CN108047407B - A kind of preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material - Google Patents
A kind of preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material, belong to the preparation field of nonlinear optical material.After the preparation method is the following steps are included: alkylamine modifying multiwall carbon nano-tube and 3- acyl pyrroline are mixed in acid condition, 4- alkyloxybenzaldehydes are added, reaction obtains carbon nano-tube/poly azadipyrromethene composite material;Quinone processing is carried out to the carbon nano-tube/poly azadipyrromethene composite material of preparation again, the carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material is made.Carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material prepared by the present invention can not only be evenly dispersed in the low boiling point solvents such as methylene chloride, chloroform, toluene, film forming is excellent, and there is relatively narrow optical band gap and biggish Third-order Nonlinear Optical Susceptibility, it has broad application prospects in fields such as optical modulator, frequency converter and all-optical switch.
Description
Technical field
The invention belongs to the preparation fields of nonlinear optical material, and in particular to a kind of carbon nano-tube/poly pyrroles methylene three
The preparation method of rank nonlinear optics composite material.
Background technique
Nonlinear optics conjugated polymer have Nonlinear optical susceptibility big, fast response time, direct current dielectric constant it is low,
The advantages that optical damage threshold is high, easy processing and MOLECULE DESIGN are easy, in optical modulator, frequency converter, optical oomputing, optical information processing
It has broad application prospects with fields such as all-optical switch.Theoretical research shows within the scope of visible region, conjugated polymer
Third-order Nonlinear Optical Susceptibility is directly proportional to 6 powers of strand conjugate length, is inversely proportional with 6 powers of optical band gap.Cause
This, the conjugated polymer with longer conjugate length and relatively narrow optical band gap is the strong candidate of third order non-linear optical material.
Polypyrrole methylene is typical conjugated polymer, has relatively narrow optical band gap and biggish Third-order Nonlinear Optical Susceptibility.
(Yi Wenhui, Yan Wei, Li WANG, Wang Minqiang, the Zhang Liangying such as Yi Wenhui.XI AN JIAOTONG UNIVERSITY Subject Index, 2000,34 (3): 5-8) system
Standby polypyrrole-{ 2,5- bis- [(to nitro) benzene methylene] } nano thin-film, research find that the film has big third-order non-linear light
Response is learned, nonlinear refractive index is 1.47 × 10-5Esu, Third-order Nonlinear Optical Susceptibility are 1.44 × 10-8esu.Wu
Seminar (Yi WH, Feng W, Cao M, the Wu HC. Polymer for Advanced of great talent leader
Technologies, 2004, 15 (7): 431-438; Zhang Zhigang, Wu Hongcai, Meng Lingjie,
Yi Wenhui. Journal of Material Science and Technology, 2005,21 (5): 715-718)
It synthesizes 3- acyl group and replaces polypyrrole methylene derivative, research finds the optical band gap of the quasi polymer in 1.44~1.85 eV models
In enclosing, Third-order Nonlinear Optical Susceptibility reaches 10-8The esu order of magnitude.
The polypyrrole methylene prepared at present can only be dissolved in the strong pole of the higher boilings such as dimethyl sulfoxide, N,N-dimethylformamide mostly
Property solvent, is not easy to form a film, solvent is difficult to remove after film forming, greatly affected the practical application of polypyrrole methylene.Chinese invention
Patent (grant number: ZL201010545653.X) discloses a kind of preparation method of polypyrrole methylene, which can be with
It is dissolved in the low boiling point solvents such as chloroform, benzene, dissolubility and film forming are excellent, optical band gap and Third-order Nonlinear Optical Susceptibility point
It Wei not 1.84 eV and 1.22 × 10-8esu.Since lijima in 1991 has found carbon nanotube, carbon nanotube is with its uniqueness
One-dimensional electronic structure and excellent mechanical performance, electric property and optical property, cause people widely to pay close attention to.Currently,
It is more compared with polymer carries out the research report of the compound mechanical property for improving polymer and electric property about carbon nanotube, but
It is that research report in terms of the non-linear optical property to carbon nano-tube/polymer composite material is fewer.Preliminary research knot
Fruit shows π-π interaction strong between pi-conjugated polymer and carbon nanotube, and the pi-electron of conjugated polymer can be caused to carbon
Significant ground delocalization occurs for nanotube, to improve the third order non-linear optical property of pi-conjugated polymer.
Summary of the invention
It is an object of the invention in view of the shortcomings of the prior art, to provide a kind of three ranks of carbon nano-tube/poly pyrroles methylene non-thread
The preparation method of property optical composite material.Carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite wood prepared by the present invention
Material can not only be evenly dispersed in the low boiling point solvents such as methylene chloride, chloroform, toluene, film forming is excellent, and have compared with
Narrow optical band gap and biggish Third-order Nonlinear Optical Susceptibility has in fields such as optical modulator, frequency converter and all-optical switch
Have broad application prospects.
To achieve the above object, the present invention adopts the following technical scheme:
The amine-modified multi-walled carbon nanotube of alkyl is added in the condensation polymerization reaction system of polypyrrole methylene, is prepared into
To carbon nano-tube/poly pyrroles's methylene third-order nonlinear optical composite material.
Preparation method the following steps are included:
(1) by alkylamine modifying multiwall carbon nano-tube and 3- acyl pyrroline adding into dichloromethane, ultrasonic disperse, simultaneously
Concentrated hydrochloric acid is added dropwise, regulates and controls the pH value of mixed system;
(2) in N2Under protection, 4- alkyloxybenzaldehydes are added in the mixed system of step (1) preparation;Ultrasonic reaction
Afterwards, it separates, impregnate, washing, drying, obtaining carbon nano-tube/poly azadipyrromethene composite material;
(3) carbon nano-tube/poly azadipyrromethene composite material prepared by step (2) is carried out at quinone using tetrachloroquinone
Reason obtains carbon nano-tube/poly pyrroles's methylene composite material, the as described carbon nano-tube/poly pyrroles first after separation, washing, drying
Alkene third-order nonlinear optical composite material.
More specifically steps are as follows:
(1) it weighs 0.2 g alkylamine modifying multiwall carbon nano-tube and 0.2 ~ 0.6 g 3- acyl pyrroline is dispersed in 100 mL
In methylene chloride, 30 ~ 60 min of ultrasonic disperse, while concentrated hydrochloric acid is added dropwise, the pH value for regulating and controlling mixed system is 1 ~ 3;
(2) in N2Under protection, 0.5 ~ 1.5 g 4- alkyloxybenzaldehydes are added to the mixed system of step (1) preparation
In, 10 ~ 30 DEG C of 6 ~ 12 h of ultrasonic reaction;Methylene chloride is evaporated, a large amount of black precipitates are obtained;It is impregnated with the ammonium hydroxide of 2 mol/L
12 h;With deionized water elution filter cake to water phase be in neutrality, then with ethanol rinse filter cake to leacheate be colourless, 80 DEG C of vacuum
Dry 24 h, obtain carbon nano-tube/poly azadipyrromethene composite material;
(3) it weighs 0.3 g carbon nano-tube/poly azadipyrromethene composite material to be dispersed in 30 mL toluene, is added 0.1 ~ 0.3
G tetrachloroquinone is stirred to react 6 ~ 12 h;Steam toluene, residue is eluted colourless to filtrate with dimethyl sulfoxide, and 80 DEG C of vacuum are dry
Dry 24 h obtains carbon nano-tube/poly pyrroles's methylene composite material, the as described carbon nano-tube/poly pyrroles methylene third-order non-linear
Optical composite material.
The amine-modified multi-walled carbon nanotube of the alkyl the preparation method comprises the following steps: first by multi-walled carbon nanotube through Carboxylation place
It after reason, is added in thionyl chloride/DMF mixed solution, after 24 h are reacted at 70 DEG C, after centrifugation, washing and drying, obtains
MWNT-COCl powder;Obtained MWNT-COCl powder is added in alkylamine, 100 DEG C of 2 d of reaction, then it is washed and
The amine-modified multi-walled carbon nanotube of the alkyl is made after drying.
The alkylamine is any in n-butylamine, n-hexylamine, n-octyl amine, n-Decylamine, lauryl amine, cetylamine and octadecylamine
Kind.
The 3- acyl pyrroline be 3- acetyl pyrrole, 3- propiono pyrroles, 3- bytyry pyrroles, 3- caproyl pyrroles,
Any one of 3- heptanoyl group pyrroles and 3- caprylyl pyrroles.
The 4- alkyloxybenzaldehydes are 4-methoxybenzaldehyde, 4- ethoxy-benzaldehyde, 4- propoxybenzaldehyde, 4- fourth
Any one of oxygroup benzaldehyde, 4- octyloxybenzaldehyde, 4- decyloxy benzaldehyde and 4- tetradecyloxyaniline benzaldehyde.
In order to further increase the third order non-linear optical property of polypyrrole methylene, condensation of the present invention in polypyrrole methylene
In polymerization process, alkylamine modifying multiwall carbon nano-tube is added, carbon nano-tube/poly pyrroles's methylene composite material is prepared.Due to carbon
Strong π-π interaction between nanotube and polypyrrole methylene, can cause the pi-electron of polypyrrole methylene to occur to carbon nanotube
Significant ground delocalization, and then improve the third order non-linear optical property of polypyrrole methylene.
Remarkable advantage of the invention is:
Composite material prepared by the present invention can be evenly dispersed in the low boiling point solvents such as methylene chloride, chloroform, toluene,
Film forming is excellent;The optical band gap and Third-order Nonlinear Optical Susceptibility of prepared composite material be respectively 0.85 eV and
9.81×10-7Esu, that be not added with the polypyrrole methylene of carbon nanotube is respectively 1.47 eV and 6.40 × 10-8esu;Because being somebody's turn to do
Kind composite material has relatively narrow optical band gap and biggish Third-order Nonlinear Optical Susceptibility, is mainly used for optical modulator, becomes
The fields such as frequency device and all-optical switch.
Detailed description of the invention
Fig. 1 is the preparation road of carbon nano-tube/poly pyrroles's methylene third-order nonlinear optical composite material prepared by the present invention
Line chart;
Fig. 2 is the infrared absorption of carbon nano-tube/poly pyrroles's methylene third-order nonlinear optical composite material made from embodiment 1
Spectrogram.
Specific embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
A kind of preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material, specific steps are as follows:
(1) it the preparation of n-butylamine modifying multiwall carbon nano-tube: weighs 1 g multi-walled carbon nanotube and is placed in three-necked flask, add
Enter suitable concentrated sulfuric acid/concentrated nitric acid (volume ratio 3:1) mixed liquor, 90 DEG C of 10 min of reaction;Reaction system is poured into a large amount of ice
In the deionized water frozen, stand overnight, filter supernatant liquor, with aperture be 0.45 μm aqueous filter membrane to lower sediment into
Row filtering, is washed to filtrate repeatedly with deionized water and is in neutrality;It is dried in vacuo 24 h at 80 DEG C, obtains the carbon of black carboxylated
Nanotube powder (MWNT-COOH);150 mg MWNT-COOH of precise is added in three-necked flask, and 30 mL volumes are added
Than the thionyl chloride for 20:1/DMF mixed solution, 70 DEG C of 24 h of reaction;Centrifugation, is washed solid five times with THF, is dried in vacuo,
Obtain MWNT-COCl powder;100 mg MWNT-COCl are weighed, are added in 50 mL n-butylamines, 100 DEG C of 2 d of reaction;It is cooling
To room temperature, with ethanol washing solid five times, to remove excessive amine;It is dried in vacuum overnight at room temperature, it is more to obtain n-butylamine modification
Wall carbon nano tube;
(2) it weighs 0.2 g n-butylamine modifying multiwall carbon nano-tube and 0.2 g 3- acetyl pyrrole is dispersed in 100 mL bis-
In chloromethanes, 30 min of ultrasonic disperse, while concentrated hydrochloric acid is added dropwise, the pH value for regulating and controlling mixed system is 1;
(3) in N2Under protection, 0.5 g 4-methoxybenzaldehyde is added in the mixed system of step (1) preparation, 10
DEG C 6 h of ultrasonic reaction;Methylene chloride is evaporated, a large amount of black precipitates are obtained;12 h are impregnated with the ammonium hydroxide of 2 mol/L;Spend from
Sub- water elution filter cake to water phase is in neutrality, then with ethanol rinse filter cake to leacheate be it is colourless, 80 DEG C of 24 h of vacuum drying are obtained
To carbon nano-tube/poly azadipyrromethene composite material;
(4) it weighs 0.3 g carbon nano-tube/poly azadipyrromethene composite material to be dispersed in 30 mL toluene, 0.3 g tetra- is added
Chloranil is stirred to react 6 h;Toluene is steamed, residue elutes, 80 DEG C vacuum drying 24 hs colourless to filtrate with dimethyl sulfoxide,
Carbon nano-tube/poly pyrroles's methylene composite material is obtained, the as described carbon nano-tube/poly pyrroles methylene third-order nonlinear optical is compound
Material.
The optical band gap and Third-order Nonlinear Optical Susceptibility of prepared composite material be respectively 0.85 eV and 9.81 ×
10-7Esu, the polypyrrole methylene for being not added with carbon nanotube is respectively 1.47 eV and 6.40 × 10-8 esu。
Figure it is seen that 3449 cm-1Absorption peak be pyrrole ring and amide=N-H stretching vibration absworption peak;2928
cm-1Absorption peak be-CH3Stretching vibration absworption peak;2850 cm-1Absorption peak be-CH2Stretching vibration absworption peak;
1645 cm-1The absorption peak at place is the stretching vibration absworption peak of C=O on acetyl group and amide;1595 cm-1Be quinoid pyrrole ring C=
C is superimposed with phenyl ring C=C stretching vibration absworption peak;1505 cm-1It is that C=C stretching vibration is inhaled on oxidation state pyrrole ring C=N and phenyl ring
Receive the superposition at peak;1466 cm-1It is C=C stretching vibration absworption peak on aromatic structure pyrrole ring;1387 cm-1The absorption peak at place is
C-N stretching vibration absworption peak;1247 cm-1It is the stretching vibration absworption peak of C-O;833 cm-1The absorption peak at place is disubstituted benzenes
The absorption peak of ring;721 cm-1It is pyrrole ring absorption peak.
Embodiment 2
A kind of preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material, specific steps are as follows:
(1) preparation of n-Decylamine modifying multiwall carbon nano-tube: n-butylamine modifying multiwall carbon is received during the preparation method is the same as that of Example 1
The preparation method of mitron, the difference is that n-butylamine is replaced with n-Decylamine;
(2) it weighs 0.2 g n-Decylamine modifying multiwall carbon nano-tube and 0.4 g 3- caproyl pyrroles is dispersed in 100 mL bis-
In chloromethanes, 45 min of ultrasonic disperse, while concentrated hydrochloric acid is added dropwise, the pH value for regulating and controlling mixed system is 2;
(3) in N2Under protection, 1.0 g 4- octyloxybenzaldehydes are added in the mixed system of step (1) preparation, 20
DEG C 9 h of ultrasonic reaction;Methylene chloride is evaporated, a large amount of black precipitates are obtained;12 h are impregnated with the ammonium hydroxide of 2 mol/L;Spend from
Sub- water elution filter cake to water phase is in neutrality, then with ethanol rinse filter cake to leacheate be it is colourless, 80 DEG C of 24 h of vacuum drying are obtained
To carbon nano-tube/poly azadipyrromethene composite material;
(4) it weighs 0.3 g carbon nano-tube/poly azadipyrromethene composite material to be dispersed in 30 mL toluene, 0.2 g tetra- is added
Chloranil is stirred to react 9 h;Toluene is steamed, residue elutes, 80 DEG C vacuum drying 24 hs colourless to filtrate with dimethyl sulfoxide,
Carbon nano-tube/poly pyrroles's methylene composite material is obtained, the as described carbon nano-tube/poly pyrroles methylene third-order nonlinear optical is compound
Material.
The optical band gap and Third-order Nonlinear Optical Susceptibility of prepared composite material be respectively 0.94 eV and 6.26 ×
10-7Esu, the polypyrrole methylene for being not added with carbon nanotube is respectively 1.55 eV and 4.87 × 10-8 esu。
Embodiment 3
A kind of preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material, specific steps are as follows:
(1) preparation of octadecyl amine modifying multiwall carbon nano-tube: n-butylamine modifying multiwall carbon during the preparation method is the same as that of Example 1
The preparation method of nanotube, the difference is that n-butylamine is replaced with octadecyl amine;
(2) it weighs 0.2 g octadecyl amine modifying multiwall carbon nano-tube and 0.6 g 3- caprylyl pyrroles is dispersed in 100 mL
In methylene chloride, 60 min of ultrasonic disperse, while concentrated hydrochloric acid is added dropwise, the pH value for regulating and controlling mixed system is 3;
(3) in N2Under protection, 1.5 g 4- tetradecyloxyaniline benzaldehydes are added to the mixed system of step (1) preparation
In, 30 DEG C of 12 h of ultrasonic reaction;Methylene chloride is evaporated, a large amount of black precipitates are obtained;12 h are impregnated with the ammonium hydroxide of 2 mol/L;
It is in neutrality with deionized water elution filter cake to water phase, then is colourless, 80 DEG C of vacuum drying 24 with ethanol rinse filter cake to leacheate
H obtains carbon nano-tube/poly azadipyrromethene composite material;
(4) it weighs 0.3 g carbon nano-tube/poly azadipyrromethene composite material to be dispersed in 30 mL toluene, 0.1 g tetra- is added
Chloranil is stirred to react 12 h;Toluene is steamed, residue elutes, 80 DEG C vacuum drying 24 colourless to filtrate with dimethyl sulfoxide
H obtains carbon nano-tube/poly pyrroles's methylene composite material, and the as described carbon nano-tube/poly pyrroles methylene third-order nonlinear optical is multiple
Condensation material.
The optical band gap and Third-order Nonlinear Optical Susceptibility of prepared composite material be respectively 1.05 eV and 3.22 ×
10-7Esu, the polypyrrole methylene for being not added with carbon nanotube is respectively 1.70 eV and 3.18 × 10-8 esu。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material, it is characterised in that: including
Following steps:
(1) by alkylamine modifying multiwall carbon nano-tube and 3- acyl pyrroline adding into dichloromethane, ultrasonic disperse is added dropwise simultaneously
Concentrated hydrochloric acid regulates and controls the pH value of mixed system;
(2) in N2Under protection, 4- alkyloxybenzaldehydes are added in the mixed system of step (1) preparation;After ultrasonic reaction, point
From, impregnate, washing and dry, obtain carbon nano-tube/poly azadipyrromethene composite material;
(3) quinone processing is carried out to carbon nano-tube/poly azadipyrromethene composite material prepared by step (2) using tetrachloroquinone, point
From, washing and it is dry after, obtain carbon nano-tube/poly pyrroles's methylene composite material, the as described carbon nano-tube/poly pyrroles methylene three
Rank nonlinear optics composite material.
2. the preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material according to claim 1,
It is characterized by: specific step is as follows:
(1) it weighs 0.2 g alkylamine modifying multiwall carbon nano-tube and 0.2 ~ 0.6 g 3- acyl pyrroline is dispersed in 100 mL dichloros
In methane, 30 ~ 60 min of ultrasonic disperse, while concentrated hydrochloric acid is added dropwise, the pH value for regulating and controlling mixed system is 1 ~ 3;
(2) in N2Under protection, 0.5 ~ 1.5 g 4- alkyloxybenzaldehydes are added in the mixed system of step (1) preparation, 10 ~
30 DEG C of 6 ~ 12 h of ultrasonic reaction;Methylene chloride is evaporated, black precipitate is obtained;12 h are impregnated with the ammonium hydroxide of 2 mol/L;It spends
Ionized water elution filter cake to water phase be in neutrality, then with ethanol rinse filter cake to leacheate be colourless, 80 DEG C of 24 h of vacuum drying,
Obtain carbon nano-tube/poly azadipyrromethene composite material;
(3) it weighs 0.3 g carbon nano-tube/poly azadipyrromethene composite material to be dispersed in 30 mL toluene, 0.1 ~ 0.3 g tetra- is added
Chloranil is stirred to react 6 ~ 12 h;Toluene is steamed, residue elutes, 80 DEG C vacuum drying 24 colourless to filtrate with dimethyl sulfoxide
H obtains carbon nano-tube/poly pyrroles's methylene composite material, and the as described carbon nano-tube/poly pyrroles methylene third-order nonlinear optical is multiple
Condensation material.
3. the preparation of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material according to claim 1 or 2
Method, it is characterised in that: the amine-modified multi-walled carbon nanotube of the alkyl the preparation method comprises the following steps: first multi-walled carbon nanotube is passed through
It after Carboxylation processing, is added in thionyl chloride/DMF mixed solution, after 24 h are reacted at 70 DEG C, through centrifugation, washing and drying
Afterwards, MWNT-COCl powder is obtained;Obtained MWNT-COCl powder is added in alkylamine, 100 DEG C of 2 d of reaction, then passed through
The amine-modified multi-walled carbon nanotube of the alkyl is made after washing and drying.
4. the preparation method of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material according to claim 3,
It is characterized by: the alkylamine is in n-butylamine, n-hexylamine, n-octyl amine, n-Decylamine, lauryl amine, cetylamine and octadecylamine
It is any.
5. the preparation side of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material according to claim 1 or 2
Method, it is characterised in that: the 3- acyl pyrroline is 3- acetyl pyrrole, 3- propiono pyrroles, 3- bytyry pyrroles, 3- caproyl
Any one of pyrroles, 3- heptanoyl group pyrroles and 3- caprylyl pyrroles.
6. the preparation side of carbon nano-tube/poly pyrroles methylene third-order nonlinear optical composite material according to claim 1 or 2
Method, it is characterised in that: the 4- alkyloxybenzaldehydes are 4-methoxybenzaldehyde, 4- ethoxy-benzaldehyde, 4- propoxyl group benzene first
Any in aldehyde, 4- butoxybenzaldehyde, 4- octyloxybenzaldehyde, 4- decyloxy benzaldehyde and 4- tetradecyloxyaniline benzaldehyde
Kind.
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CN102924717A (en) * | 2012-10-16 | 2013-02-13 | 南昌航空大学 | Method for preparing dodecylbenzene sulfonic acid (DBSA)-modified manganese-copper-cobalt-ferrite-packed nanotube-polypyrrole composite microwave absorbing material |
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