CN104151533A - Fluorescent conjugated polymer containing phenothiazine group, and synthesis method and application thereof - Google Patents
Fluorescent conjugated polymer containing phenothiazine group, and synthesis method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of conjugated polymers, and discloses a fluorescent conjugated polymer containing a phenothiazine group, and a synthesis method and an application thereof. The synthesis method comprises the following steps: firstly, synthesizing an N-alkyl-3,6-bi(acetenyl) phenothiazine monomer, then completely dissolving the N-alkyl-3,6-bi(acetenyl) phenothiazine monomer and an N-octyl-3,6-bi(acetenyl) carbazole monomer or a 4,7-diacetenyl-2,1,3-benzothiazine oxazole monomer into orthodichlorobenzene, and carrying out reaction under stirring in a catalytic system containing CuCl and TMEDA; precipitating and filtering the mixture in a mixed solution of methyl alcohol and concentrated hydrochloric acid after reaction is ended, and carrying out vacuum drying, so as to obtain the fluorescent conjugated polymer containing the phenothiazine group. According to the fluorescent conjugated polymer, the solubility of the polymer is improved by introducing an alkyl chain into the phenothiazine group, the structure is improved by introducing groups with different electron donating and withdrawing effects, and the conjugated polymer with excellent photoelectric property, solubility and heat stability is provided.
Description
Technical field
The invention belongs to conjugated polymers field, be specifically related to a kind of fluorescent conjugated polymer and synthetic method and application containing thiodiphenylamine group.
Background technology
Conjugated polymers is a kind of novel functional materials, because it has the semi-conductive photoelectric characteristic of metal, and easily processing, there is certain snappiness, therefore, in fields such as solar cell, opto-electronic conversion and optical information materials, have a wide range of applications.Fluorescent conjugated polymer, because of its unique π-π * molecular wire structure, makes it have stronger fluorescence quantum yield and molar extinction coefficient.Compare with traditional small molecules fluorescent material, it is adjustable that it has structure, highly sensitive, can directly revolve the advantages such as Tu, good stability, therefore day by day receives people's concern.
Within 1869, Carl Glaser be take phenylacetylene as raw material, take cuprous chloride as catalyzer, take ammoniacal liquor and ethanol as solvent, has successfully synthesized Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene under air atmosphere.But the phenyl ethynylation copper intermediate of gained is unstable, and explosive under drying conditions, makes aftertreatment very difficult, is difficult to obtain practical application.Until the part of Americanized scholar Hay in 1962 using Tetramethyl Ethylene Diamine as copper catalyst joins in system, take orthodichlorobenzene or acetone as solvent, under the condition of oxygen, successfully synthesize two acetylene compounds passing into.Reaction conditions after improvement is gentle, and productive rate is higher, but the polymkeric substance of gained is mostly insoluble not molten, is difficult to test and process.Kijima in 1998 etc. improve raw material, in the contraposition of Isosorbide-5-Nitrae-diethynylbenzene, introduce long oxyalkyl chain, make it in chloroform and tetrahydrofuran (THF), have good solvability.
In thiodiphenylamine molecule, containing two heteroatomss of nitrogen and sulphur, is an electron rich structure, its lone-pair electron easily with phenyl ring formation delocalization structure, there is good fluorescence, strong electron donation and hole transport performance.In addition, thiodiphenylamine molecule is the nonplanar structure of butterfly-like symmetry, can effectively stop the accumulation of π key and interchain to swash the formation of based compound, thereby improves the fluorescence quantum efficiency of polymkeric substance.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of and has good luminescent properties, and the fluorescent conjugated polymer containing thiodiphenylamine group of solvability and Heat stability is good;
Another object of the present invention is to provide the synthetic method of the above-mentioned fluorescent conjugated polymer containing thiodiphenylamine group;
A further object of the present invention is to provide the application of the above-mentioned fluorescent conjugated polymer containing thiodiphenylamine group.
Object of the present invention is achieved through the following technical solutions:
Containing a fluorescent conjugated polymer for thiodiphenylamine group, its structural formula is:
Wherein, the natural number that x is 2～100, the natural number that y is 2～200;
R
1alkyl for carbon number 1～18;
R
2for N-octyl group carbazole or Ben Bing Sai oxazole;
The structural formula of described N-octyl group carbazole is
The structural formula of described Ben Bing Sai oxazole is
The synthetic method of the above-mentioned fluorescent conjugated polymer containing thiodiphenylamine group, comprises the steps:
(1) N-alkyl-3, synthesizing of two (ethynyl) thiodiphenylamine monomers of 6-: 3,6-bis-bromo-N-alkyl thiodiphenylamine and divalence palladium catalyst are joined in reactor, add cuprous iodide (CuI), under nitrogen protection, add again toluene, triethylamine and 3,3 '-dimethyl-3-hydroxypropyn, temperature reaction, to react products therefrom filters, with anhydrous diethyl ether washing, air distillation, except desolventizing, is purified and is obtained intermediate with column chromatography;
Under nitrogen protection, the temperature rising reflux reaction in toluene solvant by described intermediate and NaOH, toluene solvant is removed in underpressure distillation, and column chromatography is purified and is obtained N-alkyl-3, two (ethynyl) thiodiphenylamine monomers of 6-;
(2) synthetic containing the fluorescent conjugated polymer of thiodiphenylamine group: by step (1) gained N-alkyl-3, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, two (ethynyl) carbazole monomers or 4 of 6-, 7-diacetylene-2,1,3-Ben Bing Sai oxazole monomer is dissolved in orthodichlorobenzene, is stirred to completely and dissolves, and obtains mixing solutions; Then gained mixing solutions is transferred in the catalyst system that contains cuprous chloride (CuCl) and Tetramethyl Ethylene Diamine (TMEDA), passed under the condition of air stirring reaction; After question response finishes, reaction solution is poured in the mixing solutions of methyl alcohol and concentrated hydrochloric acid and precipitated, filter, will filter the vacuum-drying of gained solid, obtain the described fluorescent conjugated polymer that contains thiodiphenylamine group.
In the preparation method of the above-mentioned fluorescent conjugated polymer containing thiodiphenylamine group:
Preferably, step (1) is described 3, and the alkyl carbon number of the bromo-N-alkyl of 6-bis-thiodiphenylamine is 1～18;
Preferably, step (1) is described 3, and the mol ratio of 6-bis-bromo-N-alkyl thiodiphenylamine and divalence palladium catalyst is 1:(0.02～0.05);
Preferably, step (1) is described 3, and the mol ratio of 6-bis-bromo-N-alkyl thiodiphenylamine and cuprous iodide is 1:(0.001～0.005);
Preferably, in step (1), by molar fraction, every mmole 3, the bromo-N-alkyl of 6-bis-thiodiphenylamine correspondence adds toluene 6～15mL, triethylamine 6～15mL, 3,3 '-dimethyl-3-hydroxypropyn, 0.3～1.5mL;
Preferably, the temperature of the described temperature reaction of step (1) is 80～120 ℃, and the reaction times is 10～24h;
Preferably, the mol ratio of the described intermediate of step (1) and NaOH is 1:(1～2);
Preferably, the temperature of the described temperature rising reflux reaction of step (1) is 80～120 ℃, and the reaction times is 3～10h;
Preferably, the described N-of step (2) alkyl-3, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, two (ethynyl) carbazole monomers of 6-or 4,7-diacetylene-2, the mol ratio of 1,3-Ben Bing Sai oxazole monomer is 1:(1～3);
Preferably, described in step (2), being stirred to consoluet temperature is 20～60 ℃; Preferably, the time of the described stirring reaction of step (2) is 4-～60min;
Preferably, the catalyst system that contains cuprous chloride and Tetramethyl Ethylene Diamine described in step (2) is with the corresponding cuprous chloride 20～30mg that uses of the two alkynes monomers of every mmole, Tetramethyl Ethylene Diamine 0.06～0.08mL and orthodichlorobenzene 20～50mL preparation;
Preferably, the mixing solutions of the described methyl alcohol of step (2) and concentrated hydrochloric acid is with the two corresponding use of the alkynes monomer 50～100mL methyl alcohol of every mmole and 0.1～0.3mL concentrated hydrochloric acid mixed preparing;
Described pair of alkynes monomer is N-alkyl-3, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, two (ethynyl) carbazole monomers of 6-or 4,7-diacetylene-2, the summation of 1,3-Ben Bing Sai oxazole monomer.
The application of the above-mentioned fluorescent conjugated polymer containing thiodiphenylamine group in organic luminescent device, solar cell and fluorescent optical sensor field.
The present invention is by optimizing reaction conditions, regulate temperature of reaction, time, monomer ratio etc., synthesize the fluorescent conjugated polymer containing thiodiphenylamine group, the described fluorescent conjugated polymer containing thiodiphenylamine group has good solubility and thermostability, decomposition temperature is at 373 ℃～426 ℃, and 800 ℃ of residual carbonaceous amounts are all more than 60%; In addition the described fluorescent conjugated polymer containing thiodiphenylamine group also has good photoelectric properties, and HOMO energy level, in-5.60eV left and right, is all good hole mobile material.
The present invention has following advantage and effect with respect to prior art: the fluorescent conjugated polymer containing thiodiphenylamine group of the present invention is introduced alkyl chain on thiodiphenylamine group, can improve solvability, so that characterization test and processed and applied; Synthetic method of the present invention by molecular designing, is introduced and is had the group that pushes away, draws electronic effect in conjugated system, has synthesized novel structure, has had the fluorescent conjugated polymer of good optical property and chemical property; The present invention contains the fluorescent conjugated polymer of thiodiphenylamine group at organic luminescent device, and there is good application prospect in the fields such as solar cell and fluorescent optical sensor.
Accompanying drawing explanation
Fig. 1 is N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-, N-octyl group-3, and two (ethynyl) carbazoles of 6-and gained are containing the nucleus magnetic resonance figure of the fluorescent conjugated polymer P3 of thiodiphenylamine group;
Fig. 2 N-octyl group-3, two (ethynyl) thiodiphenylamine, 4 of 6-, 7-diacetylene-2,1,3-benzene thiophene oxazole and gained are containing the nucleus magnetic resonance figure of the fluorescent conjugated polymer P7 of thiodiphenylamine group.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1, N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-synthetic:
By 3 of 2g, the bromo-N-octyl group of 6-bis-thiodiphenylamine (4.26mmol), the CuI of 2mg, the Pd (Ph of 60mg
3p)
2cl
2join successively in two mouthfuls of bottles of 100ml (19#), under nitrogen protection, add 3 of 30ml toluene, 30ml triethylamine and 1.25ml, 3 '-dimethyl-3-hydroxypropyn, is heated to 110 ℃, reaction 12h; Reaction product is filtered, and wash with anhydrous diethyl ether, solvent evaporated, purifies with column chromatography, and developping agent adopts the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of sherwood oil and ethyl acetate is 3:1, purifies and obtains yellow solid 1.384g, and productive rate is 68%;
Get the yellow solid (0.73mmol) of 0.35g above-mentioned steps gained and the NaOH (0.73mmol) of 30mg joins in two mouthfuls of bottles of 100ml (19#), under nitrogen protection, add 15ml toluene, be heated to 110 ℃ of condensing refluxes, reaction 4h; Reaction mixture is filtered, and by toluene wash, be spin-dried for solvent, with column chromatography, purify, developping agent adopts the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of sherwood oil and ethyl acetate is 5:1, purifies and obtains yellow thick liquid 0.159g, productive rate 60.7%.
By Bruker Vector33 type infrared spectrometer and Bruker AV-300 type nuclear magnetic resonance analyser, the yellow thick liquid product of gained is detected to analysis, result is as follows: IR (KBr), v (cm
-1): 3291 (≡ C-H stretching), 2925,2851 (C-H stretching), 2104 (C ≡ C stretching).
1H?NMR(500MHz，CDCl
3).δ(ppm):7.26,7.20,6.70(6H,Ph),3.81(2H,NCH
2),3.05(2H,≡C-H),1.76,1.25-1.38(12H,CH
2),0.86(3H,CH
3)。
From infrared data, can see that the yellow thick liquid product of gained is at 3291cm
-1and 2104cm
-1there is absorption peak in place, this and N-octyl group-3, and the end alkynes hydrogen (≡ C-H) in 6-pair of (ethynyl) thiodiphenylamine monomers and the stretching vibration peak of carbon carbon triple bond (C ≡ C) are corresponding; Pass through H
1-NMR analyzes, and this product exists resonance peak at chemical shift 3.05ppm place, and this is the resonance peak of end alkynes hydrogen, and the resonance peak of other chemical shift place also all belongs to clear.This product nucleus magnetic resonance figure is as shown in A in Fig. 1.
The yellow thick liquid product of susceptible of proof gained has following structure thus:
for N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-.
Embodiment 2, N-octyl group-3, two (ethynyl) carbazoles of 6-synthetic:
By 3 of 1g, the CuI (0.005mmol) of the iodo-N-octyl group of 6-bis-carbazole (1.9mmol), 1mg, the Pd (Ph of 30mg
3p)
2cl
2join successively in 100ml (19#) single necked round bottom flask, at N
2under atmosphere, add the triethylamine of 15ml, then add 3 of 0.6ml, 3 '-dimethyl-3-hydroxypropyn, at room temperature stirs 16h; After reaction stops, reaction mixture is filtered, and wash with anhydrous diethyl ether; Air distillation, except desolventizing, is carried out column chromatography purification, and developping agent adopts the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of sherwood oil and ethyl acetate is 3:1, purifies and obtains faint yellow solid 0.706g, productive rate 84.5%;
Getting the faint yellow solid (1.18mmol) of 0.5g above-mentioned steps gained and the NaOH (1.18mmol) of 0.047g joins in two mouthfuls of round-bottomed flasks of 100ml (19#), under nitrogen protection, add 15ml toluene, be heated to 110 ℃ of condensing refluxes, reaction 3h; After stopped reaction, product is filtered, and by toluene wash, underpressure distillation, except desolventizing, is purified with column chromatography, and developping agent adopts the mixed solvent of sherwood oil and methylene dichloride, the volume ratio of sherwood oil and methylene dichloride is 2:1, obtains light yellow crystal 0.33g, productive rate 85.3%.
By Bruker Vector33 type infrared spectrometer and Bruker AV-300 type nuclear magnetic resonance analyser, gained light yellow crystal product is detected to analysis, result is as follows: IR (KBr), v (cm
-1): 3296 (≡ C-H stretching), 2925,2854 (C-H stretching), 2104 (C ≡ C stretching).
1H?NMR(500MHz，CDCl
3).δ(ppm):8.24,7.64,7.61(6H,Ph),4.31(2H,NCH
2),3.10(2H,≡C-H),1.91,1.25-1.33(12H,CH
2),0.88(3H,CH
3)。
From infrared data, can see that gained light yellow crystal product is at 3296cm
-1and 2104cm
-1there is absorption peak in place, this and N-octyl group-3, and the end alkynes hydrogen (≡ C-H) in 6-pair of (ethynyl) carbazole monomers and the stretching vibration peak of carbon carbon triple bond (C ≡ C) are corresponding; Pass through H
1-NMR analyzes, and this product exists resonance peak at chemical shift 3.10ppm place, and this is the resonance peak of end alkynes hydrogen, and the resonance peak of other chemical shift place also all belongs to clear.This product nucleus magnetic resonance figure is as shown in B in Fig. 1;
Susceptible of proof gained light yellow crystal product has following structure thus:
for N-octyl group-3, two (ethynyl) carbazoles of 6-.
Embodiment 3,4,7-diacetylene-2, and 1,3-Ben Bing Sai oxazole synthetic:
By 4 of 1g, the Pd (Ph of 7-dibromo benzo thiophene oxazole (3.4mmol), micro Cu I and 48mg
3p)
2cl
2(0.068mmol) join successively in two mouthfuls of round-bottomed flasks of 100ml (19#), at N
2under atmosphere, add 3 of 15ml toluene, 15ml triethylamine and 1ml, 3 '-dimethyl-3-hydroxypropyn, is warming up to 110 ℃, condensing reflux, reaction 16h; After reaction stops, reaction mixture is filtered, and wash with anhydrous diethyl ether; Air distillation, except desolventizing, is carried out column chromatography purification, and developping agent adopts the mixed solvent of sherwood oil and ethyl acetate, and the volume ratio of sherwood oil and ethyl acetate is 2:1, the faint yellow solid 0.761g that purifies to obtain, productive rate 74.6%;
The faint yellow solid (1.67mmol) of above-mentioned steps gained and the NaOH (1.67mmol) of 0.067g that get 0.5g join in two mouthfuls of round-bottomed flasks of 100ml (19#), under nitrogen protection, add 17ml toluene, be heated to 110 ℃ of condensing refluxes, reaction 1h; After stopped reaction, product is filtered, and by toluene wash, underpressure distillation, except desolventizing, is purified with column chromatography, and developping agent adopts the mixed solvent of sherwood oil and methylene dichloride, the volume ratio of sherwood oil and methylene dichloride is 2:1, obtains brown needle-like crystal 0.175g, productive rate 55.7%.
By Bruker Vector33 type infrared spectrometer and Bruker AV-300 type nuclear magnetic resonance analyser, gained brown needle-like crystal product is detected to analysis, result is as follows: IR (KBr), v (cm
-1): 3295 (≡ C-H stretching), 3052,2107 (C ≡ C stretching).
1h NMR (300MHz, CDCl
3), δ (ppm): 7.76 (s, 2H), 3.69 (s, 2H).
From infrared data, can see that gained brown needle-like crystal product is at 3295cm
-1and 2107cm
-1there is absorption peak in place, this and 4,7-diacetylene-2, and the end alkynes hydrogen (≡ C-H) in 1,3-Ben Bing Sai oxazole monomer and the stretching vibration peak of carbon carbon triple bond (C ≡ C) are corresponding; Pass through H
1-NMR analyzes, and this product exists resonance peak at chemical shift 3.69ppm place, and this is the resonance peak of end alkynes hydrogen, and the resonance peak of other chemical shift place also all belongs to clear, and nucleus magnetic resonance figure is as shown in B in Fig. 2.
Susceptible of proof gained brown needle-like crystal has following structure thus:
be 4,7-diacetylene-2,1,3-Ben Bing Sai oxazole.
Embodiment 4
Containing a fluorescent conjugated polymer for thiodiphenylamine group, its preparation method is as follows:
Get N-octyl group-3 of 53.8mg embodiment 1 gained, N-octyl group-3 of two (ethynyl) thiodiphenylamine of 6-and 50mg embodiment 2 gained, two (ethynyl) carbazoles of 6-are put into reaction tubes No. 1, with 1.5ml orthodichlorobenzene, dissolve; 2mg cuprous chloride and 0.006ml TMEDA are put into reaction tubes No. 2, with 2ml orthodichlorobenzene, dissolve, and be heated to 50 ℃ of stirring 15min; Then the solution in No. 1 reaction tubes is joined in No. 2 reaction tubess, react 40min passing under the condition of air; After reaction stops, reaction solution being poured in the mixed solution of 50ml methyl alcohol and 0.1ml concentrated hydrochloric acid and precipitated, filter, use methanol wash, vacuum-drying, obtains yellow powder shape solid 58mg, productive rate 56.4%.
By Bruker Vector33 type infrared spectrometer and Bruker AV-300 type nuclear magnetic resonance analyser, gained yellow powder shape solid is detected to analysis, result is as follows:
IR(KBr),v(cm
-1):3300(≡C-H?stretching),2208,2137(C≡C-C≡C?stretching),2107(C≡C?stretching)。
1H?NMR(300MHz,CDCl
3),δ(ppm):8.24-6.75(Ar-H),4.31,3.81(NCH
2),3.10(≡C-H),3.05(≡C-H),1.86-1.25(CH
2),0.87(CH
3)。
From infrared data, can see that gained yellow powder shape solid is at 3300cm
-1and 2107cm
-1there is respectively the stretching vibration peak of end alkynes hydrogen (≡ C-H) and carbon carbon triple bond (C ≡ C) in place, and is 2137cm at wavelength
-1and 2208cm
-1there are two absorption peaks in place, this is the stretching vibration peak of diacetylene (C ≡ C-C ≡ C); From nuclear magnetic spectrogram, can see that this product has two resonance peaks at 3.10ppm and 3.05ppm, illustrate and in product, contain carbazole and thiodiphenylamine modular construction, end at molecular chain also contains carbazole, and thiodiphenylamine unit unreacted end alkynes hydrogen is specifically shown in Fig. 1 shown in C.More than analyze N-octyl group-3 can be described, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, having there is polyreaction in two (ethynyl) carbazole monomers of 6-, has generated multipolymer, and its structure is as follows:
X:y=1:1 wherein.Therefore gained yellow powder shape solid is the described fluorescent conjugated polymer containing thiodiphenylamine group, is designated as polymer P 3.
Embodiment 5
Containing a fluorescent conjugated polymer for thiodiphenylamine group, its preparation method is as follows:
Get N-octyl group-3 of 17.9mg embodiment 1 gained, N-octyl group-3 of two (ethynyl) thiodiphenylamine of 6-and 49.0mg embodiment 2 gained, two (ethynyl) carbazoles of 6-are put into reaction tubes No. 1, with 1.5ml orthodichlorobenzene, dissolve; 2mg cuprous chloride and 0.006ml TMEDA are put into reaction tubes No. 2, with 2ml orthodichlorobenzene, dissolve, and be heated to 50 ℃ of stirring 15min; Then the solution in No. 1 reaction tubes is joined in No. 2 reaction tubess, react 40min passing under the condition of air; After reaction stops, reaction solution being poured in the mixed solution of 50ml methyl alcohol and 0.1ml concentrated hydrochloric acid and precipitated, filter, by methanol wash, vacuum-drying, obtains yellow powder shape solid 44mg, is the described fluorescent conjugated polymer that contains thiodiphenylamine group, productive rate 65.7%.Be designated as polymer P 4.
Polymer P 1, P2, P5 and polymer P 3, P4 are the isonomic fluorescent conjugated polymer containing thiodiphenylamine group, structural similitude, and performance is consistent; Polymerization process is basic identical, and difference is N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-and N-octyl group-3, and the consumption of two (ethynyl) carbazoles of 6-is different.N-octyl group-3 in polymer P 1, P2 and P5, two (ethynyl) thiodiphenylamine of 6-and N-octyl group-3, the consumption mol ratio of two (ethynyl) carbazoles of 6-is as shown in table 1.
Embodiment 6
Containing a fluorescent conjugated polymer for thiodiphenylamine group, its preparation method is as follows:
Get N-octyl group-3 of 36mg embodiment 1 gained, 4 of two (ethynyl) thiodiphenylamine of 6-and 18.4mg embodiment 3 gained, 7-diacetylene-2,1,3-Ben Bing Sai oxazole is put into reaction tubes No. 1, with 1.5ml orthodichlorobenzene, dissolves; 2mg cuprous chloride and 0.006mlTMEDA are put into reaction tubes No. 2, with 2ml orthodichlorobenzene, dissolve, and be heated to 50 ℃ of stirring 15min; Then the solution in No. 1 reaction tubes is joined in No. 2 reaction tubess, react 40min passing under the condition of air; After reaction stops, reaction solution being poured in the mixed solution of 50ml methyl alcohol and 0.1ml concentrated hydrochloric acid and precipitated, filter, use methanol wash, vacuum-drying, obtains brown powder shape solid 30mg, and productive rate is 55.1%.
By Bruker Vector33 type infrared spectrometer and Bruker AV-300 type nuclear magnetic resonance analyser, gained brown powder shape solid is analyzed, its data are as follows:
IR(KBr),v(cm-1):3288(≡C-H?stretching),2205,2140(C≡C-C≡C?stretching),2107(C≡C?stretching)。
1H?NMR(300MHz,CDCl
3),δ(ppm):7.76-6.75(Ar-H),3.81(NCH
2),3.05(≡C-H),1.78-1.25(CH
2),0.87(CH
3)。
From infrared data, can see that gained brown powder shape solid is at 3288cm
-1and 2107cm
-1there is respectively the stretching vibration peak of end alkynes hydrogen (≡ C-H) and carbon carbon triple bond (C ≡ C) in place, and is 2205cm at wavelength
-1and 2140cm
-1there are two absorption peaks in place, this is the stretching vibration peak of diacetylene (C ≡ C-C ≡ C); From nuclear magnetic spectrogram, can see that this product has two resonance peaks at 3.81ppm and 3.05ppm, illustrate and in product, contain Ben Bing Sai oxazole and thiodiphenylamine modular construction, end at molecular chain also contains Ben Bing Sai oxazole, and thiodiphenylamine unit unreacted end alkynes hydrogen is specifically shown in Fig. 2 shown in C.More than analyze N-octyl group-3 can be described, two (ethynyl) the thiodiphenylamine monomers of 6-and 4,7-diacetylene-2, having there is polyreaction in 1,3-Ben Bing Sai oxazole monomer, has generated multipolymer, and its structure is as follows:
X:y=1:1 wherein.Therefore gained brown powder shape solid is the described fluorescent conjugated polymer containing thiodiphenylamine group, is designated as polymer P 7.
Embodiment 7
Containing a fluorescent conjugated polymer for thiodiphenylamine group, its preparation method is as follows:
Get N-octyl group-3 of 26.1mg embodiment 1 gained, 4 of two (ethynyl) thiodiphenylamine of 6-and 40.1mg embodiment 3 gained, 7-diacetylene-2,1,3-Ben Bing Sai oxazole is put into reaction tubes No. 1, with 1.5ml orthodichlorobenzene, dissolves; 2mg cuprous chloride and 0.006mlTMEDA are put into reaction tubes No. 2, with 2ml orthodichlorobenzene, dissolve, and be heated to 50 ℃ of stirring 15min; Then the solution in No. 1 reaction tubes is joined in No. 2 reaction tubess, react 40min passing under the condition of air; After reaction stops, reaction solution being poured in the mixed solution of 50ml methyl alcohol and 0.1ml concentrated hydrochloric acid and precipitated, filter, by methanol wash, vacuum-drying, obtains brown powder shape solid 30mg, is the described fluorescent conjugated polymer that contains thiodiphenylamine group, productive rate 60.4%.Be designated as polymer P 8.
Polymer P 6 and polymer P 7, P8 are the isonomic fluorescent conjugated polymer containing thiodiphenylamine group, structural similitude, and performance is consistent; Polymerization process is basic identical, and difference is N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-and 4,7-diacetylene-2, and the consumption of 1,3-Ben Bing Sai oxazole is different.N-octyl group-3 in polymer P 6, two (ethynyl) thiodiphenylamine of 6-and 4,7-diacetylene-2, the consumption mol ratio of 1,3-Ben Bing Sai oxazole is as shown in table 1.
Polymer performance detects to be analyzed:
1, contain molecular weight and the distribution thereof of the fluorescent conjugated polymer of thiodiphenylamine group:
Adopt different monomeric species and consumption to carry out the described fluorescent conjugated polymer containing thiodiphenylamine group of polyreaction preparation, the consumption mol ratio of polymerization single polymerization monomer is as shown in table 1.By GPC 2410 type gel permeation chromatographs, the molecular weight of above-mentioned polymer P 1～P8 and distribution thereof are tested, result is as shown in table 1.As seen from Table 1, in thiodiphenylamine conjugated system, introduce the molecular weight that carbazole unit can significantly improve polymkeric substance; By changing feed ratio, optimize the polymkeric substance that reaction conditions can obtain higher molecular weight; Owing to having introduced long alkyl chain in thiodiphenylamine group, can make all polymkeric substance have good solvability, they are all dissolved in conventional organic solvent, as toluene, chloroform, tetrahydrofuran (THF) etc.
The molecular weight of each polymkeric substance of table 1. and distribution situation thereof
A:o-DCB is solvent, and CuCl, TMEDA are catalyzer, pass into air, 50 ℃, and reaction 30min;
B: measured by GPC, THF is solvent, and polystyrene is reference substance.
2, contain uv-absorbing, fluorescence emission peak and the thermogravimetric analysis of the fluorescent conjugated polymer of thiodiphenylamine group:
By HP8453E type ultraviolet-visual spectrometer, record the ultraviolet-visible absorption spectroscopy of above-mentioned polymer P 1～P8, by Fluorolog-3 type fluorescence spectrophotometer, record the fluorescence emission spectrum of above-mentioned polymkeric substance, and by Netzsch TG209F1 type thermal analyzer, the thermal characteristics of above-mentioned polymkeric substance is carried out to test analysis, result is as shown in table 2, as seen from Table 2, except polymer P 5 transmitting purple lights, other polymkeric substance are all invented bright green glow; The decomposition temperature of polymkeric substance is between 373 ℃～426 ℃, and 800 ℃ of residual carbonaceous amounts, all more than 60%, have good thermostability.
Absorption emission peak and the thermostability of table 2, each polymkeric substance
| Polymkeric substance | Uv-absorbing wavelength a | Fluorescent emission wavelength b | Initial decomposition temperature | Residual carbonaceous amount |
| ? | (nm) | (nm) | (℃) c | (％) |
| P1 | 412 | 501 | 413 | 63 |
| P2 | 350，386 | 503 | — | — |
| P3 | 352，382 | 497 | 409 | 66 |
| P5 | 321，352 | 412 | 426 | 61 |
| P7 | 410，488 | 498 | 373 | 61 |
A: the uv-absorbing wavelength in trichloromethane;
B: the fluorescent emission wavelength in trichloromethane;
C: thermogravimetric analysis under nitrogen protection, 10 ℃/min of temperature rise rate.
3, uv-absorbing and the fluorescent emission analysis in different solvents containing the fluorescent conjugated polymer of thiodiphenylamine group: by changing solvent species, record respectively polymer P 7 at normal hexane, toluene, chloroform, acetone and N, ultraviolet-visible absorption spectroscopy in dinethylformamide and fluorescence emission spectrum, result is as shown in table 3.As seen from Table 3, in different solvents, ultraviolet absorption peak change in displacement is very little, illustrates that solvent is very little on its ground state impact.In different solvents, its fluorescent emission summit, along with the increase of polarity produces red shift to a certain degree, shows that this type of fluorescent conjugated polymer with D-π-A structure can be used for fluorescent optical sensor material.
Table 3, the optical property of polymer P 7 in different solvents
| Solvent | Uv-absorbing wavelength a(nm) | Fluorescent emission wavelength b(nm) |
| Normal hexane | 390，480 | 482 |
| Toluene | 408，482 | 498 |
| Chloroform | 410，488 | 498 |
| Acetone | 404，476 | 501 |
| DMF | 410，476 | 511 |
A: the uv-absorbing wavelength in trichloromethane;
B: the fluorescent emission wavelength in trichloromethane.
4, contain the electrochemical analysis of the fluorescent conjugated polymer of thiodiphenylamine group:
By cyclic voltammetry, measure the redox potential of polymer P 1, P3 and P7.Adopt CHI 660A point chem workstation, by standard, obtain three-electrode electro Chemical pond and measure; Platinum electrode closes supporting electrode as working electrode, and mercurous chloride electrode (SCE) is as reference electrode.Table 4 is the chemical property analytical results of the fluorescent conjugated polymer containing thiodiphenylamine group.As can be seen from Table 4, the HOMO energy level of polymer P 1, P3, P7 all, in-5.60eV left and right, all has good hole transport performance; The lumo energy of polymer P 7, at-3.34eV, decreases with respect to thiodiphenylamine homopolymer, is conducive to electronic injection.
The chemical property of table 4, polymkeric substance
a
A: carry out in tetrabutyl ammonium hexafluorophosphate-acetonitrile solution of 0.1M.Working electrode is platinum electrode, and reference electrode is mercurous chloride electrode, and platinum filament is supporting electrode, and sweep velocity is 50mV/s.
5, the nuclear magnetic resonance spectroscopy that contains the fluorescent conjugated polymer of thiodiphenylamine group:
N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-, N-octyl group-3, two (ethynyl) carbazoles of 6-and containing the nucleus magnetic resonance figure of the fluorescent conjugated polymer P3 of thiodiphenylamine group as shown in Figure 1, wherein A is N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-, B is N-octyl group-3, two (ethynyl) carbazoles of 6-, and C is copolymer p 3;
N-octyl group-3, two (ethynyl) thiodiphenylamine, 4 of 6-, 7-diacetylene-2,1,3-benzene thiophene oxazole and containing the nucleus magnetic resonance figure of the fluorescent conjugated polymer P7 of thiodiphenylamine group as shown in Figure 2, wherein A is N-octyl group-3, two (ethynyl) thiodiphenylamine of 6-, and B is 4,7-diacetylene-2,1,3-Ben Bing Sai oxazole, C is copolymer p 7.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. containing a fluorescent conjugated polymer for thiodiphenylamine group, it is characterized in that structural formula is:
Wherein, the natural number that x is 2～100, the natural number that y is 2～200; R
1alkyl for carbon number 1～18; R
2for N-octyl group carbazole or Ben Bing Sai oxazole.
2. the synthetic method of the fluorescent conjugated polymer containing thiodiphenylamine group according to claim 1, is characterized in that comprising the steps:
(1) N-alkyl-3, synthesizing of two (ethynyl) thiodiphenylamine monomers of 6-: 3,6-bis-bromo-N-alkyl thiodiphenylamine and divalence palladium catalyst are joined in reactor, add cuprous iodide, under nitrogen protection, add again toluene, triethylamine and 3,3 '-dimethyl-3-hydroxypropyn, temperature reaction, to react products therefrom filters, with anhydrous diethyl ether washing, air distillation, except desolventizing, is purified and is obtained intermediate with column chromatography;
Under nitrogen protection, the temperature rising reflux reaction in toluene solvant by described intermediate and NaOH, toluene solvant is removed in underpressure distillation, and column chromatography is purified and is obtained N-alkyl-3, two (ethynyl) thiodiphenylamine monomers of 6-;
(2) synthetic containing the fluorescent conjugated polymer of thiodiphenylamine group: by step (1) gained N-alkyl-3, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, two (ethynyl) carbazole monomers or 4 of 6-, 7-diacetylene-2,1,3-Ben Bing Sai oxazole monomer is dissolved in orthodichlorobenzene, is stirred to completely and dissolves, and obtains mixing solutions; Then gained mixing solutions is transferred in the catalyst system that contains cuprous chloride and Tetramethyl Ethylene Diamine, passed under the condition of air stirring reaction; After question response finishes, reaction solution is poured in the mixing solutions of methyl alcohol and concentrated hydrochloric acid and precipitated, filter, will filter the vacuum-drying of gained solid, obtain the described fluorescent conjugated polymer that contains thiodiphenylamine group.
3. synthetic method according to claim 2, is characterized in that: step (1) is described 3, and the alkyl carbon number of the bromo-N-alkyl of 6-bis-thiodiphenylamine is 1～18.
4. synthetic method according to claim 2, is characterized in that: step (1) is described 3, and the mol ratio of 6-bis-bromo-N-alkyl thiodiphenylamine and divalence palladium catalyst is 1:(0.02～0.05); Step (1) is described 3, and the mol ratio of 6-bis-bromo-N-alkyl thiodiphenylamine and cuprous iodide is 1:(0.001～0.005).
5. synthetic method according to claim 2, is characterized in that: in step (1), by molar fraction, every mmole 3, the bromo-N-alkyl of 6-bis-thiodiphenylamine correspondence adds toluene 6～15mL, triethylamine 6～15mL, 3,3 '-dimethyl-3-hydroxypropyn, 0.3～1.5mL.
6. synthetic method according to claim 2, is characterized in that: the temperature of the described temperature reaction of step (1) is 80～120 ℃, and the reaction times is 10～24h; The mol ratio of the described intermediate of step (1) and NaOH is 1:(1～2); The temperature of the described temperature rising reflux reaction of step (1) is 80～120 ℃, and the reaction times is 3～10h.
7. synthetic method according to claim 2, it is characterized in that: the described N-of step (2) alkyl-3, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, two (ethynyl) carbazole monomers or 4 of 6-, 7-diacetylene-2, the mol ratio of 1,3-Ben Bing Sai oxazole monomer is 1:(1～3).
8. synthetic method according to claim 2, is characterized in that: described in step (2), being stirred to consoluet temperature is 20～60 ℃; The time of the described stirring reaction of step (2) is 4-～60min.
9. synthetic method according to claim 2, it is characterized in that: the catalyst system that contains cuprous chloride and Tetramethyl Ethylene Diamine described in step (2) is with the corresponding cuprous chloride 20～30mg that uses of the two alkynes monomers of every mmole, Tetramethyl Ethylene Diamine 0.06～0.08mL and orthodichlorobenzene 20～50mL preparation;
The mixing solutions of the described methyl alcohol of step (2) and concentrated hydrochloric acid is with the two corresponding use of the alkynes monomer 50～100mL methyl alcohol of every mmole and 0.1～0.3mL concentrated hydrochloric acid mixed preparing;
Described pair of alkynes monomer is N-alkyl-3, two (ethynyl) the thiodiphenylamine monomers of 6-and N-octyl group-3, two (ethynyl) carbazole monomers of 6-or 4,7-diacetylene-2, the summation of 1,3-Ben Bing Sai oxazole monomer.
10. the application of the fluorescent conjugated polymer containing thiodiphenylamine group according to claim 1 in organic luminescent device, solar cell and fluorescent optical sensor field.
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| CN109942570A (en) * | 2019-03-11 | 2019-06-28 | 中南大学 | A kind of conjugation microporous polymer based on phenthazine, preparation method and efficient catalytic application |
| CN111004371A (en) * | 2019-08-05 | 2020-04-14 | 中山大学 | AB2Monomer, donor-receptor-donor-pi bridge type hyperbranched conjugated polymer prepared from monomer, preparation method and application |
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| CN105859710A (en) * | 2016-04-12 | 2016-08-17 | 南昌航空大学 | Preparation method of dye sensitizer based on phenothiazine |
| CN105859710B (en) * | 2016-04-12 | 2021-02-02 | 南昌航空大学 | Preparation method of dye sensitizer based on phenothiazine |
| CN109942570A (en) * | 2019-03-11 | 2019-06-28 | 中南大学 | A kind of conjugation microporous polymer based on phenthazine, preparation method and efficient catalytic application |
| CN111004371A (en) * | 2019-08-05 | 2020-04-14 | 中山大学 | AB2Monomer, donor-receptor-donor-pi bridge type hyperbranched conjugated polymer prepared from monomer, preparation method and application |
| CN111004371B (en) * | 2019-08-05 | 2021-02-12 | 中山大学 | AB2Monomer, donor-receptor-donor-pi bridge type hyperbranched conjugated polymer prepared from monomer, preparation method and application |
| CN112920310A (en) * | 2021-01-27 | 2021-06-08 | 三明学院 | Method for improving luminous efficiency of cluster luminous polymer and cluster luminous polymer |
| CN112920310B (en) * | 2021-01-27 | 2023-04-28 | 三明学院 | Cluster luminous polymer luminous efficiency improving method and cluster luminous polymer |
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