CN107298756A - A kind of alkynes connects anthracene/aryl copolymer and preparation method thereof - Google Patents

A kind of alkynes connects anthracene/aryl copolymer and preparation method thereof Download PDF

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CN107298756A
CN107298756A CN201710350161.7A CN201710350161A CN107298756A CN 107298756 A CN107298756 A CN 107298756A CN 201710350161 A CN201710350161 A CN 201710350161A CN 107298756 A CN107298756 A CN 107298756A
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anthracene
aryl
copolymer
double
connects
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CN107298756B (en
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吉小利
徐洪耀
光善仪
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Anhui University of Science and Technology
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Abstract

Connect anthracene/aryl copolymer and preparation method thereof the present invention relates to a kind of alkynes, the material structure to bromine aryl monomer with double comprising 9,10 pairs of acetylene anthracene monomers through Sonogashira coupling reactions by being prepared from, and its preparation includes：By 9,10 pairs of acetenyl anthracenes, it is double to bromine aryl monomer with mol ratio 1:1, it is added to and terminates reaction containing the 48h that in catalyst and organic solvent mixed system, flowed back at 80 DEG C, cool down, filtering removes solvent, dissolves crude product with a small amount of tetrahydrofuran, is added dropwise in methanol is settled out product dropwise, this process is repeated 23 times, is produced.A kind of alkynes of the present invention, which connects anthracene/aryl copolymer, has good dissolubility, stronger optical property, and good heat endurance, it can be widely used for the fields such as organic luminescent device, nonlinear optics, Microwave Absorbing Materials, lasing safety, photodynamic therapy, data storage and solar cell.

Description

A kind of alkynes connects anthracene/aryl copolymer and preparation method thereof
Technical field
The invention belongs to anthracene class organic optical materials and its preparation field, more particularly to a kind of alkynes connects anthracene/aryl copolymerization Thing and preparation method thereof.
Background technology
In numerous conjugated polymers, poly- arylalkyne (PAEs) is a kind of very important pi-conjugated polymer, its formula ForThis kind of polymer is generally made up of aryl and alkynes copolymerization, most of to have rigidity and linear structure.More Importantly, it has higher carrier mobility and the efficient characteristics of luminescence, molecule organic semiconductor may be used as such as Active layer or OTFT in light emitting diode etc..The structures of different aryl and it is connected as cutting these polymer Photoelectric properties provide very big possibility.Anthracene is used as a kind of luminescence unit of common high-fluorescence quantum yield, its introducing The pi-conjugated property of main polymer chain can not only be extended, and assign polymer good luminescence generated by light and electroluminescent properties.But It is due to the big kinds of aromatic ring conjugation system of anthracene, its molecular rigidity is stronger, causes its dissolubility and processing characteristics poor.
Research both at home and abroad on the organic molecule containing anthracene at present, is concentrated mainly on small by singly-bound or the connected anthracene core of double bond In the design and preparation of molecule and the polymer architecture containing anthracene, so as to change its optical property, it is set to obtain widely application.Arrive So far, designed and synthesized all kinds of anthracene quasi-molecules.To improve its dissolving and luminescent properties, researcher is typically in anthracene 2nd, 3,6,7,9, modified for 10.A kind of method is by being acylated to different raw materials, in obtained carboxylic acid molecules Close anthracene nucleus, can anthracene 2,3,6,7 introduce the groups such as alkyl, halogen atom, further reaction can introduce required fragrance Group；Two kinds of methods be coupled using Suzuki, bromo-reaction can anthracene 9,10 introduce aromatic group.In anthracene class material In, the most classical is the double (- naphthyl) anthracenes (α-ADN) of 9,10- and double (2- naphthyls) anthracenes (β-AND) of 9,10- and diphenylanthrancene (DPA) structure containing various substituents, is derived on the two basis.(bibliography HuangJ H, Su J H, Tian H.The development of anthracene derivatives for organic light-emitting diodes [J].J.Mater.Chem.:2012,22:10977-10989.) for the report phase for the anthracene derivative being connected by acetenyl To less.
Therefore, the present invention is passed through using double bromine aryl monomers containing flexible side-chains and the double acetenyl anthracene monomers of 9,10- The connected anthracene aryl copolymer of Sonogashira coupling reactions synthesis acetenyl, the introducing of flexible chain causes the dissolving of polymer Property preferably, the introducing that aromatic ring, the introducing of alkynyl improve alkynyl in the conjugacy and heat endurance of polymer, and main chain can be carried The relative coplanarity of macromolecule.The preparation of such material extends the species and application of optical material, the preparation method Post processing is simple, good in economic efficiency, it is adaptable to industrialized production.Such material has stronger optical absorption and fluorescent emission Can, good dissolubility, heat endurance and film forming have not been reported on such a material both at home and abroad at present.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of alkynes and connect anthracene/aryl copolymer, and the material has good Dissolubility, stronger optical absorption and fluorescent emission performance, and good thermal stability and filming performance, can be widely used for Nonlinear optics, functional fibre, wave-absorbing and camouflage material, organic luminescent device, lasing safety, photodynamic therapy, data storage, Light transmitting field-effect transistor and solar cell etc. field.
A kind of alkynes of the present invention connects anthracene/aryl copolymer, it is characterised in that：The material structure is by including the double acetylene of 9,10- Anthracene monomer is prepared from double to bromine aryl monomer through Sonogashira coupling reactions, wherein, 9,10- double acetylene anthracene monomers with Double is 1 to bromine aryl monomer mole ratio:1.
A kind of described alkynes connects anthracene/aryl copolymer, it is characterised in that with following structure：
Wherein, R is that the segment containing flexible side-chains is each independently benzene class, pyridines, fluorenes class, carbazoles, azo, thiophene Fen class, benzothiazoles, diphenyl silane class and its derivative, the dissolving of copolymer is improved by the soft segment of this monomer Property structure such as following formula, wherein R1For alkyl.
A kind of described alkynes connects anthracene/aryl copolymer, it is characterised in that：The double acetylene anthracene monomers of 9, the 10-, its structure is such as Following formula：
The double acetylene anthracene monomers of 9 described, 10-, including following synthesis step and condition：
The synthesis of I .9,10- pairs-trimethylsilyl acetylene base anthracene
In anhydrous and oxygen-free environment, 9,10- dibromoanthracenes monomer and trimethylsilyl acetylene (several times) are added to containing urging In the mixed system of agent and organic solvent, 24~48h of back flow reaction at 70~80 DEG C after reaction stops, being cooled down, filtering, Revolving removes solvent.Afterwards with CH2Cl2For organic phase, water is that inorganic phase extraction is multiple, and anhydrous magnesium sulfate is dried, and collects organic phase, And a small amount of silica gel adhesion crude product is added, revolving is removed after solvent, is dried in vacuo 12h, crude product is through silica gel column chromatography (oil Ether) purification, produce product.
The synthesis of the double acetenyl anthracenes of II .9,10-
Under nitrogen protection, by above-mentioned 9,10- pairs-trimethylsilyl acetylene base anthracene and KF with mol ratio 1:6, it is added to anhydrous In alcohol solvent, 4h is reacted at room temperature.Most of solvent is removed, with CH2Cl2For organic phase, water extracts for inorganic phase, anhydrous slufuric acid Magnesium is dried, and collects organic phase, and adds a small amount of silica gel adhesion crude product, and revolving is removed after solvent, 12h is dried in vacuo, through oil Ether silica gel column chromatography, produces product.
A kind of described alkynes connects anthracene/aryl copolymer, and its preparation method includes the steps and condition：
In anhydrous and oxygen-free environment, by the double acetenyl anthracenes of above-mentioned 9,10-, it is double to bromine aryl monomer with mol ratio 1：1, add To in containing catalyst and organic solvent mixed system, the 48h that flowed back at 80 DEG C terminates reaction, cools down, and filtering removes solvent, Crude product is dissolved with a small amount of tetrahydrofuran, is added dropwise in methanol is settled out product dropwise, this process repeatedly, produces product.
A kind of described alkynes connects the preparation method of anthracene/aryl copolymer, it is characterised in that：The catalyst is PdCl2 (PPh3)2And CuI, both mol ratios 1:1, consumption is 5~10mol% of monomer.
A kind of described alkynes connects the preparation method of anthracene/aryl oligomer, it is characterised in that：The organic solvent is tetrahydrochysene furan The mixed solvent muttered with triethylamine, both volume ratios 2:1~1:2.
A kind of described alkynes connects the preparation method of anthracene/aryl copolymer, it is characterised in that：It is described double to bromine aryl monomer, Benzene class, pyridines, fluorenes class, carbazoles, azo, thiophene-based, benzo are each independently for the dibromo monomer containing flexible side-chains Thiazoles, diphenyl silane class and its derivative, structure such as following formula：Wherein R1 is alkyl.
A kind of described alkynes connects anthracene/aryl copolymer, with good dissolubility, stronger optical property, and well Thermal stability.
A kind of described alkynes connects anthracene/aryl copolymer, can be widely used for organic luminescent device, nonlinear optics, stealthy suction Wave material, lasing safety, photodynamic therapy, data storage, light transmitting field-effect transistor and solar cell etc. field.
Beneficial effect
(1) a kind of alkynes prepared by the present invention connects anthracene/aryl copolymer maximum absorption wavelength between 400~600nm, fluorescence Emission peak is a kind of excellent organic optical materials between 450~700nm；
(2) alkynes, which connects anthracene/aryl copolymer, has a good heat endurance, the temperature range of thermal weight loss 5% for 300 DEG C~ 400 DEG C, it is possible to increase the service life of material；
(3) alkynes, which connects anthracene/aryl copolymer, has good dissolubility, can be dissolved in common solvent, such as tetrahydrofuran, two Chloromethanes, dimethyl sulfoxide, dimethylformamide etc..
(4) preparation method is simple and easy to apply, good in economic efficiency, it is adaptable to industrialized production.
Brief description of the drawings
Fig. 1 be in embodiment 1 in copolymer p 1, embodiment 2 in copolymer p 2, embodiment 3 copolymer p 3 FTIR collection of illustrative plates；
Fig. 2 is copolymer p 3 in copolymer p 2, embodiment 3 in copolymer p 1, embodiment 2 in embodiment 11H NMR Spectrogram；
Fig. 3 is copolymer p 1 in embodiment 113C NMR spectras；
Fig. 4 is copolymer p 2 in embodiment 213C NMR spectras；
Fig. 5 is copolymer p 3 in copolymer p 2, embodiment 3 in copolymer p 1, embodiment 2 in embodiment 1 in tetrahydrofuran Uv absorption spectra in solution；
Fig. 6 is copolymer p 3 in copolymer p 2, embodiment 3 in copolymer p 1, embodiment 2 in embodiment 1 in tetrahydrofuran Fluorescence emission spectrogram of compound in solution；
Fig. 7 be in embodiment 1 in copolymer p 1, embodiment 2 in copolymer p 2, embodiment 3 copolymer p 3 hot weightless picture Spectrum.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
2,7- bis- bromo- 9,9- bis- (dodecyl) fluorenes, copolymer p 1 prepared by 9,10- double-acetenyl anthracene monomers, its structure Formula is：
Bromo- (the dodecanes of 9,9- bis- of (0.33g, 1mmol) 2,7- bis- are added in the three-necked flask added with the 100ml of rotor Base) fluorenes, (0.226g, 1mmol) 9,10- pairs-acetenyl anthracene monomer, 0.035g (0.05mmol) PdCl2(PPh3)2、0.01g (0.05mmol) CuI, biexhaust pipe pumping inflation repeatedly for three times, injects the anhydrous Et of 25.0ml anhydrous THF, 25.0ml3N, 80 DEG C are returned Stream reaction 48h.After reaction terminates, cool down, filtering, revolving removes solvent, with a small amount of tetrahydrofuran lysate, is added dropwise to dropwise Precipitated in methanol to remove unreacted monomer, after this process is repeated 2~3 times, filter out precipitation, and 2 are washed with a large amount of methanol ~3 times, obtain red polymer powder, yield 35%.
Embodiment 2
2,6- bis- bromo- 3- hexyl thiophenes, alkynes prepared by 9,10- double acetenyl anthracene monomers connects copolymer p 2, and its structural formula is：
The bromo- 3- hexyl thiophenes of (0.326g, 1mmol) 2,6- bis- are added in the three-necked flask added with the 100ml of rotor, The double acetenyl anthracene monomers of (0.266g, 1mmol) 9,10-, 0.035g (0.05mmol) PdCl2(PPh3)2、0.01g(0.05mmol) CuI, biexhaust pipe pumping inflation repeatedly for three times, injects the anhydrous Et of 25.0ml anhydrous THF, 25.0ml3N, 80 DEG C of back flow reaction 48h. After reaction terminates, cool down, filtering, revolving removes solvent, with a small amount of tetrahydrofuran lysate, be added dropwise in methanol and precipitate dropwise To remove unreacted monomer, after this process is repeated 2~3 times, precipitation is filtered out, and is washed 2~3 times with a large amount of methanol, is obtained Bronzing polymer powder, yield 58%.
Embodiment 3
Two (4- bromophenyls) dimethylsilanes, alkynes prepared by 9,10- double acetenyl anthracene monomers connects copolymer p 3, its structural formula For：
(370.2mg, 1mmol) two (4- bromophenyls) dimethyl-silicon is added in the three-necked flask added with the 100ml of rotor Alkane, the double acetenyl anthracene monomers of (0.266g, 1mmol) 9,10-, 0.035g (0.05mmol) PdCl2(PPh3)2、0.01g (0.05mmol) CuI, biexhaust pipe pumping inflation repeatedly for three times, injects the anhydrous Et of 25.0ml anhydrous THF, 25.0ml3N, 80 DEG C are returned Stream reaction 48h.After reaction terminates, cool down, filtering, revolving removes solvent, with a small amount of tetrahydrofuran lysate, is added dropwise to dropwise Precipitated in methanol to remove unreacted monomer, after this process is repeated 2~3 times, filter out precipitation, and 2 are washed with a large amount of methanol ~3 times, obtain faint yellow solid product, yield 96%.

Claims (10)

1. a kind of alkynes connects anthracene/aryl copolymer, it is characterised in that：The material structure by comprising the double acetylene anthracene monomers of 9,10- with it is double Bromine aryl monomer is prepared from through Sonogashira coupling reactions, wherein, 9,10- double acetylene anthracene monomers are with double to bromine aryl Monomer mole ratio is 1:1.
2. a kind of alkynes according to claim 1 connects anthracene/aryl copolymer, it is characterised in that with following structure：
Wherein, R is that the segment containing flexible side-chains is each independently benzene class, pyridines, fluorenes class, carbazoles, azo, thiophene Class, benzothiazoles, diphenyl silane class and its derivative, the dissolving of copolymer is improved by the soft segment of this monomer Property.Structure such as following formula, wherein R1For alkyl.
3. a kind of alkynes according to claim 1 connects anthracene/aryl copolymer, it is characterised in that：The double acetylene anthracene lists of the 9,10- Body, its structure such as following formula：
4. the double acetylene anthracene monomers of 9,10-, including following synthesis step and condition according to claim 3：
The synthesis of I .9,10- pairs-trimethylsilyl acetylene base anthracene
In anhydrous and oxygen-free environment, 9,10- dibromoanthracenes monomer and trimethylsilyl acetylene (several times) are added to containing catalyst And in the mixed system of organic solvent, 24~48h of back flow reaction at 70~80 DEG C after reaction stops, being cooled down, filtered, revolving Remove solvent.Afterwards with CH2Cl2For organic phase, water is that inorganic phase extraction is multiple, and anhydrous magnesium sulfate is dried, and collects organic phase, and add Enter a small amount of silica gel adhesion crude product, revolving is removed after solvent, is dried in vacuo 12h, crude product is carried through silica gel column chromatography (petroleum ether) It is pure, produce product.
The synthesis of the double acetenyl anthracenes of II .9,10-
Under nitrogen protection, by above-mentioned 9,10- pairs-trimethylsilyl acetylene base anthracene and KF with mol ratio 1:6, it is added to absolute ethyl alcohol In solvent, 4h is reacted at room temperature.Most of solvent is removed, with CH2Cl2For organic phase, water is extracted for inorganic phase, and anhydrous magnesium sulfate is done It is dry, organic phase is collected, and a small amount of silica gel adhesion crude product is added, revolving is removed after solvent, 12h is dried in vacuo, through petroleum ether silicon Plastic column chromatography, produces product.
5. a kind of alkynes according to claim 1 connects anthracene/aryl copolymer, its preparation method includes：
In anhydrous and oxygen-free environment, by the double acetenyl anthracenes of above-mentioned 9,10-, it is double to bromine aryl monomer with mol ratio 1：1, it is added to and contains Have in catalyst and organic solvent mixed system, backflow 48h terminates reaction at 80 DEG C, cools down, filtering removes solvent, with less Tetrahydrofuran dissolving crude product is measured, is added dropwise in methanol is settled out product dropwise, this process repeatedly, produces product.
6. a kind of alkynes according to claim 5 connects the preparation method of anthracene/aryl copolymer, it is characterised in that：The catalysis Agent is PdCl2(PPh3)2And CuI, both mol ratios 1:1, consumption is 5~10mol% of monomer.
7. a kind of alkynes according to claim 5 connects the preparation method of anthracene/aryl oligomer, it is characterised in that：It is described organic Solvent is the mixed solvent of tetrahydrofuran and triethylamine, both volume ratios 2:1~1:2.
8. a kind of alkynes according to claim 5 connects the preparation method of anthracene/aryl copolymer, it is characterised in that：It is described double right Bromine aryl monomer, for the dibromo monomer containing flexible side-chains be each independently benzene class, pyridines, fluorenes class, carbazoles, azo, Thiophene-based, benzothiazoles, diphenyl silane class and its derivative, structure such as following formula：Wherein R1 is alkyl.
9. a kind of alkynes according to claim 1 connects anthracene/aryl copolymer, with good dissolubility, it can be dissolved in common Organic solvent, stronger optical property, and good thermal stability.
10. a kind of alkynes according to claim 1 connects anthracene/aryl copolymer, organic luminescent device can be widely used for, non-linear Optics, Microwave Absorbing Materials, lasing safety, photodynamic therapy, data storage, light transmitting field-effect transistor and solar-electricity The fields such as pond.
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