CN102757781B - Trapezoidal polysiloxane organic electroluminescent material with pyrene bridge base, and synthesizing method thereof - Google Patents
Trapezoidal polysiloxane organic electroluminescent material with pyrene bridge base, and synthesizing method thereof Download PDFInfo
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- CN102757781B CN102757781B CN201110104510.XA CN201110104510A CN102757781B CN 102757781 B CN102757781 B CN 102757781B CN 201110104510 A CN201110104510 A CN 201110104510A CN 102757781 B CN102757781 B CN 102757781B
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Abstract
The invention provides a trapezoidal organic electroluminescent material formed by a strongly fluorescent pyrene derivative and polyphenyl siloxane, and a preparation method thereof. According to the invention, a strongly fluorescent pyrene derivative is adopted as luminescent small molecules, and 1,6-diaminopyrene is designed and synthesized; with a super-molecular construction gradual coupling polymerization method, the 1,6-diaminopyrene is adopted as a templating agent, and a tri-functional organic silicon monomer trichlorophenyl silane is coupled, so that a trapezoidal template unit (Ph-LS) is formed; under the effect of 1,6-diaminopyrene hydrogen bond, hydrolytic condensation is carried out, and the trapezoidal polyphenyl siloxane organic electroluminescent material with 1,6-diaminopyrene bridge base (Ph-LP) is obtained. The polymer can be dissolved in a common solvent, such that a problem of poor dissolvability of pyrene small molecule luminescent materials is solved, and the strong luminescence is maintained. As a polymer, the material can be easily formed into films, and has good processing performance.
Description
Technical field
The present invention relates to ladder polysiloxane electroluminescent organic material, ladder polysiloxane and synthetic method thereof that the pyrene derivatives of hyperfluorescenceZeng Yongminggaoyingguang of particularly take is abutment, belong to luminous organic material field.
Background technology
In recent years, because life and the field of light emitting materials of luminous organic material people has been widely used, especially the fundamental research of electroluminescent organic material and application obtain develop rapidly.Luminescent material as organic EL device, there are higher fluorescence quantum efficiency and fluorescence spectrum will cover whole visible region, good characteristic of semiconductor, suitable fusing point (200-400 ℃), and there is good film forming characteristics, under filminess, there is satisfactory stability.
Luminescent material can be divided into small molecules luminescent material and polymer luminescent material by molecular size.Small molecules luminescent material has higher electroluminescent efficiency and better element function, and the control of its weather resistance, brightness and color aspect is better.And polymer electroluminescence does not have small molecules purity high, but polymer-type element has easy machine-shaping, easy song than advantages such as small molecule material are good.Aspect the preparation technology of device, small molecules device mainly adopts vacuum thermal evaporation technique; Polymer device adopts spin coating to cover or ink-jetting process.
In addition, also have the polymer luminescent material of so-called doping, be about to organic molecule luminescent material and be doped in polymeric system.Yet the poor effect of simply adulterating: on the one hand, there will be typical concentration quenching under high doping under certain condition; On the other hand, the consistency of most of small molecules luminescent materials and polymkeric substance is poor, thereby is difficult to be uniformly dispersed, and is easily separated.Moreover the material transparency variation after doping, and the mechanical properties decrease of polymkeric substance, be therefore difficult to obtain high-quality luminescent material.
Polysilane is common polymeric matrix, has similar character in many aspects to pi-conjugated polymkeric substance.The delocalization of electric charge on Si-Si reduces ionization energy, and hole mobility raises, and the hole mobility under room temperature is about 10
-5-10
-4cm
2/ eVs.On side chain, connect substituting group and can strengthen the handiness of polysilane in visible-range.PSI (PMPS) is exactly typical silicone based polymkeric substance hole mobile material, but this kind is containing the polymer chemistry less stable of Si-Si key main chain.Since 1980, the proposition supramolecule such as Zhang Rongben constructs progressively coupling and polyreaction, utilize the reactive difference of active group, synthesized first in the world oxygen abutting ladder poly-siloxane and the organic abutting ladder poly polysilsesquioxane with regular duplex structure.Solved a difficult problem for the international high molecular of 40Yu Nianlai educational circles synthetic ordered ladder-like polysiloxane, in the leading level in the world.The oxygen abutting ladder poly-siloxane of regular duplex structure, comprises that waist connects and two types of terminations.The organic abutting ladder poly-siloxane of high-regularity dissolves in usual vehicle, is convenient to make film, excellent machining performance.
Pyrene small molecules and derivative thereof, as a large condensed ring, have very high fluorescence quantum efficiency and dark blue light emission, and from device, it can improve the mobility of material and the performance that hole is injected.These character of pyrene and derivative thereof make them get a good chance of becoming the photoelectric material of high-luminous-efficiency, but the solvability of pyrene derivatives and mechanical property are poor, and its application in field of light emitting materials is restricted.
Summary of the invention
The problems referred to above that exist in order to overcome luminous organic material field, the present invention proposes to take the ladder polysiloxane electroluminescent material that pyrene derivatives is abutment.
Pyrene abutting ladder poly-siloxane provided by the invention, wherein with pyrene derivatives (as: 1,6-diamino pyrene) as ladder brace.
Structural representation is as follows:
Wherein
represent luminous base 1,6-diamino pyrenyl, structural formula is as follows:
Pyrene abutting ladder poly-siloxane synthetic method of the present invention, at least comprises following two steps: (1) monomer synthetic; (2) hydrolysis of monomer, condensation.
Wherein monomer synthesis step is by hyperfluorescenceZeng Yongminggaoyingguang pyrene derivatives and organo-siloxane bonding, and pyrene derivatives at least contains two active function groups in contraposition; Organo-siloxane at least contain one can with the functional group of pyrene derivatives active function groups generation bonding reaction.
The synthesis phase of monomer: make solvent with toluene, triethylamine is catalyzer, under argon shield, 1,6-diamino pyrene, trichlorophenyl silane react with the ratio of 2: 1, the silane coupled modular unit in echelon of organosilane monomer trichlorophenyl (Ph-LS).
The hydrolysis and condensation stage: take triethylamine as catalyzer, modular unit (Ph-LS) is hydrolytic condensation under the hydrogen bond regulating and controlling effect of 1,6-diamino pyrene, uses ClSiMe
3end-blocking obtains end product Ph-LP.
In above-mentioned reaction, 1,6-diamino pyrene abutting ladder poly phenyl silicone (Ph-LP) sterling be by 1,6-diamino pyrene abutting ladder poly phenyl silicone (Ph-LP) crude product through hexanaphthene repeatedly recrystallization obtain.
In the present invention, supermolecular module is that synthetic high regularity organic abutting ladder poly phenyl silicone obtains key; therefore in self assembling process, to guarantee to accomplish absolute water proof; before the reaction of solvent for use, reagent bottle all through dewatering, drying treatment, logical argon shield in reaction process.Reaction selects the toluene that polarity is less (Toluene) to make solvent, is conducive to hydrogen bond between supramolecule and works, and adds weak polar solvent Isosorbide-5-Nitrae-dioxane (DOX) to improve the solubleness of monomer simultaneously, guarantees to react to carry out in homogeneous system; Add triethylamine (TEA) to make catalyzer, the HCI generating can be absorbed in time in system, when adding fast response, can guarantee again that Si-N key is not destroyed by HCI, keep the regularity of polymkeric substance.Meanwhile, in whole process, the rate of addition of reaction solution is very slow, and excessive velocities will cause crosslinked or cladodification, also can affect the regularity of polymerization.
Accompanying drawing explanation
Fig. 1. in embodiment 11, the fluorogram of 6-diamino pyrene.
Fig. 2. the XRD figure spectrum of the pyrene abutment phenyl ladder polysiloxane electroluminescent material Ph-LP that embodiment 1 makes.
Embodiment
Embodiment 1:
The dry toluene of 200ml is joined in the dry there-necked flask of 500ml, vacuumize applying argon gas three times.Under argon shield, with the phenyl-trichloro-silicane that dry transfer pipet pipettes 3.3715ml, join in toluene solution, stir.Take 2.3228g 1,6-diamino pyrene is dissolved in 100ml dry toluene, then to the anhydrous triethylamine that adds 16.8ml in this solution, mixes.At 0 ℃, with dry constant pressure funnel, this solution is added drop-wise in there-necked flask solution lentamente, within 24 hours, drips off.Reaction solution continues reaction 48 hours at 0 ℃.Under argon shield, filter out rapidly the triethylamine hydrochloride generating in reaction, obtain superstructure Ph-LS solution.
Under argon shield, by gained Ph-LS solution, be transferred to rapidly in 500ml there-necked flask, stir.The mixed solution (60/40) that adds respectively 0.36g deionized water, 100ml dry toluene/anhydrous dioxane in constant pressure funnel.At 25 ℃, this solution is added drop-wise in there-necked flask lentamente, can see that triethylamine salt generates rapidly, within 24 hours, drip off, then continue reaction 24 hours.In the most backward system, add 0.2mL trimethylchlorosilane to carry out end-blocking, react 6 hours, remove by filter triethylamine hydrochloride, obtain light yellow transparent liquid, removal of solvent under reduced pressure obtains light yellow solid, in 60 ℃ of vacuum-dryings, gained crude product obtains product with hexanaphthene recrystallization, yield 70%.
Embodiment 2:
The dry toluene of 200ml is joined in the dry there-necked flask of 500ml, vacuumize applying argon gas three times.Under argon shield, with the phenyl-trichloro-silicane that dry transfer pipet pipettes 3.3715ml, join in toluene solution, stir.Take 2.3228g 1,6-diamino pyrene is dissolved in 100ml dry toluene, then to the anhydrous triethylamine that adds 16.8ml in this solution, mixes.At 25 ℃, with dry constant pressure funnel, this solution is added drop-wise in there-necked flask solution lentamente, within 48 hours, drips off.Reaction solution continues reaction 48 hours at 25 ℃.
The mixed solution (60/40) that adds respectively 0.36g deionized water, 100ml dry toluene/anhydrous dioxane in constant pressure funnel.At 25 ℃, this solution is added drop-wise in there-necked flask lentamente, can see that triethylamine salt generates rapidly, within 24 hours, drip off, then continue reaction 48 hours.In the most backward system, add 0.2mL trimethylchlorosilane to carry out end-blocking, react 6 hours, remove by filter triethylamine hydrochloride, obtain light yellow transparent liquid, removal of solvent under reduced pressure obtains light yellow solid, in 60 ℃ of vacuum-dryings, gained crude product obtains product with hexanaphthene recrystallization, yield 59%.
Claims (2)
1. a synthetic method for pyrene abutting ladder poly-siloxane electroluminescent organic material, is characterized in that, comprises the following steps:
The dry toluene of 200ml is joined in the dry there-necked flask of 500ml, vacuumize applying argon gas three times; Under argon shield, with the phenyl-trichloro-silicane that dry transfer pipet pipettes 3.3715ml, join in toluene solution, stir; Take 2.3228g1,6-diamino pyrene is dissolved in 100ml dry toluene, then to the anhydrous triethylamine that adds 16.8ml in this solution, mixes; At 0 ℃, with dry constant pressure funnel, this solution is added drop-wise in there-necked flask solution lentamente, within 24 hours, drips off; Reaction solution continues reaction 48 hours at 0 ℃; Under argon shield, filter out rapidly the triethylamine hydrochloride generating in reaction, obtain superstructure Ph-LS solution;
Under argon shield, by gained Ph-LS solution, be transferred to rapidly in 500ml there-necked flask, stir; The mixed solution that adds respectively 0.36g deionized water, 1 00ml dry toluene/anhydrous dioxane in constant pressure funnel, volume ratio is 60: 40; At 25 ℃, this solution is added drop-wise in there-necked flask lentamente, triethylamine salt generates rapidly, within 24 hours, drips off, and then continues reaction 24 hours; In the most backward system, add 0.2mL trimethylchlorosilane to carry out end-blocking, react 6 hours, remove by filter triethylamine hydrochloride, obtain light yellow transparent liquid, removal of solvent under reduced pressure obtains light yellow solid, in 60 ℃ of vacuum-dryings, gained crude product obtains product with hexanaphthene recrystallization, yield 70%.
2. a pyrene abutting ladder poly-siloxane electroluminescent organic material, is characterized in that, the synthetic method of pyrene abutting ladder poly-siloxane electroluminescent organic material according to claim 1 makes.
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