CN108084624B - A kind of preparation method having defective Responsive photonic crystals - Google Patents
A kind of preparation method having defective Responsive photonic crystals Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods for having defective Responsive photonic crystals, which is characterized in that monomer n-isopropyl acrylamide etc. is added in deionized water and reacts, initiator is then added, and the reaction was continued, obtains nano-hydrogel PNIPAM；Crosslinking agent is added, adds monomeric acrylic etc., obtains nano-hydrogel PNIPAM/PAA；Sequentially add the Fe of various concentration2+Deng obtaining nano-hydrogel IPN/Fe3O4；Monomer n-isopropyl acrylamide etc. is added, temperature reaction, initiator is added, and the reaction was continued, obtains nano-hydrogel PNIPAM@(IPN/Fe3O4)；By IPN/Fe3O4It is mixed, it is concentrated to get the defective Responsive photonic crystals of tool.The photonic crystal has responsiveness to temperature, and when the temperature rises, defect disappears, and when being cooled to room temperature, defect occurs.
Description
Technical field
The present invention relates to a kind of preparation methods for having defective Responsive photonic crystals, and it is brilliant to belong to nano-hydrogel photon
The preparation technical field of body.
Background technique
Photonic crystal (is a kind of to be had in certain space by the two or more material with different refractivity
Material with periodic structure made of sequence arrangement.This unique periodic structure can be such that electromagnetic wave generates, and " Prague dissipates
Penetrate ", to form " forbidden photon band ".When frequency of light wave is fallen in forbidden band, light just not can be carried out propagation.Photon band gap and photon
The lattice constant of crystal, structure, the refractive index of material packing ratio and material etc. are related.Therefore we can by change these because
Element produces the photon crystal material of variety classes, different function.Another important feature of photonic crystal is the office of photonic crystal
Domain property, i.e., when photon crystal material has certain defect (degree of order of photonic crystal is destroyed), part is former in photonic crystal
Some periodic arrangements are destroyed, and corresponding forbidden photon band position also occurs to change accordingly.In the photonic crystal, defective form master
There are point defect, line defect, planar defect etc., controls propagation of the light inside photonic crystal by artificially manufacturing certain defect
Mode.Having defective photonic crystal can be applied to optical waveguide, laser emitter, increase or inhibition spontaneous radiation etc..
Currently, the method that preparation has defective photonic crystal has a mechanical processing method, and laser ablation method, electroetching method etc.,
Although these methods have design flexibility, time-consuming for they, trivial operations, is not suitable for being mass produced.Compared to this
A little methods, the method for hydrogel particle self assembly have easy to operate, low manufacture cost and the time-consuming characteristics such as short.For example, C.L
ó pez etc. is by being presented tool to polymethyl methacrylate (PMMA) polystyrene doped microballoon (PS) after colloidal solid self assembly
Defective photonic crystal, and by the unordered degree of the dosage and particle size adjustment photonic crystal that adjust PS, to regulate and control it
The property of forbidden photon band
(Palacios-Lidon E, Juarez B H, Castillo-Martinez E, et al.Optical and
Morphological study of disorder in opals [J] .Journal ofApplied Physics, 2005,97
(6): 063502-063502-7.).In addition, Koen Clays is in SiO2The photonic crystal of assembling passes through doping different-grain diameter
SiO2Particle prepares photonic crystal (Kurt Wostyn, Yuxia Zhao, G the D S, et with planar defect
al.Insertion of a Two-Dimensional Cavity into a Self-Assembled Colloidal
Crystal [J] .Langmuir, 2003,19 (10): 4465-4468.).However, this kind of defective photonic crystal of tool is to the external world
Non-responsiveness is stimulated, its application range is limited.Currently, controllably introducing the side of defect in responsiveness aquagel photonic crystal
The rare report of method.
Summary of the invention
Problem to be solved by this invention is: a kind of preparation method having defective Responsive photonic crystals is provided,
Have a wide range of application.
To solve the above-mentioned problems, the present invention provides a kind of preparation method for having defective Responsive photonic crystals,
Characterized by comprising the following steps:
Step 1): monomer n-isopropyl acrylamide (NIPAM), crosslinking agent, emulsifier are added in deionized water, room temperature
Nitrogen charging deoxygenation, stirring and dissolving are reacted under nitrogen atmosphere, and initiator is then added, and the reaction was continued, are dialysed, obtain Thermo-sensitive
Nano-hydrogel PNIPAM；
Step 2): the nano-hydrogel PNIPAM that step 1) obtains is diluted with deionized water, and crosslinking agent, nitrogen gas is added
It is stirred under atmosphere, sequentially adds monomeric acrylic (AA), initiator, catalyst at room temperature and persistently stir, dialysed, obtain interpenetrating net
The nano-hydrogel PNIPAM/PAA of network IPN structure；
Step 3): the nano-hydrogel PNIPAM/PAA that step 2) obtains is divided into more parts after nitrogen charging deoxygenation, room temperature
Under be sequentially added into the Fe of various concentration2+、NaNO2, ammonium hydroxide, be stirred to react under nitrogen atmosphere, dialysed, obtain Thermo-sensitive magnetic
The nano-hydrogel IPN/Fe of property IPN structure3O4；
Step 4): the nano-hydrogel IPN/Fe obtained to step 3)3O4Monomer n-isopropyl acrylamide, crosslinking is added
Agent, room temperature nitrogen charging deoxygenation stir under nitrogen atmosphere, then temperature reaction, and initiator is added, and the reaction was continued, are dialysed, are had
There is the magnetic Nano hydrogel PNIPAM@(IPN/Fe of core-shell structure3O4)；
Step 5): contain Fe for what step 3) obtained3O4Measure different nano-hydrogel IPN/Fe3O4It is obtained with step 4)
The magnetic Nano hydrogel PNIPAM@(IPN/Fe of core-shell structure3O4) mixing, it is concentrated into 2~8wt%, is stood at room temperature from group
Dress, obtains having defective Responsive photonic crystals.
Preferably, the crosslinking agent in the step 1) is N, and bis- (propylene acyl) cystamines (BAC) of N '-, emulsifier is dodecane
Base sodium sulphate (SDS), initiator are ammonium persulfate (APS)；Crosslinking agent in step 2) is N, N '-methylene-bisacrylamide
(BIS), initiator is ammonium persulfate (APS), and catalyst is sodium pyrosulfite (Na2S2O5)；The quality of ammonium hydroxide in step 3) is dense
Degree is 25~30%；Crosslinking agent in step 4) is N, and N '-methylene-bisacrylamide (BIS), initiator is ammonium persulfate
(APS)。
Preferably, monomer n-isopropyl acrylamide in the step 1), crosslinking agent, emulsifier, initiator, catalyst
Mass ratio is 100: 1~3: 2~5: 3~6: 3~6；PNIPAM, monomeric acrylic, crosslinking agent, initiator, catalysis in step 2)
The mass ratio of agent is 100: 5~20: 5~30: 3~6: 3~6；PNIPAM/PAA, Fe in step 3)2+、NaNO2, ammonium hydroxide dosage
Than for 100g:0.007~0.07g:0.001~0.100g:0.01~1mL；IPN/Fe in step 4)3O4, monomer N- isopropyl third
Acrylamide, crosslinking agent, initiator amount ratio be 100mL: 0.05~0.3g: 0.0025~0.075g: 0.005~0.09g；
Preferably, stirring uses magnetic agitation in the step 1), and mixing time is 25~35min；The temperature of first set reaction
Degree is 60~80 DEG C, and the reaction time is 30~50min；The time that the reaction was continued is 1~4h.
Preferably, the diluted multiple of deionization is 5~10 times in the step 2)；Stirring is all made of magnetic agitation；For the first time
Mixing time is 15~40min；Continuing mixing time is 15~60min.
Preferably, the time of nitrogen charging is 20~40min in the step 3)；Stirring uses mechanical stirring；Fe is added2+Afterwards
Mixing time is 20~60min；NaNO is added2Mixing time afterwards is 5~20min；Be added ammonium hydroxide after mixing time be 1~
3h。
Preferably, the time of nitrogen charging is 30~50min in the step 4)；Stirring uses magnetic agitation, and mixing time is
20~40min；The temperature of temperature reaction is 50~70 DEG C, and the reaction time is 30~40min；Initiator the reaction was continued time is added
For 1~4h.
Preferably, the step 1) -4) in the technological parameter dialysed are as follows: being packed into molecular cut off is 8000~14000
It is impregnated 3~7 days in deionized water in bag filter, changes 3 water daily.
Preferably, nano-hydrogel IPN/Fe in the step 5)3O4With magnetic Nano hydrogel PNIPAM@(IPN/
Fe3O4) mass percent be 0%~5%；The temperature of concentration is 40~70 DEG C.
The present invention by responsiveness aquagel introduce with body granules partial size, refractive index, the different emulsion particle of structure,
By colloidal solid self assembly, the photonic crystal with point defect is prepared.The photonic crystal has responsiveness to temperature, in temperature
When raising, defect disappears, and when being cooled to room temperature, defect occurs.
Compared with prior art, the beneficial effects of the present invention are:
(1) method and process that the present invention uses is simple, and raw material is easy to get, environmentally protective；
(2) present invention preparation has defective Responsive photonic crystals, and forbidden photon band position can be by adulterating latex
Grain concentration, partial size, the properties such as refractive index are adjusted；
(3) hydrogel particle after present invention preparation doping, by heating-falling temperature technique, can Rapid self assembly at having
The photonic crystal of defect, and defect disappears at high temperature, and defect occurs when cooling.
Detailed description of the invention
Fig. 1 is the optics picture of the defective Responsive photonic crystals of tool obtained of embodiment 1；
Fig. 2 is that responsiveness aquagel made from embodiment 1 is hydrated grain-size graph；
Fig. 3 is pair of the reflectance spectrum figure obtained for having defective Responsive photonic crystals and each intermediate of embodiment 1
Than figure；
Fig. 4 is the reflectance spectrum figure of the defective Responsive photonic crystals of tool obtained of embodiment 2；
Fig. 5 be the defective Responsive photonic crystals of tool obtained of embodiment 2 40 DEG C with 25 DEG C when reflectance spectrum figure.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
A kind of preparation method having defective Responsive photonic crystals:
(1) by 1.9825g monomer n-isopropyl acrylamide NIPAM, 0.0321g crosslinking agent B AC, 0.1008g emulsifier
SDS is dissolved in 250mL deionized water, and blasts N at room temperature2Deoxygenation, magnetic agitation 30min, in a nitrogen atmosphere 70 DEG C it is anti-
30min is answered, then 0.0815g initiator A PS is dissolved in 10mL deionized water, above-mentioned solution is added, keeps nitrogen atmosphere, after
Continuous reaction 4h, is then soaked in deionized water with the bag filter that molecular cut off is 8000~14000 and is dialysed 7 days, changed daily
Water three times, removal remain electrolyte in reaction raw materials and reaction system, obtain temperature-sensitive nano hydrogel PNIPAM.
(2) PNIPAM that 60mL step (1) obtains is diluted to 440mL with deionized water, 0.5954g crosslinking agent is added
3g monomeric acrylic AA magnetic agitation 20min is added, then by 0.2g initiator in BIS, magnetic agitation 30min under nitrogen atmosphere
APS, 0.2g catalyst n a2S2O5It is dissolved in 5mL deionized water respectively, sequentially adds above-mentioned solution, keep nitrogen atmosphere, continued
30min is reacted, is then soaked in deionized water and is dialysed 7 days with the bag filter that molecular cut off is 8000~14000, changed daily
Water three times, removal remain electrolyte in reaction raw materials and reaction system, obtain interpenetrating networks IPN structure nano hydrogel
PNIPAM/PAA。
(3) the IPN structure nano hydrogel PNIPAM/PAA for taking 300g step (2) to obtain is equally divided into 2 parts, every part
150mL, N2Deoxygenation 30min is separately added into 0.0125g, 0.0432g Fe at room temperature2+, N2Lower mechanical stirring 40min is protected, so
0.01g NaNO is added afterwards2, the ammonium hydroxide that 0.05mL concentration is 25wt% is added after 5min, keeps nitrogen atmosphere sustained response 1h,
Then it is soaked in deionized water and is dialysed 7 days with the bag filter that molecular cut off is 8000~14000, changed water three times daily, go
Except electrolyte in residual reaction raw materials and reaction system, inierpeneirating network structure magnetic Nano hydrogel IPN/Fe is obtained3O4It orders respectively
Entitled M1, M2.
(4) the M2 nano-hydrogel IPN/Fe for taking step (3) to obtain3O4, 0.2105g monomer NIPAM, 0.0203g is added and hands over
Join agent BIS, room temperature nitrogen charging deoxygenation 40min, magnetic agitation 30min, temperature rises to 50 DEG C of reaction 30min, then draws 0.0214g
Hair agent APS is dissolved in 2mL deionized water, is added in above-mentioned solution, keeps nitrogen atmosphere, the reaction was continued 4h, then with retention molecule
The bag filter that amount is 8000~14000, which is soaked in deionized water, dialyses 7 days, changes water three times, removal residual reaction raw materials daily
And electrolyte in reaction system, it obtains with core-shell structure magnetic nano-hydrogel PNIPAM@(IPN/Fe3O4), it is named as PM2.
(5) in 50g M2,1.25wt%M1 is added, is uniformly mixed, is named as M1:M21.25%；In 50g M2, add
Enter 1.25wt%PM2, is uniformly mixed, is named as PM2:M21.25%；Above-mentioned mixed liquor is placed in baking oven, is concentrated at 50 DEG C
3.5wt%, taking-up are stood at room temperature, are carried out self assembly, are obtained having defective Responsive photonic crystals.
The present embodiment defective Responsive photonic crystals M1:M21.25% of tool obtained shows noticeable color
Coloured silk, as shown in Figure 1.
It is as shown in Figure 2 that responsiveness aquagel made from the present embodiment is hydrated partial size.
The reflectance spectrum figure of Responsive photonic crystals made from the present embodiment is as shown in Figure 3, it is known that in Bragg diffraction peak
The defective locations of appearance and the intensity of defect are influenced by the latex particle size and structure that adulterate.
Embodiment 2
A kind of preparation method having defective Responsive photonic crystals:
(1) by 1.8754g monomer n-isopropyl acrylamide NIPAM, 0.0314g crosslinking agent B AC, 0.1056g emulsifier
SDS is dissolved in 250mL deionized water, and blasts N at room temperature2Deoxygenation, magnetic agitation 30min, in a nitrogen atmosphere 70 DEG C it is anti-
30min is answered, then 0.0812g initiator A PS is dissolved in 10mL deionized water, above-mentioned solution is added, keeps nitrogen atmosphere, after
Continuous reaction 4h, is then soaked in deionized water with the bag filter that molecular cut off is 8000~14000 and is dialysed 7 days, changed daily
Water three times, removal remain electrolyte in reaction raw materials and reaction system, obtain temperature-sensitive nano hydrogel PNIPAM.
(2) PNIPAM for obtaining 60mL step (1) dilutes 440mL with deionized water, and 0.6012g crosslinking agent B IS is added,
Magnetic agitation 30min under nitrogen atmosphere, be added 3g monomeric acrylic AA magnetic agitation 20min, then by 0.2g initiator A PS,
0.2g catalyst n a2S2O5It is dissolved in 5mL deionized water respectively, sequentially adds above-mentioned solution, keep nitrogen atmosphere, sustained response
Then 30min is soaked in deionized water with the bag filter that molecular cut off is 8000~14000 and is dialysed 7 days, changed daily three times
Water, removal remain electrolyte in reaction raw materials and reaction system, obtain interpenetrating networks IPN structure nano hydrogel PNIPAM/
PAA。
(3) the IPN structure nano hydrogel PNIPAM/PAA for taking 300g step (2) to obtain is equally divided into 2 parts, every part
150mL, N2Deoxygenation 30min is separately added into 0.0857g Fe at room temperature2+, N2Lower mechanical stirring 40min is protected, is then added
0.01g NaNO2, the ammonium hydroxide that 0.1mL concentration is 25wt% is added after 5min, keeps nitrogen atmosphere sustained response 1h, then with cutting
Staying molecular weight is that 8000~14000 bag filter is soaked in deionized water and dialyse 7 days, changes water three times daily, removal residual is instead
Electrolyte in raw material and reaction system is answered, inierpeneirating network structure magnetic Nano hydrogel IPN/Fe is obtained3O4It is respectively designated as M3.
(4) the M3 nano-hydrogel IPN/Fe for taking step (3) to obtain3O4, 0.2007g monomer NIPAM, 0.0205g is added and hands over
Join agent BIS, room temperature nitrogen charging deoxygenation 40min, magnetic agitation 30min, temperature rises to 50 DEG C of reaction 30min, then draws 0.0201g
Hair agent APS is dissolved in 2mL deionized water, is added in above-mentioned solution, keeps nitrogen atmosphere, the reaction was continued 4h, then with retention molecule
The bag filter that amount is 8000~14000, which is soaked in deionized water, dialyses 7 days, changes water three times, removal residual reaction raw materials daily
And electrolyte in reaction system, it obtains with core-shell structure magnetic nano-hydrogel PNIPAM@(IPN/Fe3O4), it is named as PM3.
(5) 50g M3 is taken, 1.25wt%PM3 is added, is uniformly mixed, is named as PM3:M31.25%, takes 50g M3, is added
2.5wt%PM3 is uniformly mixed, is named as PM3:M32.5%；Above-mentioned mixed liquor is placed in baking oven, is concentrated at 50 DEG C
3.5wt%, taking-up are stood at room temperature, are carried out self assembly, are obtained having defective Responsive photonic crystals.
The reflectance spectrum figure of the present embodiment defective Responsive photonic crystals of tool obtained is as shown in Figure 4, it is known that Bradley
The position of defect can be adjusted by the concentration of the emulsion particle adulterated in lattice diffraction maximum.
The present embodiment defective Responsive photonic crystals of tool obtained 40 DEG C with 25 DEG C when reflectance spectrum figure such as Fig. 5
It is shown, it is known that photonic crystal has sensibility, high temperature defect erasing to temperature, and cold temperature deficiency shows.
Claims (9)
1. a kind of preparation method for having defective Responsive photonic crystals, which comprises the following steps:
Step 1): monomer n-isopropyl acrylamide, crosslinking agent, emulsifier are added in deionized water, room temperature nitrogen charging deoxygenation stirs
Dissolution is mixed, is reacted under nitrogen atmosphere, initiator is then added, and the reaction was continued, is dialysed, obtains the nanometer water-setting of Thermo-sensitive
Glue PNIPAM；
Step 2): the nano-hydrogel PNIPAM that step 1) obtains is diluted with deionized water, addition crosslinking agent, under nitrogen atmosphere
Stirring, sequentially adds monomeric acrylic, initiator, catalyst at room temperature and persistently stirs, dialysed, and obtains interpenetrating networks IPN knot
The nano-hydrogel PNIPAM/PAA of structure；
Step 3): the nano-hydrogel PNIPAM/PAA that step 2) obtains is divided into more parts after nitrogen charging deoxygenation, is divided at room temperature
The Fe of various concentration is not sequentially added2+、NaNO2, ammonium hydroxide, be stirred to react under nitrogen atmosphere, dialysed, obtain Thermo-sensitive magnetism
The nano-hydrogel IPN/Fe of IPN structure3O4；
Step 4): the nano-hydrogel IPN/Fe obtained to step 3)3O4Monomer n-isopropyl acrylamide, crosslinking agent, room is added
Warm nitrogen charging deoxygenation stirs under nitrogen atmosphere, then temperature reaction, and initiator is added, and the reaction was continued, is dialysed, is obtained with nucleocapsid
The magnetic Nano hydrogel PNIPAM@(IPN/Fe of structure3O4)；
Step 5): contain Fe for what step 3) obtained3O4Measure different nano-hydrogel IPN/Fe3O4The nucleocapsid knot obtained with step 4)
The magnetic Nano hydrogel PNIPAM@(IPN/Fe of structure3O4) mixing, it is concentrated into 2~8wt%, stands self assembly at room temperature, is obtained
Have defective Responsive photonic crystals.
2. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
1) crosslinking agent in is N, and bis- (propylene acyl) cystamines of N'-, emulsifier is lauryl sodium sulfate, and initiator is ammonium persulfate；Step
It is rapid 2) in crosslinking agent be N, N'- methylene-bisacrylamide, initiator is ammonium persulfate, and catalyst is sodium pyrosulfite；Step
It is rapid 3) in ammonium hydroxide mass concentration be 25~30%；Crosslinking agent in step 4) is N, and N'- methylene-bisacrylamide causes
Agent is ammonium persulfate.
3. having the preparation method of defective Responsive photonic crystals as claimed in claim 1 or 2, which is characterized in that described
Monomer n-isopropyl acrylamide in step 1), crosslinking agent, emulsifier, initiator, catalyst mass ratio be 100:1~3:2
~5:3~6:3~6；PNIPAM in step 2), monomeric acrylic, crosslinking agent, initiator, catalyst mass ratio be 100:5~
20:5~30:3~6:3~6；PNIPAM/PAA, Fe in step 3)2+、NaNO2, ammonium hydroxide amount ratio be 100g:0.007~
0.07g:0.001~0.100g:0.01~1mL；IPN/Fe in step 4)3O4, monomer n-isopropyl acrylamide, crosslinking agent, draw
The amount ratio for sending out agent is 100mL:0.05~0.3g:0.0025~0.075g:0.005~0.09g；
4. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
1) stirring uses magnetic agitation in, and mixing time is 25~35min；The temperature of first set reaction is 60~80 DEG C, and the reaction time is
30~50min；The time that the reaction was continued is 1~4h.
5. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
2) the diluted multiple of deionized water is 5~10 times in；Stirring is all made of magnetic agitation；First mixing time is 15~40min；It holds
Continuous mixing time is 15~60min.
6. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
3) time of nitrogen charging is 20~40min in；Stirring uses mechanical stirring；Fe is added2+Mixing time afterwards is 20~60min；Add
Enter NaNO2Mixing time afterwards is 5~20min；Mixing time after ammonium hydroxide is added is 1~3h.
7. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
4) time of nitrogen charging is 30~50min in；Stirring uses magnetic agitation, and mixing time is 20~40min；The temperature of temperature reaction
It is 50~70 DEG C, the reaction time is 30~40min；It is 1~4h that initiator the reaction was continued time, which is added,.
8. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
1) technique dialysed in -4) are as follows: be fitted into the bag filter that molecular cut off is 8000~14000 and impregnate 3~7 in deionized water
It, changes 3 water daily.
9. having the preparation method of defective Responsive photonic crystals as described in claim 1, which is characterized in that the step
5) nano-hydrogel IPN/Fe in3O4With magnetic Nano hydrogel PNIPAM@(IPN/Fe3O4) mass percent be 1.25%
~5%；The temperature of concentration is 40~70 DEG C.
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