CN107057060A - Tin porphyrin polyaniline nonlinear optical material and preparation method thereof - Google Patents
Tin porphyrin polyaniline nonlinear optical material and preparation method thereof Download PDFInfo
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- CN107057060A CN107057060A CN201710368602.6A CN201710368602A CN107057060A CN 107057060 A CN107057060 A CN 107057060A CN 201710368602 A CN201710368602 A CN 201710368602A CN 107057060 A CN107057060 A CN 107057060A
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- polyaniline
- porphyrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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Abstract
The invention belongs to military project laser protection Material Field, disclose a kind of covalent bond connection and prepare tin porphyrin polyaniline non-linear absorption optical functional materialses, the nano material has preferable non-linear absorption performance.The problem of present invention is primarily intended to exist for current laser protective material and the poor limitation of polyaniline compound material dissolubility, the polyaniline compound non-linear absorption optical functional materialses of novel porphyrin covalent functionalization of the exploitation with good solubility.The present invention is by using covalent bond by metallic tin porphyrin covalent modification on polyaniline surface, the organic polymer photosensitive functional material of preparation integrates the characteristic of porphyrin and both polyanilines, make hybrid material that there is the non-linear optical property more more excellent than its homogenous material using the cooperative effect between component simultaneously, and the dissolubility and dispersion stabilization of polyaniline are improved, is had a good application prospect.
Description
Technical field
The invention belongs to military project laser protection Material Field, it is related to class organic polymer conjugation hybridized nanometer non-linear
Absorb optical functional materialses, and in particular to the tin porphyrin covalent functionalization polyaniline nano with preferable non-linear absorption performance is non-
Linear optics functional material and preparation method thereof.
Background technology
Because polyaniline is in conducting film, electromagnetic shielding, sensor, antistatic protection, electronic instrument and electroluminescent material
Excellent performance is respectively provided with Deng field and is received significant attention, the focus studied as high polymer material.As people are to non-thread
Property optical research deepen continuously, the application of nonlinear optics functional material in military and people's daily life is more prevalent.
Therefore the application of intense light source is also continuously increased, and in order to protect some optical sensors and human eye from the injury of laser, needs badly and gathers around
There is the material of preferable nonlinear optical response.Although polyaniline has preferable optical property, its design feature makes it not
Easy processing, and dissolubility in organic solvent is poor, this greatly limits its practical application.
Porphyrin be exist in the organic compound that a class has big ring conjugated structure, nature a variety of natural porphyrins and its
Derivative, such as vitamin B1 (Cob altporphyrin), chlorophyll (magnesium porphyrin), ferroheme (ferriporphyrin) and keyhole limpet hemocyanin (copper porphyrin).Porphyrin
It can be generally defined as being connected with a class macrocyclic compound of substituent on porphin ring.Porphines refers to by 4 pyrrole rings and 4 times
The big ring conjugate planes type system that methyl bridging gets up, with armaticity, the hydrogen of 4 middle positions of 4 pyrrole rings in porphines molecule
Atom and 8 β can be replaced by other groups, generate various porphines class derivative compounds, i.e. porphyrin.Due to porphin
Quinoline molecule is big ring pi-electron conjugated system, and its periphery can be by a variety of substituent groups, and central metallic ions can also make corresponding change,
The size of even ring can also extend, i.e., Porphyrin Molecule has preferable modifiability, so being particularly suitable for non-linear
The MOLECULE DESIGN of optical functional materialses；In addition, Porphyrin Molecule also has preferably chemistry and heat endurance, it is easy to which film forming is made
Waveguiding structure, has potential application value in photoelectron technical field.In order to obtain excellent nonlinear optical absorption function
Material, it is necessary to overcome above-mentioned deficiency, by being chemically modified from suitable organic material to polyaniline, so as to improve polyphenyl
Dissolubility and dispersion stabilization of the amine in different solvents, while improving the non-linear optical property of material.Therefore researcher
Continuous research and probe, attempts design and prepares the porphyrin covalent functionalization with preferable dissolubility and excellent non-linear absorption performance
Polyaniline hybridized photosensitive functional material.
The content of the invention
The problem of existing for current polyaniline compound material and the present Research of nonlinear optical absorption material, it is of the invention
Purpose is to absorb light by the polyaniline nano hybridized non-linear that easy chemical synthesis process prepares porphyrin covalent functionalization
Learn functional material.In the present invention polyaniline used by aniline under the conditions of 1mol/L hydrochloric acid, by adding ammonium persulfate,
Obtain doped polyaniline macromolecule conjugated material.
Tin porphyrin-polyaniline nonlinear optical material, the organic polymer binary conjugation the covalent functional material of hydridization be by
What tin porphyrin and polyaniline were constituted, the tin porphyrin is modified on polyaniline surface with covalent bond；Obtain tin porphyrin covalent functionalization
Polyaniline nano hybridized non-linear absorb optical functional materialses structure be：
The preparation method of the compound SnTPP-PANI, using the method for nucleophilic displacement of fluorine, comprises the following steps：
Highly polar organic solvent add polyaniline, after being uniformly dispersed according to certain mass than add tin porphyrin SnTPP and
Potassium carbonate, being placed in oil bath makes it fully react；After covalent functionalization reaction terminates, mixed solution is obtained；Then gained is mixed
Solution is cooled to room temperature；Reactant mixture is filtered, excessive tin porphin is removed using dichloromethane and deionized water washing respectively
Quinoline and potassium carbonate, polyaniline of the tin porphyrin through free radical addition covalent functionalization is produced after drying；
The highly polar organic solvent is N,N-dimethylformamide, chloroform or methanol.
Described polyaniline is：Under the conditions of 1mol/L hydrochloric acid, the polyaniline adulterated using ammonium persulfate；
The tin porphyrin is：5- (4- (2- bromine oxethyls phenyl)) -10,15,20- tetraphenyltin porphyrins；
The tin porphyrin, polyaniline, the mass ratio of potassium carbonate are 1：0.2：5；
The temperature of the covalent functionalization reaction is 80-120 DEG C, and the reaction time is 2-3 days；
Reactant mixture is passed through 0.45m nylon membrane filtrations by described be filtered into；
The washing is to remove the tin porphyrin of excess using dichloromethane and remove potassium carbonate impurity with deionized water.
Described organic transition metal tin porphyrin covalent functionalization polyaniline nano hydridization photosensitive functional material SnTPP-
PANI, has preferable nonlinear optical absorption effect, normalized transmittance reaches 0.54 under the irradiation of 532nm, 4ns laser.
Beneficial effects of the present invention are：
(1) the polyaniline nano hydridization photosensitive functional material of tin porphyrin covalent functionalization of the present invention can be used as non-thread
Property absorbing material, realize to optical sensitive device and eye protection from laser.
(2) the polyaniline N-H of tin porphyrin covalent functionalization of the present invention is strong is modified, have in polar solvent compared with
Good dissolubility and dispersion stabilization.
(3) in the tin porphyrin covalent functionalization polyaniline nano hydridization photosensitive functional material for preparing of the present invention, tin porphyrin with
Polyaniline is covalently attached, and the π having between tin porphyrin and polyaniline-pi-conjugated interaction so that it is mixed relative to physics
Combination between conjunction is even closer.
Brief description of the drawings
Fig. 1 is the preparation road of the polyaniline hybridized photosensitive functional material of the tin porphyrin covalent functionalization prepared by the present invention
Line；
Fig. 2 is the polyaniline nano hydridization photosensitive functional material of tin porphyrin covalent functionalization prepared by the present invention and its preceding
The infrared spectrum of body；
Fig. 3 is the polyaniline nano hydridization photosensitive functional material of tin porphyrin covalent functionalization prepared by the present invention and its preceding
The uv-visible absorption spectra of body；
Fig. 4 is the transmission of the polyaniline nano hydridization photosensitive functional material of the tin porphyrin covalent functionalization prepared by the present invention
(A is local overall diagram to electron microscope；B enlarged fragmentary portions figure)；
Polyaniline nano hydridization photosensitive functional materials and reduction of the Fig. 5 for the tin porphyrin covalent functionalization prepared by the present invention
The x-ray photoelectron power spectrum of graphene oxide；
Fig. 6 is the presoma being related in the claims in the present invention 1 and the nonlinear optics of prepared nano-hybrid material
Absorb figure.
Embodiment
Below by way of specific embodiment, present invention is described or is described further, and gives detailed embodiment
With specific operating process, its object is to be better understood from the technical connotation of the present invention, but protection scope of the present invention is not limited
In following embodiments.
Embodiment 1：
Polyaniline (PANI) the nano hybridization photosensitive functional material SnTPP-PANI's of tin porphyrin (SnTPP) covalent functionalization
Prepare：
By 500mg PANI in 20mL DMF ultrasonic disperse 0.5 hour, then mixed liquor is transferred to containing 100mg
In SnTPP 50mL round-bottomed flasks, potassium carbonate is added as catalyst, reaction solution heating stirring at 120 DEG C in oil bath pan
72 hours.After reaction terminates, solvent is removed by vacuum distillation, and obtained solid ultrasonic disperse and is used in dichloromethane
0.45 μm of nylon membrane filtration, then with dichloromethane and deionized water wash colourless to filtrate respectively, obtained blue solid powder
End, vacuum drying obtains the polyaniline nano hydridization photosensitive functional material SnTPP-PANI of tin porphyrin covalent functionalization for 24 hours
(45mg)。
Embodiment 2
By 500mg PANI in 20mL DMF ultrasonic disperse 0.5 hour, then mixed liquor is transferred to containing 100mg
In SnTPP 50mL round-bottomed flasks, potassium carbonate is added as catalyst, reaction solution heating stirring at 100 DEG C in oil bath pan
72 hours.After reaction terminates, solvent is removed by vacuum distillation, and obtained solid ultrasonic disperse and is used in dichloromethane
0.45 μm of nylon membrane filtration, then with dichloromethane and deionized water wash colourless to filtrate respectively, obtained blue solid powder
End, vacuum drying obtains the polyaniline nano hydridization photosensitive functional material SnTPP-PANI of tin porphyrin covalent functionalization for 24 hours
(55mg)。
Embodiment 3
By 500mg PANI in 20mL DMF ultrasonic disperse 0.5 hour, then mixed liquor is transferred to containing 100mg
In SnTPP 50mL round-bottomed flasks, potassium carbonate is added as catalyst, reaction solution heating stirring 60 at 80 DEG C in oil bath pan
Hour.After reaction terminates, solvent is removed by vacuum distillation, and obtained solid ultrasonic disperse and uses 0.45 in dichloromethane
μm nylon membrane filtration, then with dichloromethane and deionized water wash colourless to filtrate respectively, obtained blue solid powder, very
Sky dries the polyaniline nano hydridization photosensitive functional material SnTPP-PANI (36mg) for obtaining tin porphyrin covalent functionalization for 24 hours
Represent glycol dibromide through nucleophilic displacement of fluorine covalent modification in 5- (4- (2- hydroxy phenyls)) -10,15,20- in Fig. 1
On tetraphenylporphyrin, 5- (4- (2- bromine oxethyls phenyl)) -10,15,20- tetraphenyltin porphyrins are obtained, then with gathering in DMF
Aniline heating response obtains the polyaniline nano hybrid material SnTPP-PANI of porphyrin covalent functionalization.
Fig. 2 shows tin porphyrin covalent modification on polyaniline surface.
Fig. 3 shows tin porphyrin covalent modification on polyaniline surface and there is π-π interactions therebetween
Fig. 4 can be shown that tin porphyrin covalent modification on polyaniline surface.
Fig. 5 shows tin porphyrin covalent modification on polyaniline surface.
Fig. 6 shows in the case where 532nm, 4ns laser are irradiated, and is 25cm along the displacement of Z-direction.Material is for high energy
The transmitance for measuring incident light is relatively low.Distance focal point (at abscissa Z=0) farther out when, the light energy incided on material is smaller,
The transmitance of light is higher；During close to focus, the light energy incided on material is very big, transmitance reduction.Fig. 6 shows covalent nanometer
Hybrid material SnTPP-PANI has than single polyaniline and the more preferable nonlinear optical absorptive property of tin porphyrin, and SnTPP
With nonlinear optical absorptive property more more preferable than TPPOBr, tin porphyrin-polyaniline has extraordinary anti-laser ability,
The normalization transmission that the normalized transmittance that TPPOBr normalized transmittance is 0.81, SnTPP is 0.59 and SnTPP-PANI
Rate is 0.54.
Claims (7)
1. tin porphyrin-polyaniline nonlinear optical material, it is characterised in that be made up of tin porphyrin and polyaniline, the tin porphin
Quinoline is modified on polyaniline surface with covalent bond；The polyaniline nano hybridized non-linear for obtaining tin porphyrin covalent functionalization absorbs optics
Functional material structure is：
2. the preparation method of tin porphyrin-polyaniline nonlinear optical material as claimed in claim 1, it is characterised in that use
The method of nucleophilic displacement of fluorine, is concretely comprised the following steps：
Polyaniline is added in highly polar organic solvent, according to certain mass than adding tin porphyrin SnTPP and carbonic acid after being uniformly dispersed
Potassium, being placed in oil bath makes it fully react；After covalent functionalization reaction terminates, mixed solution is obtained；Then by gained mixed solution
It is cooled to room temperature；Reactant mixture is filtered, respectively using dichloromethane and deionized water washing remove excessive tin porphyrin and
Potassium carbonate, polyaniline of the tin porphyrin through free radical addition covalent functionalization is produced after drying.
3. the preparation method of tin porphyrin-polyaniline nonlinear optical material as claimed in claim 2, it is characterised in that described
Highly polar organic solvent is N,N-dimethylformamide, chloroform or methanol；
Described polyaniline is：Under the conditions of 1mol/L hydrochloric acid, the polyaniline adulterated using ammonium persulfate；
The tin porphyrin is：5- (4- (2- bromine oxethyls phenyl)) -10,15,20- tetraphenyltin porphyrins.
4. the preparation method of tin porphyrin-polyaniline nonlinear optical material as claimed in claim 2, it is characterised in that described
Tin porphyrin, polyaniline, the mass ratio of potassium carbonate are 1：0.2：5.
5. the preparation method of tin porphyrin-polyaniline nonlinear optical material as claimed in claim 2, it is characterised in that described
The temperature of covalent functionalization reaction is 80-120 DEG C, and the reaction time is 2-3 days.
6. the preparation method of tin porphyrin-polyaniline nonlinear optical material as claimed in claim 2, it is characterised in that described
It is filtered into and reactant mixture is passed through into 0.45 μm of nylon membrane filtration；
The washing is to remove the tin porphyrin of excess using dichloromethane and remove potassium carbonate impurity with deionized water.
7. tin porphyrin-polyaniline nonlinear optical material as claimed in claim 1, has under the irradiation of 532nm, 4ns laser
Preferable nonlinear optical absorption effect, normalized transmittance reaches 0.54.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112517081A (en) * | 2020-12-25 | 2021-03-19 | 江苏特丰新材料科技有限公司 | Composite photocatalyst of metal stannum porphyrin axial functionalized titanium dioxide and preparation method thereof |
| CN113831544A (en) * | 2021-09-22 | 2021-12-24 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN116640573A (en) * | 2023-05-17 | 2023-08-25 | 同济大学 | Porphyrin axial passivation modified perovskite nano hybrid material and preparation and application thereof |
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| CN101864294A (en) * | 2010-06-09 | 2010-10-20 | 中国科学院上海微系统与信息技术研究所 | Composite sensing material of fluorescent conjugated polymer and organic metal complex and application |
| CN105254640A (en) * | 2015-09-25 | 2016-01-20 | 江苏大学 | Stannum porphyrin axial covalent functionalized reduced graphene oxide nonlinear optical materials, and preparation method thereof |
| CN105348291A (en) * | 2015-09-25 | 2016-02-24 | 江苏大学 | Tin-porphyrin axial covalent functionalization multiwalled-carbon-nanotube nonlinear optical material and preparing method thereof |
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Patent Citations (3)
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| CN101864294A (en) * | 2010-06-09 | 2010-10-20 | 中国科学院上海微系统与信息技术研究所 | Composite sensing material of fluorescent conjugated polymer and organic metal complex and application |
| CN105254640A (en) * | 2015-09-25 | 2016-01-20 | 江苏大学 | Stannum porphyrin axial covalent functionalized reduced graphene oxide nonlinear optical materials, and preparation method thereof |
| CN105348291A (en) * | 2015-09-25 | 2016-02-24 | 江苏大学 | Tin-porphyrin axial covalent functionalization multiwalled-carbon-nanotube nonlinear optical material and preparing method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517081A (en) * | 2020-12-25 | 2021-03-19 | 江苏特丰新材料科技有限公司 | Composite photocatalyst of metal stannum porphyrin axial functionalized titanium dioxide and preparation method thereof |
| CN112517081B (en) * | 2020-12-25 | 2023-08-15 | 江苏特丰新材料科技有限公司 | Composite photocatalyst of metallic tin porphyrin axial functionalization titanium dioxide and preparation method thereof |
| CN113831544A (en) * | 2021-09-22 | 2021-12-24 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN113831544B (en) * | 2021-09-22 | 2022-05-31 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN116640573A (en) * | 2023-05-17 | 2023-08-25 | 同济大学 | Porphyrin axial passivation modified perovskite nano hybrid material and preparation and application thereof |
| CN116640573B (en) * | 2023-05-17 | 2024-03-26 | 同济大学 | Porphyrin axial passivation modified perovskite nano hybrid material and preparation and application thereof |
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