CN105732977A - Novel soluble polybenzobisthiazole-amide fluorescent polymer and preparation method and application thereof - Google Patents

Novel soluble polybenzobisthiazole-amide fluorescent polymer and preparation method and application thereof Download PDF

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CN105732977A
CN105732977A CN201610077147.XA CN201610077147A CN105732977A CN 105732977 A CN105732977 A CN 105732977A CN 201610077147 A CN201610077147 A CN 201610077147A CN 105732977 A CN105732977 A CN 105732977A
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dithiazole
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fluorescent polymer
amide
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胡小兵
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Baoji University of Arts and Sciences
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    • C—CHEMISTRY; METALLURGY
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention provides a novel soluble polybenzobisthiazole-amide fluorescent polymer.2,6-diaminobenzo(1,2-d,4,5-d')bisthiazole and 1,3,5-benzenetricarboxylic acid serve as main raw materials, polymerization is carried out through an A2+B3 method, and the polymer is obtained.Molecules of the polymer have a branched structure.By adjusting the proportion of A2 monomers to B3 monomers, a polymer mainly terminated with -NH2 and/or a polymer mainly terminated with -COOH can be respectively obtained.The invention further provides a preparation method and application of the polymer.According to the polymer, the hyperbranched structure is introduced into rigid poly-(p-phenylenebenzothiazole), so that the organic solubility and processability of the polymer are greatly improved; the polymer is low in intermolecular interaction and adjustable in electron or hole transfer characteristic and optical characteristic and is an excellent optical material.

Description

A kind of novel soluble polyphenyl dithiazole-amide fluorescent polymer and its preparation method and application
Technical field
The present invention relates to macromolecular material and preparation method thereof, be specifically related to a kind of soluble poly benzo dithiazole-amide fluorescent polymer and its preparation method and application.
Background technology
Conjugated polymer can be applicable to a lot of field as conduction, photoelectricity and nonlinear optical material, and the conjugated polymer that wherein can be used for light emitting diode (light-emitting diode, LED) causes the extensive concern of whole world scientists.Increasing conjugated polymer is designed and is synthesized as luminescent material and charge transport materials.Polymer luminescent material have wide material sources, easy machine-shaping, by features such as Molecular Design scalable glow colors, become one of preferred material of preparation large area, low cost, panchromatic flexible display device.In the last few years, the aspects such as preparation, the efficiency of luminescent device, brightness and the service life at polymer electroluminescence material all obtain the biggest breakthrough, having had practical product to occur, the particularly research of the trichroism polymer luminescent material of red, green, blue achieves the most tempting progress.The emission wavelength of polymer and its structure have close relationship, therefore can obtain different colour systems by MOLECULE DESIGN.Polymer electroluminescence material PPV such as initially preparation, it is simply that send blue green light.But on its polymer segment, connect different groups, as carried out alkoxylate, the cyanalation or pyridine ring derivant of employing PPV, the different colour systems from HONGGUANG to blue green light can be obtained.And polyfluorene is the most typical blue light frequency-doubling, but on its polymer segment, connect different groups, can obtain from HONGGUANG and green glow.But in general, current research, red-green glow polymer is more, and blue light frequency-doubling is less.The preparation of blue-fluorescence polymer and performance study thereof are one of the study hotspots in macromolecular LED field.
Linear polyhenylene benzo dithiazole is the conjugation rigid rod heterocycle polymer on a kind of main chain containing benzothiazole ring.This polymer, in addition to having high intensity, high-modulus, excellent chemically and thermally stability, also has the character of high and supper-fast third-order nonlinear optical response.And, benzothiazole structure the fluorescence of conjugated system is also had important impact it is considered to be in polymer LED electron transmission and hole conduction retardance the potential material of tool.Jenekhe et al., based on Lyotropic liquid crystalline polymer, has synthesized a series of PBZT base polymer, have studied the conjugation group impact on polymer property.Result shows, along with the increase of conjugation group Central Asia vinyl segment, the light belt energy gap of this base polymer reduces, the optical absorption peak red shift of polymer.Thus be expected to make in certain wave-length coverage people can the conjugated structure of selective polymer as required, regulate color and the wavelength of luminescence generated by light.But, this base polymer is due to the rigid backbone of molecule itself and there is strong intermolecular interaction, cause it insoluble or be insoluble in conventional organic solvent, and be only dissolved in some strong Bronsted acids such as Loprazolam, sulfonic acid and trifluoromethane sulfonic acid, this causes this base polymer to be difficult to processing, thus hinders and further study this base polymer and apply.
Summary of the invention
Dissaving polymer has molecular structure and physics, the chemical property of uniqueness, in the wide application prospect that the aspects such as coating, polymer processing aid, nanotechnology and supermolecule science have.Compared with dendritic macromole, dissaving polymer is prone to processing, generally uses " one kettle way " to prepare；And compared with linear polymer, the dissolubility of dissaving polymer is preferable, viscosity is low, good processability, has regulatable luminescent properties.It also contributes to control the form of thin film, stops the generation of polymer crystallization.Additionally, the molecule of dissaving polymer typically exhibits spherical, containing substantial amounts of terminal functionality and nano level hole.
Dissaving structure is introduced the polyhenylene benzo dithiazole of rigidity and is substantially improved its Identification of Soluble Organic solution and processing characteristics by the present invention, has low intermolecular interaction, adjustable electron, hole transporting properties and optical characteristics.
Concrete, the invention provides a kind of soluble poly benzo dithiazole-amide fluorescent polymer, be with 2, and 6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1,3,5-benzenetricarboxylic acids are reaction monomers, through A2+B3Polymerization obtains, and this polymer molecule has branched structure, and each side chain comprises-NH2End-capping group and/or-COOH end-capping group.
Preferably, the molecular formula of soluble poly benzo dithiazole-amide fluorescent polymer that the present invention provides is as follows:
Present invention also offers the preparation method of soluble poly benzo dithiazole-amide fluorescent polymer, comprise the following steps:
With 2,6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1,3,5-benzenetricarboxylic acids are primary raw material, and with polyphosphoric acids as solvent with catalyst, phosphorus pentoxide is dehydrant, uses A2+B3Method obtain polyphenyl dithiazole-amide fluorescent polymer.
Preferably, the preparation method of soluble poly benzo dithiazole-amide fluorescent polymer that the present invention also provides for is, the polyphosphoric acids of 60g is added in the three-neck flask of 100mL, it is subsequently adding a certain amount of DABBT and trimesic acid, turn on agitator is also passed through argon, beginning to warm up, heating rate is 5 DEG C/h；When temperature rises to 80 DEG C, heating rate becomes 10 DEG C/h；React 2h when temperature rises to 100 DEG C, when 110 DEG C, react 1h, when 120 DEG C, react 0.5h；Then reaction system is naturally cooled to room temperature, takes out product, first wash product by massive laundering the most neutral, in apparatus,Soxhlet's, then use deionized water extraction 24h, be vacuum dried to obtain target product.
When described 2, and 6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1, when the reaction mol ratio of 3,5-benzenetricarboxylic acids is 1: 1, obtain-COOH terminated polymer；
When described 2, and 6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1, when the reaction mol ratio of 3,5-benzenetricarboxylic acids is 9: 4, obtain-NH2Terminated polymer.
Soluble poly benzo dithiazole-amide fluorescent polymer that the present invention provides can be applicable in organic electroluminescence device, specifically as embedded photoluminescent material, the application of electron transport material or hole barrier materials.
The present invention with 2,6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole (DABBT) and 1,3,5-benzenetricarboxylic acids (BTA) are reaction monomers, with polyphosphoric acids (PPA) as solvent with catalyst, phosphorus pentoxide is dehydrant, uses A2+B3Method synthesized a kind of hyperbranched poly benzo dithiazole-amide containing benzothiazole structure.By regulation A2Monomer and B3The ratio of monomer, has obtained two classes and has contained the dissaving polymer of different end group functional group, thus reached the purpose of its optical property.As the A adding reaction system2Monomer and B3When the ratio of monomer is 1: 1, obtain the polymer HB-COOH of-COOH end-blocking；And work as A2Monomer and B3When the ratio of monomer is 9: 4, the product obtained is-NH2The polymer HB-NH of end-blocking2.Made two kinds of dissaving polymers are all completely amorphous polymer, they are dissolvable in water among dimethylformamide and dimethyl sulfoxide, its DMSO solution can launch strong blue-fluorescence under the exciting of ultraviolet light, and fluoresced wavelength can be regulated by terminal functionality.Amino-terminated polymer HB-NH2Ultraviolet inhales the polymer HB-COOH, HB-NH being significantly stronger than carboxy blocking2Fluorescence intensity higher than the fluorescence intensity of HB-COOH, and HB-NH2The fluorescence spectrum fluorescence spectrum compared with HB-COOH there occurs red shift.
Accompanying drawing explanation
Fig. 1 dissaving polymer HB-COOH and HB-NH2X ray diffracting spectrum；
Fig. 2 dissaving polymer HB-COOH and HB-NH2Uv-visible absorption spectroscopy；
Fig. 3 dissaving polymer HB-COOH and HB-NH2Fluorescence spectrum.
Fig. 4 is dissaving polymer HB-COOH and HB-NH2Gel permeation chromatography (GPC) spectrogram.
Detailed description of the invention
The present invention is further described below in conjunction with the accompanying drawings with specific embodiment, the reagent of embodiment of the present invention employing and raw material 2,6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole, 1,3,5-benzenetricarboxylic acids are that reaction monomers, polyphosphoric acids, phosphorus pentoxide etc. are commercially available for conventional market.
In order to make those skilled in the art be more fully understood that, technical scheme can be practiced, and below in conjunction with specific embodiment, the invention will be further described, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
A kind of soluble poly benzo dithiazole-amide fluorescent polymer, with 2,6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1,3,5-benzenetricarboxylic acids are reaction monomers, with polyphosphoric acids (PPA) as solvent with catalyst, above-claimed cpd, as dehydrant, is placed in reactor by phosphorus pentoxide, uses A2+B3Method be polymerized, synthesized a kind of polymer being shown below.
The present invention is with 2,6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1, the preparation process figure of 3,5-benzenetricarboxylic acid synthesizing new hyperbranched poly benzo dithiazole-amide is as follows, and concrete building-up process is: add the polyphosphoric acids of 60g in the three-neck flask of 100mL, it is subsequently adding a certain amount of DABBT and trimesic acid, turn on agitator is also passed through argon, begins to warm up, and heating rate is 5 DEG C/h.When temperature rises to 80 DEG C, heating rate becomes 10 DEG C/h.React 2h when temperature rises to 100 DEG C, when 110 DEG C, react 1h, when 120 DEG C, react 0.5h.Then reaction system is naturally cooled to room temperature, takes out product, first wash product by massive laundering the most neutral, in apparatus,Soxhlet's, then use deionized water extraction 24h, be vacuum dried to obtain target product.
Testing obtained polymer, its nuclear magnetic resoance spectrum is as follows,
(1) hydrogen spectrum:
HB-COOH:1H NMR (400MHz, DMSO-d6, δ, ppm): 12.20,8.60,8.27,8.01,7.91,7.84,7.75,7.65,5.81；
HB-NH2:1H NMR (400MHz, DMSO-d6, δ, ppm): 12.19,8.61,8.28,8.02,7.92,7.85,7.75,7.68,5.39.
(2) carbon spectrum:
HB-COOH:13C NMR (100MHz, DMSO-d6, δ, ppm): 169.84,169.55,166.80,166.44,166.29,158.05,156.75,148.60,145.85,144.07,134.00,132.36,131.22,130.48,130.04,113.13,113.10,109.70,109.50.
HB-NH2:13C NMR (100MHz, DMSO-d6, δ, ppm): 169.84,169.56,169.24,166.85,166.57,166.29,162.73,158.05,156.79,148.35,144.11,134.00,132.37,131.22,130.51,129.90,113.14,109.69,109.47.
Choose the prepared polymer of embodiment 1 and at room temperature carry out X-ray diffraction experiment, through X-ray diffraction collection of illustrative plates as shown in Figure 1, as seen from Figure 1, in the range of 2 θ=5 °～80 °, obvious diffraction maximum does not occur, showing that prepared dissaving polymer is amorphous state, this structure is conducive to the dissolving in organic solvent of this base polymer.
The polymer samples being obtained embodiment 1 carries out UV-Visible absorption and solid fluorescence analysis, and its uv-visible absorption spectrum spectrogram and fluorescence spectrum spectrogram are the most as shown in Figures 2 and 3.
Fig. 2 is HB-COOH and HB-NH2Uv-visible absorption spectrum, HB-COOH and HB-NH in the polymer obtained by embodiment 12Concentration be 0.033mg/mL, solvent is DMSO, HB-COOH and HB-NH in Fig. 22Uv-visible absorption spectroscopy all occur in that three absworption peaks, its maximum absorption band lays respectively at 261nm, 308nm and 332nm；HB-NH under same concentrations2UV-Visible absorption intensity apparently higher than HB-COOH.
In figure 3, HB-NH in sample is analyzed2And the fluorescence maximum emission peak of HB-COOH lays respectively at 477nm and 468nm, HB-NH2The maximum fluorescence emission peak compared with HB-COOH, the maximum fluorescence emission peak there occurs the red shift of 9nm, and analyze HB-NH in sample2Fluorescence intensity higher than the fluorescence intensity of HB-COOH.This phenomenon can be explained with the anomeric effect of dissaving polymer, analyzes sample HB-NH2It is amino (-NH2) dissaving polymer that blocks, its molecular surface and inside has substantial amounts of amido functional group, and amino is a kind of electron donating group, and it can reduce the energy level difference between electronics highest occupied molecular orbital and the lowest unoccupied molecular orbital of polymer molecule.And HB-COOH is the dissaving polymer that carboxyl (-COOH) blocks, its molecular surface and inside are rich in carboxyl functional group, carboxyl is a kind of electron attractive functional group, and it can increase the energy level difference between electronics highest occupied molecular orbital and the lowest unoccupied molecular orbital of polymer molecule.
Therefore HB-NH in polymer2Ultraviolet spectra absorption maximum intensity and the maximum emission intensity of fluorescence spectrum be above ultraviolet spectra absorption maximum intensity and the maximum emission intensity of fluorescence spectrum of HB-COOH, and HB-NH2The maximum fluorescence emission peak compared with HB-COOH, the maximum fluorescence emission peak there occurs red shift.
Fig. 4 is HB-COOH and HB-NH2Gel permeation chromatography (GPC) spectrogram.With DMF for flowing phase during test, flow rate is 0.5mL min-1, test temperature is 30 DEG C.The molecular weight of polymer calculates with monodisperse polystyrene known to relative molecular mass for standard specimen.The molecular weight data of two kinds of polymer is shown in Table 1.Number-average molecular weight M of polymer HB-COOHnFor 3827g/mol, weight average molecular weight Mw1.07 are approximated for 4091g/mol, molecular weight distributing index PDI.Polymer HB-NH2Number-average molecular weight MnFor 3967g/mol, weight average molecular weight Mw1.07 are approximated for 4237g/mol, molecular weight distributing index PDI.Having the linear polymer of same molecular amount have less molecular volume owing to dissaving polymer compares, therefore using linear polystyrene is that standard sample calculates the molecular weight of two kinds of polymer of gained less than actual molecular weight.
The molecular weight form of table 1 polymer
Embodiment described above is only the preferred embodiment lifted by absolutely proving the present invention, and its protection domain is not limited to this.The equivalent that those skilled in the art are made on the basis of the present invention substitutes or conversion, and all within protection scope of the present invention, protection scope of the present invention is as the criterion with claims.

Claims (7)

1. soluble poly benzo dithiazole-amide fluorescent polymer, it is characterised in that be with 2,6-bis- Amino benzo (1,2-d, 4,5-d ') dithiazole and 1,3,5-benzenetricarboxylic acids are reaction monomers, through A2+B3Method is gathered Closing and obtain, this polymer molecule has branched structure, and each side chain comprises-NH2End-capping group and/or-COOH End-capping group.
Soluble poly benzo dithiazole-amide fluorescent polymer the most according to claim 1, its feature It is that there is following molecular formula:
The preparation side of soluble poly benzo dithiazole-amide fluorescent polymer the most according to claim 2 Method, it is characterised in that comprise the following steps:
With 2,6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1,3,5-benzenetricarboxylic acids are reaction monomers, with Polyphosphoric acids is solvent and catalyst, and phosphorus pentoxide is dehydrant, uses A2+B3Method obtain polyphenyl And dithiazole-amide fluorescent polymer.
The preparation side of soluble poly benzo dithiazole-amide fluorescent polymer the most according to claim 3 Method, it is characterised in that comprise the following steps:
In the three-neck flask of 100mL, add the polyphosphoric acids of 60g, be subsequently adding a certain amount of DABBT And trimesic acid, turn on agitator is also passed through argon, begins to warm up, and heating rate is 5 DEG C/h；Work as temperature When rising to 80 DEG C, heating rate becomes 10 DEG C/h；The reaction 2h when temperature rises to 100 DEG C, 110 DEG C Shi Fanying 1h, reacts 0.5h when 120 DEG C；Then reaction system is naturally cooled to room temperature, takes out product, First wash product by massive laundering the most neutral, in apparatus,Soxhlet's, then use deionized water extraction 24h, vacuum It is dried to obtain target product.
5. according to the system of the soluble poly benzo dithiazole-amide fluorescent polymer described in claim 3 or 4 Preparation Method, it is characterised in that when described 2, and 6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1,3,5-benzene When the reaction mol ratio of tricarboxylic acid is 1: 1, obtain-COOH terminated polymer；
When described 2, and 6-diaminourea benzo (1,2-d, 4,5-d ') dithiazole and 1, the reaction mole of 3,5-benzenetricarboxylic acids Than when being 9: 4, obtain-NH2Terminated polymer.
6. according to the soluble poly benzo dithiazole-amide fluorescent polymer described in any one of claim 1-2, Can be applicable in organic electroluminescence device.
7. according to the soluble poly benzo dithiazole-amide fluorescent polymer described in any one of claim 1-2, It is characterized in that, can be used as emitting layer material, electron transport material or hole barrier materials.
CN201610077147.XA 2016-01-30 2016-01-30 A kind of soluble poly benzo dithiazole acid amides fluorescent polymer and its preparation method and application Expired - Fee Related CN105732977B (en)

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