CN111875761B - Organic porous framework polymer based on tetraphenylethylene structure and synthetic method thereof - Google Patents
Organic porous framework polymer based on tetraphenylethylene structure and synthetic method thereof Download PDFInfo
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Abstract
The invention provides an organic porous framework polymer based on a tetraphenylethylene structure and a synthesis method thereof, belonging to the technical field of functional materials. The invention provides an organic porous framework polymer based on a tetraphenylethylene structure, which has a structure shown in a formula I; the organic porous skeleton polymer based on the tetraphenyl ethylene structure takes tetraphenyl ethylene aldehyde and 1,5-dinaphthol as monomers, and the molar ratio of the tetraphenyl ethylene aldehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5-2.5. In the invention, the tetraphenylethylene aldehyde and 1,5-dinaphthol are connected through aldol condensation reaction, and the formed organic porous skeleton polymer based on the tetraphenylethylene structure has regular and uniform structure and good thermal stability and chemical stability.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to an organic porous framework polymer based on a tetraphenylethylene structure and a synthesis method thereof.
Background
The organic porous framework polymer has the advantages of a permanently open pore channel structure, stable physicochemical properties, diversity in composition and the like, and is remarkably developed in the fields of adsorption storage, selective separation, carbon dioxide capture, organic pollutant control and the like of energy gases (such as hydrogen, methane and the like), so that the organic porous framework polymer is gradually developed into a novel and very potential adsorption material.
Compared with the traditional inorganic porous adsorption material, the organic porous skeleton polymer material has a plurality of unique advantages: on one hand, the porous organic polymer can only consist of light elements such as C, H, O, N, B and the like, so that the porous organic polymer has very low skeleton density; on the other hand, the synthesis method of the porous organic polymer is various and the monomer selection range is wide. In addition, the organic porous skeleton polymer can also adjust the performance thereof by modifying the functional groups of organic matters and changing the lengths of various chains, thereby achieving the specific synthesis purpose. In addition, the organic porous polymer has stable physical properties and chemical properties, and can be applied in severe environments such as acid, alkali, humidity and the like.
The organic porous skeleton polymer has wide research prospect due to a plurality of advantages.
Disclosure of Invention
In view of the above, the present invention aims to provide an organic porous skeleton polymer based on a tetraphenylethylene structure and a synthesis method thereof. The organic porous framework polymer based on the tetraphenylethylene structure provided by the invention has the advantages of regular and uniform structure, and good thermal stability and chemical stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an organic porous framework polymer based on a tetraphenylethylene structure, which has a structure shown in a formula I:
the organic porous skeleton polymer based on the tetraphenyl ethylene structure takes tetraphenyl ethylene aldehyde and 1,5-dinaphthol as monomers, and the molar ratio of the tetraphenyl ethylene aldehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5-2.5.
Preferably, the specific surface area of the organic porous skeleton polymer is 320-350 m 2 The pore diameter is 2-2.4 nm.
The invention provides a method for synthesizing organic porous framework polymer based on tetraphenylethylene, which comprises the following steps:
mixing tetraphenyl vinyl aldehyde, 1,5-dinaphthol and a polar organic solvent, and carrying out nucleophilic addition and elimination reaction under protective gas to obtain an organic porous skeleton polymer based on a tetraphenyl ethylene structure; the mole ratio of the tetraphenyl vinyl aldehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5 to 2.5.
Preferably, the polar organic solvent is one or more of 1,4-dioxane, tetrahydrofuran, toluene and mesitylene.
Preferably, the volume ratio of the mass of the tetraphenylethylenealdehyde 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 ℃ and the time is 3-5 days.
Preferably, after the nucleophilic addition and elimination reaction, the method further comprises performing post-treatment on the nucleophilic addition and elimination reaction solution, 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.
Preferably, the washing comprises acetone washing and dichloromethane washing sequentially.
The invention provides an organic porous framework polymer based on a tetraphenylethylene structure, which has a structure shown in a formula I; the organic porous skeleton polymer based on the tetraphenyl ethylene structure takes tetraphenyl ethylene aldehyde and 1,5-dinaphthol as monomers, and the molar ratio of the tetraphenyl ethylene aldehyde to the 1,5-dinaphthol is 1:2 is prepared. In the invention, the tetraphenyl vinyl aldehyde and 1,5-dinaphthol are connected through aldol condensation, and the formed organic porous skeleton polymer based on the tetraphenyl vinyl structure has regular and uniform structure, good thermal stability and chemical stability and can be used for gas separation.
The invention provides a synthetic method of the organic porous framework polymer based on the tetraphenylethylene structure, which has the advantages of short synthetic route, simple operation and easy realization of industrial production.
Drawings
FIG. 1 is an infrared spectrum of tetrabromostyrene obtained in example 1;
FIG. 2 is an infrared spectrum of tetraphenylethylenealdehyde obtained in example 1;
FIG. 3 is a solid ultraviolet spectrum of the organic porous skeleton polymer based on a tetraphenylethylene structure obtained in example 1;
FIG. 4 is an infrared spectrum of an organic porous skeleton polymer based on a tetraphenylethylene structure obtained in example 1;
FIG. 5 is a thermogravimetric analysis chart of the organic porous skeleton polymer based on a tetraphenylethylene structure obtained in example 1;
FIG. 6 is an X-ray diffraction pattern of an organic porous skeleton polymer based on a tetraphenylethylene structure obtained in example 1;
FIG. 7 is a scanning electron microscope image of the organic porous skeleton polymer based on a tetraphenylethylene structure obtained in example 1.
Detailed Description
The invention provides an organic porous framework polymer based on a tetraphenylethylene structure, which has a structure shown in a formula I:
the position of the- "and
is connected to
At the middle and four ends is ` -
The organic porous skeleton polymer based on the tetraphenylethylene structure takes tetraphenylethylenealdehyde and 1,5-dinaphthol as monomers, and the molar ratio of the tetraphenylethylenealdehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5-2.5, preferably 1:2. In the invention, the tetraphenylethylene aldehyde and 1,5-dinaphthol are subjected to aldol condensation to form covalent bonds, and the formed organic porous skeleton polymer based on the tetraphenylethylene structure has the advantages of regular and uniform structure, and good thermal stability and chemical stability.
The specific surface area of the organic porous skeleton polymer is preferably 320-350 m 2 /g, more preferably 326m 2 (ii)/g; the pore diameter is preferably 2 to 2.4nm, more preferably 2.11nm.
The invention provides a synthetic method of the organic porous framework polymer based on the tetraphenylethylene structure, which comprises the following steps:
mixing tetraphenyl vinyl aldehyde, 1,5-dinaphthol and a polar organic solvent, and carrying out nucleophilic addition and elimination reaction under protective gas to obtain the organic porous skeleton polymer based on the tetraphenyl vinyl structure.
In the invention, the mole ratio of the tetraphenylethylenealdehyde to the 1,5-binaphthol is 0.8-1.2: 1.5-2.5, preferably 1:2; the polar organic solvent is preferably one or more of 1,4-dioxane, tetrahydrofuran, toluene and mesitylene, and the volume ratio of the mass of the tetraphenylethenal to the polar organic solvent is preferably 0.8-1.2 g:15 to 25mL, more preferably 1g:20mL.
The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art. In the present invention, the protective gas is preferably saturated nitrogen. The nucleophilic addition and elimination reactions are preferably carried out in a sealed polytetrafluoroethylene reaction vessel. In the present invention, the temperature of the nucleophilic addition and elimination reaction is preferably 200 to 240 ℃, more preferably 220 ℃, and the time is preferably 3 to 5 days, more preferably 4 days.
In the invention, the nucleophilic addition and elimination reaction process is shown as formula A:
in the present invention, it is preferable that the nucleophilic addition and elimination reaction is followed by a post-treatment of the nucleophilic addition and elimination reaction solution, and the post-treatment preferably comprises the steps of:
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.
The method for filtering is not particularly required by the invention, and the filtering method well known in the field can be used, such as suction filtration. In the present invention, the washing preferably includes acetone washing and dichloromethane washing sequentially. In the present invention, the acetone washing and the dichloromethane washing are preferably performed by immersion washing, and the immersion washing is independently performed for preferably 1 day. In the present invention, the drying temperature is preferably 80 to 100 ℃ and the drying time is preferably 12 to 18 hours.
The invention has no special requirements on the sources of the tetraphenylethylenealdehyde and 1,5-dinaphthol, and can use the commercial tetraphenylethylenealdehyde and 1,5-dinaphthol or prepare the tetraphenylethylenealdehyde and the 1,5-dinaphthol by self. When tetraphenylvinylaldehyde is prepared by itself, the preparation method preferably comprises the steps of:
(a) Carrying out electrophilic substitution reaction on tetraphenyl ethylene and liquid bromine to obtain tetrabromo styrene;
(b) Under the action of a catalyst, tetrabromostyrene and tetraacylphenylboronic acid are subjected to suzuki coupling reaction to obtain tetraphenylethylenealdehyde.
In the invention, preferably, the electrophilic substitution reaction of the tetraphenylethylene and the liquid bromine is carried out to obtain the tetrabromostyrene. In the present invention, the mole ratio of tetraphenylethylene to liquid bromine is preferably 1:2, and the temperature of the electrophilic substitution reaction is preferably 60 to 80 ℃, more preferably 70 ℃, and the time is preferably 7 days. In the present invention, the electrophilic substitution reaction is preferably carried out in a dryer.
In the present invention, the electrophilic substitution reaction process is as shown in formula B:
after tetrabromostyrene is obtained, the invention preferably performs a suzuki coupling reaction of the tetrabromostyrene and the tetracarboxylphenylboronic acid under the action of a catalyst to obtain tetraphenylethylenealdehyde. In the invention, the catalyst is preferably tetrakis (triphenylphosphine) palladium (abbreviated as palladium-tetrakis) and anhydrous potassium carbonate, and the mass ratio of the palladium-tetrakis to the anhydrous potassium carbonate is preferably 1. In the present invention, the molar ratio of the tetrabromostyrene to the tetraacylphenylboronic acid is preferably 1:4, and the mass ratio of the tetrabromostyrene to the catalyst is preferably 3.8.
In the present invention, the suzuki coupling reaction is preferably performed in N 2 The suzuki coupling reaction is carried out under protection, the temperature of the suzuki coupling reaction is preferably 85 ℃, and the time is preferably 3 days.
In the invention, the suzuki coupling reaction process is shown as formula C:
in the present invention, after the suzuki coupling reaction, the method further preferably comprises performing post-treatment on the obtained suzuki coupling reaction solution, wherein the post-treatment preferably comprises the following steps:
and pouring the suzuki coupling reaction liquid into ice water containing concentrated hydrochloric acid, mixing, sequentially filtering, washing filter residues, drying and performing Soxhlet extraction, and removing a Soxhlet extraction solvent to obtain the tetraphenylethylenealdehyde pure product.
In the invention, the mass concentration of the concentrated hydrochloric acid in the ice water containing the 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. In the present invention, the mixing is preferably performed by stirring. In the present invention, the filtration is preferably performed by suction filtration, the washing is preferably performed by sequentially 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 requirement on the drying mode, and the moisture can be completely removed by using the drying mode 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 48 hours. In the present invention, the solvent is preferably removed by rotary evaporation. After the solvent is removed, the present invention preferably further comprises drying the solid after the solvent is removed.
The source of the tetrakis (triphenylphosphine) palladium is not particularly required, and the commercially available tetrakis (triphenylphosphine) palladium can be used or prepared by self. When the tetrakis (triphenylphosphine) palladium is prepared on its own, it preferably comprises the following steps:
under the nitrogen atmosphere, carrying out coordination reaction on triphenylphosphine and palladium chloride to obtain coordination reaction liquid;
and mixing the coordination reaction solution with hydrazine hydrate for reduction reaction to obtain the tetrakis (triphenylphosphine) palladium.
In the present invention, the molar ratio of 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 ratio of the mass of the triphenylphosphine to the volume of the dimethyl sulfoxide solvent is preferably 0.6532g:20mL. In the present invention, the temperature of the coordination reaction is preferably 130 ℃ and the time is preferably 1 hour.
In the present invention, it is preferable to add hydrazine hydrate to the coordination reaction solution. In the present invention, the mass ratio of the volume of hydrazine hydrate to triphenylphosphine is preferably 2mL:0.6532g. In the present invention, the temperature of the reduction reaction is preferably 130 ℃ and the time is preferably 1 hour.
After obtaining the reduction reaction solution, the present invention preferably performs a post-treatment on the reduction reaction solution, and the post-treatment preferably includes the following steps:
and sequentially filtering, washing and drying the filter residue of the reduction reaction solution to obtain a pure product of the tetrakis (triphenylphosphine) palladium.
In the invention, the filtration mode is preferably Buchner funnel filtration; the washing detergent is preferably absolute ethyl alcohol; the drying is preferably vacuum drying, the temperature of the drying is preferably 40 ℃, and the time is preferably 12 hours.
The organic porous framework polymer based on the tetraphenylethylene structure can be used for gas separation, and the separated gas is preferably carbon dioxide and methane.
The organic porous skeleton polymer based on a tetraphenylethylene structure and the synthesis method thereof provided by the present invention are described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) 5.0738g tetraphenylethylene is weighed on a watch glass, then put into a dryer, then 5 drops of liquid bromine is dripped into the dryer, after the liquid bromine is volatilized after the dryer is placed for 7 days, the tetraphenylethylene turns into light yellow, and the process product I tetrabromostyrene is prepared, wherein the weight of the product is 3.1060g.
(2) 1.0952g tetrabromostyrene, 0.9384g tetraacylphenylboronic acid, 2.1861g anhydrous potassium carbonate, palladium four and 80mL dioxane are added into a dry clean three-neck flask, the mixed solution is yellow, then the temperature is controlled to be about 85 ℃ under the protection of nitrogen, a dark yellow green solution is obtained after oil bath is carried out for 3 days, ice water containing concentrated hydrochloric acid is prepared in advance, the reaction solution is poured into the ice water for stirring immediately after the reaction is finished, yellow green solid precipitate is generated at the moment, suction filtration is carried out by a Buchner funnel, 100mL diluted hydrochloric acid and distilled water are used for washing, a filter cake is dried, yellow green solid is obtained, soxhlet extraction is carried out on the yellow green solid for 48 hours by dichloromethane, a yellow green extracting solution is obtained, the solvent is evaporated by a rotary evaporator, the mixture is placed into an oven for drying, and finally brown yellow powder, namely a process product II is obtained, and the weight is 0.3561g.
(3) Adding 400mg of tetraphenylethylene aldehyde, 196.79mg1, 5-dinaphthol and 8mL1, 4-dioxane into a polytetrafluoroethylene lining of a reaction kettle, filling saturated nitrogen, covering a cover, sealing, putting into an oven, setting the temperature at 220 ℃, preparing black suspension after 4 days, dividing into two parts, putting into a bottle, performing suction filtration to obtain reddish brown powder, performing immersion washing with acetone for one day, performing suction filtration again, performing immersion washing with dichloromethane for one day, performing suction filtration, and drying to obtain the organic porous skeleton polymer based on the tetraphenylethylene structure.
Test example 1
The infrared spectrum test is carried out on the process product I, and the result is shown in figure 1. As can be seen from FIG. 1, since 1650cm -1 And 1720cm -1 Is a skeleton vibration absorption peak of a benzene ring and is 1573.91cm -1 The existence of the benzene ring is deduced because the C-H stretching vibration characteristic peak on the benzene ring is present. And according to the standard at 1029.99cm -1 ～1572.91cm -1 The characteristic absorption peak is always strong, so that the double bond can be judged not to participate in the reaction. And the average particle size is 648.08cm -1 The characteristic absorption peak is judged to have bromine radicals from strong to weak, thereby judging that the product is tetrabromo styrene.
And (II) performing infrared spectroscopic analysis on the process product II, wherein the result is shown in figure 2. As can be seen from FIG. 2, the value is 1700.23cm -1 、2820.55cm -1 Has a characteristic absorption peak, and the-C-O stretching vibration range is known to be 1700cm -1 And left and right, so that the presence of aldehyde groups can be confirmed. In addition 2820.55cm -1 And 2370.35cm -1 Is a skeleton vibration absorber of benzene ringThe peak is reduced and is 2820.55cm -1 The existence of the benzene ring is deduced because the C-H stretching vibration characteristic peak on the benzene ring is present. The product can be judged to be the process product II tetraphenylvinylaldehyde.
And (III) carrying out solid ultraviolet data analysis on the obtained organic porous skeleton polymer based on the tetraphenylethylene structure, wherein the result is shown in figure 3, and as can be seen from figure 3, the polymer has maximum absorption at the wavelength of 423nm, which indicates that the polymer is a conjugated structure.
(IV) infrared spectroscopic analysis was performed on the obtained organic porous skeleton polymer based on a tetraphenylethylene structure, and the results are shown in FIG. 4. As can be seen from FIG. 4, 1700.25cm -1 And 1650.32cm -1 Is a skeleton vibration absorption peak of a benzene ring and is 1695.45cm -1 And 1604.79cm -1 The existence of the benzene ring is deduced because the C-H stretching vibration characteristic peak on the benzene ring is present. The thickness of the film is 794.67-1050.78 cm -1 The existence of naphthol can be judged by the strong absorption peak to the weak absorption peak. While in figure 4 it is observed that the two symmetric and anti-symmetric stretching vibrations representing the aldehydes are very weak and increasingly weak, it can be seen that the aldehyde groups gradually disappear in the reaction. At the same time, it is clearly observed that the intensity of the light beam is 1050.78cm -1 There is an-OH stretching vibration. In conclusion, it can be judged that the reaction proceeds in the ideal direction and the product obtained is of the same structure as expected.
(V) thermogravimetric analysis was performed on the obtained organic porous skeleton polymer based on the tetraphenylethylene structure, and the obtained results are shown in FIG. 5. In FIG. 5, the X-axis represents the temperature increase from 0 ℃ to 1000 ℃ and the Y-axis represents the mass loss of the organic porous skeleton polymer during the temperature increase. It can be seen from the figure that the weight loss ratio of the organic porous skeleton polymer is 68.38%, and the weight loss ratio between 20 ℃ and 100 ℃ is 32%, which is mainly because a certain amount of water is adsorbed on the surface of the original substance, and the mass is lost due to the dehydration of the structure in the temperature rise process, and just can indicate that the compound has better stability between the temperatures, can exist stably, and has no obvious structural collapse. However, a slight downward shift of the TG curve occurred from 560 ℃ to 650 ℃ and a sharp downward shift occurred between 820 ℃ and 1000 ℃, and it was found that the compound had a large-area structural collapse at this time, and it was concluded that the compound had good thermal stability before 800 ℃ and then had poor stability. In conclusion, the organic porous framework polymer provided by the invention has good thermal stability below 800 ℃.
And (VI) carrying out X-ray diffraction analysis on the obtained organic porous framework polymer based on the tetraphenylethylene structure, wherein the obtained result is shown in figure 6. As can be seen from fig. 6, the curve in the graph is overall relatively mild, and the peak shape is not sharp and narrow, so that it can be seen that the organic porous framework polymer provided by the present invention does not exhibit a certain crystalline structure.
(VII) scanning electron microscope analysis is carried out on the obtained organic porous skeleton polymer based on the tetraphenylethylene structure, and the obtained result is shown in FIG. 7, wherein a is a scanning electron microscope image under 200 times magnification, and b is a scanning electron microscope image under 1000 times magnification in FIG. 7. Therefore, the final product is found to be in a coralline microstructure, the frameworks are in cluster-like, compact and orderly and regularly arranged, deep and shallow pore canals are also seen in the frameworks, the pores are staggered, and the uniform, regular and amorphous polymer organic framework is finally formed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (6)
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 tetraphenylethylene structure takes tetraphenylethylenealdehyde and 1,5-dinaphthol as monomers, and the molar ratio of the tetraphenylethylenealdehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5-2.5;
the organic porous skeleton polymerThe specific surface area of the compound is 320-350 m 2 Per gram, the aperture is 2-2.4 nm;
the tetraphenylethylenealdehyde has the following structure:
the method for synthesizing the organic porous skeleton polymer based on tetraphenyl vinyl aldehyde comprises the following steps:
mixing tetraphenyl vinyl aldehyde, 1,5-dinaphthol and a polar organic solvent, and carrying out nucleophilic addition and elimination reaction under protective gas to obtain an organic porous skeleton polymer based on a tetraphenyl ethylene structure; the mole ratio of the tetraphenyl vinyl aldehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5 to 2.5; the polar organic solvent is 1,4-dioxane.
2. The method for synthesizing organic porous skeleton polymer based on tetraphenylethylene structure as claimed in claim 1, comprising the steps of:
mixing tetraphenyl vinyl aldehyde, 1,5-dinaphthol and a polar organic solvent, and carrying out nucleophilic addition and elimination reaction under protective gas to obtain an organic porous skeleton polymer based on a tetraphenyl ethylene structure; the mole ratio of the tetraphenyl vinyl aldehyde to the 1,5-dinaphthol is 0.8-1.2: 1.5 to 2.5; the polar organic solvent is 1,4-dioxane.
3. The synthesis method according to claim 2, wherein the mass-to-volume ratio of the tetraphenylethylenealdehyde to the polar organic solvent is 0.8-1.2 g: 15-25 mL.
4. The synthesis method according to claim 2, wherein the temperature of the nucleophilic addition and elimination reaction is 200-240 ℃ and the time is 3-5 days.
5. The synthesis method according to claim 2, wherein after the nucleophilic addition and elimination reaction, the method further comprises post-treating the nucleophilic addition and elimination reaction solution, 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.
6. The synthesis method according to claim 5, wherein the washing comprises acetone washing and dichloromethane washing sequentially.
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