CN109503814A - One kind having photoactive electricity storage polymer and preparation method thereof - Google Patents
One kind having photoactive electricity storage polymer and preparation method thereof Download PDFInfo
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- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/411—Suzuki reactions
Abstract
The present invention relates to one kind to have photoactive electricity storage polymer and preparation method thereof.The method for producing polymer includes: the alkylation of 3,4- Dithiophene maleimide；The bromination of N- alkyl -3,4- Dithiophene maleimide；N- alkyl -3,4- Dithiophene maleimide monomer and the copolymerization of dialkyl fluorene monomer.The electricity storage polymer that the present invention obtains has photolytic activity, i.e., after illumination, ring closure reaction can occur for Dithiophene maleimide, so that the structure of polymer, Electronic Performance and electric storage performance change.The advantages that electric storage polymer of the invention also has preparation method simple, and synthesis temperature is low, and stability is good, is suitble to industrialized production, has practicability, has broad application prospects in encrypted message storage and anti-fake equal fields.
Description
Technical field
The invention belongs to Organic Electricities to store polymer manufacturing field, and in particular to one kind has photoactive electricity storage polymerization
Object and preparation method thereof can be used for electrical storage device.
Background technique
Electrostrictive polymer memory device can be divided into volatile memory and nonvolatile memory two be big according to the type of storage
Class.The data storage information of volatile memory needs applied voltage to maintain, once lose additional power source, the information of storage also with
Lose.This kind of memory needs lasting power supply to supply the storage to maintain data.The data of nonvolatile memory store
The maintenance of applied voltage is not needed, even if additional power source is closed, the data information having been written into can also be retained, will not be disappeared
It loses.Whether can be wiped according to the information of write-in, non-volatile electrical storage shows two kinds of electric storage lines respectively are as follows: once writes
Enter the WORM type repeatedly read and erasable FLASH type.
Studying more non-volatile electrostrictive polymer storage material at present has polyimide, polyfluorene class, polycarbazole class etc.
Conjugated polymer, polyvinylcarbazole class non-conjugated polymeric object and the types such as polymer and inorganic, organic material intermingling material.
In numerous electrostrictive polymer storage materials, at the same have donor, receptor D-A type polymer material due to its excellent charge
Transfer characteristic and adjustability of structure and have become a hot topic of research.Different molecular structures has different electrons or electrophilic energy
Power selects electron or the appropriate group of electron-withdrawing ability, is advantageously implemented excellent electric bi-stable property.Not isoplastic choosing
It selects, or existing group is reasonably modified, it is possible to the molecular structure and photoelectric properties of subject polymer are influenced, thus
Influence the electric storage behavior of electrostrictive polymer memory device.But the electric storage performance of D-A type polymer is regulated and controled at present, is needed
Design synthesis has the push-and-pull electronic unit of different structure, and synthesis is comparatively laborious, if can be by simple environmental stimuli (such as
Light, electrically or thermally etc.) realize electrostrictive polymer storage performance, it will largely promote the development and application of electrical storage device.
Summary of the invention
The object of the present invention is to provide a kind of based on the organic of photoactive 3,4- Dithiophene maleimide amine unit
Polymer.The electric storage performance of polymer can be changed by illumination, can be applied to encrypted message storage and anti-counterfeit field etc..
An object of the present invention, providing one kind, there is photoactive electricity to store polymer, it is by 3,4- Dithiophene
Unit and fluorenes unit composition, molecular formula are as follows:
Wherein, R1, R2 are containing the identical alkyl of carbon atom number or different alkyl between 1 to 16；
Wherein, n is the integer between 5 to 100.
After illumination, ring closure reaction, cyclic product structure formula such as following formula institute can occur for 3,4- Dithiophene maleimide amine units
Show:
Wherein, R1, R2 are containing the identical alkyl of carbon atom number or different alkyl between 1 to 16；
Wherein, n is the integer between 5 to 100.
The second object of the present invention provides the electricity for containing 3,4- Dithiophene maleimide amine unit in a kind of molecular structure and deposits
Store up the preparation method of polymer.3,4- Dithiophene maleimide is mainly first alkylated by this method, then bromination, most
It is copolymerized afterwards with alkyl fluorenes monomer.It is specific the preparation method is as follows:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 4mmol and 15mL acetone are mixed, stir 15 minutes at 40 DEG C, then plus
Enter the brominated alkanes of 4.4mmol；After continuing stirring 8 hours, it is spin-dried for solvent, ethyl acetate and saturated salt solution extraction is added, uses
Anhydrous magnesium sulfate is purified using column chromatography after drying, filtering to get N- alkyl -3,4- Dithiophene maleimide is arrived；
2) bromination of N- alkyl -3,4- Dithiophene maleimide
N- alkyl -3,4- Dithiophene maleimide of 3mmol is dissolved in the chloroform solvent of 15mL, is added
The N- bromo-succinimide (NBS) of 6.6mmol, room temperature are protected from light 24 hours；Through washing, extraction, anhydrous magnesium sulfate it is dry,
After filtering, dibromo thiophene maleimide monomer is obtained with ethyl alcohol recrystallization；
3) preparation of polymer
The dibromo thiophene maleimide monomer and 2mmol dialkyl group of 2mmol is added into reaction flask under nitrogen protection
Fluorenes boron ester monomer adds the 2M wet chemical of 10-40mmol, the palladium catalyst of 0.01-0.1mmol, organic with 10mL
Solvent dissolution after back flow reaction 48 hours, is added methanol, crude product is precipitated, and crude product successively uses acetone extraction 24 hours, chloroform
Extracting 24 hours, extract vacuum drying store polymer to get to photoactive electricity.
The carbon atom number of the brominated alkanes is between 1-16.
The carbon number of alkyl is between 1-16 in the dialkyl fluorene boron ester monomer.
The organic solvent is one of toluene, tetrahydrofuran, N,N-dimethylformamide.
The electric storage performance of traditional D-A type electricity storage polymer is not easy to adjust, and the present invention will have photoactive 3,4-
Dithiophene maleimide is introduced into main chain as receptor unit, obtains a kind of new electricity storage polymer, 3,4- bis- after illumination
Ring closure reaction can occur for thiophene maleimide amine unit, so that the electron-withdrawing ability of receptor unit changes in polymer, give
There is more appropriate interaction between receptor, be more likely formed charge-transfer complex, therefore illumination post-consumer polymer electrical storage device
It is changed into the non-volatile electric storage behavior of preferably erasable FLASH type from WORM type, on-off ratio is high, and stability is good, can follow
Ring.The advantages that polymer material of the invention also has preparation method simple, and synthesis temperature is low, and stability is good is suitble to industrialization
Production has practicability, has broad application prospects in encrypted message storage and anti-fake equal fields.
Detailed description of the invention
The hot weight curve of the electricity storage polymer prepared in Fig. 1 embodiment 1.
UV absorption spectrogram of the electricity storage polymer prepared in Fig. 2 embodiment 1 in chloroform before and after illumination.
UV absorption spectrogram before and after the electricity storage thin polymer film illumination prepared in Fig. 3 embodiment 1.
Electric current of the electrical storage device prepared in Fig. 4 embodiment 6 before illumination is with voltage change curve.
Electric current of the electrical storage device prepared in Fig. 5 embodiment 6 after illumination is with voltage change curve.
Specific embodiment
Following embodiments are not intended to limit the scope of the invention to further explanation of the invention.Without departing substantially from this hair
Under the premise of bright background and spirit, those skilled in the art can carry out equivalencing on the basis of reading the contents of the present invention
And modification, content are also included in the scope of protection of present invention.
Embodiment 1:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 1.04g (4mmol) and 15mL acetone are mixed, 15 points are stirred at 40 DEG C
Then the bromooctane of 0.85g (4.4mmol) is added in clock；After continuing stirring 8 hours, it is spin-dried for solvent, ethyl acetate and saturation is added
Saline solution extraction is purified after being dried, filtered with anhydrous magnesium sulfate using column chromatography to get N- octyl -3,4- Dithiophene horse is arrived
Carry out acid imide；
2) bromination of N- octyl -3,4- Dithiophene maleimide
N- octyl -3,4- Dithiophene maleimide of 1.12g (3mmol) is dissolved in the chloroform solvent of 15mL, is added
Enter the NBS of 1.17g (6.6mmol), room temperature is protected from light 24 hours；After washing, extraction, anhydrous magnesium sulfate drying, filtering, use
Ethyl alcohol recrystallization obtains N- octyl -3,4- two (5- bromothiophene) maleimide monomer；
3) preparation of polymer
N- octyl -3,4- two (5- bromothiophene) the Malaysia acyl of 0.84g (2mmol) is added into reaction flask under nitrogen protection
Imines and 0.78g (2mmol) dioctyl fluorene boron ester, add 2M wet chemical, the 18.5mg of 5mL (10mmol)
The tetrakis triphenylphosphine palladium catalyst of (0.016mmol) is dissolved with 10mL toluene, and after back flow reaction 48 hours, methanol, analysis is added
Crude product out, and with acetone extraction 24 hours, chloroform 24 hours, extract vacuum drying is to get photoactive to having
Electricity storage polymer.Polymer yield is 63%, number-average molecular weight 14373, weight average molecular weight 25590.
The thermal stability that electricity storage polymer manufactured in the present embodiment has had, hot weight curve show 5% weightless peak
At 390 DEG C, as shown in Figure 1.
Electricity storage polymer manufactured in the present embodiment has strong at the UV absorption spectrogram display 568nm in chloroformic solution
Absorption peak, with the extension of light application time, which fades away, as shown in Figure 2.The UV absorption spectrogram of thin polymer film
Also identical change is presented, as shown in figure 3, showing that illumination makes Dithiophene maleimide that ring closure reaction have occurred.
Embodiment 2:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 1.04g (4mmol) and 15mL acetone are mixed, 15 points are stirred at 40 DEG C
Then the bromooctane of 0.85g (4.4mmol) is added in clock；After continuing stirring 8 hours, it is spin-dried for solvent, ethyl acetate and saturation is added
Saline solution extraction is purified after being dried, filtered with anhydrous magnesium sulfate using column chromatography to get N- octyl -3,4- Dithiophene horse is arrived
Carry out acid imide；
2) bromination of N- octyl -3,4- Dithiophene maleimide
N- octyl -3,4- Dithiophene maleimide of 1.12g (3mmol) is dissolved in the chloroform solvent of 15mL, is added
Enter the NBS of 1.17g (6.6mmol), room temperature is protected from light 24 hours；After washing, extraction, anhydrous magnesium sulfate drying, filtering, use
Ethyl alcohol recrystallization obtains N- octyl -3,4- two (5- bromothiophene) maleimide monomer；
3) preparation of polymer
N- octyl -3,4- two (5- bromothiophene) the Malaysia acyl of 0.84g (2mmol) is added into reaction flask under nitrogen protection
Imines and 0.67g (2mmol) dihexyl fluorenes boron ester, add 2M wet chemical, the 11.6mg of 10mL (20mmol)
The tetrakis triphenylphosphine palladium catalyst of (0.01mmol) is dissolved with 10mL toluene, and after back flow reaction 48 hours, methanol, analysis is added
Crude product out, and with acetone extraction 24 hours, chloroform 24 hours, extract vacuum drying is to get photoactive to having
Electricity storage polymer.Polymer yield is 73%, number-average molecular weight 10534, weight average molecular weight 18624.
Embodiment 3:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 1.04g (4mmol) and 15mL acetone are mixed, 15 points are stirred at 40 DEG C
Then the bromohexane of 0.73g (4.4mmol) is added in clock；After continuing stirring 8 hours, it is spin-dried for solvent, ethyl acetate and saturation is added
Saline solution extraction is purified after being dried, filtered with anhydrous magnesium sulfate using column chromatography to get N- hexyl -3,4- Dithiophene horse is arrived
Carry out acid imide；
2) bromination of N- hexyl -3,4- Dithiophene maleimide
N- hexyl -3,4- Dithiophene maleimide of 1.04g (3mmol) is dissolved in the chloroform solvent of 15mL, is added
Enter the NBS of 1.17g (6.6mmol), room temperature is protected from light 24 hours；After washing, extraction, anhydrous magnesium sulfate drying, filtering, use
Ethyl alcohol recrystallization obtains N- hexyl -3,4- two (5- bromothiophene) maleimide monomer；
3) preparation of polymer
N- hexyl -3,4- two (5- bromothiophene) the Malaysia acyl of 0.84g (2mmol) is added into reaction flask under nitrogen protection
Imines and 0.78g (2mmol) dioctyl fluorene boron ester, add 2M wet chemical, the 37mg of 15mL (30mmol)
The tetrakis triphenylphosphine palladium catalyst of (0.032mmol) is dissolved with 10mL tetrahydrofuran, and after back flow reaction 48 hours, first is added
Crude product is precipitated in alcohol, and with acetone extraction 24 hours, chloroform 24 hours, extract vacuum drying was lived to get to light
Property electricity storage polymer.Polymer yield is 68%, number-average molecular weight 11589, weight average molecular weight 19365.
Embodiment 4:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 1.04g (4mmol) and 15mL acetone are mixed, 15 points are stirred at 40 DEG C
Then the bromo- 2- ethyl hexane of 1- of 0.85g (4.4mmol) is added in clock；After continuing stirring 8 hours, it is spin-dried for solvent, acetic acid is added
Ethyl ester and saturated salt solution extraction, are purified after being dried, filtered with anhydrous magnesium sulfate using column chromatography to get N- (2- ethyl is arrived
Hexyl) -3,4- Dithiophene maleimide；
2) bromination of N- (2- ethylhexyl) -3,4- Dithiophene maleimide
The chloroform that N- (2- ethylhexyl) -3,4- Dithiophene maleimide of 1.12g (3mmol) is dissolved in 15mL is molten
In agent, the NBS of 1.17g (6.6mmol) is added, room temperature is protected from light 24 hours；Through washing, extraction, anhydrous magnesium sulfate drying, mistake
After filter, N- (2- ethylhexyl) -3,4- bis- (5- bromothiophene) maleimide monomer is obtained with ethyl alcohol recrystallization；
3) preparation of polymer
N- (2- ethylhexyl) (the 5- bromine thiophene of -3,4- two of 0.84g (2mmol) is added into reaction flask under nitrogen protection
Pheno) maleimide and 0.67g (2mmol) dihexyl fluorenes boron ester, add 20mL (40mmol) 2M wet chemical,
The tetrakis triphenylphosphine palladium catalyst of 55.5mg (0.048mmol) is dissolved with 10mL tetrahydrofuran, after back flow reaction 48 hours,
Methanol is added, crude product is precipitated, and with acetone extraction 24 hours, chloroform 24 hours, extract was dried in vacuo to arrive tool
There is photoactive electricity storage polymer.Polymer yield is 76%, number-average molecular weight 15697, weight average molecular weight 25285.
Embodiment 5:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 1.04g (4mmol) and 15mL acetone are mixed, 15 points are stirred at 40 DEG C
Then the bromooctane of 0.85g (4.4mmol) is added in clock；After continuing stirring 8 hours, it is spin-dried for solvent, ethyl acetate and saturation is added
Saline solution extraction is purified after being dried, filtered with anhydrous magnesium sulfate using column chromatography to get N- octyl -3,4- Dithiophene horse is arrived
Carry out acid imide；
2) bromination of N- octyl -3,4- Dithiophene maleimide
N- octyl -3,4- Dithiophene maleimide of 1.12g (3mmol) is dissolved in the chloroform solvent of 15mL, is added
Enter the NBS of 1.17g (6.6mmol), room temperature is protected from light 24 hours；After washing, extraction, anhydrous magnesium sulfate drying, filtering, use
Ethyl alcohol recrystallization obtains N- octyl -3,4- two (5- bromothiophene) maleimide monomer；
3) preparation of polymer
N- octyl -3,4- two (5- bromothiophene) the Malaysia acyl of 0.84g (2mmol) is added into reaction flask under nitrogen protection
Imines and 0.89g (2mmol) didecyl base fluorenes boron ester, add 2M wet chemical, the 116mg of 5mL (10mmol)
The tetrakis triphenylphosphine palladium catalyst of (0.1mmol), with 10mLN, dinethylformamide dissolves, after back flow reaction 48 hours,
Methanol is added, crude product is precipitated, and with acetone extraction 24 hours, chloroform 24 hours, extract was dried in vacuo to arrive tool
There is photoactive electricity storage polymer.Polymer yield is 65%, number-average molecular weight 9651, weight average molecular weight 14669.
Embodiment 6: the application with photolytic activity electricity storage polymer
Electric current-of the electric storage performance of polymer with electrical storage device (tin indium oxide/polymer/aluminium) under applied voltage
Voltage (I-V) curve carries out test analysis.The test of all electric storage performances is carried out under atmospheric environment.Before illumination
The current -voltage curve of device shows that polymer has the non-volatile electrically storage performance of WORM type (write-once is repeatedly read),
As shown in Figure 4.And the current -voltage curve of device shows that polymer shows the non-volatile of FLASH type (erasable) after illumination
Electric storage performance, as shown in Figure 5.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. there is one kind photoactive electricity to store polymer, it is characterised in that it is by 3,4- Dithiophene unit that the electricity, which stores polymer,
It is formed with fluorenes unit, structural formula is shown below:
Wherein, R1, R2 are containing the identical alkyl of carbon atom number or different alkyl between 1 to 16；
Wherein, n is the integer between 5 to 100.
2. it is according to claim 1 a kind of with photoactive electricity storage polymer, it is further characterized in that electricity storage is poly-
Object is closed under sunlight irradiation, ring closure reaction can occur for 3,4- Dithiophene maleimide amine units, and cyclic product structure formula is as follows
Shown in formula:
Wherein, R1, R2 are containing the identical alkyl of carbon atom number or different alkyl between 1 to 16；
Wherein, n is the integer between 5 to 100.
3. a kind of preparation method with photoactive electricity storage polymer, it is characterised in that:
1) alkylation of 3,4- Dithiophene maleimide
3, the 4- Dithiophene maleimide of 4mmol and 15mL acetone are mixed, stirs 15 minutes at 40 DEG C, is then added
The brominated alkanes of 4.4mmol；After continuing stirring 8 hours, it is spin-dried for solvent, ethyl acetate and saturated salt solution extraction is added, with nothing
Water magnesium sulfate is purified using column chromatography after drying, filtering to get N- alkyl -3,4- Dithiophene maleimide is arrived；
2) bromination of N- alkyl -3,4- Dithiophene maleimide
N- alkyl -3,4- Dithiophene maleimide of 3mmol is dissolved in the chloroform solvent of 15mL, is added 6.6mmol's
N- bromo-succinimide, room temperature are protected from light 24 hours；After washing, extraction, anhydrous magnesium sulfate drying, filtering, ethyl alcohol is used
Recrystallization obtains dibromo thiophene maleimide monomer；
3) preparation of polymer
The dibromo thiophene maleimide monomer and 2mmol dialkyl fluorene boron of 2mmol is added into reaction flask under nitrogen protection
Ester monomer adds the 2M wet chemical of 10-40mmol, the palladium catalyst of 0.01-0.1mmol, with 10mL organic solvent
Dissolution after back flow reaction 48 hours, is added methanol, crude product is precipitated, and with acetone extraction 24 hours, chloroform 24 hours,
Extract vacuum drying stores polymer to get to photoactive electricity.
4. according to claim 3 a kind of with photoactive electricity storage method for producing polymer, it is characterised in that described
Brominated alkanes carbon atom number between 1-16.
5. according to claim 3 a kind of with photoactive electricity storage method for producing polymer, it is characterised in that described
Dialkyl fluorene boron ester monomer in alkyl carbon number between 1-16.
6. according to claim 3 a kind of with photoactive electricity storage method for producing polymer, it is characterised in that described
Organic solvent be one of toluene, tetrahydrofuran, N,N-dimethylformamide.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002145878A (en) * | 2000-11-08 | 2002-05-22 | Japan Science & Technology Corp | Dithienylethene derivative and light-control type conjugated polymer |
| WO2004026988A1 (en) * | 2002-09-11 | 2004-04-01 | Heinrich-Heine-Universitaet Duesseldorf | Photochromic polymer composition and production, post-processing and use thereof |
| CN1775778A (en) * | 2005-12-01 | 2006-05-24 | 复旦大学 | Dithiophene ethene functional material, and its preparing method and use |
| CN101239976A (en) * | 2007-12-19 | 2008-08-13 | 华东理工大学 | Dithienylethene compounds containing naphthalimide unit |
| CN101497610A (en) * | 2009-03-06 | 2009-08-05 | 华东理工大学 | Dithiazole ethylene compound containing 2,1,3-diazosulfide unit |
| CN102286140A (en) * | 2010-06-18 | 2011-12-21 | 海洋王照明科技股份有限公司 | Perylene tetracarboxylic diimide copolymer containing dithieno quinoxaline unit as well as preparation method and application thereof |
| CN102344548A (en) * | 2010-07-30 | 2012-02-08 | 海洋王照明科技股份有限公司 | Copolymer containing fluorene and thiophene pyrroledione unit and preparation method and application of copolymer containing fluorene and thiophene pyrroledione unit |
| CA2494920C (en) * | 2002-08-09 | 2013-01-22 | Simon Fraser University | Photochromic and electrochromic compounds and methods of synthesizing and using same |
| CN103467461A (en) * | 2013-09-03 | 2013-12-25 | 福建师范大学 | Preparation of multi-stimulating responsive material containing thienyl maleimide by substitution reaction method |
| CN103484104A (en) * | 2013-09-03 | 2014-01-01 | 福建师范大学 | Method for preparing multiple-stimulation respond material containing thienylmaleimide by virtue of two-step process |
| CN103483327A (en) * | 2013-09-03 | 2014-01-01 | 福建师范大学 | Method for preparing multiple-stimulation respond material containing thienylmaleimide by virtue of dehydration reaction process |
| CN103635505A (en) * | 2011-07-05 | 2014-03-12 | 巴斯夫欧洲公司 | Dithienophthalimide semiconductor polymers |
| CN103804343A (en) * | 2014-03-04 | 2014-05-21 | 华东理工大学 | Bisphenol A-bonded dithienylethene compound and preparation and applications thereof |
| CN106700035A (en) * | 2016-12-05 | 2017-05-24 | 福建师范大学 | Dual-core three-arm star-type white light-emitting polymer and preparation method thereof |
-
2018
- 2018-11-05 CN CN201811310338.1A patent/CN109503814A/en not_active Withdrawn
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002145878A (en) * | 2000-11-08 | 2002-05-22 | Japan Science & Technology Corp | Dithienylethene derivative and light-control type conjugated polymer |
| CA2494920C (en) * | 2002-08-09 | 2013-01-22 | Simon Fraser University | Photochromic and electrochromic compounds and methods of synthesizing and using same |
| WO2004026988A1 (en) * | 2002-09-11 | 2004-04-01 | Heinrich-Heine-Universitaet Duesseldorf | Photochromic polymer composition and production, post-processing and use thereof |
| CN1775778A (en) * | 2005-12-01 | 2006-05-24 | 复旦大学 | Dithiophene ethene functional material, and its preparing method and use |
| CN101239976A (en) * | 2007-12-19 | 2008-08-13 | 华东理工大学 | Dithienylethene compounds containing naphthalimide unit |
| CN101497610A (en) * | 2009-03-06 | 2009-08-05 | 华东理工大学 | Dithiazole ethylene compound containing 2,1,3-diazosulfide unit |
| CN102286140A (en) * | 2010-06-18 | 2011-12-21 | 海洋王照明科技股份有限公司 | Perylene tetracarboxylic diimide copolymer containing dithieno quinoxaline unit as well as preparation method and application thereof |
| CN102344548A (en) * | 2010-07-30 | 2012-02-08 | 海洋王照明科技股份有限公司 | Copolymer containing fluorene and thiophene pyrroledione unit and preparation method and application of copolymer containing fluorene and thiophene pyrroledione unit |
| CN103635505A (en) * | 2011-07-05 | 2014-03-12 | 巴斯夫欧洲公司 | Dithienophthalimide semiconductor polymers |
| CN103467461A (en) * | 2013-09-03 | 2013-12-25 | 福建师范大学 | Preparation of multi-stimulating responsive material containing thienyl maleimide by substitution reaction method |
| CN103484104A (en) * | 2013-09-03 | 2014-01-01 | 福建师范大学 | Method for preparing multiple-stimulation respond material containing thienylmaleimide by virtue of two-step process |
| CN103483327A (en) * | 2013-09-03 | 2014-01-01 | 福建师范大学 | Method for preparing multiple-stimulation respond material containing thienylmaleimide by virtue of dehydration reaction process |
| CN103804343A (en) * | 2014-03-04 | 2014-05-21 | 华东理工大学 | Bisphenol A-bonded dithienylethene compound and preparation and applications thereof |
| CN106700035A (en) * | 2016-12-05 | 2017-05-24 | 福建师范大学 | Dual-core three-arm star-type white light-emitting polymer and preparation method thereof |
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