CN1803877A - Hyperbranched second order differential non-linear optical high molecule, its preparation method and use - Google Patents
Hyperbranched second order differential non-linear optical high molecule, its preparation method and use Download PDFInfo
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- CN1803877A CN1803877A CN 200510019998 CN200510019998A CN1803877A CN 1803877 A CN1803877 A CN 1803877A CN 200510019998 CN200510019998 CN 200510019998 CN 200510019998 A CN200510019998 A CN 200510019998A CN 1803877 A CN1803877 A CN 1803877A
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- linear optical
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Abstract
The related new hyperbranched second-order nonlinear optical macromolecule has structural formula as I (R for nitro, sulfuryl or other electron-attacting groups; n=10-120, can be prepared with composed second-order nonlinear optical chromophore and triphenylaminotrialdehyde, and has practical application in remote communication, data storage and conversion, etc.
Description
Technical field
The present invention relates to a kind of novel hyperbranched second order differential non-linear optical high molecule and method for making and purposes.
Background technology
Development of science and technology is maked rapid progress, and human pursuit also is endless.Current, rely on the development of electronics and microtronics technology, the mankind have set up the information network that quite improves with system., along with the progress of society, the existing information system still can't satisfy human to aspect requirements fast and accurately such as information processing, transmission, conversions.Simultaneously because the physics limit of electronics itself mainly is as the transmission speed limit of information carrier and the DENSITY LIMIT of information storage, electronics the potentiality of message context almost be excavate most.Comparatively speaking, photon is just just come upon the stage as the carrier of information.Replace electronics with photon, can accelerate information processing speed greatly, increase the capacity of process information, can overcome the bottleneck of microelectronics, more accurate, more efficient, farther distance ground transmission information.Development for full optical information technology, nonlinear optics (NLO) is indispensable crucial subject, it has very important effect in practical fields such as high-speed light communication, optical information processing and photoelectronics, and nonlinear optical material obtains more and more widely attention in these Application for Field prospects.
Common polymer nonlinear optical material is divided into two big classes substantially: linear macromolecule material and dendrimer.This two classes material differs from one another, and has its weak point.Generally speaking, the linear macromolecule material prepares easily, and cost is relatively low, but its non-linear optical effect also is difficult to the index that reaches higher; And the non-linear optical property of dendrimer can reach result preferably, but its preparation is comparatively loaded down with trivial details, and each is for the suitable difficulty of the separation and purification of molecule, how reaches the regular of structure for polymer is difficult.Therefore, the various countries scientist all wishes the advantage in conjunction with the two, develop novel non-linear optical polymer materials, wish that new macromolecular material can possess big nonlinear optical response simultaneously, high thermostability and workability etc., simultaneously, in order to reduce the cost of material, the preparation process of material needs to simplify as much as possible.
Summary of the invention
Purpose of the present invention just is to provide a kind of novel hyperbranched second order differential non-linear optical high molecule, and it has bigger second-order nonlinear optical property, higher thermostability and good processability.
Another object of the present invention provides the preparation method of this hyperbranched second order differential non-linear optical high molecule, and this preparation method is simple.
Purpose in addition of the present invention is as the application of a kind of novel second-order non-linear optical materials at aspects such as telecommunication, data storage, phase conjugation, data-switching with hyperbranched second order differential non-linear optical high molecule of the present invention.
The technical scheme that hyperbranched second order differential non-linear optical high molecule of the present invention adopted is: have the represented structural formula of general formula I:
R is nitro, sulfuryl or other electron-withdrawing group in the formula, n=10～120.
The present invention also provides the preparation method of above-mentioned hyperbranched second order differential non-linear optical high molecule; its difference is: with synthetic second-order nonlinear optical chromophore and triphenylamine three aldehyde is raw material; the mol ratio of second-order nonlinear optical chromophore and triphenylamine three aldehyde is 1: 1～3; with DMF as reaction solvent; the quality of DMF is 20～30 times of second-order nonlinear optical chromophore quality; under argon shield; 80～150 ℃ of controlled temperature; reacted 1～4 hour; the question response liquid cooling is during to room temperature; reaction solution is just slowly splashed in the methyl alcohol of vigorous stirring, the volume of methyl alcohol be used DMF 15-25 doubly, filter; use the methanol wash filter cake; used methyl alcohol volume is 2～5 times of DMF, gets the pulverulent solids product, is described hyperbranched second order differential non-linear optical high molecule.
Hyperbranched second order differential non-linear optical high molecule of the present invention can be used as second-order non-linear optical materials and obtains practical application at aspects such as telecommunication, data storage, phase conjugation, data-switching.
Beneficial effect of the present invention is:
1, novel hyperbranched second order differential non-linear optical high molecule of the present invention is synthetic quite easy, and it is also very easy to purify, and this is that the dendrimer material is incomparable.
2, novel hyperbranched second order differential non-linear optical high molecule of the present invention have very high second order nonlinear optical effect (as the second-order nonlinear optical property d33 value of the hyperbranched second order differential non-linear optical high molecule among embodiment 1 and the embodiment 2 be respectively 65.9 and 14.4pm/V).
3, the invention describes a kind of preparation of novel hyperbranched second order differential non-linear optical high molecule, this is the nonlinear optical material of a class brand new, has extremely strong novelty, enriched the content of organic polymer second-order non-linear optical materials research, expanded the method and the mentality of designing of second-order non-linear optical materials chemistry to a certain extent, had the important theory directive significance for the structure sexual intercourse between research material microtexture and the macro property.
Embodiment
Embodiment 1:
When R was nitro, synthetic route was as follows:
Synthetic method is:
(1) compound 3 is synthetic
P-Nitroaniline 2 joins in the aqueous solution of 35% concentrated hydrochloric acid (quality of water is 3 times of concentrated hydrochloric acid), and wherein the quality of concentrated hydrochloric acid is 2.5 times of p-Nitroaniline 2, carries out vigorous stirring.Under ice bath, in reaction solution, slowly drip the aqueous solution of Sodium Nitrite, wherein the mass percent concentration of Sodium Nitrite is 10%-20%, keeps 0 ℃ to stir 15 minutes, removes by filter insolubles then.Compound 1 is dissolved in the suitable ethanol, slowly is added drop-wise in the filtrate of vigorous stirring, after dropwising, keep 0 ℃ to stir 1 hour, adding sodium bicarbonate adjusting pH value is 7, after continuing under the room temperature to stir half an hour, filters, and washes filter cake with water 3 times.Thick product gets dark red solid with the ethanol/water recrystallization, is compound 3.Wherein, the mol ratio of compound 1, compound 2, Sodium Nitrite is 1: 1.1: 1.3.
Fusing point: 205-207 ℃; IR:1601cm
-1(-C=C-), 1512,1330cm
-1(NO
2).
(2) synthetic second-order nonlinear optical chromophore 4
In the round-bottomed flask of 50mL, add compound 3, cyanoacetic acid, 4-(N, the N-dimethyl) aminopyridine (catalytic amount) adds the exsiccant tetrahydrofuran (THF) then, and wherein the quality of tetrahydrofuran (THF) is 100 times of compound 3, it is fully dissolved, and then add N, N-dicyclohexylcarbodiimide.At room temperature stir 48 hours after-filtration, remove insolubles, and extremely white with the chloroform washing leaching cake, get the scarlet transparent liquid, remove then and desolvate, get dark red solid.(2/1, V/V) mixed solvent is an elutriant to thick product, after silica gel column chromatography separates, gets scarlet powder (productive rate 86%) with ethyl acetate/petroleum ether.Wherein, compound 3, cyanoacetic acid, N, the mol ratio of N-dicyclohexylcarbodiimide is 1: 3: 5.
mp＝137～138℃.FTIR(cm
-1)：2264(CN)，1739(C＝O)，1340cm
-1(-NO
2-).FABMS?m/z[M
+]：512.1。
(3) compound 6 is synthetic
Take by weighing triphenylamine as in the flask, add dry DMF, fill N
2Protection under condition of ice bath, dropwise adds phosphorus oxychloride with syringe, and the mixture of reaction was in 90～100 ℃ of following reacting by heating 48 hours.Reaction gained mixed solution is poured in the frozen water, and with the neutralization of 10%NaOH solution, pH value is transferred to neutrality, and filtering solution gets black-and-blue solid then.(1/4, V/V) mixed solvent is an elutriant to thick product, after silica gel column chromatography separates, gets compound 6 triphenylamines three aldehyde with ethyl acetate/petroleum ether.Wherein, triphenylamine, dry DMF, the mol ratio of phosphorus oxychloride are 1: 26: 21.
1H-NMR(CDCl
3)δ(ppm)：7.19(d，6H，ArH)，7.76(d，6H，ArH)，9.88(s，3H)。
(4) hyperbranched second order differential non-linear optical high molecule P1's is synthetic
Get triphenylamine three aldehyde 6 (0.057g); second-order nonlinear optical chromophore 4 (0.1207g); DMF (3mL) is in the Schlenk pipe; make catalyzer with hexahydropyridine; charge into argon gas protection, controlled temperature reacted 2 hours down for 110 ℃, when question response is cooled to room temperature; reaction solution just slowly splashed in the 100mL of vigorous stirring methyl alcohol, carry out reprecipitation, the burgundy muddiness occurs.Filter, use the methanol wash filter cake, used methyl alcohol volume is 5 times of DMF, gets pulverulent solids product 0.0816g, is hyperbranched second order differential non-linear optical high molecule.
Productive rate: 48.47%; FTIR (cm
-1): 2205 (CN), 1695 (C=O), 1334cm
-1(NO
2-).
Embodiment 2:
When R was sulfuryl, synthetic route was as follows:
Synthetic method is:
(1) compound 8 is synthetic
To join in the aqueous solution of 35% concentrated hydrochloric acid (quality of water is 3 times of concentrated hydrochloric acid) ethyl sulfuryl aniline 7, wherein the quality of concentrated hydrochloric acid is to ethyl sulfuryl aniline 7 2.5 times, carries out vigorous stirring.Under ice bath, slowly drip the aqueous solution of Sodium Nitrite to reaction solution, wherein the mass percent concentration of Sodium Nitrite is 10%-20%, keeps 0 ℃ to stir after 15 minutes, removes by filter insolubles.Compound 1 is dissolved in the suitable ethanol, slowly is added drop-wise in the filtrate of vigorous stirring, after dropwising, keep 0 ℃ to stir 1 hour, adding sodium bicarbonate adjusting pH value is 7, after continuing under the room temperature to stir half an hour, filters washing filter cake 3 times.Thick product gets the orange solid with the ethanol/water recrystallization, is compound 8.Wherein, the mol ratio of compound 1, compound 7, Sodium Nitrite is 1: 1.1: 1.3.
Fusing point: 129-130 ℃; IR:1601,1512cm
-1(-C=C-), 1299,1131cm
-1(SO
2).
(2) synthetic second-order nonlinear optical chromophore 9
In the round-bottomed flask of 50mL, add compound 8, cyanoacetic acid, 4-(N, the N-dimethyl) aminopyridine (catalytic amount) adds the exsiccant tetrahydrofuran (THF) then, and wherein the quality of tetrahydrofuran (THF) is 100 times of compound 8, it is fully dissolved, and then add N, N-dicyclohexylcarbodiimide.At room temperature stir 48 hours after-filtration, remove insolubles, and extremely white with the chloroform washing leaching cake, get the scarlet transparent liquid, remove then and desolvate, get dark red solid.(2/1, V/V) mixed solvent is an elutriant to thick product, after silica gel column chromatography separates, gets scarlet powder (productive rate 80%) with ethyl acetate/petroleum ether.Wherein, compound 8, cyanoacetic acid, N, the mol ratio of N-dicyclohexylcarbodiimide is 1: 3: 5.
mp＝50～51℃.FTIR(cm
-1)：2264(CN)，1750(C＝O)，1129cm
-1(-SO
2-)。
(3) hyperbranched second order differential non-linear optical high molecule polymer P2's is synthetic
Get embodiment 1 described triphenylamine three aldehyde (0.075g); second-order nonlinear optical chromophore 9 (0.1753g); DMF (4mL) is in the Schlenk pipe; make catalyzer with hexahydropyridine; charge into argon gas protection; controlled temperature reacted 2 hours down for 110 ℃; question response is cooled to room temperature; reaction solution just slowly splashed in the 100mL of vigorous stirring methyl alcohol, carry out reprecipitation; filter, use the methanol wash filter cake, used methyl alcohol volume is 5 times of DMF; get pulverulent solids product 0.161g, be hyperbranched second order differential non-linear optical high molecule.
Productive rate: 67.65%; FTIR (cm
-1): 2214 (CN), 1725 (C=O), 1129cm
-1(SO
2-).
Claims (3)
1, hyperbranched second order differential non-linear optical high molecule has the represented structural formula of general formula I:
R is nitro, sulfuryl or other electron-withdrawing group in the formula; N=10～120.
2; the preparation method of the described hyperbranched second order differential non-linear optical high molecule of claim 1; it is characterized in that; with synthetic second-order nonlinear optical chromophore and triphenylamine three aldehyde is raw material; the mol ratio of second-order nonlinear optical chromophore and triphenylamine three aldehyde is 1: 1～3; with DMF as reaction solvent; the quality of DMF is 20～30 times of second-order nonlinear optical chromophore quality; under argon shield; 80～150 ℃ of controlled temperature; reacted 1～4 hour, the question response liquid cooling slowly splashes into reaction solution just in the methyl alcohol of vigorous stirring during to room temperature; the volume of methyl alcohol is 15～25 times of used DMF; filter, use the methanol wash filter cake, used methyl alcohol volume is 2～5 times of DMF; get the pulverulent solids product, be described hyperbranched second order differential non-linear optical high molecule.
3, the described hyperbranched second order differential non-linear optical high molecule of claim 1 as second-order non-linear optical materials in the application aspect telecommunication, data storage, data-switching, the phase conjugation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100504565C (en) * | 2006-07-28 | 2009-06-24 | 中国科学院理化技术研究所 | Nonlinear optically active organic silicon polymer and preparation method and application thereof |
| CN104402870A (en) * | 2014-11-06 | 2015-03-11 | 武汉大学 | X-type second-order nonlinear optical macromolecule, preparation method and application thereof |
| CN111040186A (en) * | 2019-12-27 | 2020-04-21 | 华中科技大学 | AB2Second-order nonlinear optical hyperbranched polymer, and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7019453B2 (en) * | 2000-08-17 | 2006-03-28 | Lumera Corporation | Polymers having pendant nonlinear optical chromophores and electro-optic devices therefrom |
| CN1214058C (en) * | 2003-05-28 | 2005-08-10 | 武汉大学 | Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use |
| CN1228364C (en) * | 2003-09-27 | 2005-11-23 | 武汉大学 | Second-order non-linear optical polyphosphazene connecting sulfuryl-azo chromophor lateral group, and preparing method and use thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100504565C (en) * | 2006-07-28 | 2009-06-24 | 中国科学院理化技术研究所 | Nonlinear optically active organic silicon polymer and preparation method and application thereof |
| CN104402870A (en) * | 2014-11-06 | 2015-03-11 | 武汉大学 | X-type second-order nonlinear optical macromolecule, preparation method and application thereof |
| CN104402870B (en) * | 2014-11-06 | 2016-06-15 | 武汉大学 | A kind of X-type second nonlinear optic macromole and its production and use |
| CN111040186A (en) * | 2019-12-27 | 2020-04-21 | 华中科技大学 | AB2Second-order nonlinear optical hyperbranched polymer, and preparation and application thereof |
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