CN110396195B

CN110396195B - Polyarylsulfone polymer containing reduced phenazine structure and preparation method thereof

Info

Publication number: CN110396195B
Application number: CN201910729390.9A
Authority: CN
Inventors: 陈峥; 韩韫韬; 邢真; 罗浩; 李苏
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2019-08-08
Filing date: 2019-08-08
Publication date: 2021-11-16
Anticipated expiration: 2039-08-08
Also published as: CN110396195A

Abstract

The invention relates to a polyarylsulfone polymer containing a reduced phenazine structure and a preparation method thereof, wherein the polymer comprises a structural chain segment shown in the following formula (I):

in the formula (I), n is the degree of polymerization; m is copolymerization proportion, m is more than 0 and less than or equal to 1; ar is one of the following formulas (a) to (d):

in the formula (c), X is an integer of 1, 2 or 3, and in the formula (d), R is 1, 4-position disubstituted naphthalene, 1, 5-position disubstituted naphthalene, 2, 6-position disubstituted naphthalene or 2, 7-position disubstituted naphthalene. The polymer not only has good photoelectric activity, but also has good thermal stability, and the polymer can be expected to have wide development prospect and huge application potential in the photoelectric field, in particular to the aspects of electrochromism, information storage, carbon nanotube coating, thermal response delayed fluorescence and the like.

Description

Polyarylsulfone polymer containing reduced phenazine structure and preparation method thereof

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a polyarylsulfone polymer containing a reduced phenazine structure and a preparation method thereof.

Background

The wide application of information system transmission and display technology has marked the opening of the "information age" by human beings in the early 21 st century, and the life style of human beings has revolutionized and benefited from this time. The rapid development of the information industry technology requires the continuous improvement of the technology and the development and innovation of theoretical knowledge, and the development of novel materials can provide a basis for theoretical research, can better meet the requirements of the production process and promote the improvement of the production process, so the development of novel functional materials becomes the key of the development of the field, and the development of novel organic polymer photoelectric functional materials becomes important.

The currently common polymer organic photoelectric functional materials are mainly conjugated polymer materials, and the practical application of the materials is limited due to high synthesis cost, poor solubility, dark neutral state color and the like. Therefore, attention has been paid to a main chain nonconjugated redox type photoelectric polymer such as polyamide, polyimide, or the like. The polyarylsulfone serving as a special engineering plastic is excellent in chemical stability and thermal stability, and is very suitable for being used as a main chain structure of a non-conjugated photoelectric material. Meanwhile, the reduced phenazine is a common compound with excellent photoelectric function, and due to good photoelectric activity of the reduced phenazine, the high-molecular photoelectric functional material constructed by the reduced phenazine is widely applied to the photoelectric fields of hole transmission, electrochromism, electroluminescence, information storage, solar cells and the like, but the high-molecular photoelectric functional material constructed by the reduced phenazine compound is difficult to simultaneously have good photoelectric activity, electrochemical stability, thermal stability and solubility.

Disclosure of Invention

The invention aims to provide a polyarylsulfone polymer containing a reduced phenazine structure and a preparation method thereof, so as to improve the photoelectric activity, the electrochemical stability, the thermal stability and the solubility of a high-molecular photoelectric functional material constructed by the reduced phenazine compound at present.

The invention relates to a polyarylsulfone polymer containing a reduced phenazine structure, which comprises a structural chain segment shown in the following formula (I):

in the formula (c), X is an integer of 1, 2 or 3,

in the formula (d), R is 1, 4-position disubstituted naphthalene, 1, 5-position disubstituted naphthalene, 2, 6-position disubstituted naphthalene or 2, 7-position disubstituted naphthalene.

The invention relates to a preparation method of a polyarylsulfone polymer containing a reduced phenazine structure, which comprises the following steps:

putting a difluoride monomer containing a sulfonyl group, bisphenol A, a reducing phenol oxazine, catalyst potassium carbonate, a solvent sulfolane or N-methyl pyrrolidone and toluene as a water-carrying agent into a three-neck flask provided with a nitrogen port, an oil-water separator and mechanical stirring, stirring and heating to 140-150 ℃ in the nitrogen atmosphere to enable the toluene to reflux for 3h, discharging the toluene and water by the oil-water separator after fully carrying water, and then increasing the temperature to 200-220 ℃ to stir and react for 3-8h to obtain a reducing phenol oxazine-containing polyarylsulfone polymer, wherein the reaction formula is as follows:

in the formula, n is the degree of polymerization, m is the copolymerization proportion, and m is more than 0 and less than or equal to 1; ar is one of the following formulas (a) to (d):

in the formula (c), X is an integer of 1, 2 or 3,

Wherein, the corresponding molecular structure is obtained by changing different difluoride monomers containing sulfonyl, and the selected (a) is a residue obtained after 4, 4' -difluoro diphenyl sulfone reacts; (b) is a residue from the reaction of 4, 4' -bis (4-fluoro-diphenylsulfone) ether; (c) is a residue from the reaction of 1, 4-bis (4-fluorophenylsulphonyl) benzene or 4, 4 '-bis (4-fluorophenylsulphonyl) biphenyl or 4, 4' -bis (4-fluorophenylsulphonyl) terphenyl; (d) is the residue from the reaction of 1, 4-bis ((4-fluorophenyl) sulfonyl) naphthalene or 1, 5-bis ((4-fluorophenyl) sulfonyl) naphthalene or 2, 6-bis ((4-fluorophenyl) sulfonyl) naphthalene or 2, 7-bis ((4-fluorophenyl) sulfonyl) naphthalene.

The reaction charge amount of the catalyst potassium carbonate is preferably 2 times of that of the difluoride monomer.

According to the polyarylsulfone polymer containing the reduced phenazine structure and the preparation method thereof, from the perspective of molecular design, the reduced phenazine with the photoelectric active group is introduced into polyarylsulfone, and the polymer not only can show good photoelectric activity, but also has good thermal stability and solubility. Meanwhile, the good electron-donating ability of the reduced phenazine is directly connected with the strong electron-withdrawing sulfuryl through a benzene ring to form a donor-acceptor structure (D-A), so that an internal charge migration phenomenon is generated, and the photoelectric property of the polymer is further enhanced. In addition, because the phenazine is a large rigid group, a relatively fixed torsion angle can be formed between the phenazine and a sulfone group, so that the difference between the singlet state energy level and the triplet state energy level of the material is relatively small, and the phenomenon of thermal response delayed fluorescence is caused. In addition, the polyarylsulfone as a special engineering plastic has good mechanical property, so that the solubility of the polymer is further improved after bisphenol A copolymerization is introduced, the polymer is very easy to process into a film and keeps good mechanical property, and therefore, the polyarylsulfone has very wide application fields and practical value. According to the structural characteristics and photoelectric characteristics of the polymer provided by the invention, the material can be expected to have wide development prospect and great application potential in the photoelectric field, particularly in the aspects of electrochromism, information storage, carbon nanotube coating, thermal response delayed fluorescence and the like.

The experimental results show that: the polyarylsulfone polymer containing a reduced phenazine structure provided by the invention has the 5% thermal weight loss of more than 470 ℃, can be dissolved in organic solvents such as tetrahydrofuran, dichloromethane, trichloromethane, N '-Dimethylformamide (DMF), N' -dimethylformamide (DMAc), N-methylpyrrolidone (NMP) and the like, and can show the photoelectric characteristics of corresponding photoelectric active groups.

Compared with common polyarylsulfone materials, the polymer provided by the invention has the advantages that a new polymerization method is improved, so that nucleophilic substitution is directly carried out on the difluoride monomer and the imino monomer, and a novel photoelectric material can be obtained in a very low-cost mode. Meanwhile, the introduction of the tertiary amine structure completely or partially replaces ether bonds, so that the rigidity of the main chain of the material is increased, the thermal stability of the material is greatly improved, and the practical application of the material is facilitated. The sulfone group is a strong electron-withdrawing structure, so that a donor-acceptor structure is formed by directly connecting the sulfone group with the phenazine, and compared with other non-conjugated photoelectric materials, the material has the advantages that the internal charge migration is easier, the starting voltage of the material is obviously reduced, the service life of the material is prolonged, and the energy consumption is reduced. In conclusion, the polyarylsulfone material with the introduced phenazine structure not only has good photoelectric activity, but also has good electrochemical stability, thermal stability and solubility.

Drawings

FIG. 1 is an infrared spectrum of polymer P1 provided in example 1 of the present invention;

FIG. 2 is a thermogravimetric plot under nitrogen atmosphere provided in example 1 of the present invention;

FIG. 3 is a differential scanning calorimetry thermogram under a nitrogen atmosphere provided in example 1 of the present invention;

FIG. 4 is a cyclic voltammogram provided in example 1 of the present invention;

FIG. 5 shows the NMR spectrum of P1-50% of the polymer provided in example 2 of the present invention;

FIG. 6 is a cyclic voltammogram provided in example 2 of the present invention;

FIG. 7 is an electrochromic spectrum provided in example 2 of the present invention;

FIG. 8 is a nuclear magnetic spectrum of the polymer P2 provided in example 3 of the present invention;

FIG. 9 shows a nuclear magnetic spectrum of the polymer P6 provided in example 4 of the present invention;

FIG. 10 is a UV-VIS absorption spectrum of polymer P6 provided in example 4 of the present invention.

Detailed Description

The technical solution of the present invention is further clearly and completely described by the following examples. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.

The invention relates to a polyarylsulfone polymer containing a reduced phenazine structure, which comprises a structural chain segment shown in a formula (I):

in the formula (I), n is polymerization degree, m is more than 0 and less than or equal to 1, and Ar is one of the formulas (a) to (d):

in the formula (c), X is selected from one of

integers

1, 2 and 3; in the formula (d), R is selected from one of 1, 4-position, 1, 5-position, 2, 6-position and 2, 7-position disubstituted naphthalene.

In some embodiments provided herein, the main chain of the polymer is polyarylsulfone, which may be specifically of the following P1-P9 structures:

in P1-P9, n is the degree of polymerization, and m is more than 0 and less than or equal to 1, which represents the copolymerization ratio.

The polymer provided by the invention introduces a photoelectric activity reduction phenazine group with a specific structure into the polyarylsulfone polymer, so that the polymer not only can show good photoelectric activity and photoelectric functional characteristics, but also has good thermal stability and solubility. The polymer provided by the invention has very wide application fields and practical values, and according to the structural characteristics and photoelectric characteristics of the polymer, the polymer can be expected to have wide development prospects and huge application potentials in the photoelectric field, particularly in the aspects of electrochromism, information storage, carbon nanotube coating, thermal response delayed fluorescence and the like.

The experimental results show that: the 5% thermal weight loss of the polymer containing the reduced phenazine polyarylsulfone provided by the invention is above 470 ℃, the polymer can be dissolved in organic solvents such as tetrahydrofuran, dichloromethane, trichloromethane, DMF, DMAc, NMP and the like, and the polymer can show the photoelectric characteristics of corresponding photoelectric active groups.

The preparation method of the polyarylsulfone polymer containing the reduced phenazine structure comprises the following steps:

putting a difluoride monomer containing a sulfonyl group, bisphenol A, a reducing phenol oxazine, catalyst potassium carbonate, a solvent sulfolane or N-methyl pyrrolidone and toluene as a water-carrying agent into a three-neck flask provided with a nitrogen port, an oil-water separator and mechanical stirring, stirring and heating to 140-150 ℃ in the nitrogen atmosphere to enable the toluene to reflux for 3h, discharging the toluene and water by the oil-water separator after fully carrying water, and then increasing the temperature to 200-220 ℃ to stir and react for 3-8h to obtain a reducing phenol oxazine polyarylsulfone polymer, wherein the reaction formula is (i):

wherein n is the degree of polymerization, 0< m.ltoreq.1 represents the copolymerization ratio, and Ar is one of the formulae (a) to (d):

in the formula (c), X is selected from one of

integers

In the present production method, the catalyst and the reactants are first charged into the reaction apparatus. Wherein the reactants include a reduced phenazine monomer and a difluoride monomer. When the copolymer is prepared according to the present invention, the reactants further comprise bisphenol a.

The catalyst is preferably potassium carbonate, and the feeding amount of the catalyst is preferably 2 times of the molar amount of the sulfuryl-containing difluoride monomer.

Then, a solvent such as sulfolane or N-methylpyrrolidone and toluene as a water-carrying agent are added into the reaction device. And after the catalyst, the reactant, the solvent and the water-carrying agent are added, the reaction is carried out. Wherein, the reaction is preferably carried out under the condition of removing water by toluene as a water-carrying agent; the water carrying temperature of the reaction is 140-150 ℃, toluene and water are discharged from the oil-water separator after the water is carried, the reaction temperature is increased to 200-220 ℃, and the reaction time is 3-8 h. After the reaction reaches a certain time, the viscosity of the system rises rapidly, and the reactant is poured into deionized water to terminate the reaction. And finally, crushing, washing and drying the solid obtained by the reaction to obtain the polyarylsulfone polymer containing the reduced phenazine.

The method provided by the invention can be used for preparing the polymer containing the reduced phenazine polyarylsulfone with good photoelectric activity, thermal stability and solubility, and the method is simple, controllable in polymerization degree, easy for commercial production and practical.

For the sake of clarity, the following examples are given in detail.

Example 1: preparation of Polymer P1

Reduced phenazine (3.685g, 20mmol), 4' -difluorodiphenyl sulfone (5.334g, 20mmol), catalyst potassium carbonate (5.521g, 40mmol), 26mL NMP, and 20mL water-carrying agent toluene were put into a 100mL three-necked flask equipped with a nitrogen vent, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene refluxed for 3 hours, and after sufficient water was carried out, toluene and water were discharged with the oil-water separator. Then the temperature is increased to 200 ℃ and the reaction is stirred for 8 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times, 800mL each time) and ethanol (3 times, 300mL each time), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. An orange-yellow polymer powder (7.433g, 90% yield) was obtained. The results of structural analysis of the polymer obtained in this example are shown in fig. 4 and 5.

The polymer P1 obtained in this example was subjected to IR spectroscopy, the results of which are shown in FIG. 1. FIG. 1 is an infrared spectrum provided in example 1 of the present invention, in FIG. 1, P1 represents polymer P1, and DHPZ represents reduced phenazine. In FIG. 1 we can see that in the IR spectrum of the polymer, 3400cm is compared with the IR spectrum of the monomer^-1Is characterized by a characteristic absorption peak of 1260cm^-1Is attributed to-NHAr₂All the characteristic absorption peaks of (a) have disappeared; and at 1315cm^-1， 1340cm^-1In the presence of C-N and-NAr₃While retaining 3090cm^-1Has a characteristic absorption peak of 1500cm and is assigned to Ar-H^-1Characteristic absorption peak of 1150cm^-1Characteristic absorption peak of (a) assigned to S ═ O. The appearance of these characteristic absorption peaks indicates that the benzene ring structure and sulfone group of the two reactants are preserved during the polymerization process; and N-H, -NHAr in the monomer₂The disappearance of the characteristic absorption peak in the polymer infrared spectrogram indicates that hydrogen atoms connected with nitrogen atoms participate in the polymerization reaction in the polymerization to generate a new C-N bond, and the fact that C-N and-NAr appear in the polymer infrared spectrogram is proved₃Characteristic absorption peak of (1). Through infrared spectrum analysis, we can preliminarily determine the structure of the target polymer which we have synthesized.

The polymer P1 prepared in this example was subjected to a thermal stability test, and the results are shown in fig. 2 and 3. FIG. 2 is a graph showing the thermogravimetric analysis of polymer P1 provided in example 1 of the present invention under a nitrogen atmosphere. It can be seen from figure 2 that the 5% thermal weight loss of the polymer is above 494 ℃. FIG. 3 is a Differential Scanning Calorimetry (DSC) curve under nitrogen atmosphere for polymer P1 provided in example 1 of the present invention. It can be seen from FIG. 3 that the glass transition temperature of the polymer is 246 ℃. The results of fig. 2 and 3 show that the polymer has excellent thermal stability.

The cyclic voltammetry curve analysis of the polymer P1 prepared in this example was performed (electrolyte was 0.1M acetonitrile solution of tetrabutylammonium perchlorate, reference electrode was silver/silver nitrate reference electrode, counter electrode was platinum wire, material was a working electrode coated in NMP on ITO glass, test conditions were 100mV/, s test range was-0.2-1.2V, and the results are shown in FIG. 4. FIG. 4 is the cyclic voltammetry curve provided in example 1 of the present invention. it can be seen from FIG. 4 that the polymer has two pairs of reversible redox peaks, which are substantially the same as those of phenazine, and a smaller pair of redox peaks was present between the two pairs of peaks, which is caused by incomplete oxidation.

Example 2: preparation of Polymer P1-50%

Reduced phenazine (1.842g, 10mmol), 4' -difluorodiphenyl sulfone (5.334g, 20mmol), bisphenol A (2.284g, 10mmol), potassium carbonate catalyst (5.521g, 40mmol), 34mL sulfolane, and 20mL toluene as a water-carrying agent were put in a 100mL three-necked flask equipped with a nitrogen vent, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene refluxed for 3 hours, and after sufficiently carrying water, toluene and water were discharged with the oil-water separator. The temperature is raised to 220 ℃ and the reaction is stirred for 4 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times, 800mL each time) and ethanol (3 times, 300mL each time), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. An orange polymer powder (7.917g, 91% yield) was obtained. The number average molecular weight is 40.9kDa, the weight average molecular weight is 56.5kDa, and the dispersity is 1.4. The polymer obtained in this example was subjected to structural analysis, and the results are shown in FIG. 1.

The results of nuclear magnetic analysis of the polymer obtained in this example are shown in FIG. 5. FIG. 5 is a nuclear magnetic spectrum of the reduced phenazine monomer used in example 2 of the present invention and the resulting polymer P1-50%.

Nuclear magnetic analyses were conducted on the reduced phenazine monomer of this example and the resulting polymer P1-50%, and the results are shown in FIG. 5. FIG. 5 is a nuclear magnetic spectrum of example 2 of the present invention, wherein P1-50% in FIG. 5 represents polymer P1-50%, and DHPZ represents reduced phenazine monomer. Compared with the nuclear magnetic resonance hydrogen spectrum of the monomer, the short and wide proton peak appearing at the position of 5.99ppm of chemical shift obviously disappears, and a plurality of peaks overlapping each other appear in the area of 7.25-8.05ppm, because the repeated segment structure of the polymer contains a large amount of hydrogen atoms with similar but different chemical environments. The sulfone group is a strong electron-withdrawing group, so that the chemical potential of the hydrogen atom of the benzene ring close to the sulfone group is shifted to low field (peaks 3 and 4); the electron-withdrawing ability of the alkoxy group is inferior to that of the sulfone group, so that the chemical shift migration (peak 1, 2) of the hydrogen atom of the benzene ring close to the alkoxy group is less than that of the hydrogen atom of the benzene ring connected with the sulfone group; the N-containing heterocyclic ring has the weakest electron-withdrawing ability, and the hydrogen atom chemical shift (peak 5, peak 6) of the benzene ring close to the N-containing heterocyclic ring is moved to the low field to the minimum. The hetero-peak at the 3.70ppm position is likely the methylene quartet of residual ethanol in the sample. The sharp peak at the 1.70ppm position is a signal of the hydrogen atom of the methyl group in the bisphenol A unit.

The cyclic voltammetry curve analysis (electrolyte is 0.1M acetonitrile solution of tetrabutylammonium perchlorate, reference electrode is silver/silver nitrate reference electrode, counter electrode is platinum wire, material is coated on ITO glass in NMP in a spinning way to be used as a working electrode, the test condition is 100mV/s, and the test range is-0.2-1.1V) is carried out on the polymer P1-50% prepared in the embodiment, and the result is shown in figure 6, and figure 6 is the cyclic voltammetry curve graph provided by the embodiment 2 of the invention. It can be seen from FIG. 6 that the polymer possesses two pairs of reversible redox peaks, which are located close to but lower than the reduced phenazine, due to internal charge transfer occurring during the formation of the D-A structure of the polymer.

Electrochromic analysis is performed on the polymer P1-50% prepared in the embodiment (an electrochemical workstation is used with an ultraviolet-visible spectrometer, the electrochemical test conditions are the same as the cyclic voltammetry curve analysis, a constant voltage test is selected, changes of ultraviolet absorption curves of the material under the influence of different voltages within the range of 0.00-1.20V are respectively measured, the ultraviolet test conditions are 1.0nm wavelength intervals, and the test range is 300-900 nm), and the result is shown in FIG. 6, which is an electrochromic curve graph provided in the embodiment 2 of the invention. As can be seen from FIG. 6, when the original ultraviolet absorption of the polymer is changed when the voltage is increased, a strong absorption peak appears at 450nm, and the peak can be attributed to the single cation formed by reducing the phenazine; thereafter, at higher voltages a new UV absorption peak at 700nm appeared, this broad peak can be attributed to the dication of reduced phenazine formation.

Through cyclic voltammetry and electrochromic analysis, the polymer P1-50% provided by the embodiment has good photoelectric activity and can show the photoelectric characteristics of corresponding photoelectric active groups.

The polymer P1-50% prepared in this example was subjected to a thermal stability test, and the results were: the 5% thermal weight loss of the polymer is above 476 ℃, indicating that the polymer possesses excellent thermal stability.

Example 3: preparation of Polymer P2

Reduced phenazine (3.685g, 20mmol), 4' -bis (4-fluoro-diphenylsulfone) ether (9.721g, 20mmol), catalyst potassium carbonate (5.521g, 40mmol), 53mL NMP, 20mL water-carrying agent toluene were put in a 100mL three-necked flask equipped with a nitrogen vent, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene refluxed for 3 hours, and after sufficient water was carried out, toluene and water were discharged with the oil-water separator. Then the temperature is increased to 200 ℃ and the reaction is stirred for 6 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times, 800mL each time) and ethanol (3 times, 300mL each time), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. An orange polymer powder (10.875g, 86% yield) was obtained. The polymer obtained in this example was subjected to structural analysis, and the results are shown in FIG. 8.

The results of nuclear magnetic analysis of the polymer obtained in this example are shown in FIG. 8. FIG. 8 shows the NMR spectrum of a polymer P2 obtained in example 3 of the present invention. Compared with the hydrogen nuclear magnetic resonance spectrum of P1-50%, the hydrogen atom signal peak of the methyl group in the bisphenol A unit at the position of 1.70ppm disappears, and other peaks are basically consistent.

Example 4: preparation of Polymer P6

Reduced phenazine (3.685g, 20mmol), 1, 4-bis ((4-fluorophenyl) sulfonyl) naphthalene (8.889g, 20mmol), catalyst potassium carbonate (5.521g, 40mmol), 49mL NMP, and 20mL toluene as a water-carrying agent were put in a 100mL three-necked flask equipped with a nitrogen vent, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until the toluene refluxed for 3 hours, and after sufficient water was carried out, the toluene and water were discharged with the oil-water separator. Then the temperature is increased to 200 ℃ and the reaction is stirred for 6 hours. At the end of the reaction, the solution was poured into 800mL of cold water with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times, 800mL each time) and ethanol (3 times, 300mL each time), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. An orange polymer powder (10.875g, 92% yield) was obtained. The polymer obtained in this example was subjected to structural analysis, and the results are shown in FIG. 8.

The results of nuclear magnetic analysis of the polymer obtained in this example are shown in FIG. 9. FIG. 9 shows the NMR spectrum of a polymer P6 obtained in example 4 of the present invention. Compared with the nuclear magnetic resonance hydrogen spectrum of P2, the peak positions are basically consistent, but the hydrogen atom signal peaks on the benzene ring are obviously increased at high field.

The polymer obtained in the benzene example was subjected to ultraviolet-visible spectrum absorption analysis, and the results are shown in FIG. 10. As the rigidity of the material is obviously increased and a donor-acceptor structure is formed, the ultraviolet absorption peak of the material is very wide due to the increase of the pi electron degree of the material, and the internal charge migration of the material is proved.

Solubility test

The solubility of a series of polymers prepared according to the invention was tested and the results are shown in table 1:

table 1 solubility test table

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 decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A polyarylsulfone polymer containing a reduced phenazine structure, which comprises a structural segment of the following formula (I):

in the formula (I), the compound is shown in the specification,

n is the degree of polymerization; m is copolymerization proportion, m is more than 0 and less than or equal to 1; ar is one of the following formulas (a) to (d):

in the formula (c), X is an integer of 1, 2 or 3,

2. The method for preparing the polyarylsulfone polymer containing a reduced phenazine structure according to claim 1, comprising the steps of:

in the formula (c), X is an integer of 1, 2 or 3,

in the formula (d), R is 1, 4-disubstituted naphthalene, 1, 5-disubstituted naphthalene, 2, 6-disubstituted naphthalene or 2, 7-disubstituted naphthalene

3. The preparation method according to claim 2, wherein the reaction charge amount of the catalyst potassium carbonate is 2 times of the molar amount of the sulfuryl-containing difluoride monomer.