CN111100131B - Preparation method and application of pyrrolopyrroledione derivative - Google Patents

Preparation method and application of pyrrolopyrroledione derivative Download PDF

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CN111100131B
CN111100131B CN201911396425.8A CN201911396425A CN111100131B CN 111100131 B CN111100131 B CN 111100131B CN 201911396425 A CN201911396425 A CN 201911396425A CN 111100131 B CN111100131 B CN 111100131B
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pyrrolopyrroledione
diethyl succinate
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CN111100131A (en
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杨龙
彭宇婷
黄宇洁
罗雪丹
谢芸
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Southwest University of Science and Technology
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a preparation method and application of a pyrrolopyrrole dione derivative, and relates to the technical field of pyrrolopyrrole dione catalysts, wherein the preparation method comprises the following steps: adding a cyano heterocyclic compound into a sodium tert-amylate solution, heating to 110-115 ℃, then dropwise adding a tert-amyl alcohol solution of diethyl succinate for reaction, and filtering, washing and drying the reaction solution after the reaction is finished to obtain the pyrrolopyrrole dione derivative. The invention also discloses the application of the pyrrolopyrrole-dione derivative in the photocatalytic polar monomer polymerization reaction, which can be used as a catalyst for the photocatalytic polar monomer polymerization reaction, so that the polymerization reaction can occur under the visible light condition, and the reaction can occur only by adding the initiator, the catalyst and the monomer for the polymerization reaction in the polymerization reaction without adding a reducing agent and other auxiliary agents.

Description

Preparation method and application of pyrrolopyrroledione derivative
Technical Field
The invention relates to the technical field of pyrrolopyrroledione catalysts, in particular to a preparation method and application of pyrrolopyrroledione derivatives.
Background
Atom Transfer Radical Polymerization (ATRP), a commonly used polymerization method, has evolved over the last 20 years to a mature polymerization strategy that allows for precise control of polymer synthesis. However, the ATRP method is adopted to synthesize the polymer with controllable structure, polymerization degree and dispersity, and the method strongly depends on the transition metal catalyst. Even though researchers have developed methods to reduce the amount of transition metal used or purify it, the problem of residual transition metal in polymers still limits the practical application of materials in living and electronic fields. The diversity of organic compounds also offers more possibilities for the design of high efficiency catalysts than the singleness and restriction of metal ions and organic ligands in inorganic complexes. In addition, compared with thermal initiation polymerization, photo-initiation has the characteristics of time and space controllability in the aspect of regulating and controlling polymerization reaction, and block or graft polymers are easier to obtain. Therefore, a non-metallic organic photocatalyst must be developed, the balance between the alkyl halide initiator and the polymer lengthening chain is regulated, the molecular weight of the polymer is controlled, the low dispersion degree is obtained, the chemical composition and the branching structure are defined, and meanwhile, the metal pollution, the poisoning and the interference are avoided, so that the polymer has wider application space in the fields of biology, life, medicine and electronic products.
At present, the non-metal organic photocatalyst can not completely replace a transition metal catalyst and is used for ATRP reaction. In the field of the emerging catalyst, three points are provided for the reason: 1, the variety of the non-metal organic photocatalyst is few; 2, initiation efficiency is not high; 3, the catalysts with visible light initiation activity are only reported, so that the structure-performance relationship is not clear. The reported maximum light absorption wavelength of the non-metal organic photocatalyst is usually about 400nm, and the light absorption wavelength is difficult to effectively extend to the visible light region, so that the initiation efficiency of the visible light is low. In the ultraviolet light catalysis initiation process, more side reactions are brought because of higher light energy, so that the structure of the polymer is difficult to accurately regulate and control.
Disclosure of Invention
The invention aims to provide a preparation method of a pyrrolopyrroledione derivative, which adopts a one-step method to realize the preparation of the pyrrolopyrroledione derivative.
The invention also provides application of the pyrrolopyrrole-dione derivative in polymerization reaction of a photocatalytic polar monomer.
The invention also provides a photocatalysis method of the pyrrolopyrrole-dione derivative in polar monomer polymerization reaction.
The invention provides a preparation method of a pyrrolopyrrole-dione derivative, which comprises the following steps:
adding a cyano heterocyclic compound into a sodium tert-amylate solution, heating to 110-115 ℃, then dropwise adding a tert-amyl alcohol solution of diethyl succinate for reaction, filtering, washing and drying a generated crude product to obtain the pyrrolopyrrole dione derivative.
Preferably, the cyano heterocyclic compound is any one of cyanothiophene, cyanopyridine, cyanofuran, cyanopyrrole and halogenated compounds thereof.
Preferably, the concentration of diethyl succinate in the tert-amyl alcohol solution of diethyl succinate is 0.017-0.020 g/ml; the concentration of the cyano heterocyclic compound in the sodium tert-amylate solution of the cyano heterocyclic compound is 0.007-0.009 g/ml; the molar ratio of diethyl succinate to cyano heterocyclic compound added during the reaction is 1: 2.
Preferably, when the tert-amyl alcohol solution of diethyl succinate is dropwise added, the dropwise addition of diethyl succinate is continued after the reaction of the dropwise added diethyl succinate is finished each time.
Preferably, the dropping speed of the tert-amyl alcohol solution of diethyl succinate is 0.5 drops/s.
Preferably, the reaction temperature of the diethyl succinate is 110-115 ℃, and the reaction time is 2.5-5 hours after the dropwise addition of the tert-amyl alcohol solution of the diethyl succinate is finished.
Preferably, the sodium tert-amylate is prepared at present in the following way: adding small pieces of simple substance sodium or sodium filaments into the tert-amyl alcohol at the temperature of 80 ℃ under the protection of nitrogen, heating to 110-115 ℃, and finishing the reaction of sodium and the tert-amyl alcohol to obtain the sodium tert-amyl alcohol.
Preferably, the reaction solution after the reaction is completed is filtered, washed and dried in the following manner: after the reaction is finished, adding a mixed solution of methanol and concentrated hydrochloric acid into the reaction solution, filtering, and washing and filtering by using methanol, water and methanol in sequence to obtain a filter cake; and adding the filter cake into DMSO, stirring and heating to 95-110 ℃, continuously stirring and preserving heat for 40-50 h, then carrying out hot filtration, washing and filtering with methanol, water and methanol in sequence, and carrying out vacuum drying on the washed and filtered solid for 3-5 h at 35-45 ℃ to obtain the product.
The pyrrolopyrrole dione derivative prepared by the invention can be applied to the polymerization reaction of the photocatalytic polar monomer. Specifically, the pyrrolopyrrole dione derivative can be used as a catalyst in a photocatalytic polar monomer polymerization reaction, so that the polar monomer polymerization reaction can occur under the visible light condition, and the polymerization reaction can be realized without adding a reducing agent in the polar monomer polymerization reaction.
The polar monomer may be: any of polar monomers such as methyl methacrylate, styrene, and acrylonitrile.
Preferably, in the photocatalytic polymerization of the polar monomer, the solvent used may be any one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or acetonitrile.
The invention discloses a photocatalysis method of a pyrrolo-pyrrole-dione derivative in polar monomer polymerization reaction, which specifically comprises the following steps:
slowly adding a polar monomer and an initiator into a DMF (dimethyl formamide) solution in which a pyrrolopyrrole dione derivative is dissolved, introducing inert gas into the solution to remove water and oxygen, starting a light source and stirring simultaneously, carrying out a polymerization reaction on a reaction system, reacting for 15-25 h, slowly adding the reaction solution into methanol, filtering, washing and drying to obtain the polar monomer polymer.
Wherein the light source is visible light.
Preferably, the initiator is any one of ethyl alpha-bromobenzoate, methyl 2-bromoisobutyrate, methyl alpha-bromoisopropanoate, diethyl 2-bromo-2-methylmalonate or ethyl 2-bromoisobutyrate.
Preferably, the pyrrolopyrroledione derivative is dissolved in a DMF solution under ultrasound and with heating.
Preferably, the inert gas is argon.
Preferably, the time for introducing the argon into the reaction system is 20-40 min, preferably 30 min.
Preferably, the concentration of the solution of the pyrrolopyrroledione derivative in DMF is 0.5 g/L; the volume of the initiator and the polar monomer is 1: 100; the volume ratio of the DMF solution of the pyrrolopyrroledione derivative to the polar monomer is 1: 1.
Preferably, the catalytic product is washed with methanol.
Has the advantages that:
(1) the preparation method of the pyrrolopyrrole dione derivative disclosed by the invention adopts a one-step reaction of a cyano heterocyclic compound and diethyl succinate to obtain a product, and the yield of the product can reach 80%.
(2) The invention discloses application of a pyrrolopyrrole dione derivative in photocatalysis polar monomer polymerization reaction, which can be used as a catalyst for photocatalysis polar monomer polymerization reaction, so that the polymerization reaction can occur under the condition of visible light, and the reaction can occur only by adding an initiator, the catalyst and the monomer for polymerization reaction in the polymerization reaction without adding a reducing agent and other auxiliary agents, so that the use of the reducing agent and the auxiliary agents is reduced, and the interference, the poisoning and the pollution in the reaction process are reduced.
(3) The invention discloses a photocatalysis method of pyrrolo-pyrrole-dione derivatives in polar monomer polymerization, which has less side reaction and is convenient for accurately regulating and controlling a polymer structure.
Drawings
FIG. 1 is a nuclear magnetic spectrum of DPP-P prepared in example 1;
FIG. 2 is a UV-VIS absorption spectrum of DPP-P prepared in example 1;
FIG. 3 is an infrared spectrum of the polymerization product PMMA prepared in example 1;
FIG. 4 is an infrared spectrum of a polymerization product PS prepared in example 1;
FIG. 5 is a nuclear magnetic spectrum of a polymerization product PS prepared in example 1;
FIG. 6 is an optical picture of the polymers PMMA and PS prepared in example 1;
FIG. 7 is an XRD pattern of the polymer PMMA prepared in example 1;
FIG. 8 is an optical picture of a PMMA precipitate of the polymer prepared in example 1;
fig. 9 is an optical picture of the polymers PMMA (left) and PS (right) prepared in example 1 swollen in THF.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
Example 1
The embodiment discloses a specific process for synthesizing a pyrrolopyrroledione derivative from 4-cyanopyridine and diethyl succinate, wherein the reaction formula is as follows:
Figure GDA0003077824040000051
the preparation method comprises the following specific steps:
measuring tert-amyl alcohol (30.0mL), and heating to 80 ℃ under the protection of nitrogen; quickly weighing small pieces of simple substance sodium metal (0.80g), adding the small pieces of simple substance sodium metal into tertiary amyl alcohol, heating to 115 ℃, and reacting to completely dissolve the metal sodium to obtain sodium tert-amyl alcohol; weighing diethyl succinate (0.20g) and adding the diethyl succinate into tertiary amyl alcohol to prepare 10mL diethyl succinate solution; adding 3-cyanopyridine (0.20g) into sodium tert-amylate, and preserving the temperature for 10min to obtain reaction liquid; and dropwise adding 10ml of diethyl succinate solution into the reaction solution at a speed of 2 seconds, continuing to perform heat preservation reaction for 3 hours after dropwise adding is finished, and obtaining the reaction solution after the reaction is finished. Then adding a mixed solution of 80mL of methanol and 5mL of concentrated hydrochloric acid into the reaction solution; filtering, washing and filtering by using methanol (100mL), water (100mL) and methanol (100mL) in sequence to obtain a filter cake, then adding the filter cake into dimethyl sulfoxide (DMSO), stirring and heating to 100 ℃, continuing stirring and keeping the temperature for 48 hours, then carrying out hot filtration, washing and filtering by using methanol (100mL), water (100mL) and methanol (100mL) in sequence, and drying the washed and filtered solid for 4 hours in vacuum at 40 ℃ to obtain a brown product 3, 6-bis (4-pyridine) -pyrrolopyrroledione (DPP-P), wherein the yield is 80.1%. Nuclear magnetic spectrum of the product: (1HNMR，CDCl3) As shown in fig. 1.
As shown in FIG. 2, the UV-visible absorption spectrum (DMF, 0.5 x 10) of the above product is-5M) with a visible DPP-P maximum absorption wavelength of 530nm, in the visible light region (400-760 nm).
The above product was used to catalyze the polymerization of polar monomers, exemplified by Methyl Methacrylate (MMA), as follows:
MMA and Dimethylformamide (DMF) were redistilled and freshly activated 4A ° molecular sieve was added, dried and stored. DPP-P prepared above was dried in vacuum at 60 ℃ for 6h before use. DPP-P (0.005g) was dissolved in DMF (10ml) under ultrasound and heating. MMA (10ml) and ethyl 2-bromoisobutyrate (EBiB, 0.1ml) as an initiator were then added to the solution; argon gas is introduced (30min) to remove oxygen. And (3) starting illumination (LED white light, 500W) and stirring, and carrying out polymerization reaction on the system for 16 h. After the reaction was completed, the reaction solution was slowly added dropwise to methanol, and a white flocculent precipitate appeared. Filtration, washing with methanol and drying gave a pale red product, Polymethylmethacrylate (PMMA), as shown in FIG. 6.
Taking styrene (St) as an example, the polymerization process is as follows:
st and Dimethylformamide (DMF) are redistilled and freshly activated 4A molecular sieves are added and stored dry. DPP-P prepared above was dried in vacuum at 60 ℃ for 6h before use. DPP-P (0.005g) was dissolved in DMF (10ml) under ultrasound and heating. St (10ml) and the initiator ethyl 2-bromoisobutyrate (EBiB, 0.1ml) were then added to the solution; argon gas is introduced (30min) to remove oxygen. And (3) starting illumination (LED white light, 500W) and stirring, and carrying out polymerization reaction on the system for 16 h. After completion of the reaction, the reaction solution was slowly added dropwise to methanol, and white flocculent precipitates appeared as shown in FIG. 8. Filtration, methanol washing and drying gave a pale pink product Polystyrene (PS) as shown in figure 6.
As shown in FIGS. 3 and 4, the infrared spectra of PMMA and PS, which are the products of the above polymerization reaction, are shown. From the ir spectrum of PS in the figure, it can be seen that: PS appears at 1693cm-1、1518cm-1And 1372cm-1Characteristic absorption peak of (a); from the IR spectrum of PMMA in the figure, it appears that PMMA is 1654cm-1、1582cm-1、1449cm-1、1262cm-1The presence of PMMA and PS in the product is proved by the characteristic absorption peak, and the polymerization reaction is carried out. Meanwhile, by comparing the characteristic absorption peak of DPP-P, the DPP-P residue in the product can be found, so that the product is light pink.
FIG. 5 shows a nuclear magnetic spectrum of the polymerization product PS: (1HNMR, d-DMF), wherein the PS characteristic peaks are in the interval of 0.5-2.0ppm and 6.5-7.5 ppm. The peaks at 9.0 and 8.7ppm are the signal peaks of the residual catalyst DPP-P, and at 8.0, 3.4, 2.9 and 2.7ppm are the peaks of the nuclear magnetic reagent (d-DMF). It can be seen that, in the example of St, a polymerization reaction occurs,the produced PS has DPP-P residue in the product, so that the product is pink. Therefore, DPP-P can be used as a catalyst for producing PS and PMMA by polymerizing St and MMA, and St and MMA can be catalyzed to produce PS and PMMA under the condition of visible light by only adding an initiator and a catalyst without adding a reducing agent. Therefore, DPP-P can be used as a non-metal organic photocatalyst for visible light catalytic polymerization of polar monomers.
Fig. 7 is an XRD pattern of the above polymerization product, PMMA, showing that the product shows new signal peaks at 8.2, 9.8, 16.4, and 17.5 °, etc., indicating that the product is a crosslinked MMA polymer.
FIG. 9 is a diagram showing the swelling of the above polymerization products PMMA (left) and PS (right) with Tetrahydrofuran (TFH), and it can be seen that the above products are high molecular polymers, not monomeric compounds.
Example 2
The embodiment discloses a specific process for synthesizing a pyrrolopyrrole dione derivative by using 2-cyanothiophene and diethyl succinate, and the reaction formula is as follows:
Figure GDA0003077824040000081
the specific preparation steps are basically the same as those of the example 1, so that the product 3, 6-di (2-thiophene) -pyrrolopyrroledione (DPP-T) is obtained, the yield is 82.5%, and an ultraviolet-visible absorption spectrum of the product is tested by an ultraviolet-visible spectrophotometer, the maximum absorption wavelength of the product is 550nm, and the maximum absorption wavelength is within a visible light region (400-760 nm).
The product is used for catalyzing the polymerization reaction of polar monomers, taking styrene as an example, the process of the polymerization reaction is basically the same as that of the example 1, the obtained product is respectively characterized by infrared spectroscopy, and PS (polystyrene) appears to be 1693cm-1、1518cm-1And 1372cm-1Characteristic absorption peak of (a). Therefore, DPP-T can be used as a catalyst for St, and St can be catalyzed to generate PS under visible light conditions by adding only an initiator and a catalyst, and not adding a reducing agent.
Example 3
The embodiment discloses a specific process for synthesizing a pyrrolopyrrole-dione derivative from 2-cyanopyrrole and diethyl succinate, and the reaction formula is as follows:
Figure GDA0003077824040000091
the specific procedure was substantially the same as in example 1 to give 3, 6-bis (2-pyrrole) -pyrrolopyrroledione (DPP-Py) as a product in 81.3% yield. And testing the ultraviolet-visible absorption spectrum of the product by using an ultraviolet-visible spectrophotometer, wherein the maximum absorption wavelength of the ultraviolet-visible absorption spectrum is 525nm and is in a visible light region (400-760 nm).
The product is used for catalyzing the polymerization reaction of polar monomers, taking styrene as an example, the polymerization reaction process is basically the same as that of the example 1, the obtained product is characterized by infrared spectroscopy, and the PS (polystyrene) is 1693cm-1、1518cm-1And 1372cm-1Characteristic absorption peak of (a). Thus, DPP-Py can be used as a catalyst for St, and St can be catalyzed to form PS under visible light conditions by adding only an initiator and a catalyst, and not adding a reducing agent.
Example 4
The embodiment discloses a specific process for synthesizing a pyrrolopyrrole dione derivative by using 2-cyano furan and diethyl succinate, and the reaction formula is as follows:
Figure GDA0003077824040000092
the specific preparation procedure was substantially the same as in example 1 to give the product 3, 6-bis (2-furan) -pyrrolopyrroledione (DPP-F) in 81.1% yield. And testing the ultraviolet-visible absorption spectrum of the product by using an ultraviolet-visible spectrophotometer, wherein the maximum absorption wavelength is 513nm and is in a visible light region (400-760 nm).
The product was used to catalyze the polymerization of polar monomers, exemplified by methyl methacrylate, the procedure of which was as in example 1The same applies to the obtained product, and the characterization of the polymerization product is carried out by infrared spectroscopy, and the appearance of PMMA is 1654cm-1、1582cm-1、1449cm-1、1262cm-1The characteristic absorption peak proves that PMMA exists in the product respectively and the polymerization reaction occurs.
Example 5
This example discloses a specific process for synthesizing a pyrrolopyrroledione derivative from 2-cyano-5-bromo-furan and diethyl succinate, the reaction formula of which is as follows:
Figure GDA0003077824040000101
the specific preparation procedure was substantially the same as in example 1 to give the product 3, 6-bis (2- (5-bromo) furan) -pyrrolopyrroledione (DPP-F-Br) in 81.5% yield. And testing the ultraviolet-visible absorption spectrum of the product by using an ultraviolet-visible spectrophotometer, wherein the maximum absorption wavelength of DPP-F-Br is 528nm and is within a visible light region (400-760 nm).
The product obtained by using the above product for catalyzing the polymerization of polar monomers, taking methyl methacrylate as an example, in substantially the same manner as in example 1, and characterizing the polymerization product by means of infrared spectroscopy, showed PMMA at 1654cm-1、1582cm-1、1449cm-1、1262cm-1The characteristic absorption peak proves that PMMA exists in the product respectively and the polymerization reaction occurs.
Example 6
This example discloses a specific process for synthesizing a pyrrolopyrroledione derivative from 2-cyano-5-bromo-pyrrole and diethyl succinate, the reaction formula of which is as follows:
Figure GDA0003077824040000111
the specific preparation procedure was substantially the same as in example 1, to give the product 3, 6-bis (2- (5-bromo) furan) -pyrrolopyrroledione (DPP-Py-Br) in 80.2% yield. And testing the ultraviolet-visible absorption spectrum of the product by using an ultraviolet-visible spectrophotometer to obtain DPP-Py-Br with the maximum absorption wavelength of 535nm and the visible light region (400-760 nm).
The product obtained by using the above product in the catalysis of the polymerization of polar monomers, using methyl methacrylate as an example, in substantially the same manner as in example 1, was characterized by infrared spectroscopy, giving rise to PMMA at 1654cm-1、1582cm-1、1449cm-1、1262cm-1The characteristic absorption peak proves that PMMA exists in the product respectively and the polymerization reaction occurs.
The product c contained PMMA and DPP-Py-Br, which shows that; the product d contains Polyacrylonitrile (PACN) and DPP-Py-Br; therefore, DPP-Py-Br can be used as a catalyst for producing PMMA and PACN by polymerizing MMA and ACN, and MMA and ACN can be catalyzed to produce PMMA and ACN under the condition of visible light by only adding an initiator and a catalyst without adding a reducing agent. Therefore, DPP-Py-Br can be used as a non-metal organic photocatalyst for visible light catalytic polymerization of polar monomers.
Example 7
This example discloses a specific process for synthesizing a pyrrolopyrroledione derivative from 2-cyano-5-bromo-thiophene and diethyl succinate, the reaction formula of which is as follows:
Figure GDA0003077824040000121
the specific preparation steps are basically the same as those of the example 1, so that the product 3, 6-bis (2- (5-bromo) thiophene) -pyrrolopyrroledione (DPP-T-Br) is obtained, the yield is 80.2%, an ultraviolet-visible absorption spectrum of the product is tested by adopting an ultraviolet-visible spectrophotometer, and the maximum absorption wavelength of visible DPP-T-Br is 560nm and is within a visible light region (400-760 nm).
The product obtained by using the above product for catalyzing the polymerization of polar monomers, in the case of methyl methacrylate, in substantially the same manner as in example 1, and subjecting the polymerization product to infrared spectroscopyCharacterization revealed PMMA at 1654cm-1、1582cm-1、1449cm-1、1262cm-1The characteristic absorption peak proves that PMMA exists in the product respectively and the polymerization reaction occurs.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A method for producing a pyrrolopyrroledione derivative, comprising the steps of: adding a cyano heterocyclic compound into a sodium tert-amylate solution, heating to 110-115 ℃, dropwise adding a tert-amyl alcohol solution of diethyl succinate for reaction, filtering, washing and drying the reaction solution after the reaction is finished to obtain a pyrrolopyrrole dione derivative; the molar ratio of diethyl succinate to the cyano heterocyclic compound added during the reaction is 1: 2;
the reaction solution after the reaction is finished is filtered, washed and dried in the following modes: after the reaction is finished, adding a mixed solution of methanol and concentrated hydrochloric acid into the reaction solution, washing and filtering the reaction solution by using methanol, water and methanol in sequence after filtering to obtain a filter cake, adding the filter cake into DMSO, stirring and heating the mixture to 95-110 ℃, continuously stirring and preserving heat for 40-50 h, then carrying out hot filtration, washing and filtering the mixture by using methanol, water and methanol in sequence, and carrying out vacuum drying on the washed and filtered solid for 3-5 h at 35-45 ℃ to obtain a product;
wherein the cyanoheterocyclic compound is 2-cyano-5-bromo-furan or 2-cyano-5-bromo-pyrrole;
the chemical formula of the pyrrolopyrroledione derivative is as follows:
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。
2. the preparation method of the pyrrolopyrrole-dione derivative according to claim 1, wherein the concentration of diethyl succinate in the solution of diethyl succinate in tert-amyl alcohol is 0.017 to 0.02 g/ml; the concentration of the cyano heterocyclic compound in the tert-amyl alcohol sodium solution of the cyano heterocyclic compound is 0.007-0.009 g/ml.
3. The method for preparing a pyrrolopyrrole dione derivative according to claim 1, wherein when dropwise adding the tert-amyl alcohol solution of diethyl succinate, the dropwise adding diethyl succinate is continuously added after the reaction of each dropwise adding diethyl succinate is completed.
4. Application of pyrrolo-pyrrole-dione derivatives in photocatalytic polar monomer polymerization reaction; the formula of the pyrrolopyrroledione derivative is as follows:
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5. use according to claim 4, characterized in that the pyrrolopyrroledione derivatives prepared by the process of any one of claims 1 to 3 are used as catalysts in photocatalytic polar monomer polymerization.
6. Use according to claim 4, wherein the polar monomer is any one of methyl methacrylate, styrene or acrylonitrile.
7. A photocatalytic method of pyrrolopyrroledione derivatives in polar monomer polymerization is characterized in that polar monomers and DMF are redistilled and a newly activated 4A molecular sieve is added; under the conditions of ultrasound and heating, dissolving a pyrrolopyrrole dione derivative in a DMF solution, slowly adding a polar monomer and an initiator into the DMF solution in which the pyrrolopyrrole dione derivative is dissolved, then introducing an inert gas into the solution to remove water and oxygen, turning on a light source and stirring simultaneously, carrying out a polymerization reaction on a reaction system, after reacting for 15-25 h, slowly adding a reaction solution into methanol, filtering, washing and drying to obtain a polar monomer polymer;
the pyrrolopyrroledione derivative is:
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、
Figure 468753DEST_PATH_IMAGE007
。
8. the photocatalytic method according to claim 7, wherein the light source is visible light.
9. The photocatalytic method according to claim 7, characterized in that the initiator is any one of ethyl α -bromophenylacetate, methyl 2-bromoisobutyrate, methyl α -bromoisopropanoate, diethyl 2-bromo-2-methylmalonate, or ethyl 2-bromoisobutyrate.
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