CN105218779B - The preparation and application of the graphene oxide of amino functional/azobenzene polymer composite waveguide material - Google Patents
The preparation and application of the graphene oxide of amino functional/azobenzene polymer composite waveguide material Download PDFInfo
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Abstract
The invention belongs to high molecule nano composite material to synthesize field, is related to the preparation and application of a kind of graphene oxide/azobenzene polymer composite waveguide material of amino functional.Of the invention that 1,3 diamines of azo chromophore 4 (4 nitroalkenyl) phenyl first is prepared by paranitroanilinum and m-phenylene diamine (MPD), then the azobenzene performed polymer of isocyano end-blocking is made in NAPD and IPDI under the catalysis of T 12；Then graphite oxide ultrasound is peeled off and graphene oxide dispersion is made, in 2 (7 azo benzotriazole) N, N, N', the graphene oxide of amino functional is made under the action of N' tetramethylurea hexafluorophosphoric acid esters with reacting ethylenediamine；By isocyano end-blocking azobenzene performed polymer add EAGO in, it is vacuum dried into.The graphene oxide of obtained amino functional/azobenzene polymer composite waveguide material, thermo-optical coeffecient（dn/dT）It is bigger than common organic material and be more than 10 times of traditional inorganic material, it can be applied 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 to synthesize field, is related to functional graphene oxide and azobenzene polymer
The preparation of series compound, graphene oxide/azobenzene polymer composite waveguide material of more particularly to a kind of amino functional
Prepare and apply.
Background technology
Waveguide optical switch research hotspot is concentrated mainly on electrooptical switching and thermo-optical switch, waveguide type electrooptical switching speed in recent years
Degree is fast, but needs harsh Polarization technique, and cost related with polarization is higher.It is to utilize thermo-optic effect for thermo-optical switch
The modulation to light field is realized so as to fulfill switching function, the thermo-optical coeffecient of wherein material is influence thermo-optical switch driving power and sound
Answer the principal element of speed.Common thermal-photo switch material has inorganic (such as lithium niobate, SiO2Deng) and organic polymer material.Have
The thermo-optical coeffecient (dn/dT, refractive index vary with temperature) of organic polymeric material is order of magnitude greater compared with inorganic material and organic
Polymeric material has the advantages that technique is simple, cheap, filming performance is good and low etc. in 1.55 μm of window loss, therefore,
Thermo-optical switch based on polymer causes great attention.
Azobenzene polymer under being stimulated in light, heat, pressure, electric field, magnetic field, pH changes etc. because that can cause molecular isomerism to show
As the transformation between isomers can cause the refractive index of material to change so that azobenzene polymer has good optical activity
With high thermo-optical coeffecient.The preparation and thermo-optical switch analog study of the present inventor's long campaigns azobenzene polymer material, find to contain
The polymer of azo chromophore, under certain wavelength light action, the more non-azobenzene polymer of its thermo-optical coeffecient is 3~6 times high, research knot
Fruit is also shown that the waveguide material using azobenzene polymer as thermo-optical switch, and the power consumption for obtaining thermo-optical switch is less than 2.5mW, more non-
The thermo-optical switch of azobenzene polymer has in power consumption to be obviously improved, and further demonstrate that azobenzene polymer has big hot spectrum
The excellent specific property of the power consumption of number and reduction thermo-optical switch.
But during practical, for azobenzene polymer, there are the saturating of heat endurance during long-time service and film (dark color)
Key issues of bright property is not good enough, significantly limit the high temperature long-time service of azo material, this also becomes based on polymer
Stumbling-block in the practical distance of thermo-optical switch.
For optical angle, the thickness of single-layer graphene only has the thickness (about 0.35nm) of a carbon atom, even if through
Multiple stripping is crossed, the crystal structure of graphene is still quite complete, and this special structure assigns graphene special optics
Property, such as high transmittance (97.7%) to visible ray, are the most thin two-dimensional materials being currently known in the world, are had extremely
Excellent translucency.
In addition, A graphene-based broadband optical modulator, Nature, 2011,474
(7349):64-67, it was recently reported that with single-layer graphene be waveguide material, have developed the optical modulator of a world's minimum, have
Standby high speed transmission of signals ability, is expected to interconnection net spee improving 10,000 times, this report causes optics researcher immediately
Concern.
Femtosecond population inversion and stimulated emission of dense
dirac fermions in graphene,Phys.Rev.Lett.,2012,108(16):167401, disclose graphene tool
There are two critical natures：The residence amount reversion and the gain of light of electronics, again demonstrate graphene and can be used to make various photoelectric devices,
Include the absorber needed for wide-band optical amplifier, high-speed modulator, and optical communication and ultrafast laser.
But single-layer graphene is unstable two dimensional crystal, is not easy for composite with other materials.Graphene oxide because
It is associated with epoxy bond, hydroxyl and carboxyl and there is hydrophily, dispersiveness and chemism, so graphene oxide can be doped in respectively
Kind material is bonded by chemically reacting with a variety of materials, and graphene oxide can be shelled by small molecule or polyalcohol intercalation
From available for various aspects of performance such as the mechanics of improvement material, electricity, optics.
Functionalized graphene oxide with ethylenediamine and 1,6-
hexanediamine,New Carbon Materials,2012,27(5):370-376 a, it is proposed that side efficiently, economic
Method realizes the amino functional to GO.Result of study shows：Compared with GO, the graphene oxide of the amino functional of preparation is shown
The heat endurance of higher is shown, and ethylene diamine-modified graphene oxide shows fabulous dispersiveness in DMF.
Study on the effect of hexamethylene diamine functionalized graphene
oxide on the curing kinetics of epoxy nanocomposites,European Polymer
Journal,2014,52:88-97, is prepared for the epoxy resin nano composites of the filling for the GO being modified with hexamethylene diamine, as a result
Show to be significantly improved, disclose at the same time with compound preceding two single phases ratio, the machinery of the composite material, conductive and bending property
The curing mechanism and dynamics of curing reaction Kinetics.
Therefore, material of the coupling with good optical Response and big thermo-optical coeffecient azobenzene polymer and with high transparency
With the grapheme material of heat endurance, graphene/azobenzene polymer composite waveguide material of development of new, is expected to obtain great Rong
Amount, exchange at a high speed, be transparent, low-loss photoswitch, so as to preferably be applied in optical-fiber network.
The content of the invention
It is an object of the invention to prepare the composite waveguide material with good thermo-optical property, a kind of amino functional is disclosed
The preparation method of the graphene oxide of change/azobenzene polymer composite waveguide material.
It is of the invention that graphite oxide is first prepared by Hummers methods；Again by diazo coupling, by paranitroanilinum and isophthalic
Azo chromophore 4- (4- nitros-alkenyl) phenyl -1,3- diamines (NAPD) is prepared in diamines, then NAPD and isophorone
Diisocyanate (IPDI) reacts the azo that isocyano end-blocking is made under dibutyl tin laurate (T-12) catalytic action
Benzene performed polymer；Then graphite oxide ultrasound is peeled off and graphene oxide dispersion is made, in 2- (7- azos benzotriazole)-N,
Amino functional is prepared with ethylenediamine (EDA) reaction under the action of N, N', N'- tetramethylurea hexafluorophosphoric acid ester (HATU)
Graphene oxide (EAGO)；Finally, the azobenzene performed polymer of obtained isocyano end-blocking is added in EAGO and reacted, through vacuum
Dry graphene oxide/azobenzene polymer composite waveguide material (APU/EAGO, the abbreviation that amino functional is made to constant weight
NC)。
Graphite oxide is prepared in Hummers methods：The concentrated sulfuric acid of 115mL is added in 1000mL beakers, is placed in 0 DEG C
In ice-water bath, 5g natural graphite powders, 15g potassium permanganate and 2.5g sodium nitrate are slowly added to successively, reacts 1h at less than 10 DEG C,
35 DEG C are warming up to, reacts 2h；Then, 90 DEG C are warming up to, the deionized water of 230mL is slowly added dropwise with normal pressure funnel, then 100
2h is reacted under DEG C oil bath；Stop heating, first add the deionized water of 350mL and 30% hydrogen peroxide of 25mL, stirring reaction
Centrifuged after 30min；The deionized water of 350mL and 30% hydrogen peroxide of 25mL are added again, are centrifuged after stirring reaction 30min；
Washed with 5% hydrochloric acid solution, the product after most centrifuging at last is placed in 60 DEG C of vacuum drying chambers and dries 24h, up to graphite oxide.
Diazo coupling method prepares azo chromophore：Weigh the conical flask that 2.76g paranitroanilinum adds belt stirrer
In, 50g distilled water and 5.9g concentrated hydrochloric acids (37%) are added, is stirred to dissolve under room temperature；Then it is slowly dropped under the conditions of 0 DEG C
Containing 2.07g sodium nitrite solutions (52.07g), after being added dropwise, filter, obtain immediately after continuing stirring reaction 1h under ice bath
To yellow transparent diazonium salt solution；The pH that diazonium salt solution is adjusted with the sodium carbonate liquor of saturation is 7.0, will under condition of ice bath
Diazonium salt solution is slowly dropped into the DMF solution of m-phenylene diamine (MPD) (2.16g m-phenylene diamine (MPD)s are dissolved in 9.45g DMF)；It is added dropwise
Stirring reaction 1h under condition of ice bath；Filter, and be washed with distilled water filter cake to neutrality, then product is placed in fume hood and is done
It is dry, obtain brownish red azo solid powder 4- (4- nitros-alkenyl) phenyl -1,3- diamines (NAPD).
The preparation method of the graphene oxide of amino functional/azobenzene polymer composite waveguide material, includes the following steps：
Step A, with blender, by suitable isophorone diisocyanate in the reaction vessel of thermometer and return duct
Ester (IPDI) and azo chromophore 4- (4- nitros-alkenyl) phenyl -1,3- diamines (NAPD) are dissolved in DMF, are warming up to 40
After~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 the NAPD and IPDI are 1:2~10, preferably 1:3.5；The mass ratio of NAPD and DMF is 1:10~50, it is excellent
Select 1:18；Preferably 80 DEG C of temperature, time preferred 4h；
Step B, graphite oxide is placed in ultrasound in DMF and peels off 5~6h, then through centrifuging up to graphene oxide dispersion,
Wherein, the mass ratio of the graphite oxide and DMF is 1:500~1000, preferably 1:785；
Step C, in graphene oxide dispersion, appropriate ethylenediamine (EDA) is added, stirs 30min at room temperature；It is warming up to
30~90 DEG C, 2- (7- azos benzotriazole)-N, N is added, N', N'- tetramethylurea hexafluorophosphoric acid esters (HATU), continue to stir
3~9h is reacted, up to amido modified graphene oxide；Wherein, the mass ratio of the graphite oxide and EDA is 1:500~
1000, preferably 1:750；The mass ratio of HATU and graphite oxide is 1:5~15, preferably 1:12；Preferably 60 DEG C of temperature, the time is preferred
6h；
Step D, the performed polymer for blocking the isocyano obtained by step A adds oxygen amido modified made from step C
In graphite alkene system, 30~90 DEG C are warming up to, continues stirring 1~7h of reaction, reaction system is placed in 40~90 DEG C of vacuum and is done
Dry case dries to constant weight, up to graphene oxide/azobenzene polymer composite waveguide material (NC) of amino functional, wherein reaction temperature
Preferably 80 DEG C, the preferred 4h of mixing time of degree, preferably 60 DEG C of vacuum drying temperature.
The graphene oxide of amino functional made from the method/azobenzene polymer composite waveguide material according to the present invention
Material, there is higher thermo-optical coeffecient (dn/dT), than common organic material greatly and be more than 10 times of traditional inorganic material, can answer
For developing 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, the concentrated sulfuric acid, dibutyl tin dilaurate (T-12), nitric acid used in the present invention
Sodium, ethylenediamine (EDA), m-phenylene diamine (MPD), paranitroanilinum, 2- (7- azos benzotriazole)-N, N, N', N'- tetramethylureas six
Fluorophosphoric acid ester (HATU), potassium permanganate and n,N-Dimethylformamide (DMF), Sinopharm Chemical Reagent Co., Ltd.；30%
Hydrogen peroxide and different Buddhist diisocyanates (IPDI), Shanghai Ling Feng chemical reagent Co., Ltd；Disperse red -19 (DR-19),
Acros Organics Co.Ltd.,(New Jersey,America)。
Beneficial effect
Preparation process of the present invention is simple, the azo group contained in molecule and the functional graphene oxide nanometer material introduced
Material improves thermo-optical property, mechanical performance and the heat endurance of azobenzene polymer material.The oxidation of obtained amino functional
Graphene/azobenzene polymer composite waveguide material, has higher thermo-optical coeffecient (dn/dT), in contrast, the composite material ratio
Common organic material is big and is more than 10 times of traditional inorganic material.The composite material has low driving power and very fast to develop
The new digital thermo-optical switch of response speed is laid a good foundation.
Embodiment
With reference to embodiment, the present invention is described in detail, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following embodiments.
Embodiment 1
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 2.12g IPDI are dissolved in 18.9g's
In DMF, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 45 DEG C, 0.5g is added
T-12, reacts 1h, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 6g DMF and peel off 5h, then disperseed through centrifuging up to graphene oxide
Liquid；Dispersion liquid is placed in the round-bottomed flask of 250mL, then 6g EDA are added in graphene oxide dispersion, is stirred at room temperature
30min；Then, after being warming up to 30 DEG C, 2- (7- azos benzotriazole)-N, N of 0.8mg, N', N'- tetramethylureas six are added
Fluorophosphoric acid ester (HATU), continues stirring reaction 3h, up to the graphene oxide (EAGO) of ethylenediamine functionalization；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 30 DEG C, after
Continuous stirring reaction 1h.Most product is placed in 40 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-1).
Embodiment 2
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 2.12g IPDI are dissolved in 21.2g's
In DMF, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 50 DEG C, 0.5g is added
T-12, reacts 2h, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 7.2g DMF and peel off 6h, then through centrifuging up to graphene oxide point
Dispersion liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 8.4g EDA are added in graphene oxide dispersion, at room temperature
Stir 30min；Then, after being warming up to 40 DEG C, 0.8mg HATU are added, continue stirring reaction 4h, up to ethylenediamine functionalization
Graphene oxide (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 40 DEG C, after
Continuous stirring reaction 2h.Most product is placed in 50 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-2).
Embodiment 3
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 3.71g IPDI are dissolved in 19.08g's
In DMF, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 80 DEG C, 0.5g is added
T-12, reacts 4h, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 9.42g DMF and peel off 6h, then through centrifuging up to graphene oxide point
Dispersion liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9g EDA are added in graphene oxide dispersion, is stirred at room temperature
Mix 30min.Then, after being warming up to 60 DEG C, 1mg HATU are added, continue stirring reaction 6h, up to the oxidation of ethylenediamine functionalization
Graphene (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 80 DEG C, after
Continuous stirring reaction 4h.Most product is placed in 60 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-3).
Embodiment 4
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 4.24g IPDI are dissolved in the DMF of 48g
In, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 95 DEG C, 0.5g T- are added
12,7h is reacted, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 8.4g DMF and peel off 6h, then through centrifuging up to graphene oxide point
Dispersion liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9.42g EDA are added in graphene oxide dispersion, at room temperature
Stir 30min.Then, after being warming up to 90 DEG C, 2.4mg HATU are added, continue stirring reaction 9h, up to ethylenediamine functionalization
Graphene oxide (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 90 DEG C, after
Continuous stirring reaction 7h.Most product is placed in 90 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-4).
Embodiment 5
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 6.36g IPDI are dissolved in 42.4g's
In DMF, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 70 DEG C, 0.5g is added
T-12, reacts 6h, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 9.6g DMF and peel off 6h, then through centrifuging up to graphene oxide point
Dispersion liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 8.4g EDA are added in graphene oxide dispersion, at room temperature
Stir 30min.Then, after being warming up to 70 DEG C, 1.2mg HATU are added, continue stirring reaction 8h, up to ethylenediamine functionalization
Graphene oxide (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 50 DEG C, after
Continuous stirring reaction 3h.Most product is placed in 70 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-5).
Embodiment 6
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 11.34g IPDI are dissolved in 15.9g's
In DMF, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 60 DEG C, 0.5g is added
T-12, reacts 5h, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 12g DMF and peel off 6h, then disperseed through centrifuging up to graphene oxide
Liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9.6g EDA are added in graphene oxide dispersion, is stirred at room temperature
Mix 30min.Then, after being warming up to 60 DEG C, 1.5mg HATU are added, continue stirring reaction 7h, up to the oxygen of ethylenediamine functionalization
Graphite alkene (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 70 DEG C, after
Continuous stirring reaction 5h.Most product is placed in 80 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-6).
Embodiment 7
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 10.6g IPDI are dissolved in the DMF of 53g
In, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 80 DEG C, 0.5g T- are added
12,7h is reacted, up to the performed polymer of isocyano end-blocking；
(4) 0.012g graphite oxides are placed in ultrasound in 10g DMF and peel off 6h, then disperseed through centrifuging up to graphene oxide
Liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 12g EDA are added in graphene oxide dispersion, is stirred at room temperature
30min.Then, after being warming up to 70 DEG C, 1mg HATU are added, continue stirring reaction 5h, up to the oxidation stone of ethylenediamine functionalization
Black alkene (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 80 DEG C, after
Continuous stirring reaction 7h.Most product is placed in 80 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-7).
Embodiment 8
(1) graphite oxide is prepared into using Hummers methods；
(2) azo chromophore NAPD is prepared into using diazo coupling method；
(3) preparation of the performed polymer of isocyano end-blocking：1.06g NAPD and 8.48g IPDI are dissolved in 26.5g's
In DMF, and add and carry stirring rod, in the four-hole boiling flask of thermometer and return duct.Then, after being warming up to 60 DEG C, 0.5g is added
T-12, the performed polymer that reaction 4h blocks up to isocyano；
(4) 0.012g graphite oxides are placed in ultrasound in 10.5g DMF and peel off 6h, then through centrifuging up to graphene oxide point
Dispersion liquid, dispersion liquid is placed in the round-bottomed flask of 250mL, then 9.6g EDA are added in graphene oxide dispersion, at room temperature
Stir 30min.Then, after being warming up to 50 DEG C, 1.8mg HATU are added, continue stirring reaction 5h, up to ethylenediamine functionalization
Graphene oxide (EAGO)；
(5) and then by the performed polymer of isocyano end-blocking add in reaction solution made from step 2, after being warming up to 70 DEG C, after
Continuous stirring reaction 6h.Most product is placed in 60 DEG C of vacuum drying chambers and dries to constant weight at last, up to amino functional graphene oxide/
Azobenzene polymer composite waveguide material (NC-8).
Experimental method
Suitable NC-1, NC-2, NC-3, NC-4, NC-5, NC-6, NC-7 and NC-8 sample is taken, is dissolved in N respectively, N '-
In dimethylformamide, it is configured to the solution that concentration is 0.5g/mL and is spun on quartz plate, is dried in vacuo at 15 DEG C
72h.Its refractive index under different temperatures is tested using fiber waveguide measuring instrument, one-variable linear regression is carried out, obtains thermo-optical coeffecient
Dn/dT, such as following table：
The present invention obtains new thermoluminescent material, has higher thermo-optical coeffecient (dn/dT), compared with organic material such as polystyrene
(-1.23×10-4℃-1), polymethyl methacrylate (- 1.20 × 10-4℃-1), azo-nitrobenzene thiazole polyimides (-
1.460×10-4℃-1) and DR1 polyimides (- 1.331 × 10-4℃-1) big；Compared with inorganic material, such as borosilicate glass
(4.1×10-6℃-1), zinc silicate glass (5.5 × 10-6℃-1) and silica glass (10.8 × 10-6℃-1) etc., it is its heat
More than 10 times of backscatter extinction logarithmic ratio；The material provides possibility to develop the new digital thermo-optical switch with low driving power.
The foregoing is merely the embodiment of the present invention, is not intended to limit the scope of the invention, every to utilize this hair
The equivalent structure or equivalent flow shift that bright specification is made, is directly or indirectly used in other related technical areas,
Similarly it is included within the scope of the present invention.
Claims (7)
1. the preparation method of the graphene oxide of amino functional/azobenzene polymer composite waveguide material, first by Hummers legal systems
Standby graphite oxide；Again by diazo coupling, azo chromophore 4- (4- are prepared by paranitroanilinum and m-phenylene diamine (MPD)
Nitro-alkenyl) phenyl -1,3- diamines NAPD, then NAPD and isophorone diisocyanate IPDI is in di lauric dibutyl
The azobenzene performed polymer that isocyano end-blocking is made is reacted under tin T-12 catalytic action；Then graphite oxide ultrasound is peeled off and be made
Graphene oxide dispersion, in 2- (7- azos benzotriazole)-N, N, N', the work of N'- tetramethylurea hexafluorophosphoric acid esters HATU
With the lower graphene oxide EAGO that amino functional is made with ethylenediamine EDA reactions；The azo that obtained isocyano is blocked
Benzene performed polymer, which is added in EAGO, to react, vacuum dried to constant weight, it is characterised in that：Include the following steps：
Step A, with blender, by suitable isophorone diisocyanate in the reaction vessel of thermometer and return duct
IPDI and azo chromophore 4- (4- nitros-alkenyl) phenyl -1,3- diamines NAPD are dissolved in DMF, are warming up to 40~95 DEG C
Afterwards, add catalyst dibutyltin dilaurylate T-12 and react 1~7h, obtain the performed polymer of isocyano end-blocking, wherein, it is described
The mass ratio of 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 ultrasound in DMF and peels off 5~6h, then through centrifuging up to graphene oxide dispersion, its
In, the mass ratio of the graphite oxide and DMF is 1:500~1000；
Step C, in graphene oxide dispersion, appropriate ethylenediamine is added（EDA）, 30min is stirred at room temperature；It is warming up to 30~
90 DEG C, add 2- (7- azos benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid esters（HATU）, continue stirring reaction
3~9h, up to amido modified graphene oxide；Wherein, the mass ratio of the 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 for blocking the isocyano obtained by step A adds oxidation stone amido modified made from step C
In black alkene system, 30~90 DEG C are warming up to, continues stirring 1~7h of reaction, reaction system is placed in 40~90 DEG C of vacuum drying chambers
Dry to constant weight, up to graphene oxide/azobenzene polymer composite waveguide material of amino functional.
2. the preparation of the graphene oxide of amino functional according to claim 1/azobenzene polymer composite waveguide material
Method, it is characterised in that：In step A, the mass ratio of the NAPD and IPDI are 1:3.5；The mass ratio of NAPD and DMF is 1:
18；80 DEG C of temperature, time 4h.
3. the preparation of the graphene oxide of amino functional according to claim 1/azobenzene polymer composite waveguide material
Method, it is characterised in that：In step B, the mass ratio of the graphite oxide and DMF is 1:785.
4. the preparation of the graphene oxide of amino functional according to claim 1/azobenzene polymer composite waveguide material
Method, it is characterised in that：In step C, the mass ratio of the graphite oxide and EDA is 1:750；The quality of HATU and graphite oxide
Than for 1:12；Temperature 60 C, time 6h.
5. the preparation of the graphene oxide of amino functional according to claim 1/azobenzene polymer composite waveguide material
Method, it is characterised in that：In step D, 80 DEG C, mixing time 4h of reaction temperature, 60 DEG C of vacuum drying temperature.
6. according to the graphene oxide of amino functional made from any preparation method in claim 1-5/azo polymerization
Thing composite waveguide material.
7. the application of the graphene oxide of amino functional/azobenzene polymer composite waveguide material according to claim 6, its
It is characterized in that：It is applied to and develops the digital thermo-optical switch with low driving power and very fast response speed.
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