CN101840124B - Preparation method of porphyrin coupled silicon dioxide organic-inorganic nonlinear optical material - Google Patents
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Abstract
The invention discloses a preparation method of a porphyrin coupled silicon dioxide organic-inorganic nonlinear optical material, which comprises the following steps: 1. heating and reflowing a mixed solution of Msco-tetra-(4-carbomethoxyphenyl) porphyrin copper and gamma-aminopropyltriethoxysilane at the temperature of 160 to 250 DEG C for 10 to 60 hours to obtain a transparent deep red liquid; 2. dissolving a reaction product of step 1 and metal alkoxide into anhydrous ethanol, and stirring at room temperature for 1 to 2 hours; 3. dropwise adding a (H2O)/(C2H5OH) mixed liquid into the reaction product of step 2 at the room temperature for hydrolysis and polymerization reaction for 1 to 5 hours; and 4. pouring the obtained transparent sol into a glass or plastic utensil, sealing with a thin film, ageing at the room temperature for 35 to 45 days, and pricking a hole on the thin film every day to finally prepare compound dried gel. The invention has the advantages that the monomer doping concentration of porphyrin molecules in a gel solid medium can be greatly improved, and the molecular energy level structure and the spectral characteristic of the porphyrin molecules in the gel medium are kept.
Description
Technical field
The present invention relates to organic and inorganic photoelectric functional material preparation method, be specifically related to a kind of preparation method of porphyrin coupled silicon dioxide organic and inorganic nonlinear optical material.
Background technology
Composite organic-inorganic material is the new edge research field that has developed rapidly since 20th century the mid-80.This material has the characteristics of organism and inorganics concurrently, overcome the limitation of single organic or inorganic material, he is the results of fork of multidisciplinary infiltrations such as inorganic chemistry, organic chemistry, mesoscopic physics and material science, be applied in high-tech sector, will become the most rising important compound substance of 21 century
[1-2]
Dissolving-gel (sol-gel) technology is after the progressively hydrolysis and polyreaction by precursor raw materials such as metal alkoxide or inorganic chemistry things, through certain ageing, with processing procedure such as sintering, finally obtain required material.Because therefore its low temperature composite character is effective process means of preparation composite organic-inorganic material.Can be attached to organic functional molecular inorganic and in the noncrystal matrix of organically-modified organic and inorganic, thereby form the function new material of compositeness.
Porphyrin is the general name that the porphines outer shroud has substituent homolog and derivant, and 2 protons are metalloporphyrin by the metal replacement on its nitrogen-atoms.Porphyrin is widely used in various fields such as biological chemistry, analytical chemistry, catalytic chemistry, pharmaceutical chemistry, petrochemistry
[3]Since 1985, the Blau of Irish Trinity university
[4]Reported first the optical limiting properties of porphyrin compound, the various countries scholar has carried out the nonlinear optical effect research of porphyrin in succession
[5-6]Because porphyrin is the plane molecule with the big π system of 18 electronics, its skeleton structure feature makes can be by selecting central ion, axial ligand and introducing method such as functional substituting group on outer shroud its molecule is modified, this feature makes them have special physics, chemical property, particularly nonlinear optical effect.Therefore make such material become the focus of non-linear optical field research, potential using value is arranged in photoelectron technology and integrated optics field.
The present Material Used form of porphyrin and derivant thereof, mainly contain the powder attitude, be dissolved in liquid in the organic solvent, be deposited on polymeric form on the substrate, be doped in the high polymer solid-state etc.Preparing even, transparent, as to have certain porphyrin doping content organic and inorganic complex solid material is to carry out its importance in optics, electrical application, thereby realizes the device of such material, solidifies entirely and widen it in the new application of photoelectric field
[7-8]Sol-gel technique is a kind of effective process means in conjunction with organic functional molecular and inorganic matrix.But, much discover, use this technology, when being doped in the inorganic gel,, thereby produce serious concentration quenching effect to porphyrin because the contraction of gel structure and the volatilization of solvent very easily cause its polymerization.How to improve the doping content of porphyrin molecule in inorganic matrix, make them be dispersed in not polymerization in the matrix with the unimolecule form, thereby acquisition has the high light electrical effect, integrates the compound substance of porphyrin and inorganic medium performance, for the performance of porphyrin with widen its applied research and play important role, also be the difficult point of this research field.
List of references:
[1] Zhang Lide, Mu Jimei. nanomaterial science. Liaoning science tech publishing house, 1994,124.
[2] Liping Wang, Hong Guangyan. an inorganic organic nanocomposite [J]. functional material, 1998,29 (4): 343-347.
[3] Chen Hongxiang, tight coal, Sun Wenbo. porphyrin nonlinear optical material progress. New Chemical Materials .2002,30 (11): 35-38.
[4]Blau?W，Byrne?H，Dennis?W?M，Kelly?J?M.Reverse?saturable?absorption?intetraphenylporphyrins.Opt.Commun.，1985，56(1)：25-29.
[5]S.Venugopal?Rao，N.K.M.Naga?Srinivas，D.Narayana?Rao，L.Giribabu?Bhaskar?G.Maiya，Reji?Philip，G.Ravindra?Kumar.Studies?of?third-order?optical?nonlinearity?andnonlinearabsorption?in?tetra?tolyl?porphyrins?using?degenerate?four?wavemixing?andZ-scan.Opt.Commun.2000，182(1-3)：255-264.
[6] Chen Yuming, Wang Yuxiao, Jiang Li, Zhang Xueru, Yang Junyi, Li Yuliang, Song Yinglin. the refraction of metal porphyrins excited state strengthens thermal transient refraction competition research with excited state absorption. Acta Physica Sinica, 2009,58 (2): 995-1000.
[7]Kai?Dou，Xiaodong?Sun，Xiaojun?Wang，Robert?Parkhill，Yin?Guo，EdwardT.Knobbe.Optical?limiting?and?nonlinear?absorption?of?excited?states?inmetalloporphyrin-doped?Sol?gels.IEEE?J.Quantum?Electron.，1999，35(7)：1004-1014.
[8]Arun?K.Sinha，Bipin?Bihari，and?Braja?K.Mandal，Lin?Chen.Nonlinear?OpticalProperties?of?a?NewPorphyrin-Containing?Polymer.Macromolecules，1995，28(16)：5681-5683.
Summary of the invention
Technical matters to be solved by this invention provides and a kind ofly can overcome the porphyrin molecule that solvent evaporates and volumetric contraction cause in the sol-gel effectively and reunite, realize that the porphyrin molecule mixes at the matrix middle and high concentration, make grafting be connected to porphyrin in the gel and keep preparation method with molecule porphyrin coupled silicon dioxide organic and inorganic nonlinear optical material of similar light absorption characteristics in liquid on the whole.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of porphyrin coupled silicon dioxide organic and inorganic nonlinear optical material is characterized in that comprising following concrete steps:
(1) the mixed solution of Meso-four (4-carboxyl phenyl) porphyrin copper and γ-An Jibingjisanyiyangjiguiwan 160～250 ℃ of following reflux 10～60 hours, obtain transparent dark red liquid;
(2) reaction product and the metal alkoxide with step (1) is dissolved in the absolute ethyl alcohol, at room temperature stirs 1～2 hour;
(3) at room temperature in the reaction product of step (2), dropwise add (H
2O)/(C
2H
5OH) mixed liquor is hydrolyzed and polyreaction 1～5 hour;
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 35～45 days, and on film, prick 1 hole every day, make composite xerogel at last.
Metal alkoxide described in the step (2) is γ-(2, the 3-glycidoxy) propyl trimethoxy silicane, tetraethoxysilance.
The mol ratio of (4-carboxyl phenyl) porphyrin copper of the Meso-four described in the step (1) and γ-An Jibingjisanyiyangjiguiwan is 1.5 * 10
-5～2 * 10
-4
Described in the step (2) in the reaction product of step (1) mol ratio of Meso-four (4-carboxyl phenyl) porphyrin copper and described metal alkoxide be 10
-6～10
-4, the mol ratio of described absolute ethyl alcohol and metal alkoxide is 1～4.
(H described in the step (3)
2O)/(C
2H
5OH) volume ratio of mixed liquor is 1/2, the H in the mixed liquor
2The mol ratio of O and metal alkoxide is 0.3～3.
Compared with prior art, the invention has the advantages that chemical connection process, make and contain-NH through step (1)
2Among the KH550 of group and Cu (the II)-TCPP-chemical coupled reaction (see figure 1) takes place in COOH group, thereby these porphyrin compound graftings in KH550 (show external spectrum Fig. 2), along with among the KH550-OC
2H
5The hydrolysis of group and the carrying out of polyreaction, mutually compound with other metal alkoxides such as KH560 again, form the advanced composite material (ACM) that an end is connected in network.By this method, can increase substantially the doping content of porphyrin molecule monomer in the gel solid dielectric, and the porphyrin molecule in the gel media kept assertive evidence molecular entergy level structure and spectral characteristic, along with doping content from 3.128 * 10
-8Mol% is increased to 2.626 * 10
-7During mol%, still there is (see figure 3) in Cu (the II)-TCPP porphyrin that takes place in the gel sample after chemistry connects with monomer.Be connected but chemistry does not take place, be doped in micropore 30TiO with medium
2-70SiO
2Soluble Cu in the gel (II)-TPPS porphyrin is when doping content reaches 1.012 * 10
-7Tangible dimer agglomeration takes place during mol%.Work as doping content up to 2.626 * 10 with the gel of this method preparation
-7During mol%, porphyrin can also keep the monomer molecule state.Therefore method of the present invention can increase substantially the doping content of monomer.The porphyrin that is connected in the gel shows original optical non-linear effect (see figure 4).The n of the gel sample of Cu (II)-TCPP
2For～-1.1161 * 10
-16m
2/ W.The nonlinear refractive index n of water-soluble Cu (the II)-TPPS porphyrin that is not connected with medium
2For～-4.6941 * 10
-17m
2/ W is slightly less than situation about being connected with medium, this mainly be since porphyrin and medium take place chemical be connected effect after, further increased the size of organic functional molecular to a certain extent, cause the outer-shell electron layer to be more prone to polarize.Therefore this method can also improve the nonlinear refractive index size of porphyrin molecule.
Description of drawings
Fig. 1 is the reaction mechanism figure of tetracarboxylic phenyl porphyrin copper Cu (II)-TCPP and KH550:
Fig. 2 is the infrared spectrum before and after tetracarboxylic phenyl porphyrin copper Cu (II)-TCPP and the KH550 reaction:
A Cu (II)-TCPP; B KH550; The c reaction product;
Fig. 3 is the absorption spectrum of gel sample;
(a) be the absorption spectrum of Cu (II)-TCPP-KH550-KH560 gel sample of making among the embodiment 1,2,3, curve 1,2,3 expression porphyrin content are 3.128 * 10
-8Mol%, 4.233 * 10
-8Mol%, 2.626 * 10
-7The absorption spectrum of the sample of mol% is that water miscible tetrasulfonic acid phenyl porphyrin copper (abbreviating Cu (II)-TPPS as, water-soluble) porphyrin is doped to 30TiO (b)
2-70SiO
2The absorption spectrum of solid gel, curve 1,2,3,4 represent that respectively doping content is 5.560 * 10
-8Mol%, 7.587 * 10
-8Mol%, 1.012 * 10
-7Mol%, 1.517 * 10
-7The absorption spectrum of mol% sample;
Fig. 4 is the Z scanning curve figure of Cu (II)-TCPP-KH550 gel sample of making among the embodiment 2,3, and curve 1,2 expression porphyrin content are respectively 2.645 * 10 among the figure
-7Mol%, 1.830 * 10
-6Mol%, horizontal ordinate are sample position, and ordinate is the normalization transmitance; (a) be normalization perforate (S=1) the Z scanning curve of Cu (II)-TCPP; (b) be normalization closed pore (S＜1) the Z scanning curve of Cu (II)-TCPP; (c) indicated concentration is 2.645 * 10
-7The Z scanning curve of the pure refractive index of mol%; (d) indicated concentration is 1.830 * 10
-6The Z scanning curve of the pure refractive index of mol%.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
(1) Cu (II)-TCPP and KH550 in molar ratio 1.955 * 10
-5/ 1, join in the chemical reaction bottle that condensing unit is housed, hydrolysis and polyreaction take place to prevent the moisture absorption of KH550 alkoxide in the air interface feeding nitrogen at reflux, and potpourri obtains transparent dark red liquid at 160 ℃ of following heated and stirred backflow 15h.
(2) get above-mentioned reaction product, carry out compoundly with the KH560 metal alkoxide, the Cu in the reaction product (II)-TCPP and K H560 mol ratio are 3.724 * 10
-6/ 1, place beaker to stir 1h mixed solution, in beaker, add anhydrous C simultaneously
2H
5OH, with the mol ratio of alkoxide KH560 be 1.53/1.
(3) with (H
2O)/(C
2H
5OH) volume ratio is that 1/2 mixed liquor dropwise adds in people's beaker, is hydrolyzed and polyreaction the H of adding
2The O integral molar quantity is 0.83/1 of all metal alkoxide mole total amounts, adds back hydrolysis 1h under room temperature.
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 45 days, and on film, prick 1 hole every day, making the porphyrin doping content at last is 3.128 * 10
-8Mol% even, transparent, be dark brown red composite xerogel.
Embodiment 2:
(1) Cu (II)-TCPP and KH550 are pressed certain molar ratio 2.645 * 10
-5/ 1, join in the chemical reaction bottle that condensing unit is housed, hydrolysis and polyreaction take place to prevent the moisture absorption of KH550 alkoxide in the air interface feeding nitrogen at reflux, and potpourri obtains transparent dark red liquid at 200 ℃ of following heated and stirred backflow 30h.
(2) get above-mentioned reaction product, carry out compoundly with the KH560 metal alkoxide, the Cu in the reaction product (II)-TCPP and KH560 mol ratio are 5.039 * 10
-6/ 1, place beaker to stir 1.5h mixed solution, in beaker, add anhydrous C simultaneously
2H
5OH, with the mol ratio of alkoxide KH560 be 3.05/1.
(3) with (H
2O)/(C
2H
5OH) volume ratio is that 1/2 mixed liquor dropwise adds in people's beaker, is hydrolyzed and polyreaction the H of adding
2The O integral molar quantity is 1.25/1 of all metal alkoxide mole total amounts, adds back hydrolysis 3h under room temperature.
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 43 days, and on film, prick 1 hole every day, making the porphyrin doping content at last is 4.233 * 10
-8Mol% even, transparent, be dark brown red composite xerogel.
Embodiment 3:
(1) Cu (II)-TCPP and KH550 are pressed certain molar ratio 1.830 * 10
-4/ 1, join in the chemical reaction bottle that condensing unit is housed, at the air interface feeding nitrogen of reflux, hydrolysis and polyreaction take place to prevent the moisture absorption of KH550 alkoxide, potpourri carries out chemical reaction at 250 ℃ of following heated and stirred backflow 50h, obtains transparent dark red liquid.
(2) get above-mentioned reaction product, carry out compoundly with the KH560 metal alkoxide, the Cu in KH560 and the reaction product (II)-TCPP mol ratio is 3.487 * 10
-5/ 1, mixed solution places beaker to stir 2h, adds anhydrous C simultaneously in mixed solution
2H
5OH, with the mol ratio of alkoxide KH560 be 3.82/1.
(3) with (H
2O)/(C
2H
5OH) volume ratio is that 1/2 mixed liquor dropwise adds in people's beaker, is hydrolyzed and polyreaction the H of adding
2The O integral molar quantity is 1.66/1 of all metal alkoxide mole total amounts, adds back hydrolysis 5h under room temperature.
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 42 days, and on film, prick 1 hole every day, making the porphyrin doping content at last is 2.626 * 10
-7Mol% even, transparent, be dark brown red composite xerogel.
Embodiment 4:
(1) Cu (II)-TCPP and KH550 are pressed certain molar ratio 1.955 * 10
-5/ 1 joins in the chemical reaction bottle that condensing unit is housed, air interface at reflux feeds nitrogen, to prevent the moisture absorption of KH550 alkoxide hydrolysis and polyreaction takes place, and potpourri is at 160 ℃ of following heated and stirred backflow 15h, carry out chemical reaction, obtain transparent dark red liquid.
(2) get above-mentioned reaction product, carry out compoundly with ethyl orthosilicate (TEOS), the Cu in the reaction product (II)-TCPP and TEOS mol ratio are 3.717 * 10
-6/ 1, mixed solution places beaker to stir 1h, adds anhydrous C in the mixed solution
2H
5OH, with the mol ratio of alkoxide TEOS be 3.81/1.
(3) with (H
2O)/(C
2H
5OH) volume ratio is that 1/2 mixed liquor dropwise adds in people's beaker, is hydrolyzed and polyreaction the H of adding
2The O integral molar quantity is 2.98/1 of all metal alkoxide mole total amounts, adds back hydrolysis 1h under room temperature.
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 40 days, and on film, prick 1 hole every day, making the porphyrin doping content at last is 3.123 * 10
-8Mol% even, transparent, be dark brown red composite xerogel.
Embodiment 5:
(1) Cu (II)-TCPP and KH550 are pressed certain molar ratio 2.645 * 10
-5/ 1 joins in the chemical reaction bottle that condensing unit is housed, air interface at reflux feeds nitrogen, to prevent the moisture absorption of KH550 alkoxide hydrolysis and polyreaction takes place, and potpourri is at 200 ℃ of following heated and stirred backflow 30h, carry out chemical reaction, obtain transparent dark red liquid.
(2) get above-mentioned reaction product, carry out compoundly with ethyl orthosilicate (TEOS), the Cu in the reaction product (II)-TCPP and TEOS mol ratio are 5.030 * 10
-6/ 1, mixed solution places beaker to stir 1.5h, adds anhydrous C simultaneously in mixed solution
2H
5OH, with the mol ratio of alkoxide TEOS be 2.86/1.
(3) with (H
2O)/(C
2H
5OH) volume ratio is that 1/2 mixed liquor dropwise adds in people's beaker, is hydrolyzed and polyreaction the H of adding
2The O integral molar quantity is 1.0/1 of all metal alkoxide mole total amounts, adds back hydrolysis 3h under room temperature.
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 38 days, and on film, prick 1 hole every day, making the porphyrin doping content at last is 4.226 * 10
-8Mol% even, transparent, be dark brown red composite xerogel.
Embodiment 6:
(1) Cu (II)-TCPP and KH550 are pressed certain molar ratio 1.830 * 10
-4/ 1 joins in the chemical reaction bottle that condensing unit is housed, air interface at reflux feeds nitrogen, to prevent the moisture absorption of KH550 alkoxide hydrolysis and polyreaction takes place, and potpourri is at 250 ℃ of following heated and stirred backflow 50h, carry out chemical reaction, obtain transparent dark red liquid.
(2) get above-mentioned reaction product, carry out compoundly with ethyl orthosilicate (TEOS), the Cu in the reaction product (II)-TCPP and TEOS mol ratio are 3.481 * 10
-5/ 1, mixed solution places beaker to stir 2h, adds anhydrous C simultaneously in mixed solution
2H
5OH, with the mol ratio of alkoxide TEOS be 1.91/1.
(3) with (H
2O)/(C
2H
5OH) volume ratio is that 1/2 mixed liquor dropwise adds in people's beaker, is hydrolyzed and polyreaction the H of adding
2The O integral molar quantity is 0.50/1 of all metal alkoxide mole total amounts, adds back hydrolysis 5h under room temperature.
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 35 days, and on film, prick 1 hole every day, making the porphyrin doping content at last is 2.925 * 10
-7Mol% even, transparent, be dark brown red composite xerogel.
Claims (1)
1. the preparation method of a porphyrin coupled silicon dioxide organic and inorganic nonlinear optical material is characterized in that comprising following concrete steps:
(1) the mixed solution of Meso-four (4-carboxyl phenyl) porphyrin copper and γ-An Jibingjisanyiyangjiguiwan 160～250 ℃ of following reflux 10～60 hours, obtain transparent dark red liquid, the mol ratio of described Meso-four (4-carboxyl phenyl) porphyrin copper and γ-An Jibingjisanyiyangjiguiwan is 1.5 * 10
-5～2 * 10
-4
(2) with the reaction product and the γ-(2 of step (1), the 3-glycidoxy) propyl trimethoxy silicane or tetraethoxysilance are dissolved in the absolute ethyl alcohol, at room temperature stirred 1～2 hour, the mol ratio of (4-carboxyl phenyl) porphyrin copper of Meso-four in the reaction product of described step (1) and described γ-(2, the 3-glycidoxy) propyl trimethoxy silicane or tetraethoxysilance is 10
-6～10
-4, the mol ratio of described absolute ethyl alcohol and γ-(2, the 3-glycidoxy) propyl trimethoxy silicane or tetraethoxysilance is 1～4;
(3) at room temperature in the reaction product of step (2), dropwise add (H
2O)/(C
2H
5OH) mixed liquor is hydrolyzed and polyreaction 1～5 hour, described (H
2O)/(C
2H
5OH) volume ratio of mixed liquor is 1/2, the H in the mixed liquor
2The mol ratio of O and γ-(2, the 3-glycidoxy) propyl trimethoxy silicane or tetraethoxysilance is 0.3～3;
(4) vitreosol that obtains is poured in glass or the plastic ware used film seal, ageing at room temperature 35～45 days, and on film, prick 1 hole every day, make composite xerogel at last.
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| CN109926096B (en) * | 2017-12-15 | 2020-06-05 | 中国科学院大连化学物理研究所 | One-step method for preparing metalloporphyrin functionalized mesoporous silica material and application thereof in heterogeneous catalysis |
| CN112721492B (en) * | 2020-12-14 | 2021-12-17 | 湖北宜美特全息科技有限公司 | Temperature-resistant porphyrin grafted silica toner and preparation method and application thereof |
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