CN1683429A - Fluorene Water-Soluble Conjugated Polymer Containing Polyethylenediamine Side Chain and Its Application - Google Patents
Fluorene Water-Soluble Conjugated Polymer Containing Polyethylenediamine Side Chain and Its Application Download PDFInfo
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- CN1683429A CN1683429A CN 200510024434 CN200510024434A CN1683429A CN 1683429 A CN1683429 A CN 1683429A CN 200510024434 CN200510024434 CN 200510024434 CN 200510024434 A CN200510024434 A CN 200510024434A CN 1683429 A CN1683429 A CN 1683429A
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- fluorene
- light emitting
- water
- conjugated polymer
- side chain
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229920000547 conjugated polymer Polymers 0.000 title claims description 12
- 239000000463 material Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- 229930192474 thiophene Natural products 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 150000002220 fluorenes Chemical class 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- -1 polyethylene Polymers 0.000 abstract description 6
- 239000012769 display material Substances 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 125000004427 diamine group Chemical group 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-M disodium;4-[4-[[4-(4-sulfoanilino)phenyl]-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzenesulfonate Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-M 0.000 abstract 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 125000005968 oxazolinyl group Chemical group 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 150000002240 furans Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 150000003220 pyrenes Chemical class 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003809 water extraction Methods 0.000 description 3
- PVPORFNQRIYQRR-UHFFFAOYSA-N 2,3-dibromofluoren-1-one Chemical compound C1=CC=C2C3=CC(Br)=C(Br)C(=O)C3=CC2=C1 PVPORFNQRIYQRR-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical group C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NHFAABIHBNXKDT-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;phosphane Chemical compound P.C1CN=CO1 NHFAABIHBNXKDT-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides water soluble conjugate fluorene polymer containing polyethylene diamine side chain as blue light material and its application in ink jet printer and organic light emitting biosensor, and belongs to the field of organic polymer semiconductor light emitting material. Fluorene has its site-9 and oxazolinyl are ring-opening polymerized in carbon cation path, hydrolyzed to form water soluble substitution side chain, and finally polymerized to form substituted fluorene and obtain water soluble blue light emitting display material. The product of the present invention has excellent light emitting performance, high water solubility, few influence of the side radical on the light emitting performance of the main chain, good heat stability and excellent charge transferring performance, and may be used as blue light emitting ink for jet printing and organic light emitting 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
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 (5)
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| Application Number | Priority Date | Filing Date | Title |
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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 CN1305926C (en) | 2007-03-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US9896538B2 (en) | 2016-03-28 | 2018-02-20 | Aat Bioquest, Inc. | Polyfluoreno[4,5-cde]oxepine polymers and conjugates thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1155096B1 (en) * | 1999-02-04 | 2005-03-09 | Dow Global Technologies Inc. | Fluorene copolymers and devices made therefrom |
| KR100424073B1 (en) * | 2001-05-22 | 2004-03-22 | 한국과학기술연구원 | Fluorene compounds containing various functional groups, their polymers, and el element using the same |
| SG125077A1 (en) * | 2001-12-19 | 2006-09-29 | Sumitomo Chemical Co | Copolymer, polymer composition and polymer light-emitting device |
| CN1212318C (en) * | 2003-03-07 | 2005-07-27 | 中国科学院化学研究所 | Fluorene-naphthalene diimide derivative compound and application |
| CN1216921C (en) * | 2003-03-10 | 2005-08-31 | 四川大学 | Polyalkyl-fluorene conjugated polymer and use |
-
2005
- 2005-03-17 CN CNB2005100244346A patent/CN1305926C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US9896538B2 (en) | 2016-03-28 | 2018-02-20 | Aat Bioquest, Inc. | Polyfluoreno[4,5-cde]oxepine polymers and conjugates thereof |
| US10316136B2 (en) | 2016-03-28 | 2019-06-11 | Aat Bioquest, Inc. | Polyfluoreno[4,5-cde]oxepine conjugates and their use in methods of analyte detection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1305926C (en) | 2007-03-21 |
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