CN100381449C - Silioxane precursor containing azobenzene dye and its synthesis - Google Patents
Silioxane precursor containing azobenzene dye and its synthesis Download PDFInfo
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- CN100381449C CN100381449C CNB2006100520482A CN200610052048A CN100381449C CN 100381449 C CN100381449 C CN 100381449C CN B2006100520482 A CNB2006100520482 A CN B2006100520482A CN 200610052048 A CN200610052048 A CN 200610052048A CN 100381449 C CN100381449 C CN 100381449C
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- Prior art keywords
- azobenzene dye
- precursor body
- siloxane precursor
- synthetic method
- azobenzene
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002243 precursor Substances 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000010189 synthetic method Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000012454 non-polar solvent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- COBQHCOQMZLUPS-UHFFFAOYSA-K [di(dodecanoyloxy)-dodecylstannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCCCCCC)(OC(=O)CCCCCCCCCCC)OC(=O)CCCCCCCCCCC COBQHCOQMZLUPS-UHFFFAOYSA-K 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 230000003287 optical effect Effects 0.000 abstract description 23
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 229910052801 chlorine Chemical group 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 125000002560 nitrile group Chemical group 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 20
- 238000011160 research Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920006112 polar polymer Polymers 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 229940029329 intrinsic factor Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
A siloxane precursor containing azobenzene dye and its synthesis are disclosed. In structural formula, R is nitrile, nitryl or chlorine atom. The process is carried out by addition reacting nitrogen benzide dye containing R group with carbimide propyl triethoxy-silane to obtain final product. It is cheap and simple and can be used for linked chemical bond inorganic-organic hybrid material, electro-optic modulation, optical switch and non-linear optical fields.
Description
Technical field
The present invention relates to siloxane precursor body and synthetic method thereof that a class contains azobenzene dye.
Background technology
Because nonlinear optical material has application prospect greatly at aspects such as full optical communication, photometry calculation and optical information processing, just becomes the hot fields that the countries in the world scientist competitively studies so seek the nonlinear optical material of stability and high efficiency.Mineral crystal is the quasi-nonlinear optical material that people study the earliest and use, though the crystal technique of these materials reaches its maturity, but still exist tangible weak point: as cost an arm and a leg, be easy to damage, and can only use monocrystal material work, be difficult to realize that optics is integrated.Therefore, since the seventies in last century, people have begun exploration organic and the polymkeric substance nonlinear optical material.This class material has the nonlinear optical coefficients than the high 1-2 of a mineral crystal order of magnitude, and big optical damage threshold (can reach GW/cm
2), the polytropy of series of advantages, especially organic molecular structures such as (subpicosecond are to femtosecond) of ultrafast time of response makes people can realize that molecule cuts out and molecular designing by the understanding to its structure-performance relation, thereby satisfies the requirement of device practicability.
The proposition of initial stage eighties polar polymer notion and successful practice have worldwide started the research boom of organic non linear optical material, indicate that the polymkeric substance nonlinear optical material has entered the study period with practical prospect.The beginning of the nineties, in view of research work in the world than quantum jump, many scientists foretell that polar polymer is expected to obtain at first practicability, the electrostrictive polymer photomodulator also will come into the market in several years." chemistry and Engineering News Record " (C﹠amp of the U.S.; EN) magazine also is title and has done detailed introduction with " Devices based onelectro-optic polymers begin to enter market-place " at front cover.Yet what have no need for reticence is, because problems such as low, repeatable difference of the thermostability that the intrinsic factor of organic materials causes and loss of light propagation are big still fail to solve fully, really do not develop a kind of polymeric system that can satisfy the practical requirement of all devices simultaneously so far.Therefore, after the hot topic that has experienced initial more than ten years, the research of polar polymer is just entering relative low tide period at present.
The inorganic-organic hybridization material of sol-gel method preparation then is a kind of advanced composite material that occurs in recent years, it forms the unorganic glass network by alkoxide hydrolysis at ambient temperature, the polycondensation of Si, Al, Zr or Ti, and organic constituent then combines with inorganic matrix by the mode of mixing or key connects.Organic-inorganic hybridized non-linear optical material by this method preparation has been broken through traditional inorganic, the boundary of organic non linear optical material, organic non-linear molecule and inorganic matrix are combined together on molecular level, not only have concurrently inorganic, both performance advantages of organic materials, and can realize the compound and cooperate optimization of function, be considered to one of the novel non-linearity optical material that obtains practical application that most possibly takes the lead in, thereby various countries scientists' research interest and research enthusiasm have been attracted, wherein, structure is clear and definite, the inorganic organic hybrid nonlinear optical material of the chemical bond-linking type of stable performance gets most of the attention especially.Though the research of this respect has the history of more than ten years, but design, synthesize the siloxane dye that is connected with various function chromophore molecules and still have bigger challenge, and this prepares indispensable key link in the inorganic organic hybrid nonlinear optical material process of chemical bond-linking type just.
" pushing away-La " the type azobenzene dye is a class has electron donor(ED) and electron acceptor(EA) simultaneously at the two key two ends of azo chromophore molecule.Because the two keys of azo N=N provide excellent electron channel, make the conjugated electrons in the molecule have very big flowability, electronics is easy to migration under electric field action, is to have low π-π
*The energy system of excited electronic state.Have higher single order hyperpolarizability and thermostability owing to this quasi-molecule in recent years, and tangible intramolecular charge transfer organization feature, it is synthetic to be widely used in organic design with the polymkeric substance nonlinear optical material, and has obtained a large amount of achievements.But it is synthetic and correlative study is still rare to utilize this class dyestuff to carry out the design of siloxane precursor body.
Summary of the invention
The object of the present invention is to provide a class to contain the siloxane precursor body and the synthetic method thereof of azobenzene dye.This compounds is not only synthetic convenient, and purifying is simple, can be used as the novel non-linearity optical material and obtains practical application in fields such as Electro-optical Modulation, photoswitch and phase conjugations.
A class provided by the invention contains the siloxane precursor body of azobenzene dye, and its general structure is suc as formula 1:
Formula 1
R is cyano group or nitro in the formula.
The synthetic method that contains the siloxane precursor body of azobenzene dye of the present invention, its step is as follows:
Azobenzene dye is dissolved in the organic solvent of no water treatment, add the isocyanato propyl-triethoxysilicane again, the mol ratio of azobenzene dye and isocyanato propyl-triethoxysilicane is 1: 1～2, make catalyzer with amine or organotin, after the reflux 6～72 hours, pour reaction solution into non-polar solvent and produce precipitation, filter, drying, obtain containing the siloxane precursor body of azobenzene dye.
In the above-mentioned synthetic method, said azobenzene dye can be 4 '-(N-ethyl-N hydroxyethyl)-amido-2-cyano group-4-nitroazobenzene, 4 '-(N-ethyl-N hydroxyethyl)-amido-2,4-dinitrobenzene nitrogen benzide or 4 '-(N-ethyl-N hydroxyethyl)-amido-2-chloro-4-nitroazobenzene; Said organic solvent can be tetrahydrofuran (THF), dioxane or acetone; Said amine or organotin catalysts can be triethylamine, dodecyl tin laurate or stannous octoate; Said non-polar solvent can be normal hexane, normal heptane or sherwood oil.
Beneficial effect of the present invention is:
1. the siloxane precursor body that contains azobenzene dye of the present invention for the organic-inorganic hybridized non-linear optical material for preparing the chemical bond-linking type provides new precursor, is expanded the research contents of having enriched nonlinear optical material.
2. the siloxane precursor body synthesis technique that contains azobenzene dye of the present invention is simple, and productive rate is higher, and purifying is convenient, and the reaction conditions gentleness.
3. siloxane precursor body of the present invention has good second-order nonlinear optical property, is expected to obtain practical application in fields such as Electro-optical Modulation, photoswitch and phase conjugations.
Embodiment
Embodiment 1:
R in the general structure 1 is a cyano group.The synthetic route of siloxane precursor body that contains azobenzene dye is as follows:
Synthetic method is:
Add 4 of 10mmol '-(N-ethyl-N hydroxyethyl)-amido-2-cyano group-4-nitroazobenzene in the three-necked bottle of anhydrous and oxygen-free device toward reflux condensing tube being housed and connecting under the room temperature, open anhydrous and oxygen-free device and logical nitrogen after 30 minutes, tetrahydrofuran (THF) and 3-5 that the firm drying treatment of adding 20ml is crossed drip stannous octoate, magnetic agitation, add 2.47g (10mmol) isocyanato propyl-triethoxysilicane again, dropwise post-heating to 90 ℃, reflux after 72 hours and to pour reaction solution into normal hexane and produce precipitation, suction filtration and vacuum-drying obtain containing the siloxane precursor body of azobenzene dye.Productive rate 73% is made material second harmonic coefficient d afterwards
33Be 46.1pm/V.
Embodiment 2:
R in the general structure 1 is a nitro.The synthetic route of siloxane precursor body that contains azobenzene dye is as follows:
Synthetic method is:
Add 4 of 10mmol '-(N-ethyl-N hydroxyethyl)-amido-2 in the three-necked bottle of anhydrous and oxygen-free device toward reflux condensing tube being housed and connecting under the room temperature, 4-dinitrobenzene nitrogen benzide, open anhydrous and oxygen-free device and logical nitrogen after 30 minutes, acetone and 8-10 that the firm drying treatment of adding 30ml is crossed drip triethylamine, magnetic agitation, add 2.96g (12mmol) isocyanato propyl-triethoxysilicane again, dropwise post-heating to 110 ℃, reflux after 6 hours and to pour reaction solution into normal heptane and produce precipitation, suction filtration and vacuum-drying obtain containing the siloxane precursor body of azobenzene dye.Productive rate 62% is made material second harmonic coefficient d afterwards
33Be 39.6pm/V.
Embodiment 3:
R in the general structure 1 is the chlorine atom.The synthetic route of siloxane precursor body that contains azobenzene dye is as follows:
Synthetic method is:
Add 4 of 10mmol '-(N-ethyl-N hydroxyethyl)-amido-2-chloro-4-nitroazobenzene in the three-necked bottle of anhydrous and oxygen-free device toward reflux condensing tube being housed and connecting under the room temperature, open anhydrous and oxygen-free device and logical nitrogen after 30 minutes, dioxane and 5-6 that the firm drying treatment of adding 60ml is crossed drip the dodecyl tin laurate, magnetic agitation, add 4.94g (20mmol) isocyanato propyl-triethoxysilicane again, dropwise post-heating to 140 ℃, reflux after 48 hours and to pour reaction solution into sherwood oil and produce precipitation, suction filtration and vacuum-drying obtain containing the siloxane precursor body of azobenzene dye.Productive rate 68% is made material second harmonic coefficient d afterwards
33Be 40.7pm/V.
Siloxane precursor body synthesis technique in the foregoing description is simple, and productive rate is higher, and has good second-order nonlinear optical property, shows that fully it has great application prospect in fields such as Electro-optical Modulation.
Claims (6)
1. a class contains the siloxane precursor body of azobenzene dye, and its general structure is suc as formula 1:
Formula 1
R is cyano group or nitro in the formula.
2. the synthetic method that contains the siloxane precursor body of azobenzene dye according to claim 1 is characterized in that may further comprise the steps:
Azobenzene dye is dissolved in the organic solvent of no water treatment, add the isocyanato propyl-triethoxysilicane again, the mol ratio of azobenzene dye and isocyanato propyl-triethoxysilicane is 1: 1～2, make catalyzer with amine or organotin, after the reflux 6～72 hours, pour reaction solution into non-polar solvent and produce precipitation, filter, drying, obtain containing the siloxane precursor body of azobenzene dye.
3. the synthetic method that contains the siloxane precursor body of azobenzene dye according to claim 2, it is characterized in that said azobenzene dye be 4 '-(N-ethyl-N hydroxyethyl)-amido-2-cyano group-4-nitroazobenzene, 4 '-(N-ethyl-N hydroxyethyl)-amido-2,4-dinitrobenzene nitrogen benzide or 4 '-(N-ethyl-N hydroxyethyl)-amido-2-chloro-4-nitroazobenzene.
4. the synthetic method that contains the siloxane precursor body of azobenzene dye according to claim 2 is characterized in that said organic solvent is tetrahydrofuran (THF), dioxane or acetone.
5. the synthetic method that contains the siloxane precursor body of azobenzene dye according to claim 2 is characterized in that said amine or organotin catalysts are triethylamine, dodecyl tin laurate or stannous octoate.
6. the synthetic method that contains the siloxane precursor body of azobenzene dye according to claim 2 is characterized in that said non-polar solvent is normal hexane, normal heptane or sherwood oil.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100520482A CN100381449C (en) | 2006-06-19 | 2006-06-19 | Silioxane precursor containing azobenzene dye and its synthesis |
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|---|---|---|---|
| CNB2006100520482A CN100381449C (en) | 2006-06-19 | 2006-06-19 | Silioxane precursor containing azobenzene dye and its synthesis |
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| Publication Number | Publication Date |
|---|---|
| CN1896081A CN1896081A (en) | 2007-01-17 |
| CN100381449C true CN100381449C (en) | 2008-04-16 |
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| CNB2006100520482A Expired - Fee Related CN100381449C (en) | 2006-06-19 | 2006-06-19 | Silioxane precursor containing azobenzene dye and its synthesis |
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| CN110922860B (en) * | 2019-12-08 | 2021-07-20 | 山东大学 | Environment-friendly gas-sensitive paint for volatile acid and preparation method thereof |
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- 2006-06-19 CN CNB2006100520482A patent/CN100381449C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| writing-erasing propertiies and characterizations ofhybridmaterials based on disperse red by sol-gel process. mi pa kim et al.dyes and pigments,Vol.70 No.2006. 2005 * |
| 含对硝基偶氮苯胺生色团的键合型有机/无机复合材料的合成及其二阶非线性光学特性. 奚红霞等.高分子学报，第6期. 2000 * |
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