CN105218779A - The preparations and applicatio of the graphene oxide/azobenzene polymer composite waveguide material of amino functional - Google Patents
The preparations and applicatio of the graphene oxide/azobenzene polymer composite waveguide material of amino functional Download PDFInfo
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Abstract
The invention belongs to high molecule nano composite material synthesis field, relate to a kind of preparations and applicatio of graphene oxide/azobenzene polymer composite waveguide material of amino functional.The present invention first prepares azo chromophore 4-(4-nitro-thiazolinyl) phenyl-1,3-diamines by p-Nitroaniline and mphenylenediamine, then the nitrogen benzide performed polymer of NAPD and IPDI obtained isocyano end-blocking under T-12 catalysis; Then ultrasonic for graphite oxide stripping is obtained graphene oxide dispersion, under the effect of 2-(7-azo benzotriazole)-N, N, N ˊ, N ˊ-tetramethyl-urea phosphofluoric acid ester, obtain the graphene oxide of amino functional with reacting ethylenediamine; The nitrogen benzide performed polymer of isocyano end-blocking is added in EAGO, becomes through vacuum-drying.Graphene oxide/azobenzene polymer composite waveguide the material of obtained amino functional, thermo-optical coeffecient (<i>dn</iGreatT.G reaT.GT<i>/dT</i >) is larger and be more than 10 times of conventional inorganic material than common organic materials, can be applicable to develop the new digital thermo-optical switch with low driving power and very fast response speed.
Description
Technical field
The invention belongs to high molecule nano composite material synthesis field, relate to the preparation of functional graphene oxide and azobenzene polymer series compound, particularly a kind of preparations and applicatio of graphene oxide/azobenzene polymer composite waveguide material of amino functional.
Background technology
Waveguide optical switch study hotspot mainly concentrates on electrooptical switching and thermo-optical switch in recent years, and waveguide type electrooptical switching speed is fast, but needs harsh Polarization technique, relevant with polarization and cost is higher.For thermo-optical switch, be utilize thermo-optic effect realization to the modulation of light field thus realize switching function, wherein the thermo-optical coeffecient of material is the principal element affecting thermo-optical switch driving power and response speed.Conventional thermal-photo switch material has inorganic (as Lithium niobium trioxide, SiO
2deng) and organic polymer material.Thermo-optical coeffecient (the dn/dT of organic polymer material, specific refractory power varies with temperature) the comparatively large order of magnitude of inorganic materials, and organic polymer material has, and technique is simple, cheap, film forming properties is good and in the advantage such as 1.55 μm of window loss are low, therefore, the thermo-optical switch based on polymkeric substance causes great attention.
Azobenzene polymer can cause molecular isomerism phenomenon under stimulating in light, heat, pressure, electric field, magnetic field, pH change etc., transformation between isomer can cause the specific refractory power of material to change, and makes azobenzene polymer have good optical activity and high thermo-optical coeffecient.The preparation of the present inventor's long campaigns azobenzene polymer material and thermo-optical switch modeling effort, find the polymkeric substance containing azo chromophore, under certain wavelength light effect, the more non-azobenzene polymer of its thermo-optical coeffecient is high 3 ~ 6 times, result of study also shows, take azobenzene polymer as the waveguide material of thermo-optical switch, the power consumption obtaining thermo-optical switch is less than 2.5mW, the thermo-optical switch of more non-azobenzene polymer has had obvious improvement in power consumption, further demonstrate that azobenzene polymer has the excellent specific property of the power consumption of large thermo-optical coeffecient and reduction thermo-optical switch.
But in practical process, for azobenzene polymer, the key issue such as when there is life-time service the transparency of thermostability and film (dark color) is not good enough, significantly limit the high temperature life-time service of azo material, this also becomes based on the stumbling-block in the practical distance of the thermo-optical switch of polymkeric substance.
From optical angle, the thickness of single-layer graphene only has the thickness (about 0.35nm) of a carbon atom, even if through stripping repeatedly, the crystalline structure of Graphene is still quite complete, this special structure gives Graphene special optical property, as the high permeability (97.7%) etc. to visible ray, be the thinnest known at present in the world two-dimensional material, there is extremely excellent light transmission.
In addition, Agraphene-basedbroadbandopticalmodulator, Nature, 2011,474 (7349): 64-67, reporting with single-layer graphene is waveguide material, have developed the optical modulator that a world is minimum, possess high speed transmission of signals ability, be expected to internet speed to improve 10,000 times, this report causes the concern of optics investigator immediately.
Femtosecondpopulationinversionandstimulatedemissionofden sediracfermionsingraphene, Phys.Rev.Lett., 2012,108 (16): 167401, disclose Graphene and there are two critical natures: the residence amount reversion of electronics and the gain of light, again demonstrate Graphene to can be used to make various photoelectric device, comprise wide-band optical amplifier, high-speed modulator, and optical communication and the resorber needed for ultrafast laser.
But single-layer graphene is unstable two dimensional crystal, not easily carries out compound with other materials.Graphene oxide is because being associated with epoxy bond, hydroxyl and carboxyl and there is wetting ability, dispersiveness and chemically reactive, so graphene oxide can be doped in various material or by chemical reaction and various material binds, and graphene oxide can be peeled off by small molecules or polyalcohol intercalation, can be used for the various aspects of performance such as mechanics, electricity, optics improving material.
Functionalizedgrapheneoxidewithethylenediamineand1,6-hexanediamine, NewCarbonMaterials, 2012,27 (5): 370-376, propose efficient, an economic method and achieve amino functional to GO.Result of study shows: compared with GO, and the graphene oxide of the amino functional of preparation demonstrates higher thermostability, and ethylene diamine-modified graphene oxide presents fabulous dispersiveness in DMF.
Studyontheeffectofhexamethylenediaminefunctionalizedgrap heneoxideonthecuringkineticsofepoxynanocomposites, EuropeanPolymerJournal, 2014,52:88-97, prepare the epoxy resin nano composites of the filling of the GO with hexanediamine modification, result shows compared with two monomers before compound, the machinery of this matrix material, conduction and bending property are all significantly improved, and disclose curing mechanism and the kinetics of curing reaction Kinetics simultaneously.
Therefore, coupling has the material of good optical Response and large thermo-optical coeffecient azobenzene polymer and has the grapheme material of high transparent and thermostability, Graphene/azobenzene polymer composite waveguide the material of development of new, be expected to obtain Large Copacity, at a high speed exchange, transparent, low-loss photoswitch, thus be applied to better in optical-fiber network.
Summary of the invention
The object of the invention is to prepare the composite waveguide material with good thermo-optical property, disclose a kind of preparation method of graphene oxide/azobenzene polymer composite waveguide material of amino functional.
The present invention first by Hummers legal system for graphite oxide; Pass through diazo coupling reaction again, azo chromophore 4-(4-nitro-thiazolinyl) phenyl-1 is prepared by p-Nitroaniline and mphenylenediamine, 3-diamines (NAPD), then NAPD and isophorone diisocyanate (IPDI) react the nitrogen benzide performed polymer of obtained isocyano end-blocking under dibutyl tin laurate (T-12) katalysis; Then ultrasonic for graphite oxide stripping is obtained graphene oxide dispersion, at 2-(7-azo benzotriazole)-N, N, react the graphene oxide (EAGO) preparing amino functional with quadrol (EDA) under the effect of N', N'-tetramethyl-urea phosphofluoric acid ester (HATU); Finally, the nitrogen benzide performed polymer of the isocyano end-blocking obtained is added in EAGO and reacts, through vacuum-drying to constant weight, the graphene oxide/azobenzene polymer composite waveguide material (APU/EAGO is called for short NC) of obtained amino functional.
Hummers method prepares graphite oxide: added in 1000mL beaker by the vitriol oil of 115mL, and is placed in the ice-water bath of 0 DEG C, slowly adds 5g natural graphite powder successively, 15g potassium permanganate and 2.5g SODIUMNITRATE, at lower than 10 DEG C, react 1h, be warming up to 35 DEG C, reaction 2h; Then, be warming up to 90 DEG C, slowly drip the deionized water of 230mL with normal pressure funnel, then under 100 DEG C of oil baths, react 2h; Stop heating, first add the hydrogen peroxide of the deionized water of 350mL and 30% of 25mL, centrifugal after stirring reaction 30min; Again add the hydrogen peroxide of the deionized water of 350mL and 30% of 25mL, centrifugal after stirring reaction 30min; With the hydrochloric acid soln washing of 5%, the product after the most centrifugal is placed in 60 DEG C of vacuum drying ovens and dries 24h, obtains graphite oxide.
Diazo coupling method prepares azo chromophore: take 2.76g p-Nitroaniline and add in the Erlenmeyer flask of belt stirrer, adds 50g distilled water and 5.9g concentrated hydrochloric acid (37%), stirs and make it dissolve under normal temperature; Then under 0 DEG C of condition, slowly instillation, containing 2.07g sodium nitrite solution (52.07g), after dropwising, is filtered immediately after continuing stirring reaction 1h under ice bath, is obtained yellow transparent diazonium salt solution; The pH regulating diazonium salt solution with saturated sodium carbonate solution is 7.0, is slowly instilled by diazonium salt solution (2.16g mphenylenediamine is dissolved in 9.45gDMF) in the DMF solution of mphenylenediamine under condition of ice bath; Dropwise stirring reaction 1h under condition of ice bath; Suction filtration, and with distilled water wash filter cake to neutral, then product is placed in stink cupboard inner drying, obtains red-brown azo pressed powder 4-(4-nitro-thiazolinyl) phenyl-1,3-diamines (NAPD).
The preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional, comprises the steps:
Steps A, with agitator, temperature is taken into account appropriate isophorone diisocyanate (IPDI) and azo chromophore 4-(4-nitro-thiazolinyl) phenyl-1 in the reaction vessel of return line, 3-diamines (NAPD) is dissolved in DMF, after being warming up to 40 ~ 95 DEG C, add catalyst dibutyltin dilaurylate (T-12) and react 1 ~ 7h, obtain the performed polymer of isocyano end-blocking, wherein, the mass ratio of described NAPD and IPDI is 1:2 ~ 10, preferred 1:3.5; The mass ratio of NAPD and DMF is 1:10 ~ 50, preferred 1:18; Temperature preferably 80 DEG C, time preferred 4h;
Step B, graphite oxide is placed in the ultrasonic stripping 5 ~ 6h of DMF, more namely obtains graphene oxide dispersion through centrifugal, wherein, the mass ratio of described graphite oxide and DMF is 1:500 ~ 1000, preferred 1:785;
Step C, in graphene oxide dispersion, add appropriate quadrol (EDA), stirred at ambient temperature 30min; Be warming up to 30 ~ 90 DEG C, add 2-(7-azo benzotriazole)-N, N, N', N'-tetramethyl-urea phosphofluoric acid ester (HATU), continue stirring reaction 3 ~ 9h, obtain amido modified graphene oxide; Wherein, the mass ratio of described graphite oxide and EDA is 1:500 ~ 1000, preferred 1:750; The mass ratio of HATU and graphite oxide is 1:5 ~ 15, preferred 1:12; Temperature preferably 60 DEG C, time preferred 6h;
Step D, the performed polymer of the isocyano end-blocking obtained by steps A added in amido modified graphene oxide system that step C obtains, be warming up to 30 ~ 90 DEG C, continue stirring reaction 1 ~ 7h, reaction system is placed in 40 ~ 90 DEG C of vacuum drying ovens to dry to constant weight, obtain the graphene oxide/azobenzene polymer composite waveguide material (NC) of amino functional, wherein temperature of reaction preferably 80 DEG C, the preferred 4h of churning time, vacuum-drying temperature preferably 60 DEG C.
According to the graphene oxide/azobenzene polymer composite waveguide material of the amino functional that the method for the invention obtains, there is higher thermo-optical coeffecient (dn/dT), larger and be more than 10 times of conventional inorganic material than common organic materials, can be applicable to develop the new digital thermo-optical switch with low driving power and very fast response speed.
Agents useful for same of the present invention: Graphite Powder 99, the vitriol oil, dibutyl tin dilaurate (T-12), SODIUMNITRATE, quadrol (EDA), mphenylenediamine, p-Nitroaniline, 2-(7-azo benzotriazole)-N that the present invention is used, N, N', N'-tetramethyl-urea phosphofluoric acid ester (HATU), potassium permanganate and N, dinethylformamide (DMF), Chemical Reagent Co., Ltd., Sinopharm Group; 30% hydrogen peroxide and different Buddhist diisocyanates (IPDI), Shanghai Ling Feng chemical reagent company limited; Disperse Red-19 (DR-19), AcrosOrganicsCo.Ltd., (NewJersey, America).
Beneficial effect
Preparation technology of the present invention is simple, and the functional graphene oxide nano material of the azo group contained in molecule and introducing improves the thermo-optical property of azobenzene polymer material, mechanical property and thermostability.Graphene oxide/azobenzene polymer composite waveguide the material of obtained amino functional, has higher thermo-optical coeffecient (dn/dT), and comparatively speaking, this matrix material is larger and be more than 10 times of conventional inorganic material than common organic materials.This matrix material is develop the new digital thermo-optical switch with low driving power and very fast response speed to lay a good foundation.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, and to make those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 2.12gIPDI is dissolved in the DMF of 18.9g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 45 DEG C, add 0.5gT-12, reaction 1h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 6gDMF ultrasonic stripping 5h, more namely obtains graphene oxide dispersion through centrifugal; Dispersion liquid is placed in the round-bottomed flask of 250mL, then 6gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min; Then, after being warming up to 30 DEG C, 2-(7-azo the benzotriazole)-N of 0.8mg is added, N, N', N'-tetramethyl-urea phosphofluoric acid ester (HATU), continue stirring reaction 3h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 30 DEG C, continue stirring reaction 1h.Product is placed in 40 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-1) of amino functional.
Embodiment 2
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 2.12gIPDI is dissolved in the DMF of 21.2g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 50 DEG C, add 0.5gT-12, reaction 2h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 7.2gDMF ultrasonic stripping 6h, more namely obtains graphene oxide dispersion through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 8.4gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min; Then, after being warming up to 40 DEG C, add 0.8mgHATU, continue stirring reaction 4h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 40 DEG C, continue stirring reaction 2h.Product is placed in 50 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-2) of amino functional.
Embodiment 3
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 3.71gIPDI is dissolved in the DMF of 19.08g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 80 DEG C, add 0.5gT-12, reaction 4h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 9.42gDMF ultrasonic stripping 6h, more namely obtains graphene oxide dispersion through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min.Then, after being warming up to 60 DEG C, add 1mgHATU, continue stirring reaction 6h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 80 DEG C, continue stirring reaction 4h.Product is placed in 60 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-3) of amino functional.
Embodiment 4
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 4.24gIPDI is dissolved in the DMF of 48g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 95 DEG C, add 0.5gT-12, reaction 7h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 8.4gDMF ultrasonic stripping 6h, namely graphene oxide dispersion is obtained again through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9.42gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min.Then, after being warming up to 90 DEG C, add 2.4mgHATU, continue stirring reaction 9h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 90 DEG C, continue stirring reaction 7h.Product is placed in 90 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-4) of amino functional.
Embodiment 5
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 6.36gIPDI is dissolved in the DMF of 42.4g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 70 DEG C, add 0.5gT-12, reaction 6h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 9.6gDMF ultrasonic stripping 6h, more namely obtains graphene oxide dispersion through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 8.4gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min.Then, after being warming up to 70 DEG C, add 1.2mgHATU, continue stirring reaction 8h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 50 DEG C, continue stirring reaction 3h.Product is placed in 70 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-5) of amino functional.
Embodiment 6
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 11.34gIPDI is dissolved in the DMF of 15.9g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 60 DEG C, add 0.5gT-12, reaction 5h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 12gDMF ultrasonic stripping 6h, more namely obtains graphene oxide dispersion through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9.6gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min.Then, after being warming up to 60 DEG C, add 1.5mgHATU, continue stirring reaction 7h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 70 DEG C, continue stirring reaction 5h.Product is placed in 80 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-6) of amino functional.
Embodiment 7
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 10.6gIPDI is dissolved in the DMF of 53g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 80 DEG C, add 0.5gT-12, reaction 7h, obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 10gDMF ultrasonic stripping 6h, more namely obtains graphene oxide dispersion through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 12gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min.Then, after being warming up to 70 DEG C, add 1mgHATU, continue stirring reaction 5h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 80 DEG C, continue stirring reaction 7h.Product is placed in 80 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-7) of amino functional.
Embodiment 8
(1) Hummers method is adopted to be prepared into graphite oxide;
(2) diazo coupling method is adopted to be prepared into azo chromophore NAPD;
(3) preparation of the performed polymer of isocyano end-blocking: 1.06gNAPD and 8.48gIPDI is dissolved in the DMF of 26.5g, and add with stirring rod, temperature is taken into account in the four-hole boiling flask of return line.Then, after being warming up to 60 DEG C, add 0.5gT-12, namely reaction 4h obtains the performed polymer of isocyano end-blocking;
(4) 0.012g graphite oxide is placed in 10.5gDMF ultrasonic stripping 6h, namely graphene oxide dispersion is obtained again through centrifugal, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9.6gEDA is added in graphene oxide dispersion, stirred at ambient temperature 30min.Then, after being warming up to 50 DEG C, add 1.8mgHATU, continue stirring reaction 5h, obtain the graphene oxide (EAGO) of quadrol functionalization;
(5) then the performed polymer of isocyano end-blocking is added in the obtained reaction solution of step 2, after being warming up to 70 DEG C, continue stirring reaction 6h.Product is placed in 60 DEG C of vacuum drying ovens and dries to constant weight the most at last, obtains the graphene oxide/azobenzene polymer composite waveguide material (NC-8) of amino functional.
Experimental technique
Get appropriate NC-1, NC-2, NC-3, NC-4, NC-5, NC-6, NC-7 and NC-8 sample, be dissolved in N respectively, in N '-dimethyl methane amide, being mixed with concentration is that the solution of 0.5g/mL is spun on quartz plate, vacuum-drying 72h at 15 DEG C.Adopt optical waveguides survey meter to test its specific refractory power under differing temps, carry out one-variable linear regression, obtain thermo-optical coeffecient dn/dT, as following table:
The present invention obtains Novel hot luminescent material, and have higher thermo-optical coeffecient (dn/dT), comparatively organic materials is as polystyrene (-1.23 × 10
-4dEG C
-1), polymethylmethacrylate (-1.20 × 10
-4dEG C
-1), azo-nitrobenzene thiazole polyimide (-1.460 × 10
-4dEG C
-1) and DR1 polyimide (-1.331 × 10
-4dEG C
-1) large; Compare with inorganic materials, as borosilicate glass (4.1 × 10
-6dEG C
-1), zinc silicate glass (5.5 × 10
-6dEG C
-1) and silica glass (10.8 × 10
-6dEG C
-1) etc., be more than 10 times of its thermo-optical coeffecient; This material is develop the new digital thermo-optical switch with low driving power to provide possibility.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention to do equivalent structure or the conversion of equivalent flow process, or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (8)
1. the preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional, is characterized in that: first by Hummers legal system for graphite oxide; Pass through diazo coupling reaction again, azo chromophore 4-(4-nitro-thiazolinyl) phenyl-1 is prepared by p-Nitroaniline and mphenylenediamine, 3-diamines NAPD, then NAPD and isophorone diisocyanate IPDI reacts the nitrogen benzide performed polymer of obtained isocyano end-blocking under dibutyl tin laurate T-12 katalysis; Then ultrasonic for graphite oxide stripping is obtained graphene oxide dispersion, at 2-(7-azo benzotriazole)-N, react the graphene oxide EAGO of obtained amino functional with quadrol EDA under the effect of N, N', N'-tetramethyl-urea phosphofluoric acid ester HATU; The nitrogen benzide performed polymer of the isocyano end-blocking obtained is added in EAGO and reacts, through vacuum-drying to constant weight.
2. the preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional according to claim 1, is characterized in that: comprise the steps:
Steps A, with agitator, temperature is taken into account appropriate isophorone diisocyanate IPDI and azo chromophore 4-(4-nitro-thiazolinyl) phenyl-1 in the reaction vessel of return line, 3-diamines NAPD is dissolved in DMF, after being warming up to 40 ~ 95 DEG C, add catalyst dibutyltin dilaurylate T-12 and react 1 ~ 7h, obtain the performed polymer of isocyano end-blocking, wherein, the mass ratio of described NAPD and IPDI is 1:2 ~ 10; The mass ratio of NAPD and DMF is 1:10 ~ 50;
Step B, graphite oxide is placed in the ultrasonic stripping 5 ~ 6h of DMF, more namely obtains graphene oxide dispersion through centrifugal, wherein, the mass ratio of described graphite oxide and DMF is 1:500 ~ 1000;
Step C, in graphene oxide dispersion, add appropriate quadrol (EDA), stirred at ambient temperature 30min; Be warming up to 30 ~ 90 DEG C, add 2-(7-azo benzotriazole)-N, N, N', N'-tetramethyl-urea phosphofluoric acid ester (HATU), continue stirring reaction 3 ~ 9h, obtain amido modified graphene oxide; Wherein, the mass ratio of described graphite oxide and EDA is 1:500 ~ 1000; The mass ratio of HATU and graphite oxide is 1:5 ~ 15;
Step D, the performed polymer of the isocyano end-blocking obtained by steps A added in amido modified graphene oxide system that step C obtains, be warming up to 30 ~ 90 DEG C, continue stirring reaction 1 ~ 7h, reaction system is placed in 40 ~ 90 DEG C of vacuum drying ovens to dry to constant weight, obtains the graphene oxide/azobenzene polymer composite waveguide material of amino functional.
3. the preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional according to claim 2, is characterized in that: in steps A, and the mass ratio of described NAPD and IPDI is 1:3.5; The mass ratio of NAPD and DMF is 1:18; Temperature 80 DEG C, time 4h.
4. the preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional according to claim 2, is characterized in that: in step B, and the mass ratio of described graphite oxide and DMF is 1:785.
5. the preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional according to claim 2, is characterized in that: in step C, and the mass ratio of described graphite oxide and EDA is 1:750; The mass ratio of HATU and graphite oxide is 1:12; Temperature 60 C, time 6h.
6. the preparation method of the graphene oxide/azobenzene polymer composite waveguide material of amino functional according to claim 2, is characterized in that: in step D, temperature of reaction 80 DEG C, churning time 4h, vacuum-drying temperature 60 C.
7. graphene oxide/azobenzene polymer composite waveguide the material of the amino functional obtained according to described preparation method arbitrary in claim 1-6.
8. the application of the graphene oxide/azobenzene polymer composite waveguide material of amino functional according to claim 7, is characterized in that: be applied to develop the new digital thermo-optical switch with low driving power and very fast response speed.
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| CN105542584A (en) * | 2016-01-29 | 2016-05-04 | 天津大学 | Thermal-inductive fluorocarbon function coating containing azobenzene/carbon-hybrid material and preparation method of thermal-inductive fluorocarbon function coating |
| CN114350092A (en) * | 2021-04-15 | 2022-04-15 | 杭州安誉科技有限公司 | Polymer heating plate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105542584A (en) * | 2016-01-29 | 2016-05-04 | 天津大学 | Thermal-inductive fluorocarbon function coating containing azobenzene/carbon-hybrid material and preparation method of thermal-inductive fluorocarbon function coating |
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| CN114350092A (en) * | 2021-04-15 | 2022-04-15 | 杭州安誉科技有限公司 | Polymer heating plate and preparation method thereof |
| CN116217312A (en) * | 2023-02-22 | 2023-06-06 | 浙江大学 | Low-migration ferrocenyl functionalized graphene oxide burning rate catalyst and preparation method thereof |
| CN116217312B (en) * | 2023-02-22 | 2024-02-27 | 浙江大学 | Low-migration ferrocenyl functionalized graphene oxide burning rate catalyst and preparation method thereof |
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