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CN114133391A - Nuclei-substituted naphthalene diimide electrochemically polymerized monomer and preparation method thereof - Google Patents

Nuclei-substituted naphthalene diimide electrochemically polymerized monomer and preparation method thereof Download PDF

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CN114133391A
CN114133391A CN202111473167.6A CN202111473167A CN114133391A CN 114133391 A CN114133391 A CN 114133391A CN 202111473167 A CN202111473167 A CN 202111473167A CN 114133391 A CN114133391 A CN 114133391A
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electrochemical polymerization
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郭智勇
江神通
罗雅方
武嘉雯
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Fuzhou University
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Abstract

The invention discloses a parent nucleus substituted naphthalene diimide electrochemical polymerization monomer and a preparation method thereof. The invention synthesizes a series of D-pi-A (donor-pi-acceptor) type organic dye molecules which take mother nucleus substituted naphthalene diimide as an acceptor and take triphenylamine, carbazole or thiophene and other elements with electrochemical polymerization activity as donors. The electron cloud distribution and the molecular orbital energy level distribution of the naphthalimide are adjusted by different substituents of the parent nucleus. The synthesized D-pi-A (donor-pi-acceptor) type organic dye molecule has excellent redox activity, and can form a film through electrochemical polymerization to be applied to the photoelectric field.

Description

Mother nucleus substituted naphthalene diimide electrochemical polymerization monomer and preparation method thereof
Technical Field
The invention belongs to the technical field of photoelectric functional materials, and particularly relates to a parent nucleus substituted naphthalene diimide electrochemical polymerization monomer and a preparation method thereof.
Background
Naphthalene Diimide (NDI) as the smallest homolog of aryl diimine has the advantages of high electron affinity, good carrier mobility, good thermal stability and oxidation stability, etc., and has the structural characteristics of a larger conjugated system and delocalized pi electrons, which are easily excited due to the change of external conditions, and the central structure of the naphthalene diimide has four carbonyl groups, so that the central naphthalene mother nucleus is in an electron-deficient state under the action of strong electrons. Due to the electron-deficient characteristic of the central parent nucleus of the naphthalimide, the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of the naphthalimide can be effectively changed by substituting atoms with different electronegativities at the parent nucleus of the naphthalimide, so that the optical property and the redox property of the naphthalimide are changed. The characteristic that parent nucleus substituted naphthalene diimides (cNDIs) can realize color absorption of all visible light bands through single atom change is probably the smallest chlorophyll simulant known at present and has the most 'atomic efficiency', so that the parent nucleus substituted naphthalene diimides become the focus of the last decade. Pyrrolidine, thioether and oxygen ether are three substituent groups with different electron-withdrawing capacities, the photoelectric property and the corresponding synthesis mode of the naphthalene diimide are different due to the difference of the substituent groups, and the exploration and the application of the naphthalene diimide in the field of organic photoelectricity are limited due to the great synthesis difficulty of the naphthalene diimide substituted by different parent nucleus. The Electrochemical Polymerization (EP) film formation has the characteristics of no catalyst, controllable film thickness, easy reaction condition, large roughness compared with spin coating and the like, and is widely applied to the manufacturing of photoelectric thin film devices. An ideal method for synthesizing the parent nucleus substituted naphthalene diimide electrochemical polymerization monomer is developed by combining the unique photoelectric property of the parent nucleus substituted naphthalene diimide, and the method is favorable for expanding the application of the parent nucleus substituted naphthalene diimide in the field of organic photoelectricity.
Disclosure of Invention
The invention aims to provide a preparation method of three types of parent nucleus substituted naphthalene diimide electrochemical polymerization monomers aiming at the problem of application of the current parent nucleus substituted naphthalene diimide in the field of organic photoelectricity. The pyrrolidine, oxygen ether or thioether parent nucleus substituted naphthalene diimide has different redox characteristics, so that the three parent nucleus substituted naphthalene diimide materials have great application prospects in the photoelectric field. The invention prepares three different parent nucleus substituted naphthalene diimide units into electrochemical polymerization monomers with electrochemical polymerization activity by two different synthesis methods. Electrochemical polymerization experiments show that the prepared monomer can form a film on the conductive glass in an electrochemical polymerization manner, and the application range of the monomer is further expanded.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the technical schemes of the invention provides a parent nucleus substituted naphthalene diimide electrochemical polymerization monomer, which has a chemical structural formula as follows:
Figure 113547DEST_PATH_IMAGE001
，
wherein R is1Is a naphthalene diimide parent nucleus substituent
Figure 22423DEST_PATH_IMAGE002
Or
Figure 839069DEST_PATH_IMAGE003
Or
Figure 903977DEST_PATH_IMAGE004
；R2Is triphenylamine, carbazole or thiophene and the like which have electrochemical polymerization activity, and comprises but is not limited to the following elements:
Figure 692942DEST_PATH_IMAGE005
。
the second technical scheme of the invention provides a preparation method of pyrrolidine mother nucleus substituted naphthalene diimide electrochemical polymerization monomer, which comprises the step of carrying out a nitrogen-arylation reaction on pyrrolidine mother nucleus substituted naphthalene diimide and a boric acid monomer containing an electrochemical polymerization activity element under the catalysis of copper ions to obtain the pyrrolidine mother nucleus substituted naphthalene diimide,
pyrrolidine nucleus-substituted naphthalenedicarboximideThe chemical formula of the amine (PNDI) is
Figure 653944DEST_PATH_IMAGE006
Boronic acid monomers (R) containing electrochemically polymerizable reactive moieties2-B(OH)2) Has a chemical formula as
Figure 223466DEST_PATH_IMAGE007
。
The specific reaction process is as follows:
Figure 764169DEST_PATH_IMAGE008
。
further, the preparation method specifically comprises the following steps:
substituting pyrrolidine mother nucleus with naphthalene diimide (PNDI) and R2-B(OH)2Adding anhydrous copper acetate into an anhydrous N, N-dimethylacetamide solvent, adding a dry molecular sieve, and blowing with oxygen for 30 min; adding triethylamine into the suspension, stirring the reaction mixture for 2 days at 55 ℃, and ensuring that the oxygen content in the system is sufficient; an additional amount of R2-B(OH)2Adding copper acetate and triethylamine DMAc solution into the reaction mixture, and stirring for 3 days at 55 ℃ in an oxygen environment; after the reaction is finished, washing, cooking, filtering, extracting, rotary-steaming are sequentially carried out, impurities are removed to obtain a crude product, and finally, the pyrrolidine mother nucleus substituted naphthalimide electrochemical polymerization active monomer is obtained by utilizing column chromatography separation and purification.
In the steps: pyrrolidine mother nucleus substituted naphthalene diimide, R2-B(OH)2And the molar ratio of the anhydrous copper acetate to the triethylamine is 1: 10:10: 10.
in the steps: an additional amount of a carbazole-or triphenylamine-containing boronic acid ligand R2-B(OH)2A DMAc solution of anhydrous copper acetate and triethylamine was added to the reaction mixture in an additional amount of half the amount charged in the previous step.
The third technical scheme of the invention provides a preparation method of a thioether or oxygen ether parent nucleus substituted naphthalene diimide electrochemical polymerization monomer, wherein the thioether or oxygen ether parent nucleus substituted naphthalene tetracarboxylic anhydride and an amino monomer containing an electrochemical polymerization active group are subjected to dehydration condensation under the catalysis of isoquinoline to obtain the thioether or oxygen ether parent nucleus substituted naphthalene diimide electrochemical polymerization monomer. Wherein
The chemical structural formula of the thioether or oxygen ether mother nucleus substituted naphthalene tetracarboxylic anhydride (SNDA, ONDA) is shown in the specification
Figure 938798DEST_PATH_IMAGE009
Amino monomers containing electrochemically polymerizable active groups (R)2-NH2) Has the chemical structural formula of
Figure 601861DEST_PATH_IMAGE010
And X is S or O.
The specific reaction process is as follows:
Figure 861941DEST_PATH_IMAGE011
。
further, the preparation method specifically comprises the following steps:
thioether or oxyether mother nucleus substituted naphthalene tetracarboxylic anhydride (SNDA or ONDA) and R2-NH2Dissolving in m-cresol, reacting at 80 deg.C for 2 hr, adding small amount of isoquinoline, and heating to 180 deg.C. After 8h of reaction, centrifuging, collecting precipitate, and finally obtaining the thioether or oxygen ether parent nucleus substituted naphthalene diimide electrochemical polymerization monomer through column chromatography separation.
In the steps: thioether or oxyether nucleus substituted naphthalenetetracarboxylic anhydride (SNDA or ONDA), R2-NH2The molar ratio of (A) to (B) is 2: 7.
the invention has the beneficial effects that:
1) the invention relates to a method for preparing a polymer film by using three kinds of mother nucleus substituted naphthalimide, which comprises the steps of preparing a polymer film by using three kinds of mother nucleus substituted naphthalimides, wherein the three kinds of mother nucleus substituted naphthalimides are pyrrolidine, thioether and oxygen ether, wherein the color and the electron energy level of the naphthalimide are regulated and controlled by a mother nucleus substituent group.
2) Triphenylamine, carbazole or thiophene and other elements have electrochemical activity, during the electrochemical polymerization process, triphenylamine free radical cations, carbazole free radical cations or thiophene free radical cations are formed, the free radical cations of the parent nucleus substituted naphthalene diimide containing the elements collide with each other to generate crosslinking during the electrochemical polymerization process, and an electrochemical polymerization CV curve graph shows that as the number of cycles increases, the polymerization current slowly increases, which represents the crosslinking among the electrochemically active elements and the formation of a parent nucleus substituted naphthalene diimide polymer film on the indium tin oxide conductive glass. The synthesized parent nucleus substituted naphthalimide polymer film has great application prospect in the photoelectric fields of electrochromism and the like.
Drawings
FIG. 1 is a diagram of the compound PNDI-Cz prepared in example 1 of the present invention1H-NMR spectrum;
FIG. 2 is a drawing showing SNDI-TPA compound prepared in example 2 of the present invention1H-NMR spectrum;
FIG. 3 is a drawing showing the preparation of the compound ONDI-TPA of example 3 of the present invention1H-NMR spectrum;
FIG. 4 is a graph of the PNDI-TPA compound prepared in example 4 of the present invention1H-NMR spectrum;
FIG. 5 is a diagram of the PNDI-2CZ compound prepared in example 5 of the present invention1H-NMR spectrum;
FIG. 6 is a graph of the electrochemical polymerization CV of the compound PNDI-CZ prepared in example 1 of the present invention;
FIG. 7 is a CV diagram for electrochemical polymerization of the compound SNDI-TPA prepared in example 2 of the present invention;
FIG. 8 is a CV diagram for electrochemical polymerization of the compound ONDI-TPA prepared in example 3 of the present invention.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
Synthesis of the Compound PNDI-Cz:
a suspension mixed with PNDI (0.5 g, 1.2 mmol), Cz-E284 (3.6 g, 12.4 mmol), copper acetate anhydrous (2.2 g, 12.4 mmol), well dried molecular sieve (4 a) and anhydrous N, N-dimethylacetamide (50 mL) was continuously sparged with oxygen for 30 min, triethylamine (1.7 mL, 12.4 mmol) was added to the suspension and the resulting reaction mixture was stirred under an oxygen atmosphere at 55 ℃ for 2 days. During the reaction, the oxygen content of the system needs to be ensured to be sufficient so as to ensure the smooth operation of the reaction. Then an additional solution of Cz-E284 (1.8 g, 6.2 mmol), anhydrous copper acetate (1.1 g, 6.2 mmol) and triethylamine (0.9 mL, 6.2 mmol) in N, N-dimethylacetamide (15 mL) was added to the reaction mixture and stirred under oxygen at 55 ℃ for an additional 3 days. After 5 days, the reaction mixture was cooled to room temperature, washed with a small amount of DMF and then with CHCl3Reflux cooking is carried out, and filtrate is collected after filtration; the filtrate was extracted with water to remove residual N, N-dimethylacetamide, and after concentration of the dark blue organic phase, it was passed through SiO2Column Chromatography (CH)2Cl2purification/PE/EtOAc = 10:10: 1) afforded pure PNDI-Cz as a dark blue solid (255 mg, yield about 24%).1H NMR (600 MHz, CDCl3) δ 8.52 (s, 2H), 8.17 (d, J = 7.7 Hz, 4H), 7.80 (d, 4H), 7.62 (d, J = 8.1, 0.8 Hz, 4H), 7.58 (d, 4H), 7.46 (t, 4H), 7.33 (t, J = 7.9, 7.0, 1.0 Hz, 4H), 3.58 (t, 8H), 2.11 (t, 8H). this example relates to the following reaction equation:
Figure 206334DEST_PATH_IMAGE012
。
example 2
Synthesis of the compound PNDI-TPA:
a suspension mixed with PNDI (0.5 g, 1.2 mmol), TPA-E284 (3.6 g, 12.4 mmol), copper acetate anhydrous (2.2 g, 12.4 mmol), well dried molecular sieve (4A) and anhydrous N, N-dimethylacetamide (50 mL) was continuously sparged with oxygen for 30 min and triethylamine (1.7 mL, 12.4 m) was added to the suspensionmol) and the reaction mixture obtained is stirred at 55 ℃ for 2 days under an oxygen atmosphere. During the reaction, the oxygen content of the system needs to be ensured to be sufficient so as to ensure the smooth operation of the reaction. An additional amount of TPA-E284 (1.8 g, 6.2 mmol), copper acetate (1.1 g, 6.2 mmol) and triethylamine (0.9 ml, 6.2 mmol) in N, N-dimethylacetamide (15 ml) was then added to the reaction mixture in O2Stir at 55 ℃ for an additional 3 days under ambient. After 5 days, the reaction mixture was cooled to room temperature and quenched with CH2Cl2(100 mL) washing. After collecting the filtrate, the filtrate was extracted with water to remove residual N, N-dimethylacetamide, and the objective product was dissolved in an organic phase. After concentrating the dark blue organic phase, it is passed through SiO2Column Chromatography (CH)2Cl2/PE/EtOAc = 10:10: 0.7) to give pure PNDI-TPA as a dark blue solid (90 mg, about 8.5% yield).1H NMR (600 MHz, CDCl3) δ (ppm) 8.45 (s, 2H), 7.33-7.30 (t, 8H), 7.24-7.21 (m, 12H), 7.16-7.15 (d, 4H), 7.10-7.07 (t, 4H), 3.52 (t, 8H), 2.07 (t, 8H). The reaction equation involved in this experiment is as follows:
Figure 235470DEST_PATH_IMAGE013
。
example 3
Synthesis of compound PNDI-2 CZ:
a suspension mixed with PNDI (0.5 g, 1.2 mmol), 2Cz-E284 (5.6 g, 12.4 mmol), anhydrous copper acetate (2.2 g, 12.4 mmol), well dried molecular sieve (4 a) and anhydrous N, N-dimethylacetamide (50 mL) was continuously sparged with oxygen for 30 min, triethylamine (1.7 mL, 12.4 mmol) was added to the suspension and the resulting reaction mixture was stirred under an oxygen atmosphere at 55 ℃ for 2 days. During the reaction, the oxygen content of the system needs to be ensured to be sufficient so as to ensure the smooth operation of the reaction. An additional amount of 2Cz-E284 (2.8 g, 6.2 mmol), copper acetate (1.1 g, 6.2 mmol) and triethylamine (0.9 ml, 6.2 mmol) in N, N-dimethylacetamide (25 ml) was then added to the reaction mixture in O2Stir at 55 ℃ for an additional 3 days under ambient. After 5 days, the reaction mixture was poured into a flaskCooled to room temperature and treated with CH2Cl2(100 mL) washing. After collecting the filtrate, the filtrate was extracted with water to remove residual N, N-dimethylacetamide, and the objective product was dissolved in an organic phase. After concentrating the dark blue organic phase, the mixture is passed through SiO2Column Chromatography (CH)2Cl2purification/PE/EtOAc = 10:10: 1.5) afforded pure PNDI-2Cz as a dark blue solid (75 mg, yield about 5.1%).1H NMR (600 MHz, CDCl3): δ 8.54 (s, 2H), 8.17 (d, J = 7.7 Hz, 8H), 8.01 (t, J = 1.9 Hz, 2H), 7.77 (d, J = 8.3 Hz, 8H), 7.72 (d, J = 1.9 Hz, 4H), 7.54–7.46 (m, 8H), 7.38–7.31 (m, 8H), 3.60 (t, 8H), 2.12 (t, J= 6.4 Hz, 8H) the reaction equation involved in this experiment is as follows
Figure 69434DEST_PATH_IMAGE014
。
Example 4
Synthesis of the compound SNDI-TPA:
mixing SNDA (21.7 mg, 0.0559 mmol) and TPA-NH2(59 mg, 0.2269 mmol) was dissolved in m-phenol (10 mL), and the resulting solution was heated at 80 ℃ for 2h, 1 mL isoquinoline was added and refluxed at 180 ℃ for 8 h. Cooling to room temperature after the reaction is finished, centrifuging the reactant, taking down the precipitate, dissolving the precipitate in dichloromethane, and passing through SiO2Column Chromatography (CH)2Cl2) Purification yielded pure SNDI-TPA as a purple-red solid (10 mg, yield approx. 20%).1H NMR (600 MHz, CDCl3) δ 8.82 (s, 2H), 7.32 (t, J = 7.7 Hz, 8H), 7.26-7.17 (m, 16H), 7.09 (t, J = 7.3 Hz, 4H), 3.26 (q, J = 7.4 Hz, 4H), 1.53 (t, J = 7.4 Hz, 6H) the reaction equation involved in this example is as follows:
Figure 82389DEST_PATH_IMAGE015
。
example 5
Synthesis of Compound ONDI-TPA
Mixing ONDA (21.8 mg, 0.0612 mmol) and TPA-NH2(54.8 mg, 0.2105 mmol) was dissolved in m-phenol (10 mL), and the resulting solution was heated at 80 ℃ for 2h, 1 mL isoquinoline was added and refluxed at 180 ℃ for 8 h. Cooling to room temperature after the reaction is finished, centrifuging the reactant, taking down the precipitate, dissolving the precipitate in dichloromethane, and passing through SiO2Column Chromatography (CH)2Cl2) Purification yielded pure ONDI-TPA as an orange-yellow solid (9.5 mg, yield approx. 20%).1H NMR (600 MHz, CDCl3) δ 8.79 (s, 2H), 7.29 (t, 8H), 7.23-7.15 (m, 16H), 7.07 (t, J = 7.3, 1.3 Hz, 4H), 3.23 (q, J = 7.4 Hz, 4H), 1.51 (t, J = 7.4 Hz, 6H) the reaction equation involved in this example is as follows:
Figure 27212DEST_PATH_IMAGE016
。
the electrochemical polymerization experiment is carried out on the obtained parent nucleus substituted naphthalimide electrochemical polymerization monomer, and the electrochemical polymerization measurement uses a three-electrode electrochemical cell, wherein indium tin oxide coated glass (the working area is about 0.8 cm multiplied by 2 cm) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. Generally, for triphenylamine or thiophene as an electrochemical active element, after the electrochemical polymerization reaction generates the first oxidation peak of a CV curve, the electrochemical active element is oxidized to form radical cations, and then coupling occurs and grows on the surface of indium tin oxide conductive glass. As shown in fig. 6, PNDI-CZ in electrochemical polymerization CV experiments, a slowly increasing current indicates cross-linking between carbazole units and formation of a blue electroactive polymer film as the number of cycles increases. A new oxidation peak around 1.18V appeared after the first pass, corresponding to the typical oxidation peak of the bicarbazole group, and also indicating the formation of the corresponding linear polymer. As shown in FIGS. 7 and 8, the SNDI-TPA and ONDI-TPA showed similar behavior of polymerization current in electrochemical polymerization CV experiment, and the oxidation peak of benzidine appeared around 0.9V, indicating the cross-linking between electrochemically active moieties and the formation of thin film of thioether or oxyether parent nucleus substituted naphthalene diimide polymer.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (9)

1.一种母核取代萘二酰亚胺电化学聚合单体，其特征在于：化学结构式如下：1. a kind of parent nucleus replaces naphthalene diimide electrochemical polymerization monomer, it is characterized in that: chemical structural formula is as follows:
Figure 67471DEST_PATH_IMAGE001
，
Figure 67471DEST_PATH_IMAGE001
, 其中，R1为萘二酰亚胺母核取代基
Figure 533087DEST_PATH_IMAGE002
或
Figure 323189DEST_PATH_IMAGE003
或
Figure 874256DEST_PATH_IMAGE004
；R2为具有电化学聚合活性基元。Wherein, R 1 is a naphthalene diimide core substituent
Figure 533087DEST_PATH_IMAGE002
or
Figure 323189DEST_PATH_IMAGE003
or
Figure 874256DEST_PATH_IMAGE004
; R 2 is an active unit with electrochemical polymerization. 2.根据权利要求1所述的母核取代萘二酰亚胺电化学聚合单体，其特征在于：R2包括以下结构式的电化学聚合活性基元：2. core-substituted naphthalene diimide electrochemical polymerization monomer according to claim 1, is characterized in that: R 2 comprises the electrochemical polymerization active primitive of following structural formula:
Figure 939164DEST_PATH_IMAGE005
。
Figure 939164DEST_PATH_IMAGE005
. 3.一种如权利要求1-2任一项所述的母核取代萘二酰亚胺电化学聚合单体的制备方法，其特征在于：当R1为萘二酰亚胺母核取代基
Figure 259287DEST_PATH_IMAGE002
时，所述制备方法是将吡咯烷母核取代萘二酰亚胺与含电化学聚合活性基元的硼酸单体通过铜离子催化发生氮-芳基化反应得到吡咯烷母核取代萘二酰亚胺电化学聚合单体，其中，3. a kind of preparation method of the parent nucleus-substituted naphthalene diimide electrochemical polymerization monomer as described in any one of claim 1-2, it is characterized in that: when R 1 is naphthalenediimide parent nucleus substituent
Figure 259287DEST_PATH_IMAGE002
, the preparation method is that the pyrrolidine core substituted naphthalene diimide and the boronic acid monomer containing the electrochemical polymerization active unit are catalyzed by copper ions to undergo nitrogen-arylation reaction to obtain the pyrrolidine core substituted naphthalene diacyl Imine electrochemically polymerized monomer, wherein, 吡咯烷母核取代萘二酰亚胺的化学结构式为
Figure 751448DEST_PATH_IMAGE006
，含电化学聚合活性基元的硼酸单体的化学式结构式为
Figure 795671DEST_PATH_IMAGE007
。The chemical structural formula of pyrrolidine core substituted naphthalene diimide is
Figure 751448DEST_PATH_IMAGE006
, the chemical structural formula of the boronic acid monomer containing electrochemical polymerization active unit is:
Figure 795671DEST_PATH_IMAGE007
. 4.根据权利要求3所述的制备方法，其特征在于，包括如下步骤：4. preparation method according to claim 3, is characterized in that, comprises the steps: （1）在常温下，先将吡咯烷母核取代萘二酰亚胺衍生物，R2-B(OH)2和醋酸铜分别加入无水N,N-二甲基乙酰胺中，并向溶液中加入干燥分子筛，混合均匀并向溶液中通氧气30 min后，再向混合溶液中加入三乙胺；(1) At room temperature, firstly add pyrrolidine core substituted naphthalenediimide derivatives, R 2 -B(OH) 2 and copper acetate to anhydrous N,N-dimethylacetamide, respectively, and add them to anhydrous N,N-dimethylacetamide. Add dry molecular sieves to the solution, mix evenly and pass oxygen into the solution for 30 min, then add triethylamine to the mixed solution; 升温至55 ℃，等待反应两天，期间需要不间断向反应体系中通入氧气；The temperature was raised to 55 °C and waited for the reaction for two days, during which it was necessary to continuously feed oxygen into the reaction system; 两天后，向反应体系中加入另一份R2-B(OH)2、醋酸铜和三乙胺，再等待反应3~5天，保持温度55 ℃，期间需持续通入氧气；Two days later, add another part of R 2 -B(OH) 2 , copper acetate and triethylamine to the reaction system, wait for the reaction for 3 to 5 days, keep the temperature at 55 °C, and continuously feed oxygen during the period; 反应结束后，用DMF洗涤，再使用CHCl3进行回流蒸煮，过滤后收集滤液；用水萃取滤液以除去残留的N,N-二甲基乙酰胺，浓缩有机相后得到粗产物，最后利用柱层析分离提纯得到吡咯烷母核取代萘二酰亚胺电化学聚合单体。After the reaction, wash with DMF, then use CHCl 3 for reflux cooking, and collect the filtrate after filtration; extract the filtrate with water to remove residual N,N-dimethylacetamide, concentrate the organic phase to obtain a crude product, and finally use the column layer. The pyrrolidine core-substituted naphthalene diimide electrochemically polymerized monomer was obtained by separation and purification. 5.根据权利要求4所述的制备方法，其特征在于：步骤（1）中所述吡咯烷母核取代萘二酰亚胺衍生物、R2-B(OH)2、醋酸铜和三乙胺的摩尔比为1：10：10：10。5 . The preparation method according to claim 4 , wherein the pyrrolidine core-substituted naphthalenediimide derivatives, R 2 -B(OH) 2 , copper acetate and triethyl ether described in the step (1) are: 5 . The molar ratio of amines was 1:10:10:10. 6.根据权利要求4所述的制备方法，其特征在于：步骤（3）中，两天后，再向体系中加入步骤（1）一半量R2-B(OH)2、醋酸铜和三乙胺。6. The preparation method according to claim 4, characterized in that: in step (3), two days later, half of step (1) R 2 -B(OH) 2 , copper acetate and triethyl acetate are added to the system amine. 7.一种如权利要求1-2任一项所述的母核取代萘二酰亚胺电化学聚合单体的制备方法，其特征在于：当R1为萘二酰亚胺母核取代基
Figure 867532DEST_PATH_IMAGE003
或
Figure 573320DEST_PATH_IMAGE004
，所述制备方法是将氧醚或硫醚母核取代萘四甲酸酐与含电化学聚合活性基团的氨基单体在异喹啉的催化下脱水缩合得到硫醚或氧醚母核取代萘二酰亚胺电化学聚合单体，其中7. a kind of preparation method of the parent nucleus-substituted naphthalenediimide electrochemical polymerization monomer as described in any one of claim 1-2, it is characterized in that: when R Be the naphthalenediimide parent nucleus substituent
Figure 867532DEST_PATH_IMAGE003
or
Figure 573320DEST_PATH_IMAGE004
The preparation method is to dehydrate and condense oxyether or thioether core substituted naphthalene tetracarboxylic anhydride and amino monomer containing electrochemical polymerization active group under the catalysis of isoquinoline to obtain thioether or oxyether core substituted naphthalene The diimide electrochemically polymerized monomer, wherein 硫醚或氧醚母核取代萘四甲酸酐的化学结构式为
Figure 705224DEST_PATH_IMAGE008
，含电化学聚合活性基团的氨基单体的化学结构式为
Figure 230883DEST_PATH_IMAGE009
，X为S或O。The chemical structural formula of thioether or oxygen ether core substituted naphthalene tetracarboxylic anhydride is
Figure 705224DEST_PATH_IMAGE008
, the chemical structural formula of the amino monomer containing electrochemical polymerization active groups is
Figure 230883DEST_PATH_IMAGE009
, X is S or O. 8.根据权利要求7所述的制备方法，其特征在于，包括如下步骤：8. preparation method according to claim 7, is characterized in that, comprises the steps: （1）在常温下，将硫醚或氧醚母核取代的萘四甲酸酐、R2-NH2溶于间甲酚中；(1) Dissolve naphthalene tetracarboxylic anhydride and R 2 -NH 2 substituted with thioether or oxygen ether nucleus in m-cresol at room temperature; （2）将混合溶液加热至80 ℃反应两小时后加入异喹啉后，180 ℃回流8小时；(2) The mixed solution was heated to 80 °C for two hours, after adding isoquinoline, refluxed at 180 °C for 8 hours; （3）将反应后的溶液离心收集沉淀，将收集的沉淀溶于二氯甲烷中，经过柱层析分离提纯得到氧醚或硫醚母核取代萘二酰亚胺电化学聚合单体。(3) Centrifuging the reacted solution to collect the precipitate, dissolving the collected precipitate in dichloromethane, and separating and purifying by column chromatography to obtain an oxygen ether or thioether core-substituted naphthalene diimide electrochemically polymerized monomer. 9.根据权利要求8所述的的制备方法，其特征在于：硫醚或氧醚母核取代的萘四甲酸酐和R2-NH2的摩尔比为2：7。9 . The preparation method according to claim 8 , wherein the molar ratio of naphthalene tetracarboxylic anhydride substituted with thioether or oxygen ether core and R 2 -NH 2 is 2:7. 10 .
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