CN101405244B - Optoelectronic devices with multilayered structures - Google Patents
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- CN101405244B CN101405244B CN200780010041.7A CN200780010041A CN101405244B CN 101405244 B CN101405244 B CN 101405244B CN 200780010041 A CN200780010041 A CN 200780010041A CN 101405244 B CN101405244 B CN 101405244B
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Abstract
Optoelectronic devices include a polymer composition derived from reaction between a hydrosiloxane and a polyfluorene comprising structural units of formula (I) wherein R<1>and R<2> are independently alkyl, substituted alkyl, alkenyl, alkynyl, substituted alkenyl, substituted alkynyl, alkyloxy, substituted alkoxy, alkenoxy, alkynoxy, substituted alkenoxy, substituted alkynoxy, or a combination thereof; Ar<1> and Ar<2> are independently aryl or substituted aryl; m and n are independently 0 or 1; and at least one of R<1> and R<2> is alkenyl, alkynyl, substituted alkenyl, or substituted alkynyl.
Description
To the cross reference of related application
The application's right and wrong interim and require on March 22nd, 2006 submit to U.S. Provisional Application series number 60/784,750 right of priority, it is incorporated herein by this reference, and to relevant with its U.S. Patent application that is called " OPTOELECTRONIC DEVICES WITH MULTILAYEREDSTRUCTURES (having the opto-electronic device of multilayered structure) " of submitting in same date, it is incorporated herein by this reference.
Background
Organic Light Emitting Diode (OLED) is the sub-device of Heterolamellar photovoltaic.The current commercial use of OLED is mainly used for display applications and is made up of the small molecules as active material.The manufacture of small molecules base OLED seriously relies on vapour deposition process.Next large application space of OLED is general illumination.In order to meet large volume/low cost requirement of general illumination, low cost fabrication that need to be as roll-to-roll (roll-to-roll), news grade print process.This roll-to-roll manufacture is used solvent based methods, and therefore small molecules is changed into good film-forming polymer.Use the method for solvent-based deposition step in succession to there are potential problems, can remove the first polymer layer for the solvent that spreads the second layer.
Initial polymer-based carbon OLED is simple three layer devices, only limits to negative electrode, anode and emission layer, thereby the problem that polymkeric substance is removed by solvent is minimized.Certainly need to improve device performance, in OLED, must need thus the layer adding.
The demand of extra play is taken back again to the problem that below layer is removed; Wherein all layers are all solvent deposition.Use two elementary tactics to realize the solvent-based deposition of multiple polymer layers.Can design a kind of device, wherein by not removing the solvent deposition subsequent layer of below layer.Prototype example is, wherein by poly-(3 of poly-(styrene sulfonate) doping, 4-Ethylenedioxy Thiophene) (PEDOT:PSS) form hole injection layer from water, spread, follow-up luminescent layer, as replacing poly-fluorenes, 9,9-bis-deposits from the solvent of dimethylbenzene and so on; PDOT:PSS can not removed by dimethylbenzene.The second strategy that preparation has an OLED of the multilayer by solvent deposition be make each layer soluble before spreading lower one deck.The second strategy can be divided into two types.Solvent-soluble layer can with crosslinkable monomers, as acrylate combination.Required layer and monomer bear subsequently and make monomer crosslinked condition, are generally UV radiation.The radiation result of polymer layer and acrylate monomer is to form to interpenetrate layer, and this makes the layer of solvent deposition soluble.The insoluble better mode of layer that makes solvent deposition is that the synthetic selected layer of customization is so that it contains crosslinkable site; Do not need additional monomer.After the layer deposition of solvent deposition, heat or light make this layer soluble.
But, still need to make the layer of solvent deposition soluble to carry out the method and composition of follow-up deposition step.
Describe in detail
On the one hand, the present invention relates to the mixing organic-inorganic polymer composition that generated by the reaction between the poly-fluorenes of the structural unit of hydrogen siloxane and contained I
Wherein
R
1and R
2be alkyl, substituted alkyl, alkenyl, alkynyl, substituted alkenyl base, substituted alkynyl, alkoxyl group, substituted alkoxy, alkenyloxy, alkynyloxy group, substituted alkenyl oxygen base independently, replace alkynyloxy group or its combination;
Ar
1and Ar
2be aryl or substituted aryl independently;
M and n are 0 or 1 independently; And
R
1and R
2at least one be alkenyl, alkynyl, substituted alkenyl base or substituted alkynyl.
In specific embodiments, R
2can be C
3-20alkenyl or C
3-20alkynyl or C
3-8alkenyl or C
4-8alkynyl, or R
1can be C
3-C
8alkyl.In other embodiments, R
1and R
2can be C
3-20alkynyl, or R
1and R
2all C
4-8alkynyl.For example, polymer composition can comprise the poly-fluorenes that contains one or more following structural units:
On the other hand, the present invention relates to compound or the monomer of structural unit that can production I.This monomer has following formula
with
Wherein
R
1aand R
2abe C independently
10-20alkenyl, C
3-20alkynyl, C
3-20substituted alkenyl base, C
3-20substituted alkynyl or its combination; R
1balkyl, substituted alkyl or its combination;
And
X
1and X
2be halogen, sulphonate (sulfonate), boric acid or boric acid ester independently.
Especially, R
1aand R
2acan be C
3-20alkynyl or C
4-8alkynyl.
Exemplary monomer of the present invention comprises
With
R
2apreferred substituents comprise C
3-20alkenyl, C
3-20alkynyl, C
3-8alkenyl and C
4-8alkynyl.R
1bpreferred substituents be C
3-8alkyl.
On the other hand, the present invention relates to the polymkeric substance of the structural unit that comprises following formula
and/or
Wherein R
1a, R
1band R
2adefinition as above.
Illustrative polymers of the present invention is drawn together the structural unit of following formula
and/or
Be used in poly-fluorenes in polymer composition of the present invention and can also comprise for example following structural unit except those of formula I: unsubstituted fluorenyl unit and/or the fluorenyl unit being replaced as alkyl by saturated group.
Other structural unit can be derived from as U.S. Patent No. 6,900, the conjugated compound described in 285.Especially, can use the structural unit derived from tertiary aromatic amine.Amount derived from the structural unit of unsaturated monomer is about 0.05 % by mole to about 50 % by mole, particularly about 1 % by mole to about 25 % by mole, is more particularly about 1 % by mole to about 10 % by mole.
Poly-fluorenes can, by the method preparation of the poly-fluorenes of manufacture known in the art, comprise suitable dihalide and hypoboric acid ester/diborated Suzuki coupling and Yamamoto coupling.United States Patent(USP) Nos. 5,708,130,6,169,163,6,512,083 and 6,900285 have described the synthetic of the polymkeric substance that contains fluorenes subunit.
Can use any siloxanes being replaced by least two hydrogen atoms.In many embodiments, there is the hydrogen substituting group that exceedes two.Especially, hydrogen siloxane can comprise the structural unit of following formula
Wherein
R
3, R
4, R
5, R
6, R
7, R
8, R
9and R
10be H, C independently
1-10alkyl, phenyl or
P and q are 0 or 1 to 100 integer independently; And
R
3, R
4, R
5, R
6, R
7, R
8, R
9and R
10in at least two be H.
In various embodiments, n is 1 to 20 integer, or R
3and R
7and/or R
5h, or R
9it is phenyl; Or R
4, R
6, R
8and R
10it is methyl.In polymer composition of the present invention, available exemplary hydrogen siloxane comprises methyl hydrogen siloxane-phenyl methyl silicone copolymers, the polydimethylsiloxane of hydride end-blocking, methyl hydrogen siloxane-dimethylsiloxane copolymer, polymethyl hydrogen siloxane, poly-ethyl hydrogen siloxane, polyphenylene-(dimethyl hydrogen siloxy-) siloxanes of hydride end-blocking, methyl hydrogen siloxane-phenyl methyl silicone copolymers of hydride end-blocking, methyl hydrogen siloxane-octyl group methylsiloxane multipolymer of hydride end-blocking, and hydride Q resin.
If needed, in polymer composition of the present invention, except poly-fluorenes and hydrogen siloxane, can also use vinylsiloxane.In polymer composition of the present invention, available exemplary vinylsiloxane comprises the polydimethylsiloxane of ethenyl blocking, diphenyl siloxane-the dimethyl siloxane of ethenyl blocking, the polyphenyl methyl siloxane of ethenyl blocking, trifluoro propyl methylsiloxane-the dimethyl siloxane of ethenyl blocking, di-ethyl siloxane-the dimethyl siloxane of ethenyl blocking, vinyl methylsiloxane-the dimethylsiloxane copolymer of trimethoxy siloxy-end-blocking, vinyl methylsiloxane-the dimethylsiloxane copolymer of ethenyl blocking, vinyl Q resin and vinyl T-structural polymer.
The molecular weight of hydrogen siloxane and vinylsiloxane is not crucial, and is typically about 200 to about 200,000 dalton.The total amount of siloxanes used is about 1-50 % by weight of poly-fluorenes, and depend on hydride in hydrogen siloxane % by mole, in polymkeric substance derived from the structural unit of unsaturated monomer % by mole, the amount of polymkeric substance in composition, and using vinylsiloxane in the situation that, depend on vinylsiloxane medium vinyl % by mole and the amount of composition medium vinyl siloxanes.This stoichiometric quantity is for being less than about 1 moles of hydrogen compound than about 1 mole of total degree of unsaturation, comprise in polymkeric substance and any vinylsiloxane in degree of unsaturation, to about 4.5 moles of hydrogen compounds than about 1 mole of degree of unsaturation, particularly about 1.3 moles of hydrogen compounds than about 1 mole unsaturated.The catalyzer of hydrosilylation reaction comprises platinum complex.
Another aspect, the present invention relates to comprise the opto-electronic device of polymer composition of the present invention as at least a portion of organic field luminescence layer.
Opto-electronic device as an example of organic luminescent device example comprises multilayer conventionally, and it comprises anode layer and corresponding cathode layer and the organic field luminescence layer between described anode and described negative electrode in the simplest situation.In the time striding across electrode and apply bias voltage, negative electrode is electronic injection electroluminescent layer, simultaneously from anode from electroluminescent layer except de-electronation (or from anode by " hole " " injection " electroluminescent layer).Due to hole and electronics in electroluminescent layer in conjunction with form singlet state or triplet exciton occur luminous, due to singlet state exciton by attenuation by energy transfer in environment, occur luminous.Opto-electronic device of the present invention comprises the organic field luminescence layer being made up of polymer composition of the present invention.
Except other parts that may exist in the external organic luminescent device of anode, negative electrode and luminescent material comprise hole injection layer, electronics injecting layer and electron transfer layer.Electron transfer layer does not need to contact with negative electrode, and electron transfer layer is not that effective hole transport body is also therefore for hindering hole to cathodic migration conventionally.In the organic light-emitting device working process that comprises electron transfer layer, the most of electric charge carrier (being hole and electronics) existing in electron transfer layer is electronics, and can occur luminous by the hole that exists in electron transfer layer and the restructuring of electronics.The optional feature that may exist in organic luminescent device comprises hole transmission layer, hole transport emission layer and electric transmission emission layer.
Organic field luminescence layer is electronics and the hole of containing remarkable concentration in the time of work in organic luminescent device and provides exciton to form the layer of site and luminescence sites.Hole injection layer is the layer contacting with anode, and it promotes hole to inject the internal layer of OLED from anode; Electronics injecting layer is the layer contacting with negative electrode, and it promotes that electronics injects OLED from negative electrode; Electron transfer layer is to be conducive to the layer of electronics from negative electrode guiding charge recombination site.Electron transfer layer does not need to contact with negative electrode and electron transfer layer is not that effective hole transport body is also therefore for hindering hole to cathodic migration conventionally.In the organic light-emitting device working process that comprises electron transfer layer, the most of electric charge carrier (being hole and electronics) existing in electron transfer layer is electronics, and occurs luminous by the hole of existence in electron transfer layer and the restructuring of electronics.Hole transmission layer be in the time that OLED works, be conducive to hole from anode guiding charge recombination site and do not need contact with anode layer.Hole transport emission layer is such layer---its in the time that OLED works, be conducive to by hole lead charge recombination site and wherein most of electric charge carrier be hole and wherein transmitting not only by with residual electron recombination also by occurring from other local charge recombination zone-transfer energy of device.Electric transmission emission layer is such layer---its in the time that OLED works, be conducive to by electronic guidance charge recombination site and wherein most of electric charge carrier be electronics and wherein transmitting not only by with residual hole recombination also by occurring from other local charge recombination zone-transfer energy of device.
The material that is suitable as anode comprises the material of the volume conductance with at least about 100 ohms per squares (ohms per square) that record by four-point probe technology.Tin indium oxide (ITO) is commonly used for anode, because therefore its basic light-permeable is also conducive to the effusion of the light sending from electroactive organic layer.Other material that can be used as anode layer comprises stannic oxide, Indium sesquioxide, zinc oxide, indium zinc oxide, zinc indium tin oxide, weisspiessglanz and composition thereof.
The material that is suitable as negative electrode comprises the zero-valent metal that charge carriers (electronics) can be injected to OLED internal layer.The various zero-valent metals that are suitable as negative electrode 20 comprise K, Li, Na, Cs, Mg, Ca, Sr, Ba, Al, Ag, Au, In, Sn, Zn, Zr, Sc, Y, lanthanon, its alloy and composition thereof.The alloy material that is suitable as cathode layer comprises Ag-Mg, Al-Li, In-Mg, Al-Ca and Al-Au alloy.Also can in negative electrode, use layered non-alloy structures, the thin layer of the metal fluoride of the metal of for example calcium and so on or LiF and so on, coated with aluminium or silver and so on zero-valent metal compared with thick-layer.Especially, negative electrode can be by singly planting zero-valent metal, and especially aluminum metal forms.
Be suitable for use in material in hole injection layer and comprise 3,4-Ethylenedioxy Thiophene (PEDOT) and can be with
trade(brand)name is purchased from H.C.Stark, the adulterant of the PEDOT of Inc. and PSS (PSS), and can be purchased from the polymkeric substance based on thieno-[3,4b] thiophene (TT) monomer of Air Products Corporation.
The material being suitable for use in hole transmission layer comprises 1, two ((two-4-tolyl amino) phenyl) hexanaphthenes of 1-, N, N '-bis-(4-aminomethyl phenyl)-N, N '-bis-(4-ethylphenyl)-(1, 1 '-(3, 3 '-dimethyl) xenyl)-4, 4 '-diamines, four-(3-aminomethyl phenyl)-N, N, N ', N '-2, 5-phenylenediamine, phenyl-4-N, N-diphenyl amino vinylbenzene, p-(diethylamino) phenyl aldehyde diphenyl hydrazone, triphenylamine, 1-phenyl-3-(p-(diethylamino) styryl)-5-(p-(diethylamino) phenyl) pyrazoline, 1, 2-trans-bis-(9H-carbazole-9-yl) tetramethylene, N, N, N ', N '-tetra-(4-aminomethyl phenyl)-(1, 1 '-xenyl)-4, 4 '-diamines, copper phthalocyanine, Polyvinyl carbazole, (phenyl methyl) polysilane, poly-(3,4-Ethylenedioxy Thiophene) (PEDOT), polyaniline, Polyvinyl carbazole, triaryl diamines, tetraphenyl diamines, aromatic uncle amine, hydrazone derivative, carbazole derivative, triazole derivative, imdazole derivatives, there is amino oxadiazole derivative and Polythiophene, as U.S. Patent No. 6, disclosed in 023,371.
The material that is suitable as electron transfer layer comprises poly-(9,9-dioctyl fluorene), three (oxine root closes (quinolato)) aluminium (Alq
3), 2,9-dimethyl-4,7-phenylbenzene-1,1-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline, 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole, 3-(4-xenyl)-4-phenyl-5-(4-tert-butyl-phenyl)-1,2,4-triazole, containing 1,3, the polymkeric substance of 4-oxadiazole, containing the polymkeric substance of 1,3,4-triazole, containing polymkeric substance and the cyano group-PPV of quinoxaline.
The material being suitable for use in luminescent layer comprises electroluminescent polymer, as poly-(9,9-dioctyl fluorene) and multipolymer thereof, as F8-TFB.
Definition
In the present invention, alkyl is intended to comprise straight chain, side chain or cyclic hydrocarbon structures and combination thereof, comprises low-carbon alkyl and high-carbon alkyl.Preferred alkyl is C
20or lower those.Low-carbon alkyl refers to have 1 to 6 carbon atom, the preferably alkyl of 1 to 4 carbon atom, and comprise methyl, ethyl, n-propyl, sec.-propyl and n-, secondary-and the tertiary butyl.High-carbon alkyl refers to have seven or more carbon atoms, the preferably alkyl of 7-20 carbon atom, and comprise n-, the second month in a season-and tertiary heptyl, octyl group and dodecyl.Cycloalkyl is the subset of alkyl and comprises the cyclic hydrocarbon radical with 3 to 8 carbon atoms.The example of cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl and norcamphyl.
Aryl and heteroaryl refer to and contain 0-3 heteroatomic 5-or 6-unit's aromatics or heteroaromatic rings that is selected from nitrogen, oxygen or sulphur; Contain 0-3 heteroatomic dicyclo 9-or 10-unit's aromatics or heteroaromatic rings system that is selected from nitrogen, oxygen or sulphur; Or contain 0-3 and be selected from heteroatomic three ring 13-or 14-unit's aromatics or the heteroaromatic rings system of nitrogen, oxygen or sulphur.Aromatics 6-to 14-unit carbocyclic ring comprises, for example, and benzene, naphthalene, indane, tetraline and fluorenes; And 5-to 10-unit aromatic heterocycle comprises, for example, imidazoles, pyridine, indoles, thiophene, benzopyrone, thiazole, furans, benzoglyoxaline, quinoline, isoquinoline 99.9, quinoxaline, pyrimidine, pyrazine, tetrazolium and pyrazoles.
Aralkyl refers to the alkyl residue being connected in aryl rings.Example is benzyl and styroyl.Heteroaralkyl refers to the alkyl residue being connected on heteroaryl ring.Example comprises pyridylmethyl and pyrimidinylethyl.Alkaryl refers to the aromatic yl residue that is connecting one or more alkyl on it.Example is tolyl and mesityl.
Alkoxyl group refers to by oxygen and is connected to the group that has 1 to 8 carbon atom with straight chain, side chain or cyclic configuration on precursor structure.Example comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, ring propoxy-and cyclohexyloxy.Low-carbon alkoxy refers to the group that contains 1 to 4 carbon.Alkenyloxy, alkenyl oxy, alkynyloxy group or alkynyloxy base refer to and comprise at least one two key (for alkenyloxy) or triple bonds (for alkynyloxy group) and be connected to the group that has 2 to 20 carbon atoms with straight chain, side chain or cyclic configuration on precursor structure by oxygen.Example comprises vinyloxy group, propenyloxy group (allyloxy), hexene oxygen base, penta alkynyloxy group and tetrahydrobenzene oxygen base.
Acyl group refers to group and the combination thereof that can be connected to saturated, the unsaturated and aromatics that has 1 to 8 carbon atom with straight chain, side chain, cyclic configuration on precursor structure by carbonyl official.One or more carbon on acyl residue can be substituted by nitrogen, oxygen or sulphur, need only with the tie point of parent still on carbonyl.Example comprises ethanoyl, benzoyl, propionyl, isobutyryl, tert-butoxycarbonyl and benzyloxycarbonyl.Low carbonic acyl radical refers to the group that contains 1 to 4 carbon.
Heterocycle refers to that one or two carbon is wherein by heteroatoms cycloalkyl or aromatic yl residue as alternative in oxygen, nitrogen or sulphur.The example of heterocycle within the scope of the invention of falling comprises tetramethyleneimine, pyrazoles, pyrroles, indoles, quinoline, isoquinoline 99.9, tetrahydroisoquinoline, cumarone, benzo dioxane, benzo dioxole (in the time occurring as substituting group, being often known as methylenedioxyphenyl base), tetrazolium, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furans, oxazole, oxazoline, isoxazole, dioxane and tetrahydrofuran (THF).
" replacement " refers to residue, include but not limited to, alkyl, alkaryl, aryl, aralkyl and heteroaryl, wherein maximum three H atoms of residue are by low-carbon alkyl, substituted alkyl, aryl, substituted aryl, alkylhalide group, alkoxyl group, carbonyl, carboxyl, carboxylic alkoxyl group, carboxamido, acyloxy, amidino groups, nitro, halogen, hydroxyl, OCH (COOH)
2, cyano group, primary amino, secondary amino group, acyl amino, alkyl sulfenyl, sulfoxide, sulfone, phenyl, benzyl, phenoxy group, benzyloxy, heteroaryl or heteroaryloxy substitute.
Alkylhalide group refers to the alkyl residue that wherein one or more H atoms are substituted by halogen atom; Term alkylhalide group comprises perhaloalkyl radical.The example of alkylhalide group within the scope of the invention of falling comprises CH
2f, CHF
2and CF
3.
Chemical compound lot as herein described can contain one or more asymmetric centers and can produce thus enantiomorph, diastereomer and can with regard to absolute stereo chemistry, be designated as (R)-or (S)-other stereoisomeric forms in any ratio.The present invention is intended to the isomer and their racemize and the optical purity form that comprise that all these are possible.Optically-active (R)-can use chiral synthon or chiral reagent preparation with (S)-isomer, or use conventional art to split.In the time that compound as herein described contains olefinic double bond or other how much asymmetric centers, unless otherwise specified, this compound is intended to comprise E and Z geometrical isomer.Equally also be intended to comprise all tautomeric forms.
Oxa alkyl refers to the alkyl residue that wherein one or more carbon have been substituted by oxygen.It is connected on precursor structure by alkyl residue.Example comprises methoxy propoxy, 3,6,9-trioxa decyl and analogue.Term oxa alkyl as understood in this area, its refer to wherein oxygen through singly bound to its adjacent atom the compound of (formation ehter bond); It does not refer to the two bonded oxygens as found in carbonyl.Similarly, thia alkyl and azepine alkyl refer to that wherein one or more carbon are respectively by sulphur or the alternative alkyl residue of nitrogen.Example comprises ethylamino ethyl and methyl sulfo-propyl group.
Embodiment
Universal method
In order to prepare the poly-fluorene copolymer with crosslinkable groups, between two factors (factors), reach balance.One method is preparation so-called F6-F or F8-F multipolymer, and wherein F6 or F8 are that dihexyl or dioctyl fluorenyl unit and F are that 9,9-does not replace fluorenyl unit.Prepare required multipolymer by 2,7-dibromo and 2,7-hypoboric acid ester precursor mixture via the Suzuki coupling of Pd catalysis, this preparation is elevated to generation lower molecular weight and lower yield multipolymer more than about 50% along with not replacing the ratio of F unit.
Another strategy used be may time make suitable 9, the copolymerization of 9-substituted monomer.In some cases, exceed 5-10% in the ratio of the fluorenes unit of alkynyl substituted, the monomer of alkynyl substituted has suppressed the Suzuki reaction of Pd catalysis.
(F6)
3.0(F)
1.0copolymer precursor via Suzuki coupling method preparation and subsequently with the excessive bromo-valerylene of hexyl bromide/1-or the mixture reaction of hexyl bromide/allyl bromide 98 mixture.R-Br is desirable with respect to 9-excess hydrogen for obtaining good conversion rate.The use of the alkyl-bromine mixing with unsaturated bromide (allyl group or alkynes) is created in the final product (flow process 1) on 9-position with saturated/unsaturated unit distribution.
Flow process 1
Embodiment 1:(F6)
3.0(F)
1.0synthetic
F6
b2and F
br2purify available from Aldrich and by recrystallization from acetonitrile.F6
b2prepared by the two boric acid of F6-and ethylene glycol.Carry out purified product by recrystallization from acetonitrile.F6
b2(2.5 grams, 4.98 mmoles), F
br2(0.81 gram, 2.5 mmoles) and F6
br2(1.23 grams, 2.5 mmoles) and toluene (75 milliliters) merge under argon gas, and subsequently under agitation with K
2cO
3(2.75 grams, 20 mmoles) and water (10 milliliters) merge.After about 10 minutes, add by Pd (acetate)
2the catalyst ligand mixture that (0.030 gram, 0.13 mmole) and three-p-methylphenyl phosphine (0.14 gram, 0.46 mmole) form.This mixture is refluxed and spent the night, and then after cooling, the plunger that content is consisted of celite, drierite ze and 3-(diethylidene triamino) the propyl group functional silicon dioxide by roughly equal umber filters.Remove in a vacuum volatile matter, then residue is dissolved in to toluene.Use methanol extraction solid; Insoluble toluene fraction is dissolved in to CH
2cl
2in and be deposited in methyl alcohol.
| Gram | Mn | Mw | |
| Toluene is solvable | 0.69 | 15,500 | 55,300 |
| CH 2Cl 2Solvable | 0.40 | 16,900 | 68,000 |
Embodiment 2:(F6)
3.0(FR1R2)
1.0synthetic, R1=allyl group, R2=hexyl, R1 mole number=R2
By (F6)
3.0(F)
1.0(0.15 gram, 0.13 mmole) and hexyl bromide (0.21 gram, 1.27 mmoles) and allyl bromide 98 (0.16 gram, 1.32 mmoles) are at toluene (10 milliliters), Bu
4in NBr (0.01 gram) and 50%NaOH (aqueous solution, 10 milliliters), merge.Content is refluxed 3 days.Remove water layer by volumetric pipette, then top toluene layer is carried out to twice 10 ml waters extractions, then toluene solvend is poured into methyl alcohol to obtain solid, by its filtration and by methanol wash; Obtain 0.080 gram.
1h NMR shows (F6)
3.0(F)
1.0middle 9-hydrogen is consumed and exists owing to allylic peak.
Embodiment 3:(F6)
3.0(FR1R2)
1.0synthetic, R1=allyl group, R2=hexyl, R1 mole number=2R2
By (F6)
3.0(F)
1.0(0.1 gram, 0.086 mmole) merge in toluene (10 milliliters) with hexyl bromide (0.19 gram, 0.0012) and allyl bromide 98 (0.069 gram, 0.57 mmole), then add together Bu with 50%NaOH (aqueous solution, 10 milliliters)
4nBr (0.01 gram).Content is refluxed 2 days under argon gas.After cooling, by organic layer water, then HCl (aqueous solution) and water extraction.Pour toluene soluble layer into methyl alcohol to obtain throw out, it is dry in a vacuum, 0.11 gram.
Embodiment 4:(F6)
3.0(FR1R2)
1.0synthetic, R1=pentynyl, R2=hexyl
By (F6)
3.0(F)
1.0(0.24 gram, 0.2 mmole) and hexyl bromide (0.33 gram, 2.0 mmoles) and the bromo-valerylene of 1-(0.29 gram, 1.99 mmoles) are at toluene (10 milliliters), Bu
4in NBr (0.01 gram) and 50%NaOH (aqueous solution, 10 milliliters), merge.Content is refluxed 3 days.Remove water layer by volumetric pipette, then top toluene layer is carried out to twice 10 ml waters extractions, then toluene solvend is poured into methyl alcohol to obtain solid, by its filtration and by methanol wash; Obtain 0.010 gram.
1h NMR shows that 9-H resonance disappears.
Embodiment 5: by the insoluble layer forming by dimethylsilane oxygen base-methyl hydrogen-silicone copolymers hydrogenation silylation
Flow process 2
Preparation (F6) in 1 milliliter of dimethylbenzene
3.0(F
r1R2)
1.0liquid storage (10 milligrams), R1=allyl group, R2=hexyl, R1 mole number=2R2.On one inch of slide glass, prepare four samples.For the first sample, liquid storage rotates with 3000rpm on glass.For the second sample, liquid storage is the same as with the first sample rotation on glass.Both all cure 15 minutes at 140 DEG C.Then on the second sample, rotate xylene solvent.Black light analysis clearly shows, compared with the first sample, the polymkeric substance in the second sample is removed.For the third and fourth sample, be added in together with the platinum solution (the Pt-tetramethyl-tetrem thiazolinyl tetrasiloxane complex compound in dimethylbenzene) of 0.15 % by weight of 1 GE Silicones88346 the liquid storage and 2 (about 0.1 gram) GE Silicones 88466 first---the 1:1 multipolymer of two radical siloxane methyl hydrogen siloxanes that in the dimethylbenzene of same amount, contain same amount fluorenes polymer.By rotating solution and cure to prepare the 3rd sample as the first and second samples on slide glass.The 4th sample and the 3rd sample are similar, just after baking step, rotate xylene solvent.Result is presented in table 3.
Table 3:UV-Vis measures
Sample No. optical density (OD) (OD) relative quantum efficiency (QE)
1 0.482 0.91
2 0.18 0.9
3 0.51 0.96
4 0.53 1
Opticmeasurement shows, sample 1,3 and 4 is identical in optical physics; Sample 2 has about 60% loss.Variation between sample 1,3 and 4 may be owing to their physics ununiformity but not the QE or the OD difference that detect.
Embodiment 6:(F8)
0.95f
0.05synthetic
By F6
b2(2.5 grams, 5 mmoles), F6
br2(2.2 grams, 4.5 mmoles) and F
br2(0.16 gram, 0.5 mmole) and toluene (75 milliliters) and Pd (acetate)
2(33 milligrams, 0.15 mmole), tri-o-tolyl phosphine (0.16 gram, 0.53 mmole) merge.This solution is stirred under argon gas, then under agitation add Et
4nOH (20% solution of 18.4 milliliters) and water (18 milliliters) also heat 24 hours.By this solution with water, 10%HCl, water, saturated NaCl and water extraction.C-salt, drierite ze and 3-(diethyl triamino) propyl group functional silicon dioxide for toluene solvend are stirred to subsequent filtration.Remove in a vacuum volatile matter to obtain 4.48 grams of rough polymkeric substance, Mn=12,800, Mw=37,900.By this polymkeric substance with twice of toluene and methyl alcohol redeposition to obtain Mn=11,300 and Mw=28,500 solid.The first MU (methylene unit) of the 9-H proton vs.F8 group of F unit
1h NMR integration shows that the mol ratio of these unit is 4:96.
Embodiment 7: via Yamamoto coupling method synthetic (F8) (F)
At dimethyl formamide (dmf, 25mL), merge the following component (H.Q.Zhang of Yamamoto catalyzer, Thin Solid Films, 477 (2005) 119): (0.7 gram of zinc powder, 11 mmoles), (0.75 gram of triphenylphosphine, 2.86 mmoles), 2,2 '-dipyridyl (0.056 gram, 0.36 mmole) and NiCl
2(0.046 gram, 0.36 mmole) is also degassed under argon gas.Then by monomer F
8 br2(1 gram, 1.82 mmoles) and F
br2(0.91 gram, 1.82 mmoles) merge and mixture is stirred under argon gas at 100 DEG C, heat 17 hours.In this mixture, add THF (partial loss) and content is filtered to remove catalyzer.Pour filtrate into methyl alcohol to produce green solid product.By product CH
2cl
2with methyl alcohol redeposition.
1h NMR analyzes and shows that the ratio of F and F8 is about 1:1.2.
Embodiment 8:2,7-bis-is bromo-9,9-bis-oneself-preparation of 5-thiazolinyl-fluorenes
By 2,7-dibromo fluorenes (5 grams, 15.4 mmoles) and the bromo-5-hexene of 1-(7.5 grams, 46.0 mmoles) at toluene (50 milliliters), NaOH (50 milliliters, 50% aqueous solution) and the Bu as phase-transfer catalyst
4in NBr (0.1 gram), merge.This mixture is under agitation heated 5 hours at about 100 DEG C.Organic layer is separated with water layer, then use 10%HCl, then water treatment, then stirs MgSO
4and carbon black.By this solution filter, and remove in a vacuum all solvents to produce brown oil, 7.83 grams.
Embodiment 9:2,7-bis-is bromo-9, the preparation of 9-diallyl-fluorenes
2,7-dibromo fluorenes (5 grams, 15.4 mmoles) and allyl bromide 98 (5.6 grams, 46.2 mmoles) are merged and as above bromo-9 to 2,7-bis-, 9-bis-oneself-5-thiazolinyl-fluorenes like that and toluene, NaOH and Bu
4nBr reaction.Obtain 7.1 grams of yellow solids.
Embodiment 10: the preparation of the multipolymer of dihexyl fluorenes-bis-hexenyl fluorenes and diallyl fluorenes
By 2,7-ethylene glycolate boric acid ester-9,9-dihexyl fluorenes (2.5 grams, 5 mmoles), 2,7-bis-is bromo-9,9-bis--oneself-5-thiazolinyl-fluorenes (0.3 gram, 0.61 mmole)
-, 2,7-bis-is bromo-9,9-diallyl-fluorenes (0.7 gram, 1.74 mmoles) and 2,7-bis-are bromo-9,9-hexyl-fluorenes (1.23 grams, 2.5 mmoles) is at toluene (75 milliliters), Pd (PPh
3)
4(140 milligrams) and Et
4in NOH (25%, 10 milliliter), merge.This mixture is under agitation heated 24 hours at 80 DEG C.This mixture is filtered by 1:1:1 (w/w/w) mixture of C-salt, drierite ze and 3-(diethyl triamine) propyl group functional silicon dioxide.Filtrate is dried up in a vacuum, be then dissolved in minimum toluene.Toluene solution is poured in methyl alcohol to obtain orange solids, filtered and collect and use methanol wash.By gained solid redeposition to obtain 2.14 grams of solids, gpc Mw=35,000.Mn＝10,600。
Embodiment 11:9, the hydrogenation silylation of 9-diynyl fluorene copolymer and 9,9-, bis-alkenyl fluorene copolymers
Platinum Irgafos complex compound: by platinum Karstedt catalyzer (Pt
0complex compound with divinyl tetramethyl disiloxane, 5%Pt in dimethylbenzene, 0.25 gram, 1.28 mmole Pt), the polydimethylsiloxane (GE 88934 of ethenyl blocking, 3.3g) with Irgafos 168 (three-(2,4-di-tert-butyl-phenyl) phosphoric acid ester, Ciba Geigy; 3.31 grams, 5.12 mmoles) merge with toluene (50 milliliters), and reflux and spend the night.Then remove in a vacuum volatile matter to produce 6.76 grams of Liquid Paraffins, be estimated as 3.7%Pt.Prepared by the liquid storage of Pt Irgafos catalyzer, 0.135 gram in dimethylbenzene (50 milliliters of measuring bottles); 0.1 milligram of Pt/ milliliter.
Preparation contains PMV9925 (Gelest; 20 grams) and HPM502 (Gelest; 2.8 grams) liquid storage.
(F6)
3.0(F pentyne)
1.0
(F6)
3.0(F allyl group)
1.0
(F8)
0.9(F
allyl group)
0.1
By PMV/HPM liquid storage (1g) and Pt Irgafos catalyzer (10 microlitre) with (F6)
3.0(F pentyne)
1.0fluorene copolymer (20.7 milligrams) merges.While heating, do not form gel in deuterate benzene.Repeat experiment, just heating (F in deuterate benzene
6)
3.0(F
allyl group)
1.0(19.5 milligrams) gelling are insoluble in benzene after heating.Repeat experiment, just by (F
8)
0.9(F
allyl group)
0.1(15.1 milligrams) merge with liquid storage and heat to produce soluble gel in deuterate benzene.1H NMR analyzes confirmation, and the vinyl in the solution that contains gel polymer is consumed.
Although only illustrate herein and described some feature of the present invention, those skilled in the art can find out many amendments and variation.Therefore, it being understood that appended claims is intended to cover all such amendment and the variation that drop in true spirit of the present invention.
Claims (20)
1. the polymer composition being generated by the reaction between hydrogen siloxane and the poly-fluorenes of contained structural unit
Wherein
R
1and R
2be alkyl, alkenyl or alkynyl or its combination independently;
Ar
1and Ar
2be aryl or substituted aryl independently;
Condition is that m and n 0 make Ar
1and Ar
2do not exist; And
R
1and R
2at least one be alkenyl or alkynyl.
2. according to the polymer composition of claim 1, the structural unit that wherein hydrogen siloxane comprises following formula
Wherein
R
3, R
4, R
5, R
6, R
7, R
8, R
9and R
10be H, C independently
1-10alkyl or phenyl
P is 0 or 1 to 100 integer independently; And
R
3, R
4, R
5, R
6, R
7, R
8, R
9and R
10in at least two be H.
3. according to the polymer composition of claim 2, wherein p is 1 to 20 integer.
4. according to the polymer composition of claim 2, wherein R
3and R
7h.
5. according to the polymer composition of claim 2, wherein R
5h.
6. according to the polymer composition of claim 2, wherein R
9it is phenyl.
7. according to the polymer composition of claim 2, wherein R
4, R
6, R
8and R
10it is methyl.
8. according to the polymer composition of claim 1, generated by the reaction between poly-fluorenes and the vinylsiloxane of the structural unit of hydrogen siloxane, contained I.
9. according to the polymer composition of claim 1, wherein R
2c
3-20alkenyl.
10. according to the polymer composition of claim 1, wherein R
2c
3-20alkynyl.
11. according to the polymer composition of claim 1, wherein R
2c
3-8alkenyl.
12. according to the polymer composition of claim 1, wherein R
2c
4-8alkynyl.
13. according to the polymer composition of claim 1, wherein R
1c
3-8alkyl.
14. according to the polymer composition of claim 1, wherein R
1and R
2c
3-20alkynyl.
15. according to the polymer composition of claim 1, wherein R
1and R
2c
4-8alkynyl.
16. according to the polymer composition of claim 1, the structural unit that comprises following formula
17. according to the polymer composition of claim 1, the structural unit that comprises following formula
18. according to the polymer composition of claim 1, the structural unit that comprises following formula
19. according to the polymer composition of claim 18, comprises in addition the structural unit of following formula
20. opto-electronic devices that comprise the polymer composition generating by hydrogen siloxane with containing the reaction between the poly-fluorenes of the structural unit of formula I
Wherein
R
1and R
2be alkyl, alkenyl, alkynyl or its combination independently;
Ar
1and Ar
2be aryl or substituted aryl independently;
Condition is that m and n are 0, makes Ar
1and Ar
2do not exist; And
R
1and R
2at least one be alkenyl or alkynyl.
Applications Claiming Priority (5)
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|---|---|---|---|
| US78475006P | 2006-03-22 | 2006-03-22 | |
| US60/784,750 | 2006-03-22 | ||
| US11/610,784 US7633220B2 (en) | 2006-03-22 | 2006-12-14 | Optoelectronic devices with multilayered structures |
| US11/610,784 | 2006-12-14 | ||
| PCT/US2007/064126 WO2007109518A2 (en) | 2006-03-22 | 2007-03-16 | Optoelectronic devices with multilayered structures |
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Non-Patent Citations (3)
| Title |
|---|
| Hoon-Je Cho et al.."Synthesis and Characterization of Thermally Stable Blue Light-Emitting Polyfluorenes Containing Siloxane Bridges".《Macromolecules》.2003,第36卷(第18期),第6704-6710页. |
| Kan-Yi Pu et al.."Synthesis, morphology and photophysics of novel hybrid organic–inorganic polyhedral oligomeric silsesquioxane-tethered poly(fluorenyleneethynylene)s".《Polymer》.2006,第47卷(第6期),第1970-1978页. * |
| Kan-YiPuetal.."Synthesis morphology and photophysics of novel hybrid organic–inorganic polyhedral oligomeric silsesquioxane-tethered poly(fluorenyleneethynylene)s".《Polymer》.2006 |
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