1 h. The mixture was then moved to room temperature and stirred for 3 h. After the reaction was completed, dichloromethane was added to extract the solution. The solution was dried with anhydrous MgSO4, filtered, concentrated using a rotary evaporator, and then recrystallized from anhydrous ethanol to obtain a gray solid compound 2.

[0045] (3) Compound 2 (0.1 mmol), bromide Y1-Br (0.1 mmol), tris(dibenzylideneacetone)dipalladium (4.6 mg, 0.005 mmol), tri(o-methylphenyl)phosphine (15.2 mg, 0.05 mmol) were added to a 25 mL two-necked flask, and then 10 mL toluene was added to dissolve the monomers. After N2 was evacuated for 10 minutes, the air in the flask was drained, and the flask was placed in an oil bath at 110 °C and stirred for 48 h. After the reaction temperature dropped by 15 °C, the prepared polymer was dropped into methanol for precipitation, and then the precipitated solid was placed in a Soxhlet extractor, and the polymer was extracted in the order of methanol, n-hexane, and chloroform. After the solution was concentrated, it was dropped into methanol to obtain a blue-black solid, namely the n-type narrow bandgap polymer receptor material TVT. Then it was vacuum dried at 50 °C for 12 h and sealed for storage. (135 mg, yield 65%).

[0046] The NMR spectrum of the n-type narrow bandgap polymer acceptor material TVT is shown in Figure 1 shown.

[0047] Effect Example 1

[0048] The TVT prepared in Example 1 was dissolved in dichloromethane to prepare a stationary phase solution with a concentration of 1.0 mg / mL, and a quartz capillary chromatographic column (10 m) was prepared. The samples of this combination were separated, and the separation results are shown in Figure 2~Figure 6 ;in, Figure 2-Figure 6 The chromatographic parameters were as follows: nitrogen as carrier gas, carrier gas flow rate: 1 mL / min, flow rate was carrier gas flow rate split ratio 50:1; Figure 2 The temperature was programmed to rise from 60 °C (2 min) to 10 °C / min to 150 °C; Figure 3 Program temperature rise 90 o C (1 min)-5 o C / min-150 o C; Figure 4 Program temperature rise 40 o C -5 o C / min-150 o C; Figure 5 Program temperature rise 70 o C (2 min) -10 o C / min-150 o C; Figure 6 Constant temperature 80 o C. By Figure 2~Figure 6 It can be seen that the chromatographic peaks obtained by using TVT as the stationary phase for gas chromatography separation have good symmetry and show good chromatographic separation performance.

[0049] Figure 2The analytes are non-polar straight-chain alkanes, and all analytes have sharp and symmetrical peaks. The results show that this type of stationary phase has good separation ability for non-polar analytes. The TVT column achieves baseline separation for each pair of adjacent alkane components; Figure 3 The analytes in the column are mixtures of alcohol homologues. Alcohols have longer carbon chains and are more polar. Analytes with greater polarity tend to have tailing or stronger adsorption on the column, but on this stationary phase, the peak shape is symmetrical and the separation is good; Figure 4~Figure 6 In the chromatographic column, isomers with different polarities were selected for further investigation. These isomers include diethylbenzene with lower polarity, trichlorobenzene with medium polarity, and a mixture of chloronitrobenzene isomers. From the figure, we can see that both non-polar and highly polar isomers have achieved good separation effects on this chromatographic column.

[0050] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing an n-type narrow bandgap polymer receptor material, characterized in that: The following steps are involved: (1) 2-bromothiophene-3-carboxylic acid hexyl ester, (E)-1,2-bis(tri-n-butyltin)ethylene, and tetrakistriphenylphosphine palladium were added to toluene and dissolved, and the mixture was evacuated with nitrogen and placed in an oil bath for reaction; after the reaction was completed, the solution was extracted and dried, filtered and concentrated, and then purified by silica gel chromatography using a mixture of petroleum ether and dichloromethane as an eluent, and concentrated by rotary evaporation to obtain compound 1; (2) Compound 1 was dissolved in anhydrous THF and stirred at -78°C; n-BuLi was added dropwise under nitrogen and the stirring was continued; trimethyltin chloride solution was added and the stirring was continued while keeping the temperature constant, and then the mixture was moved to room temperature and stirred; after the reaction was completed, the solution was extracted and dried, filtered and concentrated, and then recrystallized from anhydrous ethanol to obtain compound 2; (3) Compound 2, bromide Y1-Br, tris(dibenzylideneacetone dipalladium) and tri(o-methylphenyl)phosphine were dissolved in toluene, and after N2 was evacuated, the air was drained and the mixture was placed in an oil bath for stirring and reacting; after the reaction temperature was lowered, the prepared polymer was dropped into methanol for precipitation, and then the precipitated solid was extracted with methanol, n-hexane and chloroform in sequence, and the solution was concentrated and dropped into methanol to obtain a blue-black solid; The structural formula of the polymer receptor material is: ； Wherein, n is 1-20; The structural formula of the bromide Y1-Br is: 。 2. The preparation method according to claim 1, characterized in that: In step (1), the molar ratio of 2-bromothiophene-3-carboxylic acid hexyl ester and (E)-1,2-bis(tri-n-butyltin)ethylene is 2-3:1; the mass ratio of 2-bromothiophene-3-carboxylic acid hexyl ester and tetrakistriphenylphosphine palladium is 5-6:0.04; and the volume ratio of petroleum ether and dichloromethane is 3:

1.

3. The preparation method according to claim 1 or 2, characterized in that: In step (1), the reaction is carried out at 100-120° C. for 22-25 h.

4. The preparation method according to claim 1, characterized in that: In step (2), the molar ratio of the compound 1, n-BuLi and trimethyltin chloride is 4-5:15-16:17-18; and the concentration of the trimethyltin chloride solution is 1-1.5 mol / L.

5. The preparation method according to claim 1 or 4, characterized in that: In step (2), after adding n-BuLi, stirring is continued for 1 hour; the heat preservation stirring is stirring at -78°C for 1 hour; and the stirring time at room temperature is 3-4 hours.

6. The preparation method according to claim 1, characterized in that: In step (3), the molar ratio of the compound 2 to the bromide Y1-Br is 1:1-1.5; the molar ratio of the compound 2, trisdibenzylideneacetone dipalladium and tri(o-methylphenyl)phosphine is 1:0.05:0.

05.

7. The preparation method according to claim 1 or 6, characterized in that: In step (3), the stirring reaction is carried out at 100-120°C for 46-48 hours; after the reaction temperature is reduced by 10-20°C, the prepared polymer is dropped into methanol for precipitation.

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