CN1456587A - Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use - Google Patents
Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use Download PDFInfo
- Publication number
- CN1456587A CN1456587A CN03128048A CN03128048A CN1456587A CN 1456587 A CN1456587 A CN 1456587A CN 03128048 A CN03128048 A CN 03128048A CN 03128048 A CN03128048 A CN 03128048A CN 1456587 A CN1456587 A CN 1456587A
- Authority
- CN
- China
- Prior art keywords
- polyphosphonitrile
- group
- nonlinear
- nonlinear optic
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
A two-order non-linear optical polyphosphazene with coloring side group of azoindole is prepared through reaction of polyphosphazene whose side chain is linked with indole group on p-nitrophenyl diazofluoroborate. Its advantages are high two-order non-linear optical performance and better comprehensive properties.
Description
Technical field
The present invention relates to be connected with the chromophoric second nonlinear optic polyphosphonitrile of azo indoles macromolecular material and its production and use.
Background technology
After the sixties in last century laser occurred, a brand-new period had just been stepped in the research of nonlinear optical material.As one of important substance basis of laser technology, the research of nonlinear optics (NLO) material is an important component part of high-tech research.Three during the last ten years, nonlinear optics has progressively developed into an independently optical branching, nonlinear optical material then has indispensable vital role in all respects such as frequency multiplication, mixing, parameter amplification and the vibration of laser, integrated optics, optical communications, they can be used for phase place, polarization state or the frequency of control bundle, also can be used to storage and recovery information or make beam deflection, make it between fiber channel, to transmit optical information.Common nonlinear optical material mainly contains inorganic crystal material, semiconductor material, organic crystal material, metal organic crystal material, organic polymer material etc.Wherein, second order differential non-linear optical high molecule material (comprising electrooptical material and photorefractive material) is because its good dissolving processing characteristics, adjustability of structure and high advantages such as non-linear optical property, thereby attracted numerous scientists' research interest and research enthusiasm.And structure bonding type macromolecular material clear and definite, stable performance gets most of the attention especially.Though the existing not short history of the research of this respect, the second order differential non-linear optical high molecule material of design, compound key mould assembly still has bigger challenge.The report of this respect referring to pertinent literature (as Moerner W.E., Jepsen A.G., Thompson C.L, Annu Rev Mater Sci[J], 1997,27:585-623.Moerner W.E., Silence S.M., Chem Rev, 1994,94:127.).
Polyphosphonitrile is the novel polymer with inorganic main chain of a class.Its main chain by replace banded alternative nitrogen with single, double key, phosphorus atom constitutes, and is connected with two side groups on each phosphorus atom.By research to existing polyphosphonitrile, show that polyphosphonitrile has extremely diversified special performance, as water-fast, anti-solvent, oil resistant and chemical, have good light, thermostability, oxidation-resistance, biocompatibility, radiation hardness, low temperature resistant, biodegradable, do not burn and flame retardant properties, and the advantages such as organic or inorganic functional group that are easy to introduce by side chain different qualities.These advantages have caused scientist's very big interest, and the research of polyphosphonitrile material also is subjected to the attention of national governments day by day.In the last few years, quite active about the research of polyphosphonitrile functional materials, its research range related to many aspects such as fire retardant material, specialty elastomer material, bio-medical material, liquid crystal and photoelectric functional material.Detailed report can be referring to document.(Li Zhen, Zhan Caimao, Qin Jingui, " polyphosphonitrile polymer ", functional polymer journal, 2000,13,240-247.)
Indoles is a kind of benzheterocycle, structurally similar to carbazole, but volume is little many, existing studies show that to be connected with indolyl radical substituted carbazole group can embody very big second order nonlinear optical effect, its nonlinear second-order optical susceptibility d as the chromophoric group of electric charge donor part as the polymer of side chain
33Value can reach 49pm/V.(Moon H., Hwang J., Kim N., Park S.Y., Macromolecules, 2000,33:5116-5123.), the synthetic route of bibliographical information is long, and micromolecular separation is not too easy.
Summary of the invention
Purpose of the present invention just is to provide a kind of chromophoric second nonlinear optic polyphosphonitrile of azo indoles and method for making and purposes of being connected with.This family macromolecule is not only synthetic convenient, and purifying is simple, can be used as the obtain practical application of novel optical material at aspects such as telecommunication, data storage, phase conjugations.
Technical scheme provided by the invention is: be connected with the chromophoric second nonlinear optic polyphosphonitrile of azo indoles, have following general formula:
X=0.05 in the formula～0.60, n=50-400, R are selected from various alkyl, aromatic group or other heterogeneous ring compound functional group.
The present invention also provides the preparation method of above-mentioned second nonlinear polyphosphonitrile, 1 mole of polyphosphonitrile polymer that is connected with indolyl radical and R group is dissolved in (mass percent concentration is 8～15%) in the N-Methyl pyrrolidone, add 0.05～0.60 mole of p-nitrophenyl diazonium fluoride borate, then 0～5 ℃ of reaction 6～10 hours; The Anhydrous potassium carbonate that adds 0.05～0.60 mole, 0～5 ℃ of reaction 1～2 hour, separation, purifying promptly got the required chromophoric second nonlinear polyphosphonitrile of azo indoles that is connected with.
The second nonlinear optic polyphosphonitrile polymer that is connected with azo indoles chromophoric group side group of the present invention can be used as the practical application of novel optical material at aspects such as telecommunication, data storage, phase conjugations.
Advantage of the present invention concentrates on the following aspects:
1. the second nonlinear optic polyphosphonitrile polymer that is connected with azo indoles chromophoric group side group of introduction of the present invention has very high second-order nonlinear optical property (high molecular d in example 1 and the example 2
33Be respectively 32 and 28pm/V).
2. the present invention is connected with high molecular the synthesizing simply of second nonlinear optic polyphosphonitrile of azo indoles chromophoric group side group, and purifying is convenient, and reaction conditions is comparatively gentle.
3. the invention describes a kind of brand-new high molecular preparation of second nonlinear optic polyphosphonitrile that is connected with azo indoles chromophoric group side group, enrich the content of second-order non-linear optical materials chemical research, expanded the method for second order differential non-linear optical high molecule synthetic chemistry to a certain extent.
Embodiment:
Embodiment 1:R is indolyl radical and oxyethyl group, and x is 0.30 o'clock, and synthetic route is as follows:
Synthetic method is: N-(2-hydroxyethyl) indoles (3) and sodium hydride are placed the Schlenk pipe, add tetrahydrofuran (THF), then 50 ℃ of reactions 10 hours, obtain containing the tetrahydrofuran solution (mass percent concentration is 5-8%) of compound 3 sodium salts.Again above-mentioned solution is changed in the Schlenk pipe of the tetrahydrofuran solution that the polydichlorophosphazenes intermediate is housed, reacted two days down at 50 ℃.Reduce to room temperature, add the tetrahydrofuran solution of sodium ethylate, continue at 50 ℃ of following stirring reactions four days again.After the gained miscellany taken out most of tetrahydrofuran (THF), pour in the water standing over night into.Filter, collect light-yellow precipitate, wash for several times drying with water.With the tetrahydrofuran (THF) dissolving, the elimination insolubles concentrates gained filtrate, adds the methyl alcohol reprecipitation again.Leave standstill, filter, be dissolved in tetrahydrofuran (THF) behind the gained solid drying again, use the methyl alcohol reprecipitation, quadruplication at last with the light yellow solid vacuum-drying under 40 ℃ of conditions that obtains, gets husky yellow solid powder 1.Wherein, the mole ratio of above-mentioned used N-(2-hydroxyethyl) indoles, sodium hydride, polydichlorophosphazenes intermediate, sodium ethylate is 1.6: 1.6: 1: 2.
Take by weighing 0.20 gram polyphosphonitrile 1, put into a test tube, add 1.4 milliliters of N-Methyl pyrrolidone, stirring at room to polymer dissolves fully, ice bath, treat that solution temperature is reduced to 0 ℃ after, add the p-nitrophenyl diazonium fluoride borate of 79 milligrams of new systems, reaction is 8 hours under the condition of ice bath, adds 0.2 gram anhydrous K then
2CO
3, keep condition of ice bath, continue to stir one hour, filter,, collect filtrate with tetrahydrofuran (THF) cleaning reaction test tube, tetrahydrofuran (THF) is taken out in decompression, add 30 ml methanol, can obtain the precipitation of orange, filter, collect the orange solid, with methanol wash for several times, vacuum-drying under 40 ℃ of conditions promptly gets orange product (poly-(indyl) (azo indyl) (oxyethyl group) phosphonitrile) 2.
Embodiment 2:
R is carbazole group, indolyl radical and oxyethyl group, and x is 0.10 o'clock, and synthetic route is as follows:
Synthetic method is: polyphosphonitrile 1 can be made by N-(2-hydroxyethyl) indoles, N-(2-hydroxyethyl) carbazole and sodium ethylate and polydichlorophosphazenes reaction, and its preparation method can be with reference to the preparation method of polyphosphonitrile 1 among the embodiment 1.Take by weighing 0.25 gram polyphosphonitrile 1, put into a test tube, add 2 milliliters of N-Methyl pyrrolidone, stirring at room to polymer dissolves fully, ice bath, treat that solution temperature is reduced to 0 ℃ after, add the p-nitrophenyl diazonium fluoride borate of 102 milligrams of new systems, reaction is 8 hours under the condition of ice bath, adds 0.3 gram anhydrous K then
2CO
3, keep condition of ice bath, continue to stir one hour, filter,, collect filtrate with tetrahydrofuran (THF) cleaning reaction test tube, tetrahydrofuran (THF) is taken out in decompression, add 40 ml methanol, can obtain the precipitation of orange, filter, collect the orange solid, with methanol wash for several times, vacuum-drying under 40 ℃ of conditions promptly gets orange product (poly-(carbazyl) (indyl) (azo indyl) (oxyethyl group) phosphonitrile) 2.
Claims (3)
1. second nonlinear optic polyphosphonitrile that is connected with azo indoles chromophoric group side group, its general structure is:
X=0.05 in the formula～0.60, n=50-400, R are selected from various alkyl, aromatic group or other heterogeneous ring compound functional group.
2. the method for making of the described second nonlinear optic polyphosphonitrile of claim 1, it is characterized in that: it is in 8～15% the N-Methyl pyrrolidone that 1 mole of polyphosphonitrile polymer that is connected with indolyl radical and R group is dissolved in mass percent concentration, the p-nitrophenyl diazonium fluoride borate that adds 0.05～0.60 mole is then 0～5 ℃ of reaction 6～10 hours; The Anhydrous potassium carbonate that adds 0.05～0.60 mole reacted 1～2 hour, and separation, purifying promptly get the required second nonlinear optic polyphosphonitrile that is connected with azo indoles chromophoric group side group.
3. the described second nonlinear optic polyphosphonitrile polymer that is connected with azo indoles chromophoric group side group of claim 1 is used as the optical material of telecommunication, data storage, phase conjugation aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03128048XA CN1214058C (en) | 2003-05-28 | 2003-05-28 | Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03128048XA CN1214058C (en) | 2003-05-28 | 2003-05-28 | Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1456587A true CN1456587A (en) | 2003-11-19 |
| CN1214058C CN1214058C (en) | 2005-08-10 |
Family
ID=29411666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03128048XA Expired - Fee Related CN1214058C (en) | 2003-05-28 | 2003-05-28 | Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1214058C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106149383A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of colored carbon fiber based on ring group poly phosphazene film |
| CN107522900A (en) * | 2016-06-21 | 2017-12-29 | 广东广山新材料股份有限公司 | Phosphazene compound, plastic packaging material and composite metal substrate with azo group |
| CN109613785A (en) * | 2018-09-29 | 2019-04-12 | 北京计算科学研究中心 | A kind of application of double fluorine phosphonitriles |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357334C (en) * | 2005-12-13 | 2007-12-26 | 武汉大学 | Hyperbranched second order differential non-linear optical high molecule, its preparation method and use |
-
2003
- 2003-05-28 CN CNB03128048XA patent/CN1214058C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106149383A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of colored carbon fiber based on ring group poly phosphazene film |
| CN106149383B (en) * | 2015-03-23 | 2019-08-16 | 中国科学院宁波材料技术与工程研究所 | A kind of colored carbon fiber based on ring group poly phosphazene film |
| CN107522900A (en) * | 2016-06-21 | 2017-12-29 | 广东广山新材料股份有限公司 | Phosphazene compound, plastic packaging material and composite metal substrate with azo group |
| CN109613785A (en) * | 2018-09-29 | 2019-04-12 | 北京计算科学研究中心 | A kind of application of double fluorine phosphonitriles |
| CN109613785B (en) * | 2018-09-29 | 2022-03-25 | 北京计算科学研究中心 | Application of poly (difluorophosphazene) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1214058C (en) | 2005-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sarkar et al. | Cooperative supramolecular block copolymerization for the synthesis of functional axial organic heterostructures | |
| Li et al. | A new postfunctional approach to prepare second-order nonlinear optical polyphophazenes containing sulfonyl-based chromophore | |
| Li et al. | Polyphophazene containing indole-based dual chromophores: synthesis and nonlinear optical characterization | |
| CN101930174B (en) | Two-photon photo-acid generator containing triphenylamine as electron donating group and preparation method thereof | |
| Li et al. | Second-order nonlinear optical property of polyphosphazenes containing charge-transporting agents and indole-based chromophore | |
| Tomaru et al. | Second harmonic generation in inclusion complexes | |
| JPH02288874A (en) | Nonlinear, optically active thiophene compound, substance containing the same, and apparatus | |
| CN1214058C (en) | Second order nonlinear optical polyphosphonitrile linked with azoineolol chromogen pendant group and its preparation and use | |
| Adronov et al. | Light harvesting and energy transfer within coumarin‐labeled polymers | |
| Li et al. | Synthesis and characterization of polysiloxanes containing carbazolyl and sulfonyl-indole based chromophore as side chains | |
| US5496503A (en) | Third-order nonlinear optical main chain polymer material and method for preparing the same | |
| Li et al. | Synthesis of polyphosphazenes as potential photorefractive materials | |
| EP0668529A2 (en) | Triazine polymers | |
| CN1252145C (en) | Second order nonlinear optical polyorganosiloxane linked with azoindolol chromogen pendant group and preparation and use thereof | |
| CN1228364C (en) | Second-order non-linear optical polyphosphazene connecting sulfuryl-azo chromophor lateral group, and preparing method and use thereof | |
| US6784287B2 (en) | Organic dye molecules and nonlinear optical polymeric compounds containing chromophores | |
| Gadwal et al. | Supramolecular star polymers with compositional heterogeneity | |
| CN100357334C (en) | Hyperbranched second order differential non-linear optical high molecule, its preparation method and use | |
| US20090299021A1 (en) | Diels-alder crosslinkable dendritic nonlinear optic chromophores and polymer composites | |
| CN1228363C (en) | Polysiloxane with sulphonyl indole chromophore side group, its preparation and application | |
| Qu et al. | Synthesis and properties of helical polyacetylenes carrying cholesteryl moieties | |
| Li et al. | Synthesis and nonlinear optical properties of polyphosphazenes with binaphtholyl and indole side groups | |
| Santra et al. | Syntheses, Solid-State Structures, and Solution Studies by VT 31P NMR of [Zn {Se2P (OEt) 2} 2]∞ and [Zn2 {Se2P (OiPr) 2} 4] | |
| KR0169910B1 (en) | Aromatic polyimides with nlo chromophores, their preparation and fabricating optical devices using them | |
| CN1456586A (en) | Polyphosphonitrile intermediate and its preparation and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |