CN110387020B - Metalloporphyrin polystyrene elastomer and preparation method and application thereof - Google Patents

Metalloporphyrin polystyrene elastomer and preparation method and application thereof Download PDF

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CN110387020B
CN110387020B CN201810364512.4A CN201810364512A CN110387020B CN 110387020 B CN110387020 B CN 110387020B CN 201810364512 A CN201810364512 A CN 201810364512A CN 110387020 B CN110387020 B CN 110387020B
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张爱民
汤舒嵋
徐雨
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Sichuan University
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Abstract

The invention discloses a metalloporphyrin polystyrene elastomer and a preparation method and application thereof. The metal porphyrin polystyrene elastic composite material is an organic photoelectric conversion material and is prepared by chloromethylation, hydroformylation, porphyrin and metallization in sequence. The porphyrin grafting ratio is only within 5-55%, the porphyrin polystyrene elastomer can have good photoelectric responsiveness while the elasticity and flexibility of the porphyrin polystyrene elastomer are maintained, and particularly, the porphyrin polystyrene elastomer is metalized to complex metal ions in porphyrin rings, so that the photoelectric responsiveness of the porphyrin polystyrene elastomer is further improved.

Description

Metalloporphyrin polystyrene elastomer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric conversion materials, and particularly relates to a metalloporphyrin polystyrene elastomer, and a preparation method and application thereof.
Background
The sun is a huge energy bank, and the solar energy received in one year on the earth is as high as 1.8 multiplied by 1018Kilowatt-hour. The purpose of research and development of photoelectric conversion materials is to utilize solar energy. The requirements of solar cells for photoelectric conversion materials are high conversion efficiency, and the ability to make large-area devices for further improvementAbsorbing sunlight well.
The used photoelectric conversion materials mainly comprise monocrystalline silicon, polycrystalline silicon and amorphous silicon, and devices made of the inorganic silicon-based photoelectric conversion materials are hard sectional materials, lack elasticity and flexibility, and cannot be repeatedly folded, stretched, extruded, curled or deformed. However, in many fields, such as wearable flexible optoelectronic devices, all components thereof must have both excellent mechanical strength and sufficient flexibility to ensure that the performance thereof meets various human sports requirements. For example, in order to maintain normal flight after the spacecraft is lifted off, a large number of inorganic silicon-based solar panels are carried during launching, and if the solar panels can be rolled, lifted off and then unfolded, the space load of the aircraft can be greatly reduced. Therefore, research and development of a novel flexible photoelectric conversion material are of great significance.
Meanwhile, the inorganic photoelectric material has high cost, large energy consumption of the preparation process and serious pollution. The organic photoelectric material has the advantages of good flexibility, easy manufacture, wide material source, low cost and the like, thereby having important significance for sustainable development by utilizing solar energy in a large scale and providing cheap electric energy.
Disclosure of Invention
In order to solve the problems, the invention provides a metalloporphyrin polystyrene elastomer and a preparation method and application thereof.
The invention provides an organic photoelectric conversion material, which is prepared by the following method:
(1) chloromethylation: sequentially dissolving polystyrene elastomer, chloromethylation reagent and catalyst in chloroform, and completely reacting to obtain chloromethylated polystyrene elastomer;
(2) aldehyde formation: dissolving chloromethylated polystyrene elastomer, dimethyl sulfoxide, potassium iodide and sodium bicarbonate in xylene in sequence, and completely reacting to obtain aldehyde polystyrene elastomer;
(3) porphyrization: dissolving aldehyde polystyrene elastomer, substituted or unsubstituted benzaldehyde, pyrrole and lactic acid in xylene in sequence, and completely reacting to obtain porphyrin polystyrene elastomer;
(4) metallization: dissolving the porphyrized polystyrene elastomer and the soluble metal salt in the dimethylbenzene in sequence, and completely reacting to obtain the metalloporphyrized polystyrene elastomer.
In the step (1), the polystyrene elastomer is one or two of styrene butadiene block copolymer, styrene isoprene block copolymer, hydrogenated styrene butadiene block copolymer and polystyrene isoprene butadiene rubber; and/or, the polystyrene-based elastomer is a linear structure; and/or, the chloromethylation reagent is 1, 4-dichloromethoxybutane; and/or, the catalyst is tin tetrachloride.
In the step (1), the feeding ratio of the polystyrene elastomer to chloroform, chloromethylation reagent and stannic chloride is 1: 50: 4: 0.8 g/mL/mL/mL; and/or the temperature of the reaction is 0 +/-2 ℃; and/or the reaction time is 1-9 h, preferably 2-7 h, and more preferably 3-6 h.
In the step (2), the reaction temperature is 100-120 ℃, and preferably 110 ℃; and/or the reaction time is 5-7 h, preferably 6 h.
In the step (2), the feeding ratio of the chloromethylated polystyrene elastomer to the xylene, the dimethyl sulfoxide, the potassium iodide and the sodium bicarbonate is 6: 300: 100: 4: 3 g/mL/mL/g/g.
In the step (3), the substituted or unsubstituted benzaldehyde is benzaldehyde, p-hydroxybenzaldehyde, p-nitrobenzaldehyde, p-chlorobenzaldehyde or p-aminobenzaldehyde.
In the step (3), the reaction temperature is 100-120 ℃, and preferably 110 ℃; and/or the reaction time is 4-6 h, preferably 5 h; and/or the feeding ratio of the aldehyde polystyrene elastomer to xylene, substituted or unsubstituted benzaldehyde, pyrrole and lactic acid is 1: 100: 1.8: 1.5: 2.5 g/mL/mL/mL.
In the step (4), the soluble metal salt is zinc chloride, zinc acetate, cobalt chloride, ferric chloride, magnesium nitrate or silver nitrate; and/or the reaction temperature is 100-120 ℃, preferably 110 ℃; and/or the reaction time is 30-90 min, preferably 60 min.
In the step (4), the mass-to-volume ratio of the porphyrized polystyrene to the xylene is 1:100 g/mL; the weight ratio of the porphyrized polystyrene to the soluble metal salt is 100: 1.
the organic photoelectric conversion material is applied to the field of preparing a photovoltaic device.
The temperature of the ice water bath is 0 ℃.
The invention provides a metalloporphyrin polystyrene elastomer and a preparation method and application thereof, the metalloporphyrin polystyrene elastomer is an organic photoelectric conversion material, and the porphyrin grafting ratio is only within 5-55% of the specific range of the invention, the porphyrin polystyrene elastomer can have better photoelectric responsiveness while maintaining the elasticity and flexibility thereof, particularly, the invention further improves the photoelectric responsiveness thereof by metalizing the porphyrin polystyrene elastomer and complexing metal ions in porphyrin rings.
Specifically, the organic photoelectric material of the present invention has the following advantages:
(1) the material has flexibility and elasticity, and can be folded, stretched, extruded, curled and the like;
(2) the material is a thermoplastic elastomer, is heated and plasticized, and is easy to process and mold;
(3) the leftover materials can be repeatedly plasticized and molded and recycled;
(4) the material has simple processing technology, environmental protection and low energy consumption;
(5) the raw material source is wide, and the cost is low.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is an infrared absorption spectrum of a product at different stages of the present invention.
FIG. 2 is a nuclear magnetic resonance image of SEBS.
FIG. 3 is a nuclear magnetic resonance image of CMSEBS.
FIG. 4 is a nuclear magnetic resonance image of ALSEBS.
FIG. 5 is a nuclear magnetic resonance image of PPSEBS.
FIG. 6 is a schematic diagram of a hydrogen nuclear magnetic resonance spectrum of porphyrized SEBS.
FIG. 7 shows a preparation of PPSEBS in example 11H-NMR spectrum.
Fig. 8 is a test chart of the photoelectric response of example 1.
FIG. 9 shows a preparation of PPSEBS in example 21H-NMR spectrum.
Fig. 10 is a test chart of the photoelectric response of example 2.
FIG. 11 is a representation of the PPSEBS of example 31H-NMR spectrum.
FIG. 12 is a test chart of the photoelectric response of example 3.
FIG. 13 is a PPSEBS of comparative example 11H-NMR spectrum.
Fig. 14 is a test chart of the photoelectric response of comparative example 1.
FIG. 15 is a PPSEBS of comparative example 21H-NMR spectrum.
Fig. 16 is a test chart of the photoelectric response of comparative example 2.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
The reagents used in the invention are all purchased from the chemical reagent factory of the Pandantong City.
The photoelectric response testing instrument is an electrochemical workstation, and is manufactured by: shanghai Huachen, brand: CHI 6601.
The preparation of the organic photoelectric material of the invention comprises the following steps:
(1) para-chloromethylation of benzene ring
Dissolving polystyrene elastomer in chloroform solvent, taking 1, 4-dichloromethoxybutane as chloromethylation reagent, and carrying out ice water bath for several hours under the catalysis of stannic chloride to react to obtain chloromethylated polystyrene elastomer. The grafting rate of chloromethyl increases with the reaction time extension, control different reaction times and get different grafting rates of chloromethyl.
(2) Hydroformylation of benzene ring at para position
Dissolving chloromethylated polystyrene elastomer in xylene solvent, adding potassium iodide and sodium bicarbonate by taking DMSO as a mild oxidant, and reacting at 110 ℃ for 6 hours to obtain aldehyde polystyrene elastomer. The addition amount of the hydroformylation reagent is excessive in a theoretical calculation value, so that the chloromethyl is completely converted into aldehyde groups.
(3) Porphyrization of
Dissolving the aldehyde polystyrene elastomer in a xylene solvent, adding benzaldehyde or substituted benzaldehyde (such as benzaldehyde, p-hydroxybenzaldehyde, p-nitrobenzaldehyde, p-chlorobenzaldehyde, p-aminobenzaldehyde and the like), pyrrole and lactic acid, wherein the benzaldehyde or substituted benzaldehyde and the pyrrole are used as raw materials for synthesizing a porphyrin ring, the lactic acid is used as a catalyst, and reacting for 5 hours at 110 ℃ to obtain the porphyrin polystyrene elastomer. The addition amount of the porphyrization reagent is excessive to the theoretical calculation value, and the aldehyde groups are all grafted into porphyrin rings.
(4) Metallization
Dissolving the porphyrized polystyrene elastomer in a xylene solvent, adding soluble metal salt (such as zinc chloride, zinc acetate, cobalt chloride, ferric chloride, magnesium nitrate, silver nitrate and the like), and carrying out coordination reaction at the constant temperature of 110 ℃ for 1h to obtain the metalloporphyrin polystyrene elastomer with metal ions complexed in the middle of porphyrin rings. Controlling the molecular weight of porphyrin ring on the polymer chain when the metal salt is excessive, ensuring that the metal ion is completely complexed on the center of the porphyrin ring, and obtaining the metalloporphyrin polystyrene elastomer.
Example 1 metalloporphyrin polystyrene elastomer organic photoelectric material of the present invention
Preparation of metalloporphyrin polystyrene elastomer organic photoelectric material
Figure GDA0003109036680000041
(1) Preparing CMSEBS by para-chloromethylation of benzene ring of SEBS
5.0g of hydrogenated styrene butadiene block copolymer (SEBS) (molecular weight: 5 ten thousand) was dissolved in 250ml of chloroform solvent, and 20ml of 1, 4-dichloromethoxybutane was used as a chloromethylation reagent, and the reaction was carried out in an ice-water bath for 1.5 hours under the catalysis of 4ml of tin tetrachloride to obtain chloromethylated SEBS, which was denoted as CMSEBS.
(2) ALSEBS is prepared by the para-aldehyde of benzene ring
Dissolving 3.0g of CMSEBS in 150ml of xylene solvent, adding 2.0g of potassium iodide and 1.5g of sodium bicarbonate by taking 50ml of DMSO as a mild oxidant, and reacting at 110 ℃ for 6h to obtain the aldehyde-based SEBS, which is marked as ALSEBS.
(3) Porphyrin to obtain PPSEBS
Dissolving 1.0g of ALSEBS in 100ml of xylene solvent, adding 1.8ml of benzaldehyde, 1.5ml of pyrrole and 2.5ml of lactic acid, wherein the benzaldehyde and the pyrrole are used as raw materials for synthesizing porphyrin ring, the lactic acid is used as a catalyst, and reacting for 5 hours at 110 ℃ to obtain the porphyrized SEBS, which is marked as PPSEBS.
(4) Metallization
1.0g of PPSEBS is dissolved in 100ml of xylene solvent, 0.01g of magnesium nitrate is added, and the mixture reacts for 1 hour at 110 ℃ to obtain magnesium porphyrin SEBS which is recorded as MgPPSEBS.
Second, characterize
(1) Infrared absorption of the products of each stage
The infrared absorption spectra of the products of the invention at different stages are shown in FIG. 1, wherein 676cm in CMSEBS-1C-Cl stretching vibration absorption indicates that CMSEBS is prepared; 1701cm in ALSEBS-1The position is a characteristic absorption peak of C ═ O, the disappearance of a C-Cl bond and the appearance of C ═ O, which indicates that the aldehyde SEBS is successfully synthesized; 3318cm in PPSEBS-1、965cm-1Respectively, an inner ring N-H telescopic vibration peak and an in-plane bending vibration peak, 1350cm-1、798cm-1Is vibration-absorbing of porphyrin skeleton, and 1701cm-1The characteristic absorption peak of C ═ O is obviously weakened, which indicates that the synthesis of the PPSEBS is successful.
(2) Of the products of each stage1H-NMR spectrum
FIGS. 2 to 5 are nuclear magnetic resonance diagrams of SEBS, CMSEBS, ALSEBS and PPSEBS, respectively, and FIG. 6 is a schematic diagram of nuclear magnetic vibration of H atoms on a porphyrin ring. FIG. 3 shows a resonance absorption peak of H at the p-chloromethyl position of the benzene ring at 4.53ppm in CMSEBS; 9.92ppm of ALSEBS in FIG. 4 is a resonance absorption peak of H-aldehyde group at the para position of benzene ring; 6.25-7.21ppm in the PPSEBS shown in FIG. 5 is a hydrogen resonance absorption peak on a benzene ring in a polystyrene chain segment of a molecular main chain; 8.87ppm is the hydrogen resonance absorption peak on the pyrrole ring; 8.24ppm is the resonance absorption peak of hydrogen at the ortho position of the benzene ring in the porphyrin ring; 7.78ppm is the resonance absorption peak of the meta-position and para-position hydrogen of the benzene ring in the porphyrin ring; -2.75ppm is the N-linked hydrogen resonance absorption peak on the pyrrole ring.
(3) Porphyrin ring grafting ratio
The calculation formula of the porphyrin ring grafting ratio is as follows:
Figure GDA0003109036680000051
where I is the relative integrated area.
By passing1Integration of the area data from the H-NMR spectrum (see FIG. 7) indicates that if IN-HIs 1, then IA,B,C,A’,B’Is 22.23. Calculated as porphyrin ring grafting of 11%.
(4) EXAMPLE 1 photoelectric response test Pattern
The photoelectric response test chart of the embodiment 1 of the invention is shown in fig. 8, the polymer generates photocurrent when light is irradiated, and the photocurrent of the polymer disappears immediately when no light is irradiated, so that the photoelectric response of the polymer is realized.
As can be seen from FIG. 8, the current density of the porphyrized SEBS can reach 0.058 muA/cm2The current density of the magnesium porphyrin SEBS can reach 0.060 mu A/cm2Namely, the photocurrent of the intermediate metal ions in the porphyrin ring is increased by 3.4 percent, and the photoelectric responsiveness of the polymer can be improved by the intermediate metal ions in the porphyrin ring.
(5) Elasticity of PPSEBS
The elasticity of the polymer PPSEBS was characterized using a shore durometer and the hardness was measured to be 53 HA.
Example 2 organic photoelectric Material of the invention
Preparation of organic photoelectric material PPSEBS
(1) Preparing CMSEBS by para-chloromethylation of benzene ring of SEBS
5.0g of hydrogenated styrene butadiene block copolymer (SEBS) (molecular weight: 5 ten thousand) was dissolved in 250ml of chloroform solvent, and 20ml of 1, 4-dichloromethoxybutane was used as a chloromethylation reagent, and the reaction was carried out in an ice-water bath for 4 hours under the catalysis of 4ml of tin tetrachloride, so as to obtain chloromethylated SEBS, which is denoted as CMSEBS.
(2) ALSEBS is prepared by the para-aldehyde of benzene ring
Dissolving 3.0g of CMSEBS in 150ml of xylene solvent, adding 2.0g of potassium iodide and 1.5g of sodium bicarbonate by taking 50ml of DMSO as a mild oxidant, and reacting at 110 ℃ for 6h to obtain the aldehyde-based SEBS, which is marked as ALSEBS.
(3) Porphyrin to obtain PPSEBS
Dissolving 1.0g of ALSEBS in 100ml of xylene solvent, adding 1.8ml of p-nitrobenzaldehyde, 1.5ml of pyrrole and 2.5ml of lactic acid, wherein the p-nitrobenzaldehyde and the pyrrole are used as raw materials for synthesizing porphyrin ring, the lactic acid is used as catalyst, and reacting for 5h at 110 ℃ to obtain the porphyrized SEBS, which is marked as PPSEBS.
(4) Metallization
1.0g of the CoPPSEBS is dissolved in 100ml of xylene solvent, 0.01g of cobalt chloride is added, and the mixture reacts for 1h at 110 ℃ to obtain the cobalt porphyrin SEBS which is recorded as the CoPPSEBS.
Second, characterize
(1) Porphyrin ring grafting ratio
The calculation formula of the porphyrin ring grafting ratio is as follows:
Figure GDA0003109036680000061
where I is the relative integrated area.
By passing1Integration of the area data from the H-NMR spectrum (see FIG. 9) indicates that if IN-HIs 1, then IA,B,C,A’,B’Is 10.37. Calculated as a porphyrin ring grafting yield of 23%.
(2) Photoelectric response test chart
The photoelectric response test chart of the embodiment 2 of the invention is shown in fig. 10, the polymer generates photocurrent when light is irradiated, and the photocurrent of the polymer disappears immediately when no light is irradiated, so that the photoelectric response of the polymer is realized.
As can be seen from FIG. 10, the current density of the porphyrized SEBS can reach 0.057 muA/cm2The current density of the cobalt porphyrin SEBS can reach 0.062 mu A/cm2Namely, the photocurrent of the porphyrin ring intermediate metal cobalt ion is increased by 8.8%, and the photoelectric responsiveness of the polymer can be improved by the porphyrin ring intermediate metal ion.
(3) Elasticity of PPSEBS
The elasticity of the polymer PPSEBS was characterized using a shore durometer and the hardness was measured to be 53 HA.
Example 3 organic photoelectric Material of the invention
Preparation of organic photoelectric material PPSEBS
(1) Preparing CMSEBS by para-chloromethylation of benzene ring of SEBS
5.0g of hydrogenated styrene butadiene block copolymer (SEBS) (molecular weight: 5 ten thousand) was dissolved in 250ml of chloroform solvent, and 20ml of 1, 4-dichloromethoxybutane was used as a chloromethylation reagent, and the reaction was carried out in an ice-water bath for 7 hours under the catalysis of 4ml of tin tetrachloride, so as to obtain chloromethylated SEBS, which is denoted as CMSEBS.
(2) ALSEBS is prepared by the para-aldehyde of benzene ring
Dissolving 3.0g of CMSEBS in 150ml of xylene solvent, adding 2.0g of potassium iodide and 1.5g of sodium bicarbonate by taking 50ml of DMSO as a mild oxidant, and reacting at 110 ℃ for 6h to obtain the aldehyde-based SEBS, which is marked as ALSEBS.
(3) Porphyrin to obtain PPSEBS
Dissolving 1.0g of ALSEBS in 100ml of xylene solvent, adding 1.8ml of p-chlorobenzaldehyde, 1.5ml of pyrrole and 2.5ml of lactic acid, wherein the p-chlorobenzaldehyde and the pyrrole are raw materials for synthesizing porphyrin ring, the lactic acid is used as a catalyst, and reacting for 5h at 110 ℃ to obtain the porphyrized SEBS, which is recorded as PPSEBS.
(4) Metallization
1.0g of PPSEBS is dissolved in 100ml of xylene solvent, 0.01g of zinc acetate is added, and the mixture reacts for 1h at 110 ℃ to obtain zinc porphyrin SEBS which is recorded as ZnPPSEBS.
Second, characterize
(1) Porphyrin ring grafting ratio
The calculation formula of the porphyrin ring grafting ratio is as follows:
Figure GDA0003109036680000081
where I is the relative integrated area.
By passing1Integration of the area data with H-NMR spectrum (see FIG. 11) indicates that if IN-HIs 1, then IA,B,C,A’,B’Is 5.6. Calculated as 41% porphyrin ring grafting.
(2) Photoelectric response test chart
The photoelectric response test chart of embodiment 3 of the invention is shown in fig. 12, and the polymer generates a photocurrent when light is emitted, and the photocurrent of the polymer disappears immediately when no light is emitted, so that the photoelectric response of the polymer is realized.
As can be seen from FIG. 12, the current density of the porphyrized SEBS can reach 0.059 muA/cm2The current density of the zinc porphyrin SEBS can reach 0.068 mu A/cm2Namely, the photocurrent of zinc ions in the porphyrin ring intermediate complex metal is increased by 15.3%, and the photoelectric responsiveness of the polymer can be improved by the porphyrin ring intermediate complex metal ions.
(3) Elasticity of PPSEBS
The elasticity of the polymer PPSEBS was characterized by a shore durometer and the hardness was measured to be 54 HA.
Comparative example 1
Preparation of organic photoelectric material
(1) Para-chloromethylation of benzene ring of SEBS
5.0g of SEBS (molecular weight: 5 ten thousand) is dissolved in 250ml of chloroform solvent, 20ml of 1, 4-dichloromethoxybutane is taken as chloromethylation reagent, and the reaction is carried out in ice-water bath for 0.5h under the catalysis of 4ml of stannic chloride, thus obtaining chloromethylated SEBS (CMSEBS).
(2) Para-aldehyde formation of SEBS benzene ring
3.0g of CMSEBS is dissolved in 150ml of xylene solvent, 50ml of DMSO is used as a mild oxidant, 2.0g of potassium iodide and 1.5g of sodium bicarbonate are added, and the mixture is reacted for 6 hours at 110 ℃ to obtain the aldehyde SEBS (ALSEBS).
(3) Porphyrization of
Dissolving 1.0g of ALSEBS in 100ml of xylene solvent, adding 1.8ml of benzaldehyde, 1.5ml of pyrrole and 2.5ml of lactic acid, wherein the p-hydroxybenzaldehyde and the pyrrole are raw materials for synthesizing porphyrin ring, the lactic acid is used as a catalyst, and reacting for 5h at 110 ℃ to obtain the porphyrized SEBS (PPSEBS).
(4) Metallization
1.0g of PPSEBS is dissolved in 100ml of xylene solvent, 0.01g of magnesium nitrate is added, and the mixture reacts for 1 hour at 110 ℃ to obtain magnesium porphyrin SEBS which is recorded as MgPPSEBS.
Second, characterize
(1) Porphyrin ring grafting ratio
By passing1The porphyrin ring grafting ratio was 1.5% as calculated from the integrated area data of the H-NMR spectrum (FIG. 13).
(2) Photoelectric response test chart
The photo-electric response test chart is shown in fig. 14, and due to the low porphyrin grafting rate, the photo-electric response of the polymer is very weak, the photo-electric current is very small, and almost no photo-electric response exists.
(3) Elasticity of PPSEBS
Hardness the elasticity of the polymer was characterized by a Shore durometer, hardness 49 HA.
Comparative example 2
Preparation of organic photoelectric material
(1) Para-chloromethylation of benzene ring of SEBS
5.0g of SEBS (molecular weight 5 ten thousand) is dissolved in 250ml of chloroform solvent, 20ml of 1, 4-dichloromethoxybutane is taken as chloromethylation reagent, and under the catalysis of 4ml of stannic chloride, ice-water bath is carried out for 14h, and chloromethylation SEBS (CMSEBS) is obtained through reaction.
(2) Para-aldehyde formation of SEBS benzene ring
3.0g of CMSEBS is dissolved in 150ml of xylene solvent, 50ml of DMSO is used as a mild oxidant, 2.0g of potassium iodide and 1.5g of sodium bicarbonate are added, and the mixture reacts for 6 hours at 110 ℃ to obtain the aldehyde SEBS (ALSEBS).
(3) Porphyrization of
Dissolving 1.0g of ALSEBS in 100ml of xylene solvent, adding 1.8ml of benzaldehyde, 1.5ml of pyrrole and 2.5ml of lactic acid, wherein the p-hydroxybenzaldehyde and the pyrrole are raw materials for synthesizing porphyrin ring, and the lactic acid is used as a catalyst, and reacting for 5 hours at 110 ℃ to obtain the porphyrized SEBS (PPSEBS).
(4) Metallization
1.0g of PPSEBS is dissolved in 100ml of xylene solvent, 0.01g of magnesium nitrate is added, and the mixture reacts for 1 hour at 110 ℃ to obtain magnesium porphyrin SEBS which is recorded as MgPPSEBS.
Second, characterize
(1) Porphyrin ring grafting ratio
By passing1The porphyrin ring grafting ratio was 70.3% as calculated by H-NMR spectrum (FIG. 15) and integrated area data.
(2) Photoelectric response test chart
As shown in a photoelectric response test chart of figure 16, in the first step of modification, the grafting rate of chloromethyl is higher, and in the subsequent reaction, because the reaction active points on the main chain of the macromolecule are too much, the active points between chains have cross-linking reaction, so that the molecular chains of the polymer are intertwined and are not linear any more. Therefore, in the crosslinked system, the conduction of photoelectrons is hindered, resulting in a decrease in photocurrent, thereby decreasing the photoresponsiveness of the polymer.
(3) Elasticity of PPSEBS
Hardness the elasticity of the polymer was characterized by a Shore durometer, hardness 82 HA.
From the experimental results, it can be known that in the organic photoelectric conversion material prepared by the invention, the polymer PPSEBS can have better photoelectric responsiveness and maintain the elasticity and flexibility thereof only when the porphyrin grafting rate is within 5-55% of the specific range of the invention. When the porphyrin ring grafting ratio is lower, the photoelectric effect of the polymer is increased along with the increase of the porphyrin ring grafting ratio. When the grafting ratio is increased continuously, in the process of synthesis reaction, because the reactive sites on the main chain of the macromolecule are increased, the active sites between chains are easy to generate cross-linking reaction, and the molecular chains of the polymer are intertwined and are not linear any more, so that the polymer loses elasticity and becomes insoluble and infusible, thereby limiting the grafting ratio of the porphyrin ring from being increased infinitely.
In addition, with the increase of the grafting rate, more metal can be complexed, so that the photoelectric responsiveness of the final metalloporphyrin polystyrene elastomer is further improved.
In summary, the invention provides a metalloporphyrin polystyrene elastomer, a preparation method and an application thereof, the metalloporphyrin polystyrene elastomer is an organic photoelectric conversion material, and the porphyrin grafting ratio is only within 5-55% of the specific range of the invention, so that the porphyrin polystyrene elastomer can have good photoelectric responsiveness and maintain the elasticity and flexibility thereof, and particularly, the invention further improves the photoelectric responsiveness by metalizing the porphyrin polystyrene elastomer and complexing metal ions in porphyrin rings.

Claims (15)

1. An organic photoelectric conversion material characterized in that: the preparation method comprises the following steps:
(1) chloromethylation: sequentially dissolving polystyrene elastomer, chloromethylation reagent and catalyst in chloroform, and completely reacting to obtain chloromethylated polystyrene elastomer;
(2) aldehyde formation: dissolving chloromethylated polystyrene elastomer, dimethyl sulfoxide, potassium iodide and sodium bicarbonate in xylene in sequence, and completely reacting to obtain aldehyde polystyrene elastomer;
(3) porphyrization: dissolving aldehyde polystyrene elastomer, substituted or unsubstituted benzaldehyde, pyrrole and lactic acid in xylene in sequence, and completely reacting to obtain porphyrin polystyrene elastomer;
(4) metallization: dissolving the porphyrized polystyrene elastomer and the soluble metal salt in xylene in sequence, and completely reacting to obtain the metal porphyrized polystyrene elastomer, namely the organic photoelectric conversion material;
in the porphyrin polystyrene elastomer, the porphyrin grafting rate is 5-55%.
2. The organic photoelectric conversion material according to claim 1, wherein: in the step (1), the polystyrene elastomer is one or two of styrene butadiene block copolymer, styrene isoprene block copolymer, hydrogenated styrene butadiene block copolymer and polystyrene isoprene butadiene rubber; and/or, the polystyrene-based elastomer is a linear structure; and/or, the chloromethylation reagent is 1, 4-dichloromethoxybutane; and/or, the catalyst is tin tetrachloride.
3. The organic photoelectric conversion material according to claim 1, wherein: in the step (1), the feeding ratio of the polystyrene elastomer to chloroform, chloromethylation reagent and catalyst is 1: 50: 4: 0.8 g/mL/mL/mL; and/or the temperature of the reaction is 0 +/-2 ℃; and/or the reaction time is 1-9 h.
4. The organic photoelectric conversion material according to claim 3, wherein: in the step (1), the reaction time is 2-7 h.
5. The organic photoelectric conversion material according to claim 4, wherein: in the step (1), the reaction time is 3-6 h.
6. The organic photoelectric conversion material according to claim 1, wherein: in the step (2), the reaction temperature is 100-120 ℃; and/or the reaction time is 5-7 h.
7. The organic photoelectric conversion material according to claim 6, wherein: in the step (2), the reaction temperature is 110 ℃; and/or the reaction time is 6 h.
8. The organic photoelectric conversion material according to claim 1, wherein: in the step (2), the feeding ratio of the chloromethylated polystyrene elastomer to the xylene, the dimethyl sulfoxide, the potassium iodide and the sodium bicarbonate is 6: 300: 100: 4: 3 g/mL/mL/g/g.
9. The organic photoelectric conversion material according to claim 1, wherein: in the step (3), the substituted or unsubstituted benzaldehyde is benzaldehyde, p-hydroxybenzaldehyde, p-nitrobenzaldehyde, p-chlorobenzaldehyde or p-aminobenzaldehyde.
10. The organic photoelectric conversion material according to claim 1, wherein: in the step (3), the reaction temperature is 100-120 ℃; and/or the reaction time is 4-6 h; and/or the feeding ratio of the aldehyde polystyrene elastomer to xylene, substituted or unsubstituted benzaldehyde, pyrrole and lactic acid is 1: 100: 1.8: 1.5: 2.5 g/mL/mL/mL.
11. The organic photoelectric conversion material according to claim 10, wherein: in the step (3), the reaction temperature is 110 ℃; and/or the reaction time is 5 h.
12. The organic photoelectric conversion material according to claim 1, wherein: in the step (4), the soluble metal salt is zinc chloride, zinc acetate, cobalt chloride, ferric chloride, magnesium nitrate or silver nitrate; and/or the reaction temperature is 100-120 ℃; and/or the reaction time is 30-90 min.
13. The organic photoelectric conversion material according to claim 12, wherein: in the step (4), the reaction temperature is 110 ℃; and/or the reaction time is 60 min.
14. The organic photoelectric conversion material according to claim 1, wherein: in the step (4), the mass-to-volume ratio of the porphyrized polystyrene to the xylene is 1:100 g/mL; the weight ratio of the porphyrized polystyrene to the soluble metal salt is 100: 1.
15. use of the organic photoelectric conversion material according to any one of claims 1 to 14 in the field of producing a photovoltaic device.
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