CN1305926C - Fluorene water soluble conjugate polymer containing polyethyene diamine side chain and its use - Google Patents
Fluorene water soluble conjugate polymer containing polyethyene diamine side chain and its use Download PDFInfo
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- CN1305926C CN1305926C CNB2005100244346A CN200510024434A CN1305926C CN 1305926 C CN1305926 C CN 1305926C CN B2005100244346 A CNB2005100244346 A CN B2005100244346A CN 200510024434 A CN200510024434 A CN 200510024434A CN 1305926 C CN1305926 C CN 1305926C
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Abstract
The present invention relates to a blue light material of a hydrosoluble polyfluorene class containing a polyethylenediamine side chain and application thereof to the aspects of ink jet printing and an organic luminous biosensor. The blue light material belongs to the technical field of organic polymer semiconductor luminescent materials. The hydrosoluble substitution side chain is formed by the method that the 9 position of fluorene causes oxazoline to be polymerized through a ring opening way and to hydrolyze by a carbocation line, the generated substitution fluorene is polymerized finally, and the hydrosoluble blue light display material is obtained. The product has good light emitting performance and aqueous solubility, a side group influences little on the light emitting performance of a main chain, and the product has good heat stability and charge transmission performance, and can be used as ink jet printing blue light base color ink and the organic luminous biosensor.
Description
Technical field
The present invention relates to the soluble conjugated polymer that a class contains the fluorenes class, and cause or the application of embedded photoluminescent material in organic flat-panel monitor and biosensor, belong to the technical field of organic light emitting display and biosensor as the blue light electricity.
Technical background
Since people such as the nineteen ninety Friend of univ cambridge uk R.H. have developed the electroluminescent organic material (OLED) of polyethylene base penylene structure first, caused the upsurge of studying organic panel display material and device in Materials science and areas of information technology.Luminous organic material is the functional materials of a kind of luminous, high brightness, panchromatic demonstration, and its film forming flexibility is good, in light weight, driving voltage is low, response speed is fast, in the flat pannel display field tempting prospect is arranged.Unremitting effort is all being done to the exploration of its mechanism, the exploitation and the Development of production Equipment of material by various countries scientist and more than 80 tame major companies.OLED technology on Kodak, three magnitude companies have successfully used in products such as digital camera, mobile phone.Be doubled and redoubled from OLED market in 2002,3,500,000,000 dollars market arranged approximately according to Stanford Resource company prediction OLED market before 2005.
Preparation colour light-emitting device needs the luminescent material of red-green-blue, and at present, the luminous organic material of ethereal blue light is fewer.Fluorene-based polymers is outstanding blue light emitting material, have higher brightness, fluorescence efficiency and stability, and can connect substituting group on 9 of fluorenes, can improve its solvability easily, suppress the mutual friendship lid between the conjugated main chain simultaneously, reduced the formation of excimer.It is the most useful present blue light display material.
The preparation of thin layer luminescent device at present mainly contains the method for spin-coating and vacuum plating, corresponds respectively to polymer materials and small molecule material.The latest development direction is to utilize the technology of ink jet printing, is ink with the luminescent material, evenly, fast, controllably is sprayed on and forms luminescent layer on the substrate.Therefore need the water-soluble luminescent material of development as the needs of ink with the ink-jet technology that adapts to.
Blue on the other hand organic luminescence polymer also has application promise in clinical practice aspect biosensor.Since people (Wang, S. such as the G.C.Bazan of California, USA university; Bazan G.C.Adv.Mater.2003,15,1425) proposed first by luminous high polymer since the energy of acceptor shifts the method that detects rna probe validity, the application of luminous high polymer aspect biosensor becomes an emerging focus.Its ultimate principle is as follows:
Conjugated polymers is as poly-fluorenes, polyphenyl etc. lose electronics easily in polar solvent, present positive polarity, and materials such as RNA are electronegativity in polar solvent, they will mutually combine by electrostatic force when both exist simultaneously, photoluminescence is original color, when the rna probe an of the unknown enters solution, if its probe group can successfully be gone up group with RNA and engage, it also will be approaching with RNA and luminous high polymer so, thereby may interact with luminous high polymer, if and it can not go up the group joint with RNA, will be very little with the interactional chance of luminous high polymer then.Energy acceptor group if on probe molecule, rejoin, it can move away the energy on the luminous high polymer, and from luminous or not luminous in low frequency, when it successfully engages with RNA, the luminous of solution will die down so.Otherwise solution is luminous constant substantially.So just can detect the effect situation of RNA and probe at an easy rate.Luminous high polymer conduct detector switch wherein requires its good water solubility, and its glow frequency is higher simultaneously, so just is easy to shift energy, so water-soluble blue light material is optimal selection.How the good water-soluble material of processability is a key issue.
Poly-ethylamine is good water-soluble substances, will improve water-solublely greatly if be introduced into conjugated polymers, can be used as the blue-light-emitting ink of ink-jet printing technology or water-soluble biological transmitter and uses.The soluble conjugated polymer overwhelming majority all is only to be dissolved in non-polar organic solvent at present, and soluble conjugated polymer lacks, and does not have document and patent report side chain to connect the polymkeric substance and the application in organic electroluminescent or biosensor thereof of the fluorenes of poly-ethylamine.
Summary of the invention
The object of the present invention is to provide a kind of water-soluble good fluorenes class conjugated polymers that contains poly-ethylamine side group, and be applied in flat-panel display device or the biosensor as blue organic luminous material.
The present invention is combined in the efficient blue emission effect of poly-ethylamine good water-soluble and poly-fluorenes in the same polymkeric substance, has prepared the multipolymer of a series of water-soluble fluorenes and thiophene, benzene, furans etc. with organometallic reagent catalysis coupling polycondensation.These polymkeric substance or multipolymer are the water-soluble electroluminescent materials of high comprehensive performance.
Fluorene water soluble conjugate polymer of the present invention, its general structure is as follows:
Wherein R is an alkyl; Ar is aromatic ring or fragrant heterocycle, as: benzene, anthracene, thiophene, pyrroles, furans, carbazole, imidazoles etc.; Y＞1.
Synthesis step of the present invention is: at first pass through the positively charged ion ring-opening reaction Yu the substance reaction of Han oxazoline ring on the side group of fluorenes, connect poly-ethylamine side chain, will contain the fluorenes of poly-ethylamine side chain and the luminescence polymer of other fragrant heterocycle polymerization growth conjugated structures by linked reaction again.
Major advantage of the present invention is:
1, institute's synthetic polymer dissolution degree is good, in water and most of organic solvent such as ethanol, acetone good solubleness is arranged all.
2, institute's synthetic polymer thermostable is good, and second-order transition temperature surpasses 120 ℃, and initial decomposition temperature is more than 430 ℃.
3, side chain adopts carbocation to open the phosphine-oxazoline prepared in reaction on the fluorenes, and reaction is simple, and price is low, the productive rate height.
4, all polymkeric substance are blue electroluminescent material.
9 by fluorenes form water-soluble replacement side chain with carbocation route Shi oxazoline ring-opening polymerization and hydrolysis, and the substituted fluorene that last polymerization is generated obtains water-soluble blue light display material.Product of the present invention has outstanding luminescent properties and water-soluble, and side group is very little to the influence of main chain luminescent properties, its thermostability, and charge transport properties is good, can be used as ink jet printing blue light primary colours ink and organic light emission biosensor and uses.
Embodiment
Further introduce the present invention and synthesis mode thereof below by embodiment.
1, the fluorenes of the poly-ethylamine side chain of band is pulsating synthetic
Y＞1 wherein, R represents alkyl
The pulsating synthetic route of fluorenes of the poly-ethylamine side chain of band is seen shown in the formula (I).
Concrete steps are: dibromo fluorenone (1) is dissolved in anhydrous isopropyl alcohol, and the sodium borohydride that adds the twice amount was in 60-90 ℃ of reaction 24 hours.Product gets product (2) with ether and water extraction, anhydrous magnesium sulfate drying filtration back evaporating solvent; Product (2) and excessive phosphorus tribromide are dissolved in dry DMF, stir down in 80-110 ℃ under nitrogen protection, reacted 4-6 hour, react the after product that finishes ether and water extraction, anhydrous magnesium sulfate drying filters the back evaporating solvent and gets product (3); Product (3) is dissolved in dry DMF with excessive Jia oxazolin, and nitrogen protection is stirred and is warming up to 90-110 ℃, reacts 24-48 hour, add ether and water extraction product after reaction finishes, tell ether layer, add anhydrous magnesium sulfate drying, filter, evaporating solvent gets product (4); Product (4) is added excessive aqueous sodium hydroxide solution, be heated with stirring to 70-90 ℃, reacted 24-48 hour.Add ether after reaction finishes and extract repeatedly, add sodium bicarbonate, filter, add anhydrous magnesium sulfate drying to remove acid excessive in the diethyl ether solution, filtration, evaporating solvent is crossed post with ethyl acetate and is got product (5); Product (5) and potassium ethylate are dissolved in dehydrated alcohol, under nitrogen protection, are heated to 70-90 ℃, inject bromo alkane; reacted 4-12 hour, and added ether after reaction finishes and extract repeatedly, add anhydrous magnesium sulfate drying; filter, evaporating solvent is crossed post with ethyl acetate and is got product (6).Product is a crystalline solid, good water solubility, and infrared spectra is at 3400cm
-1Near strong amido absorption peak is arranged.
2, fragrant heterocycle Ar activity unit is pulsating synthetic
The pulsating synthetic route of virtue heterocycle Ar activity unit is seen shown in the formula (II).Concrete steps are:
1) activity unit of thiophene and derivative thereof is pulsating synthetic
Thiophene and derivatives class (7a) material thereof are dissolved in anhydrous n-hexane, be cooled to-78 ℃ with dry ice, inject the n-Butyl Lithium of 2 times of amounts, stir, keep-78 ℃ 1 hour, form aryl dilithium salt 8, product does not separate, and then adds the TEMED (TMEDA) of 2 times of amounts, forms the title complex of product 8, still do not separate product, continue to add the trimethyltin chloride of 2 times of amounts, temperature slowly is raised to room temperature, gets the thiophene-based active part 9 of Fluorescence Properties of Pyrene Derivatives, product does not separate, and adds together when treating polyreaction.
2) activity unit of furans and derivative thereof is pulsating synthetic
Furans and derivatives class (7b) material thereof are dissolved in anhydrous n-hexane, be cooled to-78 ℃ with dry ice, inject the n-Butyl Lithium of 2 times of amounts, stir, keep-78 ℃ 1 hour, form aryl dilithium salt 8, product does not separate, and then adds the TEMED (TMEDA) of 2 times of amounts, forms the title complex of product 8, still do not separate product, continue to add the trimethyltin chloride of 2 times of amounts, temperature slowly is raised to room temperature, gets the furans active part 9 of Fluorescence Properties of Pyrene Derivatives, product does not separate, and adds together when treating polyreaction.
3) activity unit of benzene and derivative thereof is pulsating synthetic
Benzene and derivatives class (7c) material thereof are dissolved in anhydrous n-hexane, be cooled to-78 ℃ with dry ice, inject the n-Butyl Lithium of 2 times of amounts, stir, keep-78 ℃ 1 hour, form aryl dilithium salt 8, product does not separate, and then adds the TEMED (TMEDA) of 2 times of amounts, forms the title complex of product 8, still do not separate product, continue to add the trimethyltin chloride of 2 times of amounts, temperature slowly is raised to room temperature, gets the benzene class active part 9 of Fluorescence Properties of Pyrene Derivatives, product does not separate, and adds together when treating polyreaction.
3, the fluorenes and the pulsating polymerization of fragrant heterocycle Ar activity unit of the poly-ethylamine side chain of band
The fluorenes and the pulsating polymerization route of fragrant heterocycle Ar activity unit of the poly-ethylamine side chain of band are seen shown in the formula (III).
Concrete steps are: will wait the material 6 of amount and the active fragrant heterocycle 9 of not separated tin trimethyl to be dissolved in the exsiccant tetrahydrofuran (THF) approximately under argon shield; the dichloro triphenyl phosphorus palladium catalyst that adds about 1-5% amount again; be warming up to 70-90 ℃, reacted 24-48 hour.After reaction finishes, in apparatus,Soxhlet's, wash out wherein small molecules and oligomer, perhaps isolate small-molecule substance, use organic solvent stripping polymkeric substance wherein again, obtain polymkeric substance 10 with short silicagel column with semi-permeable membranes.
The character of polymkeric substance:
Polymkeric substance is canescence or light yellow solid.Polymeric film sends strong blue light or blue green light under ultra violet lamp; Weight-average molecular weight is 15, and 000-100 is between 000; Second-order transition temperature surpasses 120 ℃, and initial decomposition temperature is more than 430 ℃, and thermotolerance is good.Polymkeric substance water-soluble good, and along with poly-ethylamine side chain lengths increase, the solubleness in water increases gradually.Can satisfy the concentration requirement of spray ink Printing and biosensor aspect, be promising blue light material.
| The diethylamide unit number | 2 | 3 | 4 | 5 | 6 |
| Solubleness in the water (wt%) | 0.5 | 0.8 | 1.2 | 1.5 | 2 |
The fluorenes segment synthetic route of the poly-ethylamine side chain of band, y＞1 wherein, R represents alkyl
Virtue heterocycle Ar activity unit is pulsating synthetic, and wherein TMEDA is a TEMED
The fluorenes and the pulsating polymerization of fragrant heterocycle Z activity unit of the poly-ethylamine side chain of band
Claims (4)
1, a kind of fluorene water soluble conjugate polymer that contains polyethyene diamine side chain is characterized in that general structure is as follows:
Wherein R is an alkyl, and Ar is a kind of of following heteroaromatic compounds: benzene, anthracene, thiophene, pyrroles, furans, carbazole, y＞1.
2, a kind of preparation method of fluorene water soluble conjugate polymer as claimed in claim 1, it is characterized in that at first using dibromo fluorenone Yu the substance reaction of Han oxazoline ring, make the fluorenes segment that contains poly-ethylamine side chain, will contain the fluorenes segment of poly-ethylamine side chain and the luminescence polymer of described heteroaromatic compounds polymerization growth conjugated structure by linked reaction again.
3, fluorene water soluble conjugate polymer as claimed in claim 1 is as the application of blue electroluminescent material in organic flat-panel display device.
4, the fluorene water soluble conjugate polymer that contains as claimed in claim 1 causes or the application of embedded photoluminescent material in biosensor as blue electricity.
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| CNB2005100244346A CN1305926C (en) | 2005-03-17 | 2005-03-17 | Fluorene water soluble conjugate polymer containing polyethyene diamine side chain and its use |
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| CNB2005100244346A CN1305926C (en) | 2005-03-17 | 2005-03-17 | Fluorene water soluble conjugate polymer containing polyethyene diamine side chain and its use |
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| CN1305926C true CN1305926C (en) | 2007-03-21 |
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| CN101284903B (en) * | 2007-11-02 | 2013-04-24 | 北京同创海诚科技发展有限公司 | Fluorescent conjugated polymer with sensory function for nitro compound and applications |
| CN108473505B (en) | 2016-03-28 | 2019-11-05 | 阿特生物探索公司 | Polyfluorene simultaneously [4,5-cde] oxepin conjugate and its purposes in analyte detection method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1337987A (en) * | 1999-02-04 | 2002-02-27 | 陶氏化学公司 | Fluorene copolymers and devices made therefrom |
| US20030091859A1 (en) * | 2001-05-22 | 2003-05-15 | Hyun-Nam Cho | Fluorene compounds containing various functional groups, polymers thereof and el element using the same |
| EP1323762A2 (en) * | 2001-12-19 | 2003-07-02 | Sumitomo Chemical Company, Limited | Copolymer or polymer composition and polymer light-emitting device |
| CN1438254A (en) * | 2003-03-10 | 2003-08-27 | 四川大学 | Polyalkyl-fluorene conjugated polymer and use |
| CN1526702A (en) * | 2003-03-07 | 2004-09-08 | 中国科学院化学研究所 | Fluorene-naphthalene imide derivative compound and its application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1337987A (en) * | 1999-02-04 | 2002-02-27 | 陶氏化学公司 | Fluorene copolymers and devices made therefrom |
| US20030091859A1 (en) * | 2001-05-22 | 2003-05-15 | Hyun-Nam Cho | Fluorene compounds containing various functional groups, polymers thereof and el element using the same |
| EP1323762A2 (en) * | 2001-12-19 | 2003-07-02 | Sumitomo Chemical Company, Limited | Copolymer or polymer composition and polymer light-emitting device |
| CN1526702A (en) * | 2003-03-07 | 2004-09-08 | 中国科学院化学研究所 | Fluorene-naphthalene imide derivative compound and its application |
| CN1438254A (en) * | 2003-03-10 | 2003-08-27 | 四川大学 | Polyalkyl-fluorene conjugated polymer and use |
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