Polymer containing S,S-dioxide-dibenzothiophene in backbone chain with content-adjustable triarylamine end groups and preparation method and application thereof

Abstract

Provided are a polymer containing S,S-dioxide-dibenzothiophene in backbone chain with content-adjustable triarylamine end groups, and a preparation method and an application thereof. Triarylamines hole-transport small molecules are introduced into the polymer end group, and a content of the triarylamine end groups can be adjusted by controlling a polymer molecular weight, so that the polymer has better electron-transport and hole-transport capabilities, and charge carrier transport can be balanced, so that more exciton recombination takes place effectively, thus improving the luminous efficiency and stability of the polymer. The polymer is prepared by a Suzuki polymerization reaction and does not require synthesis of new monomers. The polymer material is used for preparing highly effective and stable monolayer devices, and is dissolved directly in an organic solvent, then spin-coated, ink-jet printed, or printed to form a film.

Claims

1. A polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups, comprising a structural formula as follows: ##STR00021## wherein x and y are mole fractions of monomer components, satisfying: 0<x≤0.5 and x+y=1; n is a number of repeating units, n=10 to 300; Ar.sub.1 is any one of the following chemical structural formulas containing the triarylamine end groups: ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## Ar.sub.2 is one or more of the following chemical structural formulas: ##STR00028## ##STR00029## ##STR00030## wherein, Z.sub.1 and Z.sub.2 are independently H, F, CN, alkenyl, alkynyl, nitrile group, amine group, nitro, acyl, alkoxy, carbonyl or sulfonyl; and R is a linear or branched alkyl or alkoxy having 1 to 30 carbon atoms or a cycloalkyl having 3 to 30 carbon atoms.

2. The polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 1, wherein: in the polymer, a molar content of the triarylamine end groups is: mol %=2/n*100%; by controlling the number of repeating units of the polymer as 10≤n≤300, the molar content mol % of the triarylamine end groups is adjusted between 0.67% and 20%.

3. A preparation method of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 1, comprising the following steps of: performing a Suzuki polymerization reaction to dibrominated S,S-dioxide-dibenzothiophene, a bisboronic acid ester of Ar.sub.2 and a dibromide of Ar.sub.2, and then performing terminating reactions with a bisboronic acid ester monomer of Ar.sub.2 and a monobrominated Ar.sub.1 monomer successively to obtain the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups.

4. The preparation method of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 3, wherein amounts of the dibrominated S,S-dioxide-dibenzothiophene, the bisboronic acid ester of Ar.sub.2, and the dibromofluorene of Ar.sub.2 satisfy that: a total mole number of the bisboronic acid ester monomers is equal to a total mole number of the dibrominated monomers.

5. The preparation method of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 3, wherein the Suzuki polymerization reaction lasts for 0.5 hour to 16 hours at a temperature of 50° C. to 80° C.

6. The preparation method of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 3, wherein in the terminating reactions, the terminating reactions for the bisboronic acid ester monomer of Ar.sub.2 and the monobrominated Ar.sub.1 monomer both last for 1 hour to 24 hours at a temperature of 60° C. to 90° C.

7. The preparation method of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 3, wherein a catalytic system of the Suzuki polymerization reaction and the terminating reactions comprises a palladium catalyst and a phosphine ligand; the palladium catalyst comprises palladium acetate or tris(dibenzylideneacetone)dipalladium; and the phosphine ligand comprises tricyclohexylphosphine or tri-tert-butylphosphine.

8. A method of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups according to claim 1 in preparing a light emitting layer of a light emitting diode, wherein the polymer containing S,S-dioxide-dibenzothiophene in backbone chain with triarylamine end groups is dissolved in an organic solvent, then an organic solution obtained is spin-coated, ink-jet printed, or printed to form a film, thus obtaining the light emitting layer of the light emitting diode; and the organic solvent comprises toluene, chloroform or tetrahydrofuran.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a gel permeation chromatogram (GPC) of polymers P3 and P4;

(2) FIG. 2 is a cyclic voltammogram of an electroluminescent device based on polymers P9 and P10;

(3) FIG. 3 is electroluminescent spectra of the electroluminescent device based on the polymers P9 and P10; and

(4) FIG. 4 is luminous efficiency-current density curves of a monolayer device based on the polymers P9 and P10.

DESCRIPTION OF THE EMBODIMENTS

(5) The present invention will be further described in detail hereinafter with reference to the embodiments, but the implementations of the present invention are not limited thereto.

Embodiment 1

Synthesis of poly(2,7-fluorene-co-3,7-S,S-dioxide-dibenzothiophene) with Different Molecular Weights (P1-P6)

(6) ##STR00014##

(7) Synthesis of polymer P1: under the protection of nitrogen, 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9-dioctylfluorene (192.6 mg, 0.3 mmol), 2,7-dibromo-9,9-di-n-octylfluorene (131.6 mg, 0.24 mmol) and 2,7-dibromo-S,S-dioxide-dibenzothiophene (22.4 mg, 0.06 mmol) were dissolved in 8 mL of toluene, then tetraethylhydroxylamine aqueous solution (1 mL, wt %=25%), palladium acetate (2 mg), and tricyclohexylphosphine (4 mg) were added to react at 80° C. for 0.5 hour, and then the reaction was stopped. After cooling, an organic phase was precipitated in methanol (200 mL), filtered and dried to obtain the polymer P1. A polymer molecular weight was obtained by GPC test. (P1: M.sub.n=4400, PDI=2.64)

(8) Polymer P2: the reaction conditions were the same as those of the polymer P1 except that the Suzuki polymerization lasted for 1 hour. A polymer molecular weight was obtained by GPC test. (P2: M.sub.n=1.04×10.sup.4, PDI=2.35)

(9) Polymer P3: the reaction conditions were the same as those of the polymer P1 except that the Suzuki polymerization lasted for 2 hours. A polymer molecular weight was obtained by GPC test. (P3: M.sub.n=1.89×10.sup.4, PDI=2.42)

(10) Polymer P4: the reaction conditions were the same as those of the polymer P1 except that the Suzuki polymerization lasted for 4 hours. A polymer molecular weight was obtained by GPC test. (P4: M.sub.n=2.65×10.sup.4, PDI=2.11)

(11) Polymer P5: the reaction conditions were the same as those of the polymer P1 except that the Suzuki polymerization lasted for 8 hours. A polymer molecular weight was obtained by GPC test. (P5: M.sub.n=3.38×10.sup.4, PDI=1.75)

(12) Polymer P6: the reaction conditions were the same as those of the polymer P1 except that the Suzuki polymerization lasted for 16 hours. A polymer molecular weight was obtained by GPC test. (P6: M.sub.n=5.57×10.sup.4, PDI=1.94)

(13) FIG. 1 is a gel permeation chromatogram (GPC) of polymers P3 and P4. It can be seen from FIG. 1 that the Suzuki polymerization reaction lasts for different periods of time (the reactions for the polymers P3 and P4 lasted for 2 hours and 4 hours respectively), and the obtained two polymers have different molecular weights; the polymer P3 has a number average molecular weight of M.sub.n=1.89×10.sup.4 and a polydispersity index (PDI) of 2.42, while the polymer P4 has a number average molecular weight of M.sub.n=2.65×10.sup.4, and a polydispersity index (PDI) of 2.11.

Embodiment 2

Synthesis of poly(2,7-fluorene-co-3,7-S,S-dioxide-dibenzothiophene) with Different Contents of triphenylamine End Group (P7-P12)

(14) ##STR00015##

(15) Synthesis of polymer P7: under the protection of nitrogen, the polymer P1 (150 mg) obtained in the embodiment 1 and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9-dioctylfluorene (38.5 mg, 0.06 mmol) were dissolved in 10 mL of toluene, then 1 mL of tetraethylhydroxylamine aqueous solution (1 mL, wt %=25%), palladium acetate (2 mg), and tricyclohexylphosphine (4 mg) were added to react at 80° C. for 6 hours; then, 4-bromo-N,N-diphenylaniline (M1) (77.8 mg, 0.24 mmol) was added to perform a terminating reaction for 6 hours. Then the reaction was stopped. After cooling, an organic phase was precipitated in methanol (200 mL), filtered and dried to obtain a crude product, and then the crude product was extracted successively with methanol, acetone and n-hexane. The polymer was dissolved with toluene, and subjected to column chromatography purification using neutral alumina and using toluene as an eluant. The polymer/toluene solution was concentrated, precipitated again in a methanol solution, filtered, and dried to obtain the pale yellow-green fibrous polymer P7.

(16) .sup.1H NMR results indicated that the obtained polymer was the target product; Elemental analysis test showed that a content of the N element in P7 was 0.61%, and a molar content of corresponding triphenylamine was 18.60 mol %.

(17) The synthesis method and conditions of the polymers P8-P12 were the same as those of P7.

(18) P8 was obtained from P2 by two terminating reactions, and elemental analysis test showed that a content of the N element in P8 was 0.25%, and a molar content of corresponding triphenylamine was 7.45 mol %.

(19) P9 was obtained from P3 by two terminating reactions, and elemental analysis test showed that a content of the N element in P9 was 0.15%, and a molar content of corresponding triphenylamine was 4.36 mol %.

(20) P10 was obtained from P4 by two terminating reactions, and elemental analysis test showed that a content of the N element in P10 was 0.11%, and a molar content of corresponding triphenylamine was 3.09 mol %.

(21) P11 was obtained from P5 by two terminating reactions, and elemental analysis test showed that a content of the N element in P11 was 0.08%, and a molar content of corresponding triphenylamine was 2.43 mol %.

(22) P12 was obtained from P6 by two terminating reactions, and elemental analysis test showed that a content of the N element in P12 was 0.05%, and a molar content of corresponding triphenylamine was 1.46 mol %.

Embodiment 3

Synthesis of poly(2,7-fluorene-co-3,7-S,S-dioxide-dibenzothiophene-co-4,7-benzothiadiazole) with Different Molecular Weights (P13-P16)

(23) ##STR00016##

(24) Synthesis of polymer P13: under the protection of nitrogen, 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9-dioctylfluorene (192.6 mg, 0.3 mmol), 2,7-dibromo-9,9-di-n-octylfluorene (115.2 mg, 0.21 mmol), 2,7-dibromo-S,S-dioxide-dibenzothiophene (22.4 mg, 0.06 mmol) and 4,6-dibromobenzothiadiazole (8.8 mg, 0.03 mmol) were dissolved in 8 mL of toluene, then tetraethylhydroxylamine aqueous solution (1 mL, wt %=25%), palladium acetate (2 mg), and tricyclohexylphosphine (4 mg) were added to react at 50° C. for 8 hours, and then the reaction was stopped. After cooling, an organic phase was precipitated in methanol (200 mL), filtered and dried to obtain the polymer P13. A polymer molecular weight was obtained by GPC test. (P13: M.sub.n=8500, PDI=2.55)

(25) Polymer P14: the reaction conditions were the same as those of the polymer P13 except that the Suzuki polymerization was performed at 60° C. A polymer molecular weight was obtained by GPC test. (P14: M.sub.n=1.13×10.sup.4, PDI=2.28)

(26) Polymer P15: the reaction conditions were the same as those of the polymer P13 except that the Suzuki polymerization was performed at 70° C. A polymer molecular weight was obtained by GPC test. (P15: M.sub.n=2.19×10.sup.4, PDI=1.95)

(27) Polymer P16: the reaction conditions were the same as those of the polymer P13 except that the Suzuki polymerization was performed at 80° C. A polymer molecular weight was obtained by GPC test. (P16: M.sub.n=3.28×10.sup.4, PDI=1.83)

(28) By comparing the molecular weights of the polymers P13-P16, it was found that under the conditions of the same polymerization catalyst, ligand and reaction time, as the polymerization temperature increases, the molecular weights of the polymers also increase, which achieves the gradient adjustment of the molecular weights. This is because that the polymerization rate increases as the reaction temperature increases.

Embodiment 4

Synthesis of poly(2,7-fluorene-co-3,7-S,S-dioxide-dibenzothiophene-co-4,7-benzothiadiazole) with Different Contents of 7-bromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (M2) End Group (P17-P20)

(29) ##STR00017##

(30) Synthesis of polymer P17: under the protection of nitrogen, the polymer P13 (150 mg) obtained in the embodiment 3 and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9-dioctylfluorene (38.5 mg, 0.06 mmol) were dissolved in 10 mL of toluene, then 1 mL of tetraethylhydroxylamine aqueous solution (1 mL, wt %=25%), palladium acetate (2 mg), and tricyclohexylphosphine (4 mg) were added to react at 80° C. for 6 hours; then, 7-bromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (M2) (161.4 mg, 0.24 mmol) was added to perform a terminating reaction for 6 hours. Then the reaction was stopped. After cooling, an organic phase was precipitated in methanol (200 mL), filtered and dried to obtain a crude product, and then the crude product was extracted successively with methanol, acetone and n-hexane. The polymer was dissolved with toluene, and subjected to column chromatography purification using neutral alumina and using toluene as an eluent. The polymer/toluene solution was concentrated, precipitated again in a methanol solution, filtered, and dried to obtain the pale yellow-green fibrous polymer P17.

(31) 1H NMR results indicated that the obtained polymer was the target product; a molar content of the 7-bromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (M2) was calculated to be 9.65 mol % based on the GPC test results.

(32) The synthesis method and conditions of polymers P18-P20 were the same as those of P17.

(33) P18 was obtained from P14 by two terminating reactions, and a molar content of the 7-bromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (M2) was calculated to be 7.26 mol % based on the GPC test results.

(34) P19 was obtained from P15 by two terminating reactions, and a molar content of the 7-bromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (M2) was calculated to be 3.75 mol % based on the GPC test results.

(35) P20 was obtained from P16 by two terminating reactions, and a molar content of the 7-bromo-N,N-bis(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluorene-2-amine (M2) was calculated to be 2.50 mol % based on the GPC test results.

Embodiment 5

Synthesis of poly(2,7-fluorene-co-3,7-S,S-dioxide-dibenzothiophene-co-4,7-thienyl-benzothiadiazole) with Different Molecular Weights

(36) ##STR00018##

(37) Synthesis of polymer P21: under the protection of nitrogen, 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9-bis(4-(2-ethylhexyloxy)phenyl) fluorene (248.0 mg, 0.30 mmol), 2,7-dibromo-9,9-bis(4-(2-ethylhexyloxy)phenyl)fluorene (153.8 mg, 0.21 mmol), 2,7-dibromo-S,S-dioxide-dibenzothiophene (22.4 mg, 0.06 mmol) and 4,7-bis(5-bromine(4-hexylthiophene)-2-yl)-2,1,3-benzothiadiazole (18.8 mg, 0.03 mmol) were dissolved in 8 mL of toluene, and then tetraethylhydroxylamine aqueous solution (1 mL, wt %=25%), palladium acetate (2 mg) and tricyclic hexylphosphine (4 mg) were added to react at 80° C. for 1 hour, and then the reaction was stopped. After cooling, an organic phase was precipitated in methanol (200 mL), filtered and dried to obtain the polymer P21. A polymer molecular weight was obtained by GPC test. (P21: M.sub.n=1.92×10.sup.4, PDI=2.28)

(38) Polymer P22: the reaction conditions were the same as those of the polymer P20 except that the catalyst and ligand of the Suzuki polymerization reaction were replaced by tris(dibenzylideneacetone)dipalladium and tri-tert-butylphosphine. A polymer molecular weight was obtained by GPC test. (P22: M.sub.n=9800, PDI=2.56)

(39) By comparing the molecular weights of the polymers P21 and P22, it was found that under the conditions of the same reaction temperature and reaction time, the molecular weight of P21 synthesized by using the palladium acetate as the catalyst and the tricyclohexylphosphine as the ligand was larger than that of P22 synthesized by using the tris(dibenzylideneacetone)dipalladium as the catalyst and tri-tert-butylphosphine as the ligand. In this way, the gradient adjustment of the molecular weights of the polymers was implemented by the differences of catalytic activities of different catalysts and ligands.

Embodiment 6

Synthesis of poly(2,7-fluorene-co-3,7-S,S-dioxide-dibenzothiophene-co-4,7-thienyl-benzothiadiazole) with Different Contents of N4-(4-bromophenyl)-N4,N4′,N4″-triphenyl-[1,1′-biphenyl]-4,4′-diamine (M3) Group (P23-P24)

(40) ##STR00019## ##STR00020##

(41) Synthesis of polymer P23: under the protection of nitrogen, the polymer P21 (150 mg) obtained in the embodiment 3 and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-9,9-bis(4-(2-ethylhexyloxy)phenyl)fluorene (49.6 mg, 0.06 mmol) were dissolved in 10 mL of toluene, then 1 mL of tetraethylhydroxylamine aqueous solution (1 mL, wt %=25%), and tetrakis(triphenylphosphine)palladium (10 mg) were added to react at 80° C. for 6 hours; then, N.sup.4-(4-bromophenyl)-N.sup.4,N.sup.4′,N.sup.4″-triphenyl-[1,1′-biphenyl]-4,4′-diamine (M3) (136.2 mg, 0.24 mmol) was added to perform a terminating reaction for 6 hours. Then the reaction was stopped. After cooling, an organic phase was precipitated in methanol (200 mL), filtered and dried to obtain a crude product, and then the crude product was extracted successively with methanol, acetone and n-hexane. The polymer was dissolved with toluene, and subjected to column chromatography purification using neutral alumina and using toluene as an eluent. The polymer/toluene solution was concentrated, precipitated again in a methanol solution, filtered, and dried to obtain the pale yellow-green fibrous polymer P23.

(42) 1H NMR results indicated that the obtained polymer was the target product; a molar content of the N4-(4-bromophenyl)-N4,N4′,N4″-triphenyl-[1,1′-biphenyl]-4,4′-diamine (M3) was calculated to be 5.59 mol % based on the GPC test results.

(43) The synthesis method and conditions of the P24 were the same as those of P23. P24 was obtained from P22 by two terminating reactions, and a molar content of the N4-(4-bromophenyl)-N4,N4′,N4″-triphenyl-[1,1′-biphenyl]-4,4′-diamine (M3) was calculated to be 10.96 mol % based on the GPC test results.

Embodiment 7

(44) Preparation of Polymer Electroluminescent Device

(45) Indium tin oxide (ITO) glass with a square resistance of 10Ω prepared in advance was ultrasonically cleaned with acetone, detergent, deionized water and isopropanol in sequence, and treated with plasma for 10 minutes; a film of poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) with a thickness of 40 nm was spin-coated on the ITO; the PEDOT:PSS film was dried in a vacuum oven at 80° C. for 8 hours; subsequently, a polymer/xylene solution (1 wt. %) was spin-coated on a surface of the PEDOT:PSS film to a thickness of 80 nm; and finally, a CsF layer having a thickness of 1.5 nm and a metal Al layer having a thickness of 120 nm were subjected to vapor deposition on a light emitting layer in sequence. A device structure was ITO/PEDOT:PSS/polymer/CsF/Al.

(46) FIG. 2 is a cyclic voltammogram of an electroluminescent device based on polymers P9 and P10. It can be seen from FIG. 2 that the triphenylamine-terminated polymers P9 and P10 containing S,S-dioxide-dibenzothiophene in backbone chain have lower oxidation potential E.sub.ox with a value of 1.2V. According to a formula E.sub.HOMO=−(4.4+E.sub.ox), a corresponding highest occupied molecular orbital (HOMO) energy level is calculated to be −5.6 eV. Compared with similar benzene ring-terminated polymers reported in literatures, the polymers P9 and P10 have a shallower HOMO energy level [Organic Electronics, 2009, 10,901-909], which are more favorable for hole injection.

(47) FIG. 3 is electroluminescent spectra of the electroluminescent device based on the polymers P9 and P10. It can be seen from FIG. 3 that maximum electroluminescence peaks of the polymers P9 and P10 are all located at 440 nm, the effects of different contents of triphenylamine end group on electroluminescence spectrums of the polymer containing S,S-dioxide-dibenzothiophene in backbone chain are not obvious, and the resulting polymers P9 and P10 still emit blue light.

(48) FIG. 4 is luminous efficiency-current density curves of a monolayer device based on the polymers P9 and P10. It can be seen from FIG. 4 that the luminous efficiency of the polymer P9 is close to 4.0 cd/A, the luminous efficiency of the polymer P10 is more than 3.0 cd/A, and the polymer P9 having a higher content of the triphenylamine end groups has a higher luminous efficiency than that of the P10, indicating that the introduction of the triphenylamine end group improves the hole injection and transport capabilities, so that charge carrier transport in the luminescent polymer is more balanced and the efficiency is improved.

(49) Performances of electroluminescent devices prepared by using the polymers P19, P20, P23 and P24 as light-emitting layers are respectively shown in Table 1.

(50) TABLE-US-00001 TABLE 1 Performances of polymer electroluminescent device Commission Maximum Internationale de Turn-on luminous Maximum L'Eclairage (CIE) voltage efficiency brightness coordinates Polymer (V) (cd/A) (cd/m.sup.2) (x, y) P19 3.0 10.3 9856 (0.39, 0.55) P20 3.2 9.5 7839 (0.39, 0.57) P23 4.4 3.0 1686 (0.65, 0.34) P24 4.2 2.7 1436 (0.65, 0.33)

(51) It can be seen from Table 1 that the polymer P19 has a turn-on voltage of 3.0 V, a luminous efficiency of 10.3 cd/A, a maximum brightness of 9856 cd/m.sup.2, and a CIE coordinate of (0.39, 0.55); and the polymer P20 has a turn-on voltage of 3.2 V, a luminous efficiency of 9.5 cd/A, a maximum brightness of 7839 cd/m.sup.2, and a CIE coordinate of (0.39, 0.57). By comparison, it can be found that both the polymers P19 and P20 have a lower turn-on voltage and a higher brightness, and the effects of different contents of triarylamine end group on the CIE coordinate of the device are not obvious; and the device of the polymer P19 with a higher content of triarylamine end group is more efficient than that of the polymer P20. The polymer P23 has a turn-on voltage of 4.4 V, a luminous efficiency of 3.0 cd/A, a maximum brightness of 1686 cd/m.sup.2, and a CIE coordinate of (0.65, 0.34), and the polymer P24 has a turn-on voltage of 4.2 V, a luminous efficiency of 2.7 cd/A, a maximum brightness of 1436 cd/m.sup.2, and a CIE coordinate of (0.65, 0.33). And the efficiencies of the monolayer devices of the polymers P19, P20, P23 and P24 are significantly higher than the efficiency of the monolayer device of a benzene-terminated polymer with similar backbone structure [Advanced Functional Materials, 2013, 23, 4366-4376].

(52) The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and scope of the present invention should be equivalent replacement means, and are included in the protection scope of the present invention.