CN110387020A - A kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes - Google Patents
A kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes Download PDFInfo
- Publication number
- CN110387020A CN110387020A CN201810364512.4A CN201810364512A CN110387020A CN 110387020 A CN110387020 A CN 110387020A CN 201810364512 A CN201810364512 A CN 201810364512A CN 110387020 A CN110387020 A CN 110387020A
- Authority
- CN
- China
- Prior art keywords
- porphyrin
- polystyrene type
- type elastomer
- photoelectric conversion
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes.The metalloporphyrin polystyrene type elastic composite is organic photoelectric conversion material, it passes sequentially through chloromethylation, aldehyde radical, porphyrin and metallization and is prepared.When porphyrin grafting rate is only in particular range 5%~55% of the present invention, porphyrin polystyrene type elastomer keeps its elasticity and flexibility while can having preferable photoelectric respone, particularly, the present invention is by metallizing to porphyrin polystyrene type elastomer, the complexation of metal ions among porphyrin ring further improves its photoelectric respone.
Description
Technical field
The invention belongs to organic photoelectric conversion material technical fields, and in particular to a kind of metalloporphyrin polystyrene type bullet
Property body and preparation method thereof and purposes.
Background technique
The sun is a huge energy depot, and the solar energy received in 1 year on the earth is up to 1.8 × 1018Kilowatt hour.
The purpose of research and development photoelectric conversion material is to utilize solar energy.Requirement of the solar battery to photoelectric conversion material be
High conversion efficiency, the device that large area can be made, preferably to absorb sunlight.
Used photoelectric conversion material is turned based on monocrystalline silicon, polysilicon and amorphous silicon by these inorganic silicon-based photoelectricity
Device made of conversion materials is all often hard profile, is lacked flexibility and flexible, can not carry out it is folding, stretch, squeeze,
Curling or other deformation.However in many fields, such as wearable flexible photoelectric device, all component parts must be had both
Excellent mechanical strength and enough flexibilities, to guarantee that its performance meets the various motion requirements of the mankind.Again for example in order to tie up
Normal flight after holding spacecraft lift-off, when transmitting, can carry a large amount of inorganic silicon-based solar panels, if can be by solar energy
It is reinflated after solar panel curling lift-off, the space loading of aircraft will be greatly reduced.Therefore, a kind of novel flexible is researched and developed
Photoelectric conversion material is of great significance.
Meanwhile inorganic photovoltaic material cost is high, energy consumption is high by preparation process, seriously polluted.Organic photoelectrical material is flexible, system
It is easy, material source is extensive, the advantages such as at low cost, so that providing cheap electric energy has and can hold to solar energy is utilized on a large scale
The significance of supervention exhibition.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of metalloporphyrin polystyrene type elastomer and its preparation sides
Method and purposes.
The present invention provides a kind of organic photoelectric conversion materials, it is prepared by following methods:
(1) polystyrene type elastomer, chloromethylation reagents, catalyst: being successively dissolved in chloroform by chloromethylation, reaction
Completely up to chloromethylated polystyrene class elastomer；
(2) aldehyde radical: successively that chloromethylated polystyrene class elastomer, dimethyl sulfoxide, potassium iodide, sodium bicarbonate is molten
In dimethylbenzene, fully reacting is up to aldehyde radical polystyrene type elastomer；
(3) porphyrin: successively by aldehyde radical polystyrene type elastomer, substituted or unsubstituted benzaldehyde, pyrroles, lactic acid
It is dissolved in dimethylbenzene, fully reacting is up to porphyrin polystyrene type elastomer；
(4) it metallizes: successively porphyrin polystyrene type elastomer, soluble metallic salt being dissolved in dimethylbenzene, react
Completely up to metalloporphyrin polystyrene type elastomer.
Wherein, in step (1), the polystyrene type elastomer is styrene butadiene block copolymer, styrene is different
Pentadiene block copolymer, hydrogenated styrene butadiene block copolymer, one in polystyrene isoprene butadiene rubber
Kind or two kinds；And/or the polystyrene type elastomer is linear structure；And/or the chloromethylation reagents are Isosorbide-5-Nitrae-two
Chloromethane epoxide butane；And/or the catalyst is tin tetrachloride.
In step (1), the polystyrene type elastomer and the feed ratio of chloroform, chloromethylation reagents, tin tetrachloride are
1:50:4:0.8g/mL/mL/mL；And/or the temperature of the reaction is 0 ± 2 DEG C；And/or the time of the reaction be 1h~
9h, preferably 2h~7h, more preferably 3h~6h.
In step (2), the temperature of the reaction is 100~120 DEG C, preferably 110 DEG C；And/or the time of the reaction
For 5~7h, preferably 6h.
In step (2), the chloromethylated polystyrene class elastomer and dimethylbenzene, dimethyl sulfoxide, potassium iodide, carbonic acid
The feed ratio of hydrogen sodium is 6:300:100:4:3g/mL/mL/g/g.
In step (3), the substituted or unsubstituted benzaldehyde be benzaldehyde, parahydroxyben-zaldehyde, paranitrobenzaldehyde,
P-chlorobenzaldehyde, para aminotenzaldehyde.
In step (3), the temperature of the reaction is 100~120 DEG C, preferably 110 DEG C；And/or the time of the reaction
For 4~6h, preferably 5h；And/or the aldehyde radical polystyrene type elastomer and dimethylbenzene, substituted or unsubstituted benzene first
Aldehyde, pyrroles, lactic acid feed ratio be 1:100:1.5:2.5g/mL/mL/mL/mL.
In step (4), the soluble metallic salt is zinc chloride, zinc acetate, cobalt chloride, iron chloride, magnesium nitrate or nitric acid
Silver；And/or the temperature of the reaction is 100~120 DEG C, preferably 110 DEG C；And/or the time of the reaction be 30~
90min, preferably 60min.
In step (4), the mass volume ratio of the porphyrin polystyrene and dimethylbenzene is 1:100g/mL；The porphyrin
The weight ratio for changing polystyrene and soluble metallic salt is 100:1.
Application of the organic photoelectric conversion material in preparation electroluminescent devices field.
" ice-water bath " temperature of the present invention is 0 DEG C.
The present invention provides a kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes, the metal porphins
Quinoline polystyrene type elastomer is organic photoelectric conversion material, porphyrin grafting rate only particular range of the present invention 5%~
When in 55%, porphyrin polystyrene type elastomer keeps it elastic and soft while can having preferable photoelectric respone
Property, particularly, the present invention by metallizing to porphyrin polystyrene type elastomer, among porphyrin ring complexing metal from
Son further improves its photoelectric respone.
Specifically, organic photoelectrical material of the present invention has the advantage that
(1) material has flexible and elasticity, can occur the deformation such as to fold, stretch, squeeze, crimp；
(2) material is thermoplastic elastomer (TPE), and heating plasticizing is easily processed into type；
(3) leftover pieces repeat plasticizing forming, recycle；
(4) material processing technique is simple, environmentally protective, and low energy consumption；
(5) raw material sources are extensive, at low cost.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is the infrared absorption pattern of different phase product of the present invention.
Fig. 2 is the nuclear magnetic resonance figures of SEBS.
Fig. 3 is the nuclear magnetic resonance figures of CMSEBS.
Fig. 4 is the nuclear magnetic resonance figures of ALSEBS.
Fig. 5 is the nuclear magnetic resonance figures of PPSEBS.
Fig. 6 is porphyrin SEBS nuclear magnetic resonance spectroscopy schematic diagram.
Fig. 7 is the PPSEBS's of embodiment 11H-NMR map.
Fig. 8 is 1 photoelectric respone test chart of embodiment.
Fig. 9 is the PPSEBS's of embodiment 21H-NMR map.
Figure 10 is 2 photoelectric respone test chart of embodiment.
Figure 11 is the PPSEBS's of embodiment 31H-NMR map.
Figure 12 is 3 photoelectric respone test chart of embodiment.
Figure 13 is the PPSEBS's of comparative example 11H-NMR map.
Figure 14 is 1 photoelectric respone test chart of comparative example.
Figure 15 is the PPSEBS's of comparative example 21H-NMR map.
Figure 16 is 2 photoelectric respone test chart of comparative example.
Specific embodiment
Raw material, equipment used in the specific embodiment of the invention are known product, are obtained by purchase commercial product.
Agents useful for same of the present invention is purchased from Chengdu Ke Long chemical reagent factory.
Photoelectric respone test equipment is electrochemical workstation, producer: Shanghai Huachen, the trade mark: CHI6601.
The preparation of organic photoelectrical material of the present invention:
(1) phenyl ring aligns chloromethylation
Polystyrene type elastomer is dissolved in chloroform solvent, using Isosorbide-5-Nitrae-dichloro methyl butyl ether as chloromethylation reagents,
Under stannic chloride catalysis effect, ice-water bath several hours, reaction obtains chloromethylated polystyrene class elastomer.Chloromethyl connects
Branch rate extends with the reaction time and is increased, and controls the differential responses time up to different chloromethyl grafting rates.
(2) phenyl ring aligns aldehyde radical
Chloromethylated polystyrene class elastomer is dissolved in xylene solvent, using DMSO as mild oxidizing agent, iodine is added
Change potassium and sodium bicarbonate, 110 DEG C of reaction 6h obtain aldehyde radical polystyrene type elastomer.Aldehyde radical reagent dosage is in excess in
Calculated value, it is ensured that chloromethyl is completely converted into aldehyde radical.
(3) porphyrin
Aldehyde radical polystyrene type elastomer is dissolved in xylene solvent, and benzaldehyde or substituted benzaldehyde (such as benzene is added
Formaldehyde, parahydroxyben-zaldehyde, paranitrobenzaldehyde, p-chlorobenzaldehyde, para aminotenzaldehyde etc.), pyrroles and lactic acid, wherein benzene first
Aldehyde or substituted benzaldehyde and pyrroles are the raw material for synthesizing porphyrin ring, and lactic acid is catalyst, and it is poly- that porphyrinization is obtained after 110 DEG C of reaction 5h
Styrenic elastomer.Porphyrin reagent dosage is in excess in calculated value, it is ensured that all grafting is porphyrin ring to aldehyde radical.
(4) it metallizes
Porphyrin polystyrene type elastomer is dissolved in xylene solvent, and soluble metallic salt (such as zinc chloride, acetic acid is added
Zinc, cobalt chloride, iron chloride, magnesium nitrate, silver nitrate etc.), 110 DEG C of constant temperature 1h carry out complexation reaction, obtain complexing among porphyrin ring
There is the metalloporphyrin polystyrene type elastomer of metal ion.Control metal salt is in excess in porphyrin ring molecular weight on macromolecular chain,
Ensure that upper metal ion is complexed all to get metalloporphyrin polystyrene type elastomer in porphyrin ring center.
The metalloporphyrin polystyrene type elastomer organic photoelectrical material of the present invention of embodiment 1
One, the preparation of metalloporphyrin polystyrene type elastomer organic photoelectrical material
(1) CMSEBS is made in SEBS phenyl ring contraposition chloromethylation
5.0g hydrogenated styrene butadiene block copolymer (SEBS) (molecular weight 50,000) is dissolved in 250ml chloroform solvent,
Using the Isosorbide-5-Nitrae of 20ml-dichloro methyl butyl ether as chloromethylation reagents, under the effect of 4ml stannic chloride catalysis, ice-water bath 1.5h,
Reaction obtains chloromethylation SEBS, is denoted as CMSEBS.
(2) ALSEBS is made in phenyl ring contraposition aldehyde radicalization
3.0gCMSEBS is dissolved in 150ml xylene solvent, using the DMSO of 50ml as mild oxidizing agent, 2.0g iodine is added
Change potassium and 1.5g sodium bicarbonate, 110 DEG C of reaction 6h obtain aldehyde radical SEBS, are denoted as ALSEBS.
(3) PPSEBS is made in porphyrinization
1.0gALSEBS is dissolved in 100ml xylene solvent, 1.8ml benzaldehyde, 1.5ml pyrroles and 2.5ml cream is added
Acid, wherein benzaldehyde and pyrroles are the raw material for synthesizing porphyrin ring, and lactic acid is catalyst, 110 DEG C of reaction 5h up to porphyrin SEBS,
It is denoted as PPSEBS.
(4) it metallizes
1.0gPPSEBS is dissolved in 100ml xylene solvent, the magnesium nitrate of 0.01g is added, 110 DEG C of reaction 1h are obtained
Magnesium porphyrin SEBS, is denoted as MgPPSEBS.
Two, it characterizes
(1) infrared absorption of each stage product
The infrared absorption pattern of different phase product of the present invention is as shown in Figure 1, wherein 676cm in CMSEBS-1Place is C-Cl
Stretching vibration absorbs, and shows that CMSEBS has been made；1701cm in ALSEBS-1Place is C=O characteristic absorption peak, the disappearance of C-Cl key
And the appearance of C=O, show to successfully synthesize aldehyde radical SEBS；3318cm in PPSEBS-1、965cm-1Respectively inner ring N-H
Stretching vibration peak and in-plane bending vibration peak, 1350cm-1、798cm-1For porphyrin skeleton absorption of vibrations, and 1701cm-1Locate C=O
Characteristic absorption peak obviously weakens, and shows to successfully synthesize PPSEBS.
(2) each stage product1H-NMR map
Fig. 2~Fig. 5 is respectively the nuclear magnetic resonance figures of SEBS, CMSEBS, ALSEBS, PPSEBS, and Fig. 6 is that H is former on porphyrin ring
Daughter nucleus magnetic vibration schematic diagram.4.53ppm is that phenyl ring aligns H resonance absorbing peak on chloromethyl in the CMSEBS of Fig. 3；Fig. 4's
9.92ppm is that phenyl ring aligns aldehyde radical H resonance absorbing peak in ALSEBS；6.25-7.21ppm is molecular backbone in the PPSEBS of Fig. 5
Hydrogen resonance absorbing peak on phenyl ring in polystyrene chain segment；8.87ppm is hydrogen resonance absorbing peak on pyrrole ring；8.24ppm being porphyrin
Phenyl ring ortho-hydrogens resonance absorbing peak in ring；7.78ppm is phenyl ring meta position and contraposition hydrogen resonance absorbing peak in porphyrin ring；-2.75ppm
For the hydrogen resonance absorbing peak that is connected on pyrrole ring with N.
(3) porphyrin ring grafting rate
The calculation formula of porphyrin ring grafting rate are as follows:
Wherein, I is relative integral area.
Pass through1H-NMR map (see Fig. 7) integral area data are it is found that if IN-HIt is 1, then IA,B,C,A’,B’It is 22.23.It calculates
Obtaining porphyrin ring grafting rate is 11%.
(4) 1 photoelectric respone test chart of embodiment
1 photoelectric respone test chart of the embodiment of the present invention is shown in Fig. 8, and polymer generates photoelectric current, no light Shi Juhe when having illumination
The photoelectric current of object disappears immediately, realizes the photoelectric respone of polymer.
It can be obtained by Fig. 8, the current density value of porphyrin SEBS can reach 0.058 μ A/cm2, the electric current of magnesium porphyrin SEBS is close
Degree can reach 0.060 μ A/cm2, i.e., complexing metal magnesium ion photoelectric current becomes larger among porphyrin ring, 3.4% is increased, in porphyrin ring
Between complexation of metal ions can improve the photoelectric respone of polymer.
(5) elasticity of PPSEBS
Using the elasticity of Shore durometer characterization polymer P PSEBS, measuring hardness is 53HA.
The organic photoelectrical material of the present invention of embodiment 2
One, the preparation of organic photoelectrical material PPSEBS
(1) CMSEBS is made in SEBS phenyl ring contraposition chloromethylation
5.0g hydrogenated styrene butadiene block copolymer (SEBS) (molecular weight 50,000) is dissolved in 250ml chloroform solvent,
Using the Isosorbide-5-Nitrae of 20ml-dichloro methyl butyl ether as chloromethylation reagents, under the effect of 4ml stannic chloride catalysis, ice-water bath 4h, instead
Chloromethylation SEBS should be obtained, CMSEBS is denoted as.
(2) ALSEBS is made in phenyl ring contraposition aldehyde radicalization
3.0gCMSEBS is dissolved in 150ml xylene solvent, using the DMSO of 50ml as mild oxidizing agent, 2.0g iodine is added
Change potassium and 1.5g sodium bicarbonate, 110 DEG C of reaction 6h obtain aldehyde radical SEBS, are denoted as ALSEBS.
(3) PPSEBS is made in porphyrinization
1.0gALSEBS is dissolved in 100ml xylene solvent, be added 1.8ml paranitrobenzaldehyde, 1.5ml pyrroles and
2.5ml lactic acid, wherein paranitrobenzaldehyde and pyrroles are the raw material for synthesizing porphyrin ring, and lactic acid is catalyst, and 110 DEG C of reaction 5h are
Porphyrin SEBS is obtained, PPSEBS is denoted as.
(4) it metallizes
1.0gPPSEBS is dissolved in 100ml xylene solvent, the cobalt chloride of 0.01g is added, 110 DEG C of reaction 1h are obtained
Cob altporphyrin SEBS, is denoted as CoPPSEBS.
Two, it characterizes
(1) porphyrin ring grafting rate
The calculation formula of porphyrin ring grafting rate are as follows:
Wherein, I is relative integral area.
Pass through1H-NMR map (see Fig. 9) integral area data are it is found that if IN-HIt is 1, then IA,B,C,A’,B’It is 10.37.It calculates
Obtaining porphyrin ring grafting rate is 23%.
(2) photoelectric respone test chart
2 photoelectric respone test chart of the embodiment of the present invention is shown in Figure 10, and polymer generates photoelectric current, no light Shi Juhe when having illumination
The photoelectric current of object disappears immediately, realizes the photoelectric respone of polymer.
It can be obtained by Figure 10, the current density value of porphyrin SEBS can reach 0.057 μ A/cm2, the electric current of Cob altporphyrin SEBS is close
Degree can reach 0.062 μ A/cm2, i.e., complexing metal cobalt ions photoelectric current becomes larger among porphyrin ring, 8.8% is increased, in porphyrin ring
Between complexation of metal ions can improve the photoelectric respone of polymer.
(3) elasticity of PPSEBS
Using the elasticity of Shore durometer characterization polymer P PSEBS, measuring hardness is 53HA.
The organic photoelectrical material of the present invention of embodiment 3
One, the preparation of organic photoelectrical material PPSEBS
(1) CMSEBS is made in SEBS phenyl ring contraposition chloromethylation
5.0g hydrogenated styrene butadiene block copolymer (SEBS) (molecular weight 50,000) is dissolved in 250ml chloroform solvent,
Using the Isosorbide-5-Nitrae of 20ml-dichloro methyl butyl ether as chloromethylation reagents, under the effect of 4ml stannic chloride catalysis, ice-water bath 7h, instead
Chloromethylation SEBS should be obtained, CMSEBS is denoted as.
(2) ALSEBS is made in phenyl ring contraposition aldehyde radicalization
3.0gCMSEBS is dissolved in 150ml xylene solvent, using the DMSO of 50ml as mild oxidizing agent, 2.0g iodine is added
Change potassium and 1.5g sodium bicarbonate, 110 DEG C of reaction 6h obtain aldehyde radical SEBS, are denoted as ALSEBS.
(3) PPSEBS is made in porphyrinization
1.0gALSEBS is dissolved in 100ml xylene solvent, be added 1.8ml p-chlorobenzaldehyde, 1.5ml pyrroles and
2.5ml lactic acid, wherein p-chlorobenzaldehyde and pyrroles are the raw material for synthesizing porphyrin ring, and lactic acid is catalyst, and 110 DEG C of reaction 5h to obtain the final product
Porphyrin SEBS, is denoted as PPSEBS.
(4) it metallizes
1.0gPPSEBS is dissolved in 100ml xylene solvent, the zinc acetate of 0.01g is added, 110 DEG C of reaction 1h are obtained
Zinc protoporphyrin SEBS, is denoted as ZnPPSEBS.
Two, it characterizes
(1) porphyrin ring grafting rate
The calculation formula of porphyrin ring grafting rate are as follows:
Wherein, I is relative integral area.
Pass through1H-NMR map (see Figure 11) integral area data are it is found that if IN-HIt is 1, then IA,B,C,A’,B’It is 5.6.It calculates
Obtaining porphyrin ring grafting rate is 41%.
(2) photoelectric respone test chart
3 photoelectric respone test chart of the embodiment of the present invention is shown in Figure 12, and polymer generates photoelectric current, no light Shi Juhe when having illumination
The photoelectric current of object disappears immediately, realizes the photoelectric respone of polymer.
It can be obtained by Figure 12, the current density value of porphyrin SEBS can reach 0.059 μ A/cm2, the electric current of zinc protoporphyrin SEBS is close
Degree can reach 0.068 μ A/cm2, i.e., complexing metal zinc ion photoelectric current becomes larger among porphyrin ring, increases 15.3%, porphyrin ring
Intermediate complexation of metal ions can improve the photoelectric respone of polymer.
(3) elasticity of PPSEBS
Using the elasticity of Shore durometer characterization polymer P PSEBS, measuring hardness is 54HA.
Comparative example 1
One, the preparation of organic photoelectrical material
(1) SEBS phenyl ring aligns chloromethylation
The SEBS (molecular weight 50,000) of 5.0g is dissolved in 250ml chloroform solvent, with the Isosorbide-5-Nitrae of 20ml-dichloro methyl butyl ether
For chloromethylation reagents, under the effect of 4ml stannic chloride catalysis, ice-water bath 0.5h, reaction obtains chloromethylation SEBS
(CMSEBS)。
(2) SEBS phenyl ring aligns aldehyde radical
The CMSEBS of 3.0g is dissolved in 150ml xylene solvent, using the DMSO of 50ml as mild oxidizing agent, 2.0g is added
Potassium iodide and 1.5g sodium bicarbonate, 110 DEG C of reaction 6h obtain aldehyde radical SEBS (ALSEBS).
(3) porphyrin
The ALSEBS of 1.0g is dissolved in 100ml xylene solvent, 1.8ml benzaldehyde, 1.5ml pyrroles and 2.5ml is added
Lactic acid, wherein parahydroxyben-zaldehyde and pyrroles are the raw material for synthesizing porphyrin ring, and lactic acid is catalyst, and 110 DEG C of reaction 5h are up to porphin
Quinoline SEBS (PPSEBS).
(4) it metallizes
1.0gPPSEBS is dissolved in 100ml xylene solvent, the magnesium nitrate of 0.01g is added, 110 DEG C of reaction 1h are obtained
Magnesium porphyrin SEBS, is denoted as MgPPSEBS.
Two, it characterizes
(1) porphyrin ring grafting rate
Pass through1H-NMR map (Figure 13) integral area data calculate porphyrin ring grafting rate be 1.5%.
(2) photoelectric respone test chart
Photoelectric respone test chart is shown in Figure 14, and since porphyrin grafting rate is lower, the photoelectric respone of polymer is very weak, photoelectric current
Very little, almost without photoelectric respone.
(3) elasticity of PPSEBS
Hardness characterizes polymer elasticity, hardness 49HA using Shore durometer.
Comparative example 2
One, the preparation of organic photoelectrical material
(1) SEBS phenyl ring aligns chloromethylation
5.0gSEBS (molecular weight 50,000) is dissolved in 250ml chloroform solvent, and with 20ml1,4- dichloro methyl butyl ether is chloromethane
Base reagent, under the effect of 4ml stannic chloride catalysis, ice-water bath 14h, reaction obtains chloromethylation SEBS (CMSEBS).
(2) SEBS phenyl ring aligns aldehyde radical
3.0gCMSEBS is dissolved in 150ml xylene solvent, and using 50mlDMSO as mild oxidizing agent, 2.0g potassium iodide is added
With 1.5g sodium bicarbonate, 110 DEG C of reaction 6h obtain aldehyde radical SEBS (ALSEBS).
(3) porphyrin
1.0gALSEBS is dissolved in 100ml xylene solvent, and 1.8ml benzaldehyde, 1.5ml pyrroles and 2.5ml lactic acid is added,
Wherein parahydroxyben-zaldehyde and pyrroles are the raw material for synthesizing porphyrin ring, and lactic acid is catalyst, and 110 DEG C of reaction 5h are up to porphyrin
SEBS(PPSEBS)。
(4) it metallizes
1.0gPPSEBS is dissolved in 100ml xylene solvent, the magnesium nitrate of 0.01g is added, 110 DEG C of reaction 1h are obtained
Magnesium porphyrin SEBS, is denoted as MgPPSEBS.
Two, it characterizes
(1) porphyrin ring grafting rate
Pass through1H-NMR map (Figure 15) integral area data calculate porphyrin ring grafting rate be 70.3%.
(2) photoelectric respone test chart
Photoelectric respone test chart is shown in Figure 16, since in first step modifying process, chloromethyl grafting rate is higher, subsequent reactions by
Excessive in the reaction active sites on high polymer main chain, the active site between chain and chain, which crosslinks, to react, and makes polymer molecule
Chain is intertwine with each other, and is no longer linear.Therefore in cross-linking system, photoelectronic conduction is hindered, and photoelectric current is caused to weaken, from
And reduce the photoelectric respone of polymer.
(3) elasticity of PPSEBS
Hardness characterizes polymer elasticity, hardness 82HA using Shore durometer.
By above-mentioned experimental result it is found that in the organic photoelectric conversion material that the present invention is prepared, porphyrin grafting rate only has
When in particular range 5%~55% of the present invention, guarantor while polymer P PSEBS can have preferable photoelectric respone
Hold its elasticity and flexibility.When porphyrin ring grafting rate is smaller, the photoelectric effect of polymer increases with the increase of porphyrin grafting rate.
When grafting rate continues to increase, during synthetic reaction, since the reaction active sites on high polymer main chain increase, chain and chain
Between active site easily crosslink reaction, and intertwine with each other polymer molecular chain, be no longer it is linear so that polymer loses
Elasticity becomes insoluble and does not melt, thus the grafting rate for limiting porphyrin ring cannot infinitely increase.
In addition, more metals can be complexed with the raising of grafting rate, so that final metalloporphyrin polystyrene type
The photoelectric respone of elastomer further increases.
To sum up, the present invention provides a kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes, should
Metalloporphyrin polystyrene type elastomer is organic photoelectric conversion material, and porphyrin grafting rate is only in particular range of the present invention
When in 5%~55%, porphyrin polystyrene type elastomer keeps its bullet while can having preferable photoelectric respone
Property and flexibility, particularly, the present invention is complexed among porphyrin ring by metallizing to porphyrin polystyrene type elastomer
Metal ion further improves its photoelectric respone.
Claims (10)
1. a kind of organic photoelectric conversion material, it is characterised in that: it is prepared by following methods:
(1) chloromethylation: successively polystyrene type elastomer, chloromethylation reagents, catalyst are dissolved in chloroform, fully reacting
Up to chloromethylated polystyrene class elastomer；
(2) chloromethylated polystyrene class elastomer, dimethyl sulfoxide, potassium iodide, sodium bicarbonate successively aldehyde radical: are dissolved in two
In toluene, fully reacting is up to aldehyde radical polystyrene type elastomer；
(3) porphyrin: successively aldehyde radical polystyrene type elastomer, substituted or unsubstituted benzaldehyde, pyrroles, lactic acid are dissolved in
In dimethylbenzene, fully reacting is up to porphyrin polystyrene type elastomer；
(4) it metallizes: successively porphyrin polystyrene type elastomer, soluble metallic salt being dissolved in dimethylbenzene, fully reacting
Up to metalloporphyrin polystyrene type elastomer.
2. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (1), the polystyrene type
Elastomer is styrene butadiene block copolymer, styrene isoprene block copolymer, hydrogenated styrene butadiene block
One or both of copolymer, polystyrene isoprene butadiene rubber；And/or the polystyrene type elastomer is
Linear structure；And/or the chloromethylation reagents are Isosorbide-5-Nitrae-dichloro methyl butyl ether；And/or the catalyst is four chlorinations
Tin.
3. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (1), the polystyrene type
The feed ratio of elastomer and chloroform, chloromethylation reagents, tin tetrachloride is 1:50:4:0.8g/mL/mL/mL；And/or it is described anti-
The temperature answered is 0 ± 2 DEG C；And/or the time of the reaction is 1h~9h, preferably 2h~7h, more preferably 3h~6h.
4. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (2), the temperature of the reaction
It is 100~120 DEG C, preferably 110 DEG C；And/or the time of the reaction is 5~7h, preferably 6h.
5. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (2), the chloromethylation is poly-
The feed ratio of styrenic elastomer and dimethylbenzene, dimethyl sulfoxide, potassium iodide, sodium bicarbonate is 6:300:100:4:3g/mL/
mL/g/g。
6. organic photoelectric conversion material according to claim 1, it is characterised in that: described to replace or do not take in step (3)
The benzaldehyde in generation is benzaldehyde, parahydroxyben-zaldehyde, paranitrobenzaldehyde, p-chlorobenzaldehyde, para aminotenzaldehyde.
7. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (3), the temperature of the reaction
It is 100~120 DEG C, preferably 110 DEG C；And/or the time of the reaction is 4~6h, preferably 5h；And/or the aldehyde radical
Changing polystyrene type elastomer and the feed ratio of dimethylbenzene, substituted or unsubstituted benzaldehyde, pyrroles, lactic acid is 1:100:1.5:
2.5g/mL/mL/mL/mL。
8. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (4), the soluble metal
Salt is zinc chloride, zinc acetate, cobalt chloride, iron chloride, magnesium nitrate or silver nitrate；And/or the temperature of the reaction is 100~120
DEG C, preferably 110 DEG C；And/or the time of the reaction is 30~90min, preferably 60min.
9. organic photoelectric conversion material according to claim 1, it is characterised in that: in step (4), the porphyrin polyphenyl
The mass volume ratio of ethylene and dimethylbenzene is 1:100g/mL；The weight ratio of the porphyrin polystyrene and soluble metallic salt
For 100:1.
10. organic photoelectric conversion material described in any one of claim 1 to 9 answering in preparation electroluminescent devices field
With.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810355650 | 2018-04-19 | ||
| CN2018103556506 | 2018-04-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110387020A true CN110387020A (en) | 2019-10-29 |
| CN110387020B CN110387020B (en) | 2021-08-27 |
Family
ID=68284404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810364512.4A Active CN110387020B (en) | 2018-04-19 | 2018-04-23 | Metalloporphyrin polystyrene elastomer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110387020B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499860A (en) * | 2021-07-08 | 2021-10-15 | 江西新金叶实业有限公司 | Efficient flotation method for smelting slag recycled by copper regeneration |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0261733A2 (en) * | 1986-09-22 | 1988-03-30 | Shell Internationale Researchmaatschappij B.V. | Conductive polymer compositions |
| CN101940948A (en) * | 2010-07-13 | 2011-01-12 | 中北大学 | Method for immobilizing metalloporphyrin by crosslinked polystyrene microspheres |
| CN102208557A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102786609A (en) * | 2012-07-17 | 2012-11-21 | 中北大学 | Macromolecule immobilized cationic porphyrin compound and its preparation method |
-
2018
- 2018-04-23 CN CN201810364512.4A patent/CN110387020B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0261733A2 (en) * | 1986-09-22 | 1988-03-30 | Shell Internationale Researchmaatschappij B.V. | Conductive polymer compositions |
| CN101940948A (en) * | 2010-07-13 | 2011-01-12 | 中北大学 | Method for immobilizing metalloporphyrin by crosslinked polystyrene microspheres |
| CN102208557A (en) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | Substrate for flexible luminescent device and preparation method thereof |
| CN102786609A (en) * | 2012-07-17 | 2012-11-21 | 中北大学 | Macromolecule immobilized cationic porphyrin compound and its preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499860A (en) * | 2021-07-08 | 2021-10-15 | 江西新金叶实业有限公司 | Efficient flotation method for smelting slag recycled by copper regeneration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110387020B (en) | 2021-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hao et al. | Modulating uranium extraction performance of multivariate covalent organic frameworks through donor–acceptor linkers and amidoxime nanotraps | |
| Li et al. | Recent progress in stimulus-responsive two-dimensional metal–organic frameworks | |
| CN109806842A (en) | A kind of thioether functionalization covalent organic frame material and its preparation method and application with triazine structure | |
| HK1119723A1 (en) | Improved process for substituted polythiophene polymers | |
| Huo et al. | Fabricated temperature sensitive photocatalyst of PNIPAM@ ZnO/C for controllable photocatalytic activity | |
| CA2885357A1 (en) | High-capacity macromolecular polymer hydrogen storage material and preparation method thereof | |
| CN108164667B (en) | Porphyrin organic framework membrane material and preparation method thereof | |
| CN110387001A (en) | A kind of porphyrin polystyrene type elastomer and preparation method thereof and purposes | |
| CN110387020A (en) | A kind of metalloporphyrin polystyrene type elastomer and preparation method thereof and purposes | |
| CN108440487A (en) | A kind of application process based on the catalyst of synthesizing annular carbonate under low-temperature atmosphere-pressure | |
| CN103861646A (en) | Method for synthesizing palladium catalyst by utilizing alkyne compounds | |
| Deng et al. | A simple approach to prepare isoxazoline-based porous polymer for the highly effective adsorption of 2, 4, 6-trinitrotoluene (TNT): Catalyst-free click polymerization between an in situ generated nitrile oxide with polybutadiene | |
| CN110387102A (en) | A kind of graphene/metalloporphyrin polystyrene type elastic composite and preparation method thereof and purposes | |
| CN106220662A (en) | A kind of containing carborane diamine monomer and preparation method thereof | |
| Xu et al. | A new efficient visible-light-driven composite photocatalyst comprising ZnFe2O4 nanoparticles and conjugated polymer from the dehydrochlorination of polyvinyl chloride | |
| Jia et al. | 1, 2 Enriched polymerization of isoprene by cobalt complex carrying aminophosphory fused (PN3) ligand | |
| CN105622788B (en) | Three arm ATRP initiators and its preparation and application with planar conjugate structure | |
| Yang et al. | Synthesis and adsorption properties for metal ions of mesocyclic diamine‐grafted chitosan‐crown ether | |
| CN110387101A (en) | A kind of graphene/porphyrin polystyrene type elastic composite and preparation method thereof and purposes | |
| CN110343064A (en) | The synthetic method of one kind [60] fullerene and tetrahydro cyclopentyl [2,3-b] indole derivatives | |
| Zhang et al. | S doping induces to promoted spatial separation of charge carriers on carbon nitride for efficiently photocatalytic degradation of atrazine | |
| CN113304784A (en) | Phenylacetylene copper composite photocatalyst and preparation method and application thereof | |
| CN109503419A (en) | A kind of alternately bilayer azobenzene/graphene composite energy-storage material and preparation method | |
| CN104592425B (en) | A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application | |
| Cao et al. | Preparation and characterization of Poly (4-vinylpyridine) encapsulated zinc oxide by surface-initiated RAFT polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |