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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- CN109503814A CN109503814A CN201811310338.1A CN201811310338A CN109503814A CN 109503814 A CN109503814 A CN 109503814A CN 201811310338 A CN201811310338 A CN 201811310338A CN 109503814 A CN109503814 A CN 109503814A
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- electrical storage
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- maleimide
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- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 238000003860 storage Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000005611 electricity Effects 0.000 title description 20
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 230000031709 bromination Effects 0.000 claims abstract description 9
- 238000005893 bromination reaction Methods 0.000 claims abstract description 9
- 230000029936 alkylation Effects 0.000 claims abstract description 8
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- -1 dibromothiophene maleimide Chemical compound 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 32
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000005286 illumination Methods 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000003811 acetone extraction Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000006399 behavior Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical class 0.000 description 1
- 150000002220 fluorenes Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08G2261/10—Definition of the polymer structure
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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Abstract
本发明涉及一种具有光活性的电存储聚合物及其制备方法。该聚合物制备方法包括：3,4‑二噻吩马来酰亚胺的烷基化；N‑烷基‑3,4‑二噻吩马来酰亚胺的溴化；N‑烷基‑3,4‑二噻吩马来酰亚胺单体和二烷基芴单体共聚。本发明得到的电存储聚合物具有光活性，即光照后，二噻吩马来酰亚胺会发生关环反应，使得聚合物的结构、电子性能和电存储性能发生改变。本发明的电存储聚合物还具有制备方法简单，合成温度低，稳定性好等优点，适合工业化生产，具有实用性，在密码信息储存和防伪等领域具有广阔的应用前景。
The present invention relates to a photoactive electrical storage polymer and a preparation method thereof. The polymer preparation method comprises: alkylation of 3,4-dithiophenemaleimide; bromination of N-alkyl-3,4-dithiophenemaleimide; N-alkyl-3, 4-dithiophene maleimide monomer and dialkyl fluorene monomer are copolymerized. The electrical storage polymer obtained by the present invention has photoactivity, that is, after irradiation, the dithiophene maleimide undergoes a ring-closing reaction, so that the structure, electronic properties and electrical storage properties of the polymer are changed. The electrical storage polymer of the invention also has the advantages of simple preparation method, low synthesis temperature, good stability, etc., is suitable for industrial production, has practicability, and has broad application prospects in the fields of cryptographic information storage and anti-counterfeiting.
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)
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