CN1740266A - Electroluminous phenothiazine polymer material and its prepn process - Google Patents
Electroluminous phenothiazine polymer material and its prepn process Download PDFInfo
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- CN1740266A CN1740266A CN 200510015128 CN200510015128A CN1740266A CN 1740266 A CN1740266 A CN 1740266A CN 200510015128 CN200510015128 CN 200510015128 CN 200510015128 A CN200510015128 A CN 200510015128A CN 1740266 A CN1740266 A CN 1740266A
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Abstract
The present invention is electroluminous phenothiazine polymer material and its preparation process, and aims at providing electroluminous material with high light emitting efficiency and long service life. The present invention copolymerizes phenothiazine unit, phenothiazine-S-oxide unit, thiophene or other chromophoric unit to introduce phenothiazine unit and phenothiazine-S-oxide unit into common electroluminous polymer material skeleton. The electroluminous phenothiazine polymer material has phenothiazine unit to lower the ionization potential Ip and phenothiazine-S-oxide unit to raise the electron affinity Ea and thus high comprehensive performance. The electroluminous phenothiazine polymer material can glow with yellow, green, orange and red light, is soluble in common solvent and may be used in making light emitting devices through evaporation process or rotary painting process.
Description
[technical field]: patent of the present invention relates to a kind of novel electroluminous phenothiazine polymer material and preparation method thereof.
[background technology]:, will dominate field of information display as the flat panel display of information carrier in the 21st century of information explosion.As the fresh combatants in technique of display field, organic electroluminescent (OLED) has related to different ambits such as materialogy, luminescence and microtronics, has outstanding high-performance aspect portable, dull and stereotyped and the flexible demonstration.Therefore, the research of OLED can not only drive the development of related discipline, and has the huge market of potential in the flat pannel display field.Electroluminescent organic material is mainly some conjugated organic molecule or polymkeric substance.Since Kodak (C W Tang) and univ cambridge uk (J H Burroughs) developed efficient organic and polymer electroluminescent device respectively, developing flat-panel screens efficient, panchromatic demonstration just became the target of researcher.Polymer electroluminescent device has good mechanical property, and processing and preparing is easy, is easy to realize flexible the demonstration, can be made into advantages such as broad area device.Be expected to be widely used in fields such as organic field-effect tube, electroluminescent diode, organic photovoltaic battery, organic laser, organic chemistry and biosensor.The ideal electroluminescent material should have high-level efficiency, high brightness, low start voltage, say to be exactly to have high electron affinity (Ea) and low ionizing potential (Ip) from energy band structure, help the injection and the transmission in electronics and hole, and then realize that current carrier injects and the balance of transmission.Yet polymer materials is uneven for the injection and the transmission in electronics and hole.Polyphenylene ethylene (PPV), polyphenyl (PP), poly-fluorenes (PF), Polythiophene (PAT) etc. is p type polymkeric substance, and transport property is mainly based on the hole, and electric transmission is auxilliary.It is uneven to cause electronics and hole to be injected with transmission, the efficient and the life-span of reducing polymer electroluminescent device then.For this reason, from the angle of material preparation, people attempt will having with the method for copolymerization the group introducing p type or the n type conjugated polymer backbone of electronics or hole transport function, in the hope of obtaining the better polymer electroluminescence material of over-all properties.
Thiodiphenylamine is the heterogeneous ring compound of a class electron rich, contains two heteroatomss of nitrogen and sulphur in the thiodiphenylamine molecule, and the easy and phenyl ring formation delocalization structure of its lone-pair electron makes it have very strong fluorescent characteristic and structure regulating.Thiodiphenylamine and derivative thereof have lower ionizing potential, and easily lose an electronics and form corresponding radical cation, be stronger electronic donor group, can be used for electroluminescent and nonlinear optical material.The thiodiphenylamine molecule has stronger rigidity and non-copline configuration, because the distortion of thiodiphenylamine molecule can stop the formation of accumulation of π key and interchain exciplex, thereby might improve the efficient of electroluminescent material.
Though people have carried out certain research (T.Y.WU, Y.CHEN.J.Polym.Sci:Part A:Polym.Chem., 2002,40,4452-62 for the conjugated polymer material that contains thiodiphenylamine in recent years; T.Y.WU, Y.CHEN.J.Polym.Sci.:Part A:Polym.Chem., 2002,40,4570-80; T.Y.WU, Y.CHEN.J.Polym.Sci.:Part A:Polym.Chem., 2004,42,1272-84; Y.S.HAN, S.D.KIM, et al.J.Polym.Sci:Part A:Polym.Chem.2003,41,2502-2511; X.X Kong, A.P.Kulkarni, S.A.Jenekhe.Macromol.2003,36,8992-8999; D.H.Hwang, S.K.Kim, M.J.Park.Chem.Mater.2004,16,1298-1303).But at present for thiodiphenylamine-S-oxidized derivatives (thiodiphenylamine-S-sulfoxide, thiodiphenylamine-S-sulfone) be yet there are no bibliographical information as the research of electroluminescent material structural unit.Different with thiodiphenylamine is that thiodiphenylamine-S-oxidized derivatives is will be electrophilic sulfoxide or sulfuryl group to the oxidized sulfur atom of electronics on thiodiphenylamine molecular structure basis.Therefore certain variation can take place in the character of thiodiphenylamine-S-oxidized derivatives.Owing to the existence of electrophilic sulfoxide or sulfuryl group, thiodiphenylamine-S-oxidized derivatives should be able to improve the electron affinity (Ea) of polymer materials, and then helps the injection and the transmission of electronics predictably.
[summary of the invention]: the present invention seeks to solve existing polymer electroluminescence material the efficient and the life-span problem on the low side of the polymer electroluminescent device that causes because electronics and hole are injected and transmission is uneven, a kind of novel thiodiphenylamine polymer electroluminescence material and preparation method thereof is provided.
The present invention introduces thiodiphenylamine unit, thiodiphenylamine-S-oxidation unit on polymer electroluminescence material skeletons commonly used such as poly-fluorenes, Polythiophene, polyphenylene ethylene by the copolymerization of chromophore elements such as thiodiphenylamine unit, thiodiphenylamine-S-oxidation unit and fluorenes, thiophene, benzene.By the ionizing potential Ip of thiodiphenylamine unit reduction polymer luminescent material, the electron affinity Ea by thiodiphenylamine-S-oxidation unit raising polymer luminescent material obtains the good comprehensive properties polymer electroluminescence material.
Phenothiazinyl polymer electroluminescence material provided by the invention has following structure:
In the said structure formula: R
1, R
2Be alkyl, alkyl chain length is 1-18; Substituent R
1And R
2Can be identical, also can be different; X and y are two kinds of structural unit ratio content, and x and y can adjust according to proportioning raw materials, can be thiodiphenylamine polymkeric substance, thiodiphenylamine-S-oxypolymer, or the multipolymer of the two.And satisfy 0≤X≤1; 0≤y≤1, x+y=1, n=1-100.Aromatic ring Ar and Ar ' comprise benzene and derivative, fluorenes and derivative thereof, thiophene and derivative thereof, naphthalene and derivative thereof, carbazole and derivative thereof, pyridine and derivative, oxadiazole and derivative thereof.Ar and Ar ' can be identical, also can be different.
It is monomeric synthetic and two kinds of monomers are obtained required polymkeric substance by the Witting condensation reaction that the preparation method of electroluminous phenothiazine polymer material provided by the invention relates generally to two classes, and concrete steps are as follows:
(1) N-alkyl thiodiphenylamine dialdehyde monomer
Wherein N-alkyl thiodiphenylamine dialdehyde monomer can be N-alkyl thiodiphenylamine dialdehyde, N-alkyl thiodiphenylamine-S-oxidation dialdehyde, or the mixture of the two.
Synthesizing of N-alkyl thiodiphenylamine dialdehyde:
Under 0-55 ℃ temperature, N-alkyl thiodiphenylamine and phosphorus oxychloride are (1: 2-40) join in the dimethyl formamide, be warming up to 130 ℃ gradually, react stopped reaction after 2-10 hour under the induction stirring in molar ratio; After reaction product is cooled to 100 ℃, pour in the ice, stir standing over night, use the chloroform re-extract, dried over sodium sulfate is filtered, the lower black oily liquids is revolved steaming remove chloroform, with silica gel column chromatography (eluent: sherwood oil: ethyl acetate=3: 1) make with extra care, obtain N-alkyl thiodiphenylamine dialdehyde.
N-alkyl thiodiphenylamine-monomeric the synthesizing of S-oxidation dialdehyde:
1. the protection of aldehyde radical: N-alkyl thiodiphenylamine dialdehyde and triethyl orthoformate were dissolved in the mixed solvent of anhydrous tetrahydro furan and dehydrated alcohol (1: 1) in 1: 4 in molar ratio; the ethanolic soln that adds about ten saturated hydrogenchloride then at room temperature reacts this reaction solution to 24h.After reaction stops, adding excessive yellow soda ash, filter, decompression steams excess ethanol and triethyl orthoformate.
2. thiodiphenylamine sulphur is oxidized to sulfoxide: the product that top step is obtained is dissolved in the ethanol, adds 30% hydrogen peroxide solution that contains yellow soda ash.Back flow reaction 4h, stopped reaction spends the night the pressure reducing and steaming solvent with this mixture room temperature placement.
3. the hydrolysis of acetal: above-mentioned product is dissolved in the mixed solvent of tetrahydrofuran (THF) and water (2: 1), the dilute hydrochloric acid with 10% is regulated about pH to 1, reacts 24h under room temperature.Reaction adds excessive yellow soda ash after finishing, and stirs 0.5h.Boil off tetrahydrofuran (THF), with dichloromethane extraction repeatedly, anhydrous magnesium sulfate drying filters, and is spin-dried for solvent, and thick product separates (eluent: sherwood oil: ethyl acetate=1: 3) get N-alkyl thiodiphenylamine-S-oxidation dialdehyde through column chromatography.
(2) the two phosphonium salts of fragrance are monomeric synthetic
The two phosphonium salt monomers of fragrance are:
Wherein: R
4And R
5Be hydrogen, alkyl, alkoxyl group, substituent R
4And R
5Can be identical, also can be different, alkyl chain length is 1-18, the alkoxyl group chain length is 1-18, R
3Be butyl or phenyl.
Its preparation method is as follows: respectively with 2; the two bromomethyl thiophenes, 9 of 5-, 9-octyl group-2, the two brooethyl fluorenes, 2 of 7-; the two brooethyls-1 of 5-; 4-two octyloxy benzene and trimethyl phosphite are (1: 2-3) join in the dimethyl formamide, reacted 1-24 hour the reaction mixture cool to room temperature under nitrogen protection under 120-140 ℃ of temperature in molar ratio; through ether sedimentation; behind the repetitive scrubbing, filtration, drying obtain the two phosphonium salt monomers of three kinds of fragrance at last.
(3) preparation method of electroluminous phenothiazine polymer material
The preparation method of electroluminous phenothiazine polymer material is as follows: with N-alkyl thiodiphenylamine dialdehyde monomer (N-alkyl thiodiphenylamine dialdehyde, the N-alkyl thiodiphenylamine-S-oxidation dialdehyde of preparation, or the mixture of the two) and the two phosphonium salt monomers of fragrance of preparation be dissolved in the anhydrous tetrahydro furan for (1: 1) in molar ratio, dripping mol ratio then is the tetrahydrofuran solution that 2-6 doubly measures the potassium tert.-butoxide of (comparing with N-alkyl thiodiphenylamine dialdehyde monomer), under the room temperature stirring reaction 1-24 hour, stopped reaction then.The evaporate to dryness tetrahydrofuran (THF) is used the chloroform dissolve polymer then, precipitates in methyl alcohol, filters, and 40 ℃ of vacuum-drying 24h obtain electroluminous phenothiazine polymer material of the present invention at last.
Advantage of the present invention and positively effect:
Thiodiphenylamine unit, thiodiphenylamine-S-oxidation unit are introduced polymer electroluminescence material skeletons commonly used such as poly-fluorenes, Polythiophene, polyphenylene ethylene, improved the electron affinity (Ea) of polymer materials, reduced ionizing potential (Ip), help the injection and the transmission in electronics and hole, and then realize that current carrier injects and the balance of transmission.
[embodiment]:
Embodiment 1 N-n-octyl-3, synthesizing under 0-55 ℃ temperature of 7-dialdehyde-based thiodiphenylamine, under nitrogen protection, N-alkyl thiodiphenylamine 9.3445g (30mmol) and phosphorus oxychloride 70ml (750mmol) are joined in the 60ml dimethyl formamide for (1: 25) in molar ratio, be warming up to 130 ℃ gradually, react stopped reaction after 6 hours under the induction stirring; After reaction product is cooled to 100 ℃, pour in the 350g ice, stir standing over night.Repeat repeatedly to extract with chloroform, dried over sodium sulfate is filtered.The lower black oily liquids is revolved steaming remove chloroform, with silica gel column chromatography (eluent: sherwood oil: ethyl acetate=3: 1) make with extra care, obtain N-n-octyl-3,7-dialdehyde-based thiodiphenylamine.Fusing point: 114.0-115.0 ℃
1H NMR (CDCl
3, ppm) δ 9.81 (2Hs, CHO), 7.64-7.66 (2H, d, 2,8-Ar-H), 7.57 (2H, s, 4,6-Ar-H), 6.93-6.95 (2H, d, 1,9-Ar-H), 3.90-3.93 (2H, t, ArN-CH
2), 1.78-1.85 (2H, m, β-CH
2), 1.24-1.45 (10H, m, CH
2), 0.84-0.87 (3H, t, CH
3).
Can confirm to have following structure thus:
Embodiment 2N-n-octyl-3,7-dialdehyde-based thiodiphenylamine-S-sulfoxide (M3) synthetic
(1) protection of aldehyde radical: in reaction flask, add 1.84g (5mmol) N-n-octyl-3; the mixing solutions of 7-dialdehyde-based thiodiphenylamine, 3.0g (20mmol) triethyl orthoformate and 35ml anhydrous tetrahydro furan/dehydrated alcohol (1: 1); the ethanolic soln that adds about ten saturated hydrogenchloride then at room temperature reacts this reaction solution to 24h.After reaction stops, adding excessive yellow soda ash and stir 0.5h, filter, decompression steams excess ethanol and triethyl orthoformate, gets garnet liquid.
(2) sulphur of thiodiphenylamine is oxidized to sulfoxide: the product that top step is obtained is dissolved in the 50ml ethanol, adds the hydrogen peroxide solution that 15ml contains 1g yellow soda ash then.Back flow reaction 3h adds the hydrogen peroxide solution that 5ml contains 0.5g yellow soda ash, again back flow reaction 1h.Stopped reaction spends the night this mixture room temperature placement, and the pressure reducing and steaming solvent gets yellow solid.
(3) hydrolysis of acetal: above-mentioned product is dissolved in the 30ml tetrahydrofuran (THF): in the mixed solvent of water (2: 1), regulate about pH to 1 with 10% dilute hydrochloric acid then, under room temperature, react 24h.After reaction finishes, add excessive yellow soda ash and stir 0.5h, boil off tetrahydrofuran (THF), use 30ml dichloromethane extraction 3 times then respectively, anhydrous magnesium sulfate drying filters, be spin-dried for solvent, thick product separates (eluent: sherwood oil: ethyl acetate=1: 3) get white solid through column chromatography.Output: 1.8g (83%), fusing point: 134.0-135.0 ℃.
1H NMR(CDCl
3，ppm)δ10.04(2H，s，CHO)，8.47(2H，s，4，6-Ar-H)，8.18-8.20(2H，d，2，8-Ar-H)，7.57-7.60(2H， d，1，9-Ar-H)，4.30-4.34(2H，t，ArN-CH
2)，1.98-2.03(2H，m，β-CH
2)，1.30-1.58(10H，m，CH
2)，0.87-0.90(3H，t，CH
3)。
IR(KBr，cm
-1)，3063(Ar-H)，2926(aliphatic CH)，2852(＞N-CH
2-)，2728(CHO)，1694(C＝O)，1591，1471(Ar C＝C)，1045，1022(S＝O)。
Can confirm to have following structure thus:
The poly-N-n-octyls-3 of embodiment 3, the inferior phenothiazinyl vinylidene-2 of 7-, the inferior thienyl vinylidene of 5-synthetic
Under the nitrogen protection, with 0.368g (1mmol) N-n-octyl-3,7-dialdehyde-based thiodiphenylamine, 0.80g (1mmol) 2, two (dimethoxy (phosphonomethyl)) thiophene of 5-are dissolved in the 40ml anhydrous tetrahydro furan.Dropping contains the tetrahydrofuran solution of 0.34g (3mmol) potassium tert.-butoxide, finishes, and reacts 24h under the room temperature.After reaction finished, the evaporate to dryness tetrahydrofuran (THF) with the chloroform dissolving, precipitated in methyl alcohol then, filters, and 40 ℃ of vacuum-drying 24h get the dark red solid powder.Productive rate 23%.
Performance: solid fluorescence is emitted as 609nm, and device architecture is that the maximum glow peak of the electroluminescent device of ITO/polymer/Ca/Al is positioned at 616nm, sends out orange-colored light, and high-high brightness is 50cd/m
2
The poly-N-n-octyls 3 of embodiment 4, the inferior phenothiazinyl vinylidene-2 of 7-, 7-Asia 9,9-n-octyl fluorenyl vinylidene synthetic
Under the nitrogen protection, with 0.184g (0.5mmol) N-n-octyl-3,7-dialdehyde-based thiodiphenylamine, 0.2893g (0.5mmol) 2, two (the dimethoxy (phosphonomethyl)s)-9 of 7-, 9-n-octyl fluorenes is dissolved in the 40ml anhydrous tetrahydro furan.Dropping contains the tetrahydrofuran solution of 0.17g (1.5mmol) potassium tert.-butoxide, finishes, and reacts 24h under the room temperature.After reaction finished, the evaporate to dryness tetrahydrofuran (THF) with the chloroform dissolving, precipitated in methyl alcohol then, filters, and 40 ℃ of vacuum-drying 24h get bright dark red solid powder.Productive rate 17%.
Performance: solid fluorescence is emitted as 573nm, and device architecture is that the maximum glow peak of the electroluminescent device of ITO/polymer/Ca/Al is positioned at 552nm, sends green glow, and high-high brightness is 20cd/m
2
Embodiment's 5 poly-[N-n-octyl 3, the inferior phenothiazinyl vinylidene-2 of 7-, two n-octyl oxygen bases of 5--to phenylene vinylidene-N-n-octyl 3, the basic vinylidene of 7-(inferior thiodiphenylamine-S-oxide compound)] is synthetic
For obtaining multipolymer; under nitrogen protection; in reaction flask, add N-n-octyl-3 according to different proportionings (as shown in the table); 7-dialdehyde-based thiodiphenylamine (M2), N-n-octyl-3; 7-dialdehyde-based thiodiphenylamine-S-sulfoxide (M3) is 0.5mmol and 0.2893g (0.5mmol) 1 altogether; two (the dimethoxy (phosphonomethyl)s)-2 of 4-, the 5-n-octyl is dissolved in the 40ml anhydrous tetrahydro furan.Drip the tetrahydrofuran solution that contains 0.17g (1.5mmol) potassium tert.-butoxide then, finish, react 24h under the room temperature.After reaction finished, the evaporate to dryness tetrahydrofuran (THF) with the chloroform dissolving, precipitated in methyl alcohol then, filters, and 40 ℃ of vacuum-drying 24h get bright orange/yellow solid powder.
Performance: the solid fluorescence of polymkeric substance, device architecture are the maximum glow peak of the electroluminescent device of ITO/polymer/Ca/Al, it is as shown in the table for high-high brightness:
| Feed ratio (M2/M3) | Yield (%) | The Mw molecular weight | Molecular weight distribution | PL (nm) | EL (nm) | Open bright voltage (V) | High-high brightness (cd/m 2) | |
| P1 P2 P3 P4 P5 | 1∶0 2∶1 1∶1 1∶2 0∶1 | 72 69 69 63 72 | 35200 53800 27600 39300 14500 | 3.12 4.52 2.45 3.70 2.02 | 582 583 585 589 574 | 568 569 572 576 568 | 4 6 6 6 6 | 100 100 100 100 100 |
Above description and embodiment different materials of the present invention and preparation method thereof is disclosed, but the present invention is not limited to above-mentioned specific examples, it comprises all improvement and the variation in the scope defined in claims of the present invention.
Claims (9)
1. electroluminous phenothiazine polymer material is characterized in that having following structure:
In the said structure formula: R
1, R
2Be alkyl, alkyl chain length is 1-18; Substituent R
1And R
2Can be identical, also can be different; X and y are two kinds of structural unit ratio content, and satisfy 0≤x≤1; 0≤y≤1, x+y=1, n=1-100.
2. electroluminous phenothiazine polymer material according to claim 1 is characterized in that aromatic ring Ar and Ar ' comprise benzene and derivative, fluorenes and derivative thereof, thiophene and derivative thereof, naphthalene and derivative thereof, carbazole and derivative thereof, pyridine and derivative, oxadiazole and derivative thereof.Ar and Ar ' can be identical, also can be different.
3. electroluminous phenothiazine polymer material according to claim 1 is characterized in that wherein the S oxide compound can be a sulfoxide
It also can be sulfone
4. electroluminous phenothiazine polymer material according to claim 1 is characterized in that wherein x and y can adjust according to proportioning raw materials, can be thiodiphenylamine polymkeric substance, thiodiphenylamine-S-oxypolymer, or the multipolymer of the two.
5. the preparation method of the described electroluminous phenothiazine polymer material of claim 1, it is characterized in that this method comprises three steps: 1. N-alkyl thiodiphenylamine dialdehyde is monomeric synthetic, wherein N-alkyl thiodiphenylamine dialdehyde can be N-alkyl thiodiphenylamine dialdehyde, N-alkyl thiodiphenylamine-S-oxidation dialdehyde, or the mixture of the two; 2. the two phosphonium salts of fragrance are monomeric synthetic; 3. two kinds of monomers are obtained required polymkeric substance by the Witting condensation reaction.
6. the preparation method of electroluminous phenothiazine polymer material according to claim 5, it is characterized in that monomeric the synthesizing of N-alkyl thiodiphenylamine dialdehyde, under 0-55 ℃ temperature, under nitrogen protection, N-alkyl thiodiphenylamine and phosphorus oxychloride are (1: 2-40) join in the dimethyl formamide in molar ratio, be warming up to 130 ℃ gradually, react stopped reaction after 2-10 hour under the induction stirring; After reaction product is cooled to 100 ℃, pour in the ice, stir standing over night, use the chloroform re-extract, dried over sodium sulfate is filtered, the lower black oily liquids is revolved steaming remove chloroform, with silica gel column chromatography (eluent: sherwood oil: ethyl acetate=3: 1) make with extra care, obtain the thiodiphenylamine dialdehyde.
7. the preparation method of electroluminous phenothiazine polymer material according to claim 5 is characterized in that: N-alkyl thiodiphenylamine-S-oxidation dialdehyde is monomeric synthetic:
1. the protection of aldehyde radical: N-alkyl thiodiphenylamine dialdehyde and triethyl orthoformate were dissolved in the mixed solvent of anhydrous tetrahydro furan and dehydrated alcohol (1: 1) in 1: 4 in molar ratio, the ethanolic soln that adds about ten saturated hydrogenchloride then, this reaction solution is at room temperature reacted 24h, after reaction stops, add excessive yellow soda ash, filter, decompression steams excess ethanol and triethyl orthoformate;
2. thiodiphenylamine sulphur is oxidized to sulfoxide: the product that above-mentioned steps is obtained is dissolved in the ethanol, adds 30% hydrogen peroxide solution that contains yellow soda ash, back flow reaction 4h, and stopped reaction spends the night the pressure reducing and steaming solvent with this mixture room temperature placement;
3. the hydrolysis of acetal: above-mentioned product is dissolved in the mixed solvent of tetrahydrofuran (THF) and water (2: 1), dilute hydrochloric acid with 10% is regulated about pH to 1, reacts 24h under room temperature, after reaction finishes, add excessive yellow soda ash, stir 0.5h, boil off tetrahydrofuran (THF), use dichloromethane extraction, anhydrous magnesium sulfate drying, filter, be spin-dried for solvent, thick product separates (eluent: sherwood oil: ethyl acetate=1: 3) get N-alkyl thiodiphenylamine-S-oxidation dialdehyde through column chromatography.
8. the preparation method of electroluminous phenothiazine polymer material according to claim 5, it is characterized in that fragrance, two phosphonium salt is monomeric synthesizes: respectively with 2, the two bromomethyl thiophenes of 5-, 9,9-octyl group-2, the two brooethyl fluorenes of 7-, 2, the two brooethyls-1 of 5-, 4-two octyloxy benzene and trimethyl phosphite are (1: 2-3) join in the dimethyl formamide in molar ratio, under nitrogen protection, under 120-140 ℃ of temperature, reacted 1-24 hour, the reaction mixture cool to room temperature is through ether sedimentation, behind the repetitive scrubbing, filter, drying obtains the two phosphonium salt monomers of three kinds of fragrance at last; The two phosphonium salt monomer structures of described fragrance are:
Wherein: R
4And R
5Be hydrogen, alkyl, alkoxyl group, substituent R
4And R
5Can be identical, also can be different, alkyl chain length is 1-18, the alkoxyl group chain length is 1-18, R
3Be butyl or phenyl.
9. the preparation method of electroluminous phenothiazine polymer material according to claim 5; it is characterized in that the Witting condensation reaction is: under nitrogen protection with in claim 6 and 7 preparation N-alkyl thiodiphenylamine dialdehyde monomer (N-alkyl thiodiphenylamine dialdehyde; N-alkyl thiodiphenylamine-S-oxidation dialdehyde; or the mixture of the two) the two phosphonium salt monomers of the fragrance of preparation are dissolved in the anhydrous tetrahydro furan for (1: 1) in molar ratio and in the claim 8; dripping mol ratio then is the tetrahydrofuran solution that 2-6 doubly measures the potassium tert.-butoxide of (comparing with N-alkyl thiodiphenylamine dialdehyde monomer); under the room temperature stirring reaction 1-24 hour; stopped reaction then; the evaporate to dryness tetrahydrofuran (THF); use the chloroform dissolve polymer then; in methyl alcohol, precipitate; filter; 40 ℃ of vacuum-drying 24h obtain the described electroluminous phenothiazine polymer material of claim 1 at last.
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