CN104049434B - Compound containing 1,1-dicyano-2,2-ethenylidene-bis-aryl is as the application of optical Limiting Yu light fixed ampllitude material - Google Patents
Compound containing 1,1-dicyano-2,2-ethenylidene-bis-aryl is as the application of optical Limiting Yu light fixed ampllitude material Download PDFInfo
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- CN104049434B CN104049434B CN201310076869.XA CN201310076869A CN104049434B CN 104049434 B CN104049434 B CN 104049434B CN 201310076869 A CN201310076869 A CN 201310076869A CN 104049434 B CN104049434 B CN 104049434B
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Abstract
The invention discloses the compound containing the double aryl of 1,1 dicyano 2,2 ethenylidenes in molecule structure as the application of optical Limiting Yu light fixed ampllitude material.This compounds all has obvious optical Limiting and light fixed ampllitude characteristic under nanosecond, psec or the femtosecond laser of near infrared band irradiate, and its light stability is fine, and fluorescence quantum yield is extremely low, has the most practical future in optical Limiting and light fixed ampllitude field.
Description
Technical field
The present invention relates to containing 1,1-dicyano-2, the application of the compound of 2-ethenylidene-bis-aryl, particularly relate to containing 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl is as the application of optical Limiting Yu light fixed ampllitude material.
Background technology
Fast development recently as laser technology, ultrafast laser system is obtained in the every aspect of high-tech area and is widely applied, such as fields such as satellite ranging, HIGH-DENSITY OPTICAL STORAGE, hyperfine micro Process, the medical imaging of biological vital tissue, high-resolution fluorescent confocal microtechniques.The most conventional ultrafast laser system mainly has the wavelength Nd:YAG and Nd:YVO at 1064nm4Nanosecond, picosecond laser and dominant wavelength 780～800nm Ti:Sapphire psec, fs-laser system, after adding amplifier and OPA, wavelength tuning range extends to whole visible and near infrared band.Although the average output power of this two classes laser system is the most little, general only hundreds of milliwatt to tens watts, but the instantaneous power in its pulse duration range is the highest, can reach 108-1012Watt magnitude.The highest laser power is to the optical element in light path, especially the expensive light sensors such as signal detection probe are easily caused damage, thus the material that preparation has amplitude limit effect to ultrafast laser will have the meaning of reality to the protection question of optical element in its application process of solution.Different from common optical limiting materials, optical limiting materials based on multiphoton absorption has the advantages that limiting threshold is high, damage threshold is high, linear transmittance is high, is the maximally effective material of class for ultrafast laser amplitude limit.Additionally, optical limiting materials based on multiphoton absorption is used for improving the output stability of pulse laser at the same time as light fixed ampllitude material, reduce the energy hunting that output is interpulse.
The optical limiting materials based on multiphoton absorption of report is mainly styryl pyridinium and derivant (Appl.Phys.Lett., 1995,67,2433-2435 at present;Chem.Rev., 2008,108,1245-1330), but this kind of material often has higher fluorescence quantum yield, stronger fluorescence can be produced while amplitude limit, even produce lasing (J.Appl.Phys., 1997,81,2529-2537), its application in lasing safety it is unfavorable for.
Applicant is devoted to the research at optical Limiting Yu light fixed ampllitude field of the 1,1-dicyano-2,2-ethenylidene-bi-aromatic compounds the most always.Containing 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl can refer to method synthesis (Chem.Commun., 1996,1237-1238) of document report, and corresponding reaction raw materials can directly be bought or obtain by conventional synthetic method.In aforementioned documents, it was recently reported that this compounds has big second order nonlinear optical effect, can be used as second-order non-linear optical materials.
Summary of the invention
The technical problem to be solved in the present invention is to provide containing 1,1-dicyano-2, the purposes of the compound of 2-ethenylidene-bis-aryl, i.e. in optical Limiting and the application of light fixed ampllitude Material Field, this compounds all has obvious optical Limiting and light fixed ampllitude characteristic under nanosecond, psec or the femtosecond laser of near infrared band irradiate, and its light stability is fine, and fluorescence quantum yield is extremely low.
For solving above-mentioned technical problem, the present invention relates to containing 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl is as the application of optical limiting materials.Described contain 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl is to have such as the compound of following formula M1, M2, M3 or M4 molecular structure,
Wherein, R1For alkyl, alkoxyl or amido；R2For alkyl, alkoxyl or amido.
Preferably, described alkyl is selected from methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or amyl group.
Preferably, described alkoxyl is selected from methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy.
Preferably, described amido is selected from dimethylamino, diethylin, dipropyl amido, dibutyl amino, diamyl amido, two amido, two heptyl amice bases, dioctylamine base, hexichol amido or disubstituted benzenes amidos.
Preferably, described disubstituted benzenes amido is selected from two (4-alkyl) anilino-, two (2-alkyl) anilino-s or two (2,4-dialkyl group) anilino-；Wherein alkyl is selected from methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or amyl group.
For solving above-mentioned technical problem, the invention still further relates to containing 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl is as the application of light fixed ampllitude material.Described contain 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl is to have such as the compound of following formula M1, M2, M3 or M4 molecular structure,
Wherein, R1For alkyl, alkoxyl or amido；R2For alkyl, alkoxyl or amido.
Preferably, described alkyl is selected from methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or amyl group.
Preferably, described alkoxyl is selected from methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy.
Preferably, described amido is selected from dimethylamino, diethylin, dipropyl amido, dibutyl amino, diamyl amido, two amido, two heptyl amice bases, dioctylamine base, hexichol amido or disubstituted benzenes amidos.
Preferably, described disubstituted benzenes amido is selected from two (4-alkyl) anilino-, two (2-alkyl) anilino-s or two (2,4-dialkyl group) anilino-；Wherein alkyl is selected from methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or amyl group.
In order to be better understood from the essence of the present invention, below will be with containing 1,1-dicyano-2, the experimental result of 2-ethenylidene-bi-aromatic compounds illustrates that this compounds is shown in Fig. 1 to Figure 23 as optical Limiting and the application of light fixed ampllitude material, the effect of its application.
Preferably, containing 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl is as follows as optical Limiting and light fixed ampllitude materials application condition: laser parameter scope is wavelength 700～1100nm, pulsewidth 50fs～20ns, repetition 1～100MHz, peak power density 10MW/cm2～1TW/cm2。
nullPreferably，Containing 1,1-dicyano-2,The compound of 2-ethenylidene-bis-aryl specifically used method in optical Limiting and light fixed ampllitude is as follows: will contain 1,1-dicyano-2,The compound dissolution of 2-ethenylidene-bis-aryl is in polar non-solute，Polar non-solute is selected from dimethylformamide、Dimethyl acetylamide、N-Methyl pyrrolidone、One or more in dimethyl sulfoxide，It is configured to that there is certain density solution material，The concentration range of solution material is 0.005～0.1mol/L，This solution material is poured in a quartz colorimetric utensil，Or 1 will be contained by method disclosed in Chinese invention patent (ZL200910084464.4),1-dicyano-2,The compound of 2-ethenylidene-bis-aryl is prepared as solid polymer bulk.The quartz colorimetric utensil or polymer bulk that are filled with solution material are positioned in the laser optical path needing to carry out optical Limiting or light fixed ampllitude technological adjustment.When specifically used, for the laser optical path of given parameters, selection is needed to have corresponding light amplitude limit or the material of light fixed ampllitude performance.The optical limiting properties method of testing of material is: using titanium-doped sapphire psec, fs-laser system (Tsunami mode-locked Ti:Sapphire), titanium-doped sapphire regenerative amplification system (Spitfire F-1K) or Nd:YAG nanosecond, picosecond laser (1064nm) as light source, after adding amplifier and OPA, wavelength tuning range can cover whole visible near-infrared district, carry out testing that (test philosophy and light path are built and seen document J.Mod.Opt. by nonlinear transmission method, 1995,42,1361-1366;Opt.Commun., 2001,191,235-243).
More than containing 1, 1-dicyano-2, the experimental result of 2-ethenylidene-bi-aromatic compounds is shown in Fig. 1 to Figure 23, stain in Fig. 1 is by containing 1, 1-dicyano-2, the compound of 2-ethenylidene-bis-aryl inserts the Input output Relationship data recorded in light path, curve is theoretical fitting result, Input output Relationship when straight line is to insert in light path without material, Fig. 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23 is identical with the diagram implication of Fig. 1, pass through Fig. 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, can be seen that containing 1, 1-dicyano-2, the compound of 2-ethenylidene-bis-aryl has good Limiting effect as optical limiting materials.Left figure in Fig. 2 is the laser pulse output pulsation situation before material inserts, and right figure is the laser pulse output pulsation situation after material inserts.Fig. 4,6,8,10,12,14,16,18,20,22 is identical with the diagram implication of Fig. 2, by Fig. 4, and 6,8,10,12,14,16,18,20,22 it can be seen that contain 1,1-dicyano-2, the compound of 2-ethenylidene-bis-aryl can improve the output stability of pulse laser as light fixed ampllitude material, reduces the energy hunting that output is interpulse.
By regulation containing 1 during application, 1-dicyano-2, the compound of 2-ethenylidene-bis-aryl concentration in liquid medium or solid dielectric and the thickness of material, the optical Limiting that material is final can be regulated on a large scale with light fixed ampllitude character.
Accompanying drawing explanation
Optical limitation diagram in the light path of the femtosecond laser that the material that Fig. 1 is made up of formula M1-1 compound is placed into 700nm wavelength；
Light fixed ampllitude effect diagram in the light path of the picosecond laser that the material that Fig. 2 is made up of formula M1-2 compound is placed into 1064nm wavelength；
The light path of the femtosecond laser that the material that Fig. 3 is made up of formula M1-3 compound is placed into 750nm wavelength obtains optical limitation diagram；
Light fixed ampllitude effect diagram in the light path of the picosecond laser that the material that Fig. 4 is made up of formula M1-4 compound is placed into 1053nm wavelength；
Optical limitation diagram in the light path of the picosecond laser that the material that Fig. 5 is made up of formula M1-5 compound is placed into 800nm wavelength；
Light fixed ampllitude effect diagram in the light path of the nanosecond laser that the material that Fig. 6 is made up of formula M1-6 compound is placed into 1053nm wavelength；
Optical limitation diagram in the light path of the picosecond laser that the material that Fig. 7 is made up of formula M2-1 compound is placed into 750nm wavelength；
Light fixed ampllitude effect diagram in the light path of the femtosecond laser that the material that Fig. 8 is made up of formula M2-2 compound is placed into 1000nm wavelength.
Optical limitation diagram in the light path of the picosecond laser that the material that Fig. 9 is made up of formula M2-3 compound is placed into 800nm wavelength；
Light fixed ampllitude effect diagram in the light path of the nanosecond laser that the material that Figure 10 is made up of formula M2-4 compound is placed into 1064nm wavelength；
Optical limitation diagram in the light path of the femtosecond laser that the material that Figure 11 is made up of formula M2-5 compound is placed into 800nm wavelength；
Light fixed ampllitude effect diagram in the light path of the picosecond laser that the material that Figure 12 is made up of formula M2-6 compound is placed into 1053nm wavelength；
Optical limitation diagram in the light path of the picosecond laser that the material that Figure 13 is made up of formula M3-1 compound is placed into 800nm wavelength；
Light fixed ampllitude effect diagram in the light path of the nanosecond laser that the material that Figure 14 is made up of formula M3-2 compound inserts 1064nm wavelength；
Optical limitation diagram in the light path of the femtosecond laser that the material that Figure 15 is made up of formula M3-3 compound is placed into 800nm wavelength；
Its light fixed ampllitude effect diagram in the light path of the femtosecond laser that the material that Figure 16 is made up of formula M3-4 compound inserts 1100nm wavelength；
Optical limitation diagram in the light path of the femtosecond laser that the material that Figure 17 is made up of formula M3-5 compound is placed into 800nm wavelength；
Light fixed ampllitude effect diagram in the light path of the femtosecond laser that the material that Figure 18 is made up of formula M3-6 compound is placed into 1064nm wavelength；
Optical limitation diagram in the light path of the picosecond laser that the material that Figure 19 is made up of formula M4-1 compound inserts 800nm wavelength；
Light fixed ampllitude effect diagram in the light path of the picosecond laser that the material that Figure 20 is made up of formula M4-2 compound is placed into 1064nm wavelength；
Optical limitation diagram in the light path of the femtosecond laser that the material that Figure 21 is made up of formula M4-3 compound is placed into 900nm wavelength；
Light fixed ampllitude effect diagram in the light path of the nanosecond laser that the material that Figure 22 is made up of formula M4-4 compound inserts 1053nm wavelength；
Optical limitation diagram in the light path of the femtosecond laser that the material that Figure 23 is made up of formula M4-5 compound is placed into 850nm wavelength.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following example.
Embodiment 1
The compound that 3.72 milligrams have formula M1-1 structure is dissolved in 100 milliliters of dimethylformamides,
It is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 2
The compound that 3.00 milligrams have formula M1-2 structure is dissolved in 100 milliliters of dimethylformamides,
It is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 3
The compound that 1.73 milligrams have formula M1-3 structure is dissolved in 20 milliliters of methyl methacrylates,
Add 0.04 gram of azodiisobutyronitrile, 2 milliliters of diethyl phthalates; logical nitrogen 10 minutes; filter membrane through 0.45 micron filters under nitrogen protection; decompression degassing; prepolymerization 90 minutes in 60 DEG C of water-baths, make methyl methacrylate polymerization conversion ratio reach 15%～20%, inject in mould by the pre-polymerization liquid obtained; it is warming up to 100 DEG C and keeps 6 hours making methyl methacrylate polymerization complete, obtaining the polymer bulk of 1 cm thick.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 4
The compound that 5.12 milligrams have formula M1-4 structure is dissolved in 20 milliliters of dimethyl acetylamide,
It is configured to the solution of 0.05mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 5
The compound that 4.25 milligrams have formula M1-5 structure is dissolved in 100 milliliters of N-Methyl pyrrolidone
In, it is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 6
The compound that 2.42 milligrams have formula M1-6 structure is dissolved in 30 milliliters of diallyl diethylene glycol two
In carbonic ester; add 0.02 gram of isopropyl benzene hydroperoxide and 2 milliliters of dibutyl phthalates; logical nitrogen 10 minutes; filter membrane through 0.45 micron filters under nitrogen protection, decompression degassing, prepolymerization 60 minutes in 60 DEG C of water-baths; diallyl diethylene glycol biscarbonate polymerisation conversion is made to reach 10%～15%; the pre-polymerization liquid obtained is injected in mould, is warming up to 120 DEG C and keeps 6 hours making the polymerization of diallyl diethylene glycol biscarbonate completely, obtaining the polymer bulk of 1 cm thick.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 7
The compound that 3.84 milligrams have formula M2-1 structure is dissolved in 50 milliliters of dimethyl sulfoxide, joins
Make the solution of 0.02mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 8
The compound that 3.42 milligrams have formula M2-2 structure is dissolved in 25 milliliters of dimethylformamides,
It is configured to the solution of 0.04mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 9
The compound that 5.37 milligrams have formula M2-3 structure is dissolved in 100 milliliters of dimethyl acetylamide,
It is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 10
The compound that 3.55 milligrams have formula M2-4 structure is dissolved in 100 milliliters of N-Methyl pyrrolidone
In, it is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 11
The compound that 2.34 milligrams have formula M2-5 structure is dissolved in 20 milliliters of styrene and 10 milliliters double
In allyl diglycol two carbonic ester; add 0.05 gram of isopropyl benzene hydroperoxide and 2 milliliters of dibutyl phthalates; logical nitrogen 10 minutes; filter membrane through 0.45 micron filters under nitrogen protection; decompression degassing; prepolymerization 2 hours in 70 DEG C of water-baths; styrene-diallyl diethylene glycol biscarbonate polymerisation conversion is made to reach 35%～40%; it is continuously heating to 160 DEG C and keeps 8 hours making styrene-diallyl diethylene glycol biscarbonate polymerization completely; melt extrusion molding, obtains the polymer bulk of 0.5 cm thick.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 12
The compound that 5.07 milligrams have formula M2-6 structure is dissolved in 100 milliliters of dimethyl acetylamide,
It is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 13
The compound that 6.36 milligrams have formula M3-1 structure is dissolved in 10 milliliters of dimethylformamides,
It is configured to the solution of 0.1mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 14
The compound that 2.33 milligrams have formula M3-2 structure is dissolved in 25 milliliters of methyl methacrylates and
In 10 milliliters of styrene; add 0.04 gram of dibenzoyl peroxide; logical nitrogen 10 minutes; filter membrane through 0.45 micron filters under nitrogen protection, decompression degassing, prepolymerization 90 minutes in 60 DEG C of water-baths; Methyl Methacrylate-Styrene polymerisation conversion is made to reach 25%～30%; it is continuously heating to 150 DEG C and keeps 10 hours making Methyl Methacrylate-Styrene polymerization completely, melt extrusion molding, obtaining the polymer bulk of 1 cm thick.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 15
The compound that 4.98 milligrams have formula M3-3 structure is dissolved in 20 milliliters of dimethyl sulfoxide, joins
Make the solution of 0.05mol/L.Take 3 milliliters of solution prepared and inject the quartz that light path is 1 centimetre
Cuvette, obtains the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 16
The compound that 2.21 milligrams have formula M3-4 structure is dissolved in 25 milliliters of styrene and 10 milliliters double
In phenol A propylene oxide acid diester monomer; add 0.04 gram of dibenzoyl peroxide and 3 milliliters of dioctyl phthalates; logical nitrogen 10 minutes; filter membrane through 0.45 micron filters under nitrogen protection; decompression degassing, prepolymerization 60 minutes in 70 DEG C of water-baths, make styrene-bisphenol A epoxy ethyl acrylate polymerisation conversion reach 15%～20%; heat up again most 160～180 DEG C and continue polymerization 10 hours, make styrene-bisphenol A epoxy ethyl acrylate polymerization completely.The diameter pellet less than 5 millimeters is made by being polymerized material completely, the pellet obtained is mixed homogeneously with the diameter polymethylmethacrylapellets pellets less than 5 millimeters, it is positioned in double roll mill, mixing roll temperature is risen to 200 DEG C, the double roller spacing of regulation is 0.2mm, through roll-in repeatedly, thin go out, after diameter styrene-bisphenol A epoxy ethyl acrylate copolymer pellets less than 5 millimeters being fully blended uniformly with the diameter polymethylmethacrylapellets pellets less than 5 millimeters, implantation temperature is to cool down molding in 200 DEG C of moulds after compacting, obtain the polymer bulk of 0.5 cm thick.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 17
The compound that 5.91 milligrams have formula M3-5 structure is dissolved in 50 milliliters of dimethylformamides,
It is configured to the solution of 0.02mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 18
The compound that 6.77 milligrams have formula M3-6 is dissolved in 100 milliliters of N-Methyl pyrrolidone, joins
Make the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 19
The compound that 2 milligrams have formula M4-1 structure is dissolved in 30 milliliters of vinylacetates, adds 0.05
Gram dibenzoyl peroxide and 0.025 gram of N; accelerine; logical nitrogen 10 minutes; filter membrane through 0.45 micron filters under nitrogen protection; decompression degassing, prepolymerization 60 minutes in 60 DEG C of water-baths, make Polymerization of Vac conversion ratio reach 15%～20%; heat up again most 140～160 DEG C and continue polymerization 8 hours, make Polymerization of Vac complete.The diameter pellet less than 5 millimeters is made by being polymerized material completely, 30 grams of nylon 6 less than 5 millimeters of the pellet obtained and diameter and 30 grams of polyethylene terephthalate pellets are mixed homogeneously, it is positioned in double roll mill, mixing roll temperature is risen to 220 DEG C, the double roller spacing of regulation is 1mm, through roll-in repeatedly, thin go out, after diameter polyvinyl acetate pellet and the diameter less than the 5 millimeters nylon 6 less than 5 millimeters and polyethylene terephthalate pellet being fully blended uniformly, implantation temperature is to cool down molding in 200 DEG C of moulds after compacting, obtain the polymer bulk of 0.5 cm thick.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 20
The compound that 6.19 milligrams have formula M4-2 structure is dissolved in 100 milliliters of N-Methyl pyrrolidone
In, it is configured to the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 21
The compound that 5.35 milligrams have formula M4-3 structure is dissolved in 200 milliliters of dimethylformamides,
It is configured to the solution of 0.005mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Embodiment 22
Compound and 20 grams of cellulose diacetates by 3.4 milligrams with formula M4-4 structure are codissolved in 100
In milliliter dichloromethane and 5 ml methanol, ultrasonic disperse becomes transparent homogeneous phase solution.Vacuum rotary steam in 60 DEG C of water-baths, makes major part solvent volatilization, then the vacuum drying oven inserting 90 DEG C is placed 20 hours, makes solvent volatilization completely, cools down molding, obtain the polymer bulk of 0.5 cm thick in temperature is 200 DEG C of moulds after compacting.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the thickness of mould, the optical Limiting threshold value of material can be adjusted.
Embodiment 23
The compound that 9.60 milligrams have formula M4-5 structure is dissolved in 100 milliliters of dimethyl sulfoxide, joins
Make the solution of 0.01mol/L.Take 3 milliliters of solution prepared and inject the quartz colorimetric utensil that light path is 1 centimetre, obtain the material with two-photon amplitude limiting characteristic.This material has the effect of two-photon amplitude limiting and fixed ampllitude in 700～1100nm wavelength band, can apply to protection and the protection of optical element in this wavelength band nanosecond, psec, fs-laser system.By regulating the concentration of solution, the optical Limiting threshold value of material can be adjusted.
Claims (7)
1. the answering as optical limiting materials of the compound containing 1,1-dicyano-2,2-ethenylidene-bis-aryl
With；
The described compound containing 1,1-dicyano-2,2-ethenylidene-bis-aryl for have as following formula M1,
The compound of M2, M3 or M4 molecular structure,
Wherein, R1For alkyl, alkoxyl or amido；R2For alkyl, alkoxyl or amido.
Chemical combination containing 1,1-dicyano-2,2-ethenylidene-bis-aryl the most according to claim 1
Thing is as the application of optical limiting materials, it is characterised in that:
Described alkyl is selected from methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or amyl group；
Described alkoxyl is selected from methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy；
Described amido selected from dimethylamino, diethylin, dipropyl amido, dibutyl amino, diamyl amido,
Two amido, two heptyl amice bases, dioctylamine base, hexichol amido or disubstituted benzenes amidos.
Chemical combination containing 1,1-dicyano-2,2-ethenylidene-bis-aryl the most according to claim 2
Thing is as the application of optical limiting materials, it is characterised in that:
Described disubstituted benzenes amido selected from two (4-alkyl) anilino-, two (2-alkyl) anilino-s or
Two (2,4-dialkyl group) anilino-；Wherein alkyl is selected from methyl, ethyl, propyl group, normal-butyl, tertiary fourth
Base or amyl group.
4. the answering as light fixed ampllitude material of the compound containing 1,1-dicyano-2,2-ethenylidene-bis-aryl
With.
Chemical combination containing 1,1-dicyano-2,2-ethenylidene-bis-aryl the most according to claim 4
Thing is as the application of light fixed ampllitude material, it is characterised in that: described contain 1,1-dicyano-2,2-ethenylidene-
The compound of double aryl is to have such as the compound of following formula M1, M2, M3 or M4 molecular structure,
Wherein, R1For alkyl, alkoxyl or amido；R2For alkyl, alkoxyl or amido.
Chemical combination containing 1,1-dicyano-2,2-ethenylidene-bis-aryl the most according to claim 5
Thing is as the application of light fixed ampllitude material, it is characterised in that:
Described alkyl is selected from methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or amyl group；
Described alkoxyl is selected from methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy；
Described amido selected from dimethylamino, diethylin, dipropyl amido, dibutyl amino, diamyl amido,
Two amido, two heptyl amice bases, dioctylamine base, hexichol amido or disubstituted benzenes amidos.
Chemical combination containing 1,1-dicyano-2,2-ethenylidene-bis-aryl the most according to claim 6
Thing is as the application of light fixed ampllitude material, it is characterised in that:
Described disubstituted benzenes amido selected from two (4-alkyl) anilino-, two (2-alkyl) anilino-s or
Two (2,4-dialkyl group) anilino-；Wherein alkyl is selected from methyl, ethyl, propyl group, normal-butyl, tertiary fourth
Base or amyl group.
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| CN101768112A (en) * | 2008-12-31 | 2010-07-07 | 中国科学院化学研究所 | Two-photon induced luminous compound with symmetrical both ends and synthesis method and purposes thereof |
| CN101885922A (en) * | 2009-05-14 | 2010-11-17 | 中国科学院理化技术研究所 | Polymer material with two-photon amplitude limiting characteristic and preparation method and usage thereof |
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| CN101768112A (en) * | 2008-12-31 | 2010-07-07 | 中国科学院化学研究所 | Two-photon induced luminous compound with symmetrical both ends and synthesis method and purposes thereof |
| CN101885922A (en) * | 2009-05-14 | 2010-11-17 | 中国科学院理化技术研究所 | Polymer material with two-photon amplitude limiting characteristic and preparation method and usage thereof |
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