CN111875761A - Organic porous framework polymer based on tetraphenylethylene structure and synthetic method thereof - Google Patents

Abstract

The invention provides an organic porous skeleton polymer based on a tetrastyrene structure and a synthesis method thereof, belonging to the technical field of functional materials. The present invention provides an organic porous skeleton polymer based on tetrastyrene structure, which has the structure shown in formula I; the organic porous skeleton polymer based on tetrastyrene structure is composed of tetrastyrylaldehyde and 1,5-dinaphthalene Phenol is used as a monomer, and is prepared according to the molar ratio of tetrastyryl aldehyde and 1,5-dinaphthol: 0.8-1.2: 1.5-2.5. In the present invention, the tetrastyryl aldehyde and 1,5-binaphthol are connected through an aldol condensation reaction, and the formed organic porous skeleton polymer based on the tetrastyryl structure has a uniform structure and is thermally and chemically stable. good sex.

Description

A kind of organic porous skeleton polymer based on tetrastyrene structure and its synthesis method

technical field

The invention relates to the technical field of functional materials, in particular to an organic porous skeleton polymer based on a tetrastyrene structure and a synthesis method thereof.

Background technique

Organic porous framework polymers have the advantages of permanent open pore structure, stable physicochemical properties and compositional diversity. They are used in the adsorption and storage of energy gases (such as hydrogen, methane, etc.) Control and other fields have been very significant development, so it has gradually developed into a new type of adsorption material with great potential.

Compared with traditional inorganic porous adsorption materials, organic porous framework polymer materials have many unique advantages: on the one hand, porous organic polymers can only be composed of light elements such as C, H, O, N, and B, so they have very low Skeletal density; on the other hand, porous organic polymers can be synthesized in a variety of ways and with a wide range of monomers to choose from. In addition, organic porous framework polymers can also adjust their properties by modifying organic functional groups and changing the length of various chains, so as to achieve specific synthetic purposes. In addition, organic porous polymers have stable physical and chemical properties, and can be used in harsh environments such as acid, alkali, and humidity.

Many advantages make organic porous framework polymers have broad research prospects.

SUMMARY OF THE INVENTION

In view of this, the present invention aims to provide an organic porous skeleton polymer based on a tetrastyrene structure and a synthesis method thereof. The organic porous skeleton polymer based on the tetrastyrene structure provided by the invention has uniform structure and good thermal stability and chemical stability.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a kind of organic porous skeleton polymer based on tetrastyrene structure, has the structure shown in formula I:

The organic porous skeleton polymer based on tetrastyryl structure uses tetrastyrylaldehyde and 1,5-binaphthol as monomers, and the molar ratio of tetrastyrylaldehyde and 1,5-binaphthol is 0.8-1.2:1.5 ~2.5 is prepared.

Preferably, the organic porous framework polymer has a specific surface area of 320-350 m ² /g, and a pore diameter of 2-2.4 nm.

The invention provides a method for synthesizing an organic porous skeleton polymer based on tetraphenylene, comprising the following steps:

Mixing tetrastyrylaldehyde, 1,5-binaphthol and polar organic solvent, and carrying out nucleophilic addition and elimination reaction under protective gas to obtain an organic porous skeleton polymer based on tetrastyryl structure; the tetraphenylene The molar ratio of vinyl aldehyde to 1,5-binaphthol is 0.8-1.2:1.5-2.5.

Preferably, the polar organic solvent is one or more of 1,4-dioxane, tetrahydrofuran, toluene and mesitylene.

Preferably, the mass ratio of the tetrastyrylaldehyde to the polar organic solvent is 0.8-1.2 g: 15-25 mL.

Preferably, the temperature of the nucleophilic addition and elimination reaction is 200-240° C., and the time is 3-5 days.

Preferably, after the nucleophilic addition and elimination reaction, it also includes post-processing the nucleophilic addition and elimination reaction solution, and the post-processing includes the following steps:

The nucleophilic addition and elimination reaction solution is sequentially filtered, washed and dried to obtain an organic porous skeleton polymer solid based on a tetrastyrene structure.

Preferably, the washing includes acetone washing and dichloromethane washing in sequence.

The present invention provides an organic porous skeleton polymer based on a tetrastyrene structure, having a structure shown in formula I; the organic porous skeleton polymer based on a tetrastyrene structure is composed of tetrastyrylaldehyde and 1,5-dinaphthalene Phenol is used as a monomer, and it is prepared according to the molar ratio of tetrastyryl aldehyde and 1,5-dinaphthol at 1:2. In the present invention, the tetrastyryl aldehyde and 1,5-binaphthol are connected by aldol condensation, and the formed organic porous skeleton polymer based on the tetrastyryl structure has a uniform structure, thermal stability and chemical stability. Yes, it can be used for gas separation.

The present invention provides a method for synthesizing the above-mentioned organic porous skeleton polymer based on a tetrastyrene structure. The method has a short synthetic route, simple operation and easy industrialized production.

Description of drawings

Fig. 1 is the infrared spectrogram of embodiment 1 gained tetrabromostyrene;

Fig. 2 is the infrared spectrogram of embodiment 1 gained tetrastyrylaldehyde;

Fig. 3 is the solid ultraviolet spectrogram of the organic porous skeleton polymer based on the tetrastyrene structure obtained in Example 1;

Fig. 4 is the infrared spectrogram of the organic porous skeleton polymer based on the tetrastyrene structure obtained in Example 1;

Fig. 5 is the thermogravimetric analysis diagram of the organic porous framework polymer based on the tetrastyrene structure obtained in Example 1;

Fig. 6 is the X-ray diffraction pattern of the organic porous skeleton polymer based on the tetrastyrene structure obtained in Example 1;

FIG. 7 is a scanning electron microscope image of the organic porous framework polymer based on the tetrastyrene structure obtained in Example 1. FIG.

Detailed ways

The invention provides a kind of organic porous skeleton polymer based on tetrastyrene structure, has the structure shown in formula I:

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The organic porous skeleton polymer based on tetrastyryl structure uses tetrastyrylaldehyde and 1,5-binaphthol as monomers, and the molar ratio of tetrastyrylaldehyde and 1,5-binaphthol is 0.8-1.2:1.5 ~2.5 is prepared, preferably 1:2. In the present invention, the tetrastyrylaldehyde and 1,5-binaphthol are condensed by aldol to form a covalent bond, and the formed organic porous skeleton polymer based on the tetrastyryl structure has a uniform structure, and has good thermal stability and good thermal stability. Good chemical stability.

The specific surface area of the organic porous framework polymer is preferably 320-350 m ² /g, more preferably 326 m ² /g; the pore size is preferably 2-2.4 nm, more preferably 2.11 nm.

The present invention provides a method for synthesizing the above-mentioned organic porous skeleton polymer based on a tetrastyrene structure, comprising the following steps:

The tetrastyrylaldehyde, 1,5-binaphthol and polar organic solvent are mixed, and nucleophilic addition and elimination reactions are carried out under protective gas to obtain an organic porous skeleton polymer based on the tetrastyryl structure.

In the present invention, the molar ratio of the tetrastyrylaldehyde to 1,5-dinaphthol is 0.8-1.2:1.5-2.5, preferably 1:2; the polar organic solvent is preferably 1,4-di-naphthol One or more of oxane, tetrahydrofuran, toluene and mesitylene, the mass ratio of the tetrastyrylaldehyde to the polar organic solvent is preferably 0.8 to 1.2 g: 15 to 25 mL, more preferably 1 g : 20mL.

The present invention has no special requirements on the mixing method, and a mixing method well-known to those skilled in the art can be used, such as stirring and mixing. In the present invention, the protective gas is preferably saturated nitrogen. In the present invention, the nucleophilic addition and elimination reactions are preferably carried out in a sealed polytetrafluoroethylene reactor. In the present invention, the temperature of the nucleophilic addition and elimination reaction is preferably 200-240°C, more preferably 220°C, and the time is preferably 3-5 days, more preferably 4 days.

In the present invention, the nucleophilic addition and elimination reaction process is shown in formula A:

In the present invention, after the nucleophilic addition and elimination reaction, it also preferably includes post-treatment of the nucleophilic addition and elimination reaction solution, and the post-treatment preferably includes the following steps:

The nucleophilic addition and elimination reaction solution is sequentially filtered, washed and dried to obtain an organic porous skeleton polymer solid based on a tetrastyrene structure.

The present invention has no special requirements for the filtration method, and a filtration method well known in the art can be used, such as suction filtration. In the present invention, the washing preferably includes acetone washing and dichloromethane washing which are performed in sequence. In the present invention, the methods of washing with acetone and washing with dichloromethane are preferably dipping, and the time of dipping is preferably 1 day independently. In the present invention, the drying temperature is preferably 80-100° C., and the time is preferably 12-18 h.

The present invention has no special requirements on the sources of the tetrastyrylaldehyde and 1,5-binaphthol, and commercially available tetrastyrylaldehyde and 1,5-binaphthol can be used or prepared by themselves. When tetrastyrylaldehyde is prepared by itself, the preparation method preferably comprises the following steps:

(a) tetraphenylethylene and liquid bromine carry out electrophilic substitution reaction to obtain tetrabromostyrene;

(b) Under the action of a catalyst, tetrabromostyrene and tetraformylbenzeneboronic acid are subjected to suzuki coupling reaction to obtain tetrastyrylaldehyde.

In the present invention, tetrabromostyrene is preferably subjected to electrophilic substitution reaction with liquid bromine to obtain tetrabromostyrene. In the present invention, the molar ratio of the tetraphenylethylene to liquid bromine is preferably 1:2, the temperature of the electrophilic substitution reaction is preferably 60-80°C, more preferably 70°C, and the time is preferably 7 days. In the present invention, the electrophilic substitution reaction is preferably carried out in a desiccator.

In the present invention, the electrophilic substitution reaction process is shown in formula B:

After the tetrabromostyrene is obtained, the present invention preferably performs a suzuki coupling reaction between tetrabromostyrene and tetraformylbenzeneboronic acid under the action of a catalyst to obtain tetrastyrylaldehyde. In the present invention, the catalyst is preferably tetrakis (triphenylphosphine) palladium (referred to as palladium tetra) and anhydrous potassium carbonate, and the mass ratio of the palladium tetra and anhydrous potassium carbonate is preferably 1:17.5. In the present invention, the molar ratio of the tetrabromostyrene to the tetraformylbenzeneboronic acid is preferably 1:4, and the mass ratio of the tetrabromostyrene to the catalyst is preferably 3.8:1.

In the present invention, the suzuki coupling reaction is preferably carried out under the protection of N ₂ , the temperature of the suzuki coupling reaction is preferably 85° C., and the time is preferably 3 days.

In the present invention, the suzuki coupling reaction process is shown in formula C:

In the present invention, after the suzuki coupling reaction, it also preferably includes post-processing the obtained suzuki coupling reaction solution, and the post-processing preferably includes the following steps:

The suzuki coupling reaction solution is poured into ice water containing concentrated hydrochloric acid and mixed, followed by filtration, filter residue washing, drying and Soxhlet extraction, and the pure product of tetrastyrylaldehyde is obtained after removing the Soxhlet extraction solvent.

In the present invention, the mass concentration of concentrated hydrochloric acid in the ice water containing concentrated hydrochloric acid is preferably 10%; the volume ratio of the suzuki coupling reaction solution to the ice water containing concentrated hydrochloric acid is preferably 1:10. In the present invention, the mixing method is preferably stirring and mixing. In the present invention, the filtering method is preferably suction filtration, the washing is preferably successive washing with dilute hydrochloric acid and distilled water, and the mass concentration of the dilute hydrochloric acid is preferably 10%. The present invention has no special requirements for the drying method, and it is sufficient to completely remove the moisture by using a drying method well known to those skilled in the art. In the present invention, the solvent for Soxhlet extraction is preferably dichloromethane, and the time for Soxhlet extraction is preferably 48h. In the present invention, the method of removing the solvent is preferably rotary evaporation. After the removal of the solvent, the present invention preferably further includes drying the solid after the removal of the solvent.

The present invention has no special requirements on the source of the tetrakis (triphenylphosphine) palladium, and commercially available tetrakis (triphenylphosphine) palladium can be used or prepared by itself. When the tetrakis(triphenylphosphine) palladium is prepared by itself, the following steps are preferably included:

Under nitrogen atmosphere, triphenylphosphine and palladium chloride carry out a coordination reaction to obtain a coordination reaction solution;

The coordination reaction solution is mixed with hydrazine hydrate, and a reduction reaction is carried out to obtain tetrakis(triphenylphosphine)palladium.

In the present invention, the molar ratio of the triphenylphosphine to palladium chloride is preferably 5:1. In the present invention, the coordination reaction is preferably carried out in a dimethyl sulfoxide solvent, and the volume ratio of the mass of the triphenylphosphine to the dimethyl sulfoxide solvent is preferably 0.6532 g: 20 mL. In the present invention, the temperature of the coordination reaction is preferably 130° C., and the time is preferably 1 h.

In the present invention, hydrazine hydrate is preferably added to the coordination reaction solution. In the present invention, the mass ratio of the volume of the hydrazine hydrate to the triphenylphosphine is preferably 2 mL: 0.6532 g. In the present invention, the temperature of the reduction reaction is preferably 130° C., and the time is preferably 1 h.

After obtaining the reduction reaction solution, the present invention preferably performs post-treatment on the reduction reaction solution, and the post-treatment preferably includes the following steps:

The reduction reaction solution is sequentially filtered, washed with the filter residue and dried to obtain pure tetrakis(triphenylphosphine)palladium.

In the present invention, the filtering method is preferably Buchner funnel suction filtration; the washing detergent is preferably absolute ethanol; the drying is preferably vacuum drying, the drying temperature is preferably 40°C, and the time is preferably is 12h.

The organic porous skeleton polymer based on the tetrastyrene structure of the present invention can be used for gas separation, and the separated gas is preferably carbon dioxide and methane.

The organic porous skeleton polymer based on tetrastyrene structure provided by the present invention and its synthesis method are described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention.

Example 1

(1) Weigh 5.0738g of tetraphenylethylene on the watch glass, then put it into the desiccator, then drop 5 drops of liquid bromine in the desiccator, and wait for the liquid bromine to be volatilized after being placed for 7 days. It turned into light yellow, namely the process product I tetrabromostyrene was obtained, and the weight was 3.1060g.

(2) 1.0952g of tetrabromostyrene, 0.9384g of tetraformylbenzeneboronic acid, 2.1861g of anhydrous potassium carbonate, palladium tetra and 80mL of dioxane were added to a dry and clean three-necked flask, the mixture was yellow at this time, Then, under nitrogen protection, the temperature was controlled at about 85°C. After 3 days in the oil bath, a dark yellow-green solution was obtained. The ice water containing concentrated hydrochloric acid was prepared in advance. After the reaction was over, the reaction solution was poured into it and stirred. The yellow-green solid precipitated, filtered with a Buchner funnel, washed with 100 mL of dilute hydrochloric acid and distilled water, and dried the filter cake to obtain a yellow-green solid. The yellow-green solid was Soxhlet extracted with dichloromethane for 48 hours to obtain a yellow-green extract. Evaporate the solvent with a rotary evaporator, put it into an oven for drying, and finally obtain a brown-yellow powder, which is the process product II, with a weight of 0.3561 g.

(3) Add 400 mg of tetrastyrylaldehyde, 196.79 mg of 1,5-binaphthol and 8 mL of 1,4-dioxane to the polytetrafluoroethylene lining of the reaction kettle, fill it with saturated nitrogen, cover it with a lid and seal it , put it in an oven and set the temperature at 220 ° C, and after 4 days, a black suspension can be obtained, and then divided into two parts into the bottle, the masses are 0.0960g and 0.1000g respectively, and after suction filtration, the red suspension is obtained. The brown powder is then firstly soaked with acetone for one day, then suction filtered, and then soaked with dichloromethane for one day, suction filtered, and dried to obtain an organic porous skeleton polymer based on a tetrastyrene structure.

Test Example 1

(1) Infrared spectrum test is carried out to process product I, and the results are shown in Figure 1. It can be seen from Figure 1 that since 1650cm ^-1 and 1720cm ^-1 are the skeleton vibration absorption peaks of the benzene ring, and there is a characteristic peak of CH stretching vibration on the benzene ring at 1573.91cm ^-1 , the existence of the benzene ring is inferred. Moreover, according to the characteristic absorption peak at 1029.99cm ^-1 ～1572.91cm ^-1 is always strong, it can be judged that the double bond is not involved in the reaction. According to the characteristic absorption peak at 648.08cm ^-1 from strong to weak, it can be judged that there is a bromine group, and thus the product is judged to be tetrabromostyrene.

(2) Infrared spectrum analysis of process product II, the results are shown in Figure 2. It can be seen from Figure 2 that there are characteristic absorption peaks at 1700.23 cm ^-1 and 2820.55 cm ^-1 , and the known -CO stretching vibration range is around 1700 cm ^-1 , so it can be determined that there is an aldehyde group. In addition, 2820.55cm ^-1 and 2370.35cm ^-1 are the skeleton vibration absorption peaks of the benzene ring, and there is a characteristic peak of CH stretching vibration on the benzene ring at 2820.55cm ^-1 , so the existence of the benzene ring is inferred. In conclusion, it can be judged that the product is the process product II tetrastyrylaldehyde.

(3) The solid UV data analysis was carried out on the obtained organic porous skeleton polymer based on the tetrastyrene structure. The results are shown in Figure 3. It can be seen from Figure 3 that the polymer has the maximum absorption at the wavelength of 423 nm, indicating that it is a conjugated structure. .

(4) Infrared spectroscopy was performed on the obtained organic porous skeleton polymer based on tetrastyrene structure, and the obtained results are shown in FIG. 4 . It can be seen from Figure 4 that 1700.25cm ^-1 and 1650.32cm ^-1 are the skeleton vibration absorption peaks of the benzene ring, and there are characteristic peaks of CH stretching vibration on the benzene ring at 1695.45cm ^-1 and 1604.79cm ^-1 , so it is inferred that the presence of benzene rings. In addition, the existence of naphthol can be judged according to the absorption peak at 794.67～1050.78cm ^-1 from strong to weak. In Fig. 4, the two symmetric and anti-symmetric stretching vibrations representing aldehydes are observed to be very weak and getting weaker, and it can be seen that the aldehyde group gradually disappears during the reaction. At the same time, the -OH stretching vibration at 1050.78 cm ^-1 can be clearly observed. In conclusion, it can be judged that the reaction proceeds in an ideal direction, and the obtained product has the same structure as expected.

(5) Thermogravimetric analysis of the obtained organic porous skeleton polymer based on the tetrastyrene structure is carried out, and the obtained results are shown in FIG. 5 . In Figure 5, the X-axis represents the temperature rise from 0 °C to 1000 °C, and the Y-axis represents the mass loss of the organic porous framework polymer during the heating process. It can be seen from the figure that the weight loss rate of the organic porous skeleton polymer is 68.38%, while its weight loss rate is 32% between 20 and 100 °C. Dehydration leads to a loss of quality, but it can also show that the compound has good stability between this temperature and can exist stably, so there is no obvious structural collapse. However, from 560 °C to 650 °C, the TG curve has a slight decline, and there is a sharp decline between 820 °C and 1000 °C. It can be seen that the compound has a large area of structural collapse at this time. The compound has good thermal stability before 800°C, and then its stability becomes poor. In conclusion, the organic porous framework polymer provided by the present invention has good thermal stability below 800°C.

(6) X-ray diffraction analysis is performed on the obtained organic porous framework polymer based on tetrastyrene structure, and the obtained results are shown in FIG. 6 . It can be seen from FIG. 6 that the curve in the figure is generally gentle, and its peak shape is not sharp and narrow. It can be seen that the organic porous framework polymer provided by the present invention does not exhibit a certain crystal structure.

(7) SEM analysis of the obtained organic porous skeleton polymer based on tetrastyrene structure, the obtained results are shown in Figure 7, in Figure 7 a is the scanning electron microscope image under 200 times magnification, and b is 1000 times magnification. Scanning electron microscope image. From this, it can be found that the final product has a coral-like microstructure, and the skeleton is neatly arranged in clusters in a tight and orderly manner. It can also be seen that the skeleton has pores of different sizes, deep and shallow. These pores are intertwined, and finally form Homogeneous, regular, amorphous polymer organic frameworks.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (8)

1. An organic porous skeleton polymer based on a tetraphenylethylene structure, which has a structure shown in formula I:

the organic porous skeleton polymer based on the tetraphenyl ethylene structure takes tetraphenyl vinyl aldehyde and 1, 5-dinaphthol as monomers, and the molar ratio of the tetraphenyl vinyl aldehyde to the 1, 5-dinaphthol is 0.8-1.2: 1.5-2.5.

2. The organic porous skeleton polymer according to claim 1, wherein the specific surface area of the organic porous skeleton polymer is 320-350 m²(ii)/g, the pore diameter is 2 to 2.4 nm.

3. The method for synthesizing the tetraphenylethylene-based organic porous skeleton polymer of claim 1 or 2, comprising the steps of:

mixing tetraphenyl vinyl aldehyde, 1, 5-dinaphthol and a polar organic solvent, and performing nucleophilic addition and elimination reaction under protective gas to obtain an organic porous skeleton polymer based on a tetraphenyl vinyl structure; the mole ratio of the tetraphenyl vinyl aldehyde to the 1, 5-dinaphthol is 0.8-1.2: 1.5 to 2.5.

4. The synthesis method according to claim 3, wherein the polar organic solvent is one or more of 1, 4-dioxane, tetrahydrofuran, toluene and mesitylene.

5. The synthesis method according to claim 3, wherein the volume ratio of the mass of the tetraphenylethylenealdehyde to the volume of the polar organic solvent is 0.8-1.2 g: 15-25 mL.

6. The synthesis method according to claim 3, wherein the temperature of the nucleophilic addition and elimination reaction is 200-240 ℃ and the time is 3-5 days.

7. The synthetic method according to claim 3, further comprising post-treating the nucleophilic addition and elimination reaction solution after the nucleophilic addition and elimination reaction, wherein the post-treatment comprises the following steps:

and sequentially filtering, washing and drying the nucleophilic addition and elimination reaction liquid to obtain the organic porous skeleton polymer solid based on the tetraphenylethylene structure.

8. The synthesis method according to claim 7, wherein the washing comprises acetone washing and dichloromethane washing sequentially.

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