CN103804700B - A kind of preparation method of photonic crystal hydrogel of chemically crosslinked of Color tunable - Google Patents
A kind of preparation method of photonic crystal hydrogel of chemically crosslinked of Color tunable Download PDFInfo
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- CN103804700B CN103804700B CN201410056696.XA CN201410056696A CN103804700B CN 103804700 B CN103804700 B CN 103804700B CN 201410056696 A CN201410056696 A CN 201410056696A CN 103804700 B CN103804700 B CN 103804700B
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Abstract
The present invention relates to a kind of preparation method of photonic crystal hydrogel of chemically crosslinked of Color tunable, comprise: NIPA, N-hydroxyethyl acrylamide, linking agent and emulsifying agent are dissolved in deionized water by (1), in nitrogen atmosphere, under 20 ~ 25 DEG C of conditions, stir, heat up, be incubated, then add initiator, continue reaction 1 ~ 4h, dialysis, obtains colloidal crystal hydrogel solution; (2) the colloidal crystal hydrogel solution of gained is concentrated, leaves standstill to room temperature, adopt NaOH solution regulate pH, add linking agent, mixing, centrifugal, take out after left at room temperature, to obtain final product.Present invention process is simple, and cost is low, and prepared photonic crystal hydrogel has temperature-responsive; In addition, the photonic crystal hydrogel stability obtained is fine, can not be hydrolyzed, solves due to hydrolysis of ester group in 2-hydroxyethylmethacry,ate and cause the labile problem of nano-hydrogel, compensate for its shortcoming in application.
Description
Technical field
The invention belongs to photonic crystal hydrogel field, the preparation method of the photonic crystal hydrogel of particularly a kind of chemically crosslinked of Color tunable.
Background technology
Photonic crystal (photoniccrystal) arranges by the two or more material with differing dielectric constant the material with ordered structure formed according to certain cycle sequences in space, and its photonic band gap structure had can carry out Effective Regulation to the propagation direction of light.Wherein, colloidal crystal (colloidalcrystal) refer to the two dimension that is made up of through specific arrangement mode in the solvent of low ionic strength the colloid micro ball of monodispersed submicron order (submicro) or nano level (nano) or three-dimensional order, the system that is similar to crystalline structure.
Hydrogel is a kind of can swell in water significantly and keep large quantity of moisture but be not dissolved in the hydrophilic polymer of water between liquid and solid, is widespread in nature as a class " soft material ".This characteristic of hydrogel makes it at the Co ntrolled release of medicine, and the fields such as enzyme immobilizatio, feed separation and bio-medical material are widely used.Temperature-responsive hydrogel be most widely used, a class enviromental sensitive hydrogel that investigator is most interested in, it is can variation with temperature and the hydrogel that reversibility shrinks-expand occurs.
In recent years, the characteristics such as the swell cross of colloidal photon crystal self-assembly characteristic and enviromental sensitive hydrogel combine by investigators, have obtained the gel photonic crystal material of series of new.This kind of gel photonic crystal material can lead to response environmental change being made to rapid sensitive, by the contraction or expansion of hydrogel, cause the change of photonic crystal photon band gap that Bragg diffraction peak is subjected to displacement, macroscopically can be changed by direct visual perception material color, its responsiveness is evaluated.Gel photonic crystal material achieves huge progress in the field such as biosensor, optical switch, bionical, paint, ceramic process and ion probe.(the HuZ such as Hu, LuX, GaoJ, Adv.Mater.2001,13,1708-1713) by with divinylsulfone (DVS) covalent cross-linking attached gel self-assembly in the basic conditions, synthesize the opal gel poly-(NIPA-co-vinylformic acid (2-hydroxy ethyl methacrylate)) (PNIPAM-co-AA(HEAc) with temperature-responsive).This material has color dazzling as native protein stone, substituted dyes, fluorescent agent etc. can play chromogenesis.But due to the facile hydrolysis in alkali of ester group in HEAc, the nanogel physical strength causing NIPAM and HEAc crosslinking copolymerization to be formed is very poor, limit its application.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of photonic crystal hydrogel of chemically crosslinked of Color tunable, and the method technique is simple, and cost is low, and prepared photonic crystal hydrogel has temperature-responsive; In addition, the introducing of comonomer HEAA, the photonic crystal hydrogel stability obtained is fine, can not be hydrolyzed, solves due to hydrolysis of ester group in HEAc and cause the labile problem of nano-hydrogel, compensate for its shortcoming in application.
Described multipolymer is the two kinds of monomer copolymerization synthesis having monomer structure AN-N-isopropylacrylamide (N-isopropylacrylamide, NIPAM) and monomer structure BN-hydroxyethyl acrylamide (N-Hydroxyethylacrylamide, HEAA).
The preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable of the present invention, comprising:
(1) NIPA (NIPAM), N-hydroxyethyl acrylamide (HEAA), linking agent and emulsifying agent are dissolved in deionized water, in nitrogen atmosphere, under 20 ~ 25 DEG C of conditions, stir 80 ~ 120min, be then warming up to 50-80 DEG C, insulation 30 ~ 50min, then initiator is added, continue reaction 1 ~ 4h, dialysis, obtains colloidal crystal hydrogel solution; Wherein the mass ratio of NIPA and N-hydroxyethyl acrylamide is 1:0.1 ~ 0.9, and NIPA accounts for 1 ~ 4% of reaction raw materials gross weight;
(2) the colloidal crystal hydrogel solution of gained is concentrated, leaves standstill to room temperature, adopt NaOH solution regulate pH, add linking agent, mixing, centrifugal, take out after left at room temperature, obtain the photonic crystal hydrogel of the chemically crosslinked of Color tunable.
Linking agent in described step (1) is N, N '-methylene-bisacrylamide, add-on is 1% ~ 2% of NIPA and N-hydroxyethyl acrylamide quality summation.
Emulsifying agent in described step (1) is sodium lauryl sulphate, and add-on is 0.6% ~ 5% of NIPA and N-hydroxyethyl acrylamide quality summation.
Initiator in described step (1) is ammonium persulphate, and add-on is 1% ~ 6% of NIPA and N-hydroxyethyl acrylamide quality summation.
Dialysis in described step (1) soaks 3-7 days for adopting deionized water, changes a water every day; The molecular weight cut-off of dialysis tubing used is 8000 ~ 14000.
The concentration of the colloidal crystal hydrogel solution after concentrated in described step (2) is 1 ~ 10wt%.
PH is regulated to be 9 ~ 15 in described step (2).
Linking agent in described step (2) is divinylsulfone (DVS), and add-on is 0.2% ~ 5% of NIPA and N-hydroxyethyl acrylamide quality summation.
Centrifugal speed in described step (2) is 4000r/min, and centrifugation time is 5min.
Time of repose in described step (2) is 20 ~ 300min.
The present invention has prepared the homogeneous and particle diameter of size distribution at adjustable poly-(NIPA-co-N-hydroxyethyl acrylamide) (P(NIPAM-co-HEAA) of wide range) complex microsphere, the microballoon that wherein monodispersity is good is one of primary condition of the opal photonic crystal of processability excellence; Then use linking agent divinylsulfone (DVS) to be cross-linked it under certain pH value, the wherein selection of comonomer HEAA, solve the problem that the nano-hydrogel physical strength that causes due to hydrolysis of ester group in HEAc is weak, compensate for its shortcoming in application.The color of obtained photonic crystal hydrogel can be regulated by change hydrogel particle diameter and mass concentration two kinds of modes.
beneficial effect
Present invention process is simple, and cost is low, and prepared photonic crystal hydrogel has temperature-responsive; By controlling particle diameter and the concentration of photonic crystal hydrogel, realize the feature of its Color tunable; By adding of linking agent DVS, improve its mechanical strength thus expand its using value; In addition, the introducing of comonomer HEAA, the photonic crystal hydrogel stability obtained is fine, can not be hydrolyzed, and solves the nano-hydrogel physical strength caused due to hydrolysis of ester group in HEAc weak, labile problem, compensate for its shortcoming in application.
Accompanying drawing explanation
Fig. 1 is P(NIPAM-co-HEAA) nano-hydrogel (ratio of NIPAM:HEAA is 1:0.1, w/w) when concentration is 6.7wt% by colloidal crystal that DVS is cross-linked to form.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
1. the preparation of colloidal crystal hydrogel solution:
(1) get 3.7903gNIPAM, 0.3808gHEAA, 0.0725gN, N '-methylene-bisacrylamide and 0.1095g sodium lauryl sulphate are dissolved in 250g deionized water, and blast N2 deoxygenation under room temperature, magnetic agitation 120 minutes;
(2) temperature of reaction rises to 70 DEG C, and is incubated 40 minutes under N2 protection;
(3) getting 0.17g ammonium persulphate adds in above-mentioned solution, keeps N2 atmosphere, continues reaction 4 hours;
(4) then gained reactant is soaked in deionized water and dialyses 7 days, change a water every day, remove ionogen in residual reaction raw materials and reaction system.Dialysis tubing molecular weight cut-off used is 8000 ~ 14000.Obtain.
2. the solidification treatment of colloidal crystal hydrogel:
The colloidal crystal hydrogel solution of gained is put into baking oven for heating concentrate, regulate its concentration to be 6.74wt%, leave standstill to room temperature, pour in test tube, dripping NaOH solution regulation system pH is 12, rapid dropping linking agent 0.0304g, vortex oscillation mixes, and then puts into whizzer, centrifugal 5min under 4000r/min, to remove the bubble in gel, take out left at room temperature 2hr, namely complete the crosslinking curing of colloidal crystal hydrogel.
Embodiment 2
1. the preparation of colloidal crystal hydrogel solution:
(1) get 3.7903gNIPAM, 0.3808gHEAA, 0.0725gN, N '-methylene-bisacrylamide and 0.1095g sodium lauryl sulphate are dissolved in 250g deionized water, and blast N2 deoxygenation under room temperature, magnetic agitation 120 minutes;
(2) temperature of reaction rises to 70 DEG C, and is incubated 40 minutes under N2 protection;
(3) getting 0.17g ammonium persulphate adds in above-mentioned solution, keeps N2 atmosphere, continues reaction 4 hours;
(4) then gained reactant is soaked in deionized water and dialyses 7 days, change a water every day, remove ionogen in residual reaction raw materials and reaction system.Dialysis tubing molecular weight cut-off used is 8000 ~ 14000.Obtain.
2. the solidification treatment of colloidal crystal hydrogel:
The colloidal crystal hydrogel solution of gained is put into baking oven for heating concentrate, regulate its concentration to be 6.74wt%, leave standstill to room temperature, pour in test tube, dripping NaOH solution regulation system pH is 11, rapid dropping linking agent 0.0289g, vortex oscillation mixes, and then puts into whizzer, centrifugal 5min under 4000r/min, to remove the bubble in gel, take out left at room temperature 2hr, namely complete the crosslinking curing of colloidal crystal hydrogel.
Embodiment 3
1. the preparation of colloidal crystal hydrogel solution:
(1) get 3.7864gNIPAM, 0.3960gHEAA, 0.0701gN, N '-methylene-bisacrylamide and 0.0505g sodium lauryl sulphate are dissolved in 250g deionized water, and blast N2 deoxygenation under room temperature, magnetic agitation 120 minutes;
(2) temperature of reaction rises to 70 DEG C, and is incubated 40 minutes under N2 protection;
(3) getting 0.17g ammonium persulphate adds in above-mentioned solution, keeps N2 atmosphere, continues reaction 4 hours;
(4) then gained reactant is soaked in deionized water and dialyses 7 days, change a water every day, remove ionogen in residual reaction raw materials and reaction system.Dialysis tubing molecular weight cut-off used is 8000 ~ 14000.Obtain.
2. the solidification treatment of colloidal crystal hydrogel:
The colloidal crystal hydrogel solution of gained is put into baking oven for heating concentrate, regulate its concentration to be 6.22wt%, leave standstill to room temperature, pour in test tube, dripping NaOH solution regulation system pH is 12, rapid dropping linking agent 0.0268g, vortex oscillation mixes, and then puts into whizzer, centrifugal 5min under 4000r/min, to remove the bubble in gel, take out left at room temperature 2hr, namely complete the crosslinking curing of colloidal crystal hydrogel.
Claims (8)
1. a preparation method for the photonic crystal hydrogel of the chemically crosslinked of Color tunable, comprising:
(1) NIPA, N-hydroxyethyl acrylamide, linking agent and emulsifying agent are dissolved in deionized water, in nitrogen atmosphere, under 20 ~ 25 DEG C of conditions, stir 80 ~ 120min, be then warming up to 50-80 DEG C, insulation 30 ~ 50min, then initiator is added, continue reaction 1 ~ 4h, dialysis, obtains colloidal crystal hydrogel solution; Wherein the mass ratio of NIPA and N-hydroxyethyl acrylamide is 1:0.1 ~ 0.9, and NIPA accounts for 1 ~ 4% of reaction raw materials gross weight;
(2) the colloidal crystal hydrogel solution of gained is concentrated, leaves standstill to room temperature, adopt NaOH solution regulate pH, add linking agent, mixing, centrifugal, take out after left at room temperature, obtain the photonic crystal hydrogel of the chemically crosslinked of Color tunable; Wherein, linking agent is divinylsulfone, and add-on is 0.2% ~ 5% of NIPA and N-hydroxyethyl acrylamide quality summation, regulates pH to be 9 ~ 15.
2. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, it is characterized in that: the linking agent in described step (1) is N, N '-methylene-bisacrylamide, add-on is 1% ~ 2% of NIPA and N-hydroxyethyl acrylamide quality summation.
3. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, it is characterized in that: the emulsifying agent in described step (1) is sodium lauryl sulphate, add-on is 0.6% ~ 5% of NIPA and N-hydroxyethyl acrylamide quality summation.
4. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, it is characterized in that: the initiator in described step (1) is ammonium persulphate, add-on is 1% ~ 6% of NIPA and N-hydroxyethyl acrylamide quality summation.
5. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, is characterized in that: the dialysis in described step (1) soaks 3-7 days for adopting deionized water, changes a water every day; The molecular weight cut-off of dialysis tubing used is 8000 ~ 14000.
6. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, is characterized in that: the concentration of the colloidal crystal hydrogel solution after concentrated in described step (2) is 1 ~ 10wt%.
7. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, is characterized in that: the centrifugal speed in described step (2) is 4000r/min, and centrifugation time is 5min.
8. the preparation method of the photonic crystal hydrogel of the chemically crosslinked of a kind of Color tunable according to claim 1, is characterized in that: the time of repose in described step (2) is 20 ~ 300min.
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| WO2015184551A1 (en) * | 2014-06-04 | 2015-12-10 | Klox Technologies Inc. | Biophotonic hydrogels |
| CN104893709A (en) * | 2015-06-09 | 2015-09-09 | 西北核技术研究所 | Surface treatment method for scintillator |
| CN105646904B (en) * | 2016-01-05 | 2018-04-20 | 东华大学 | A kind of preparation method of conduction photon crystal water gel |
| CN107236085B (en) * | 2017-06-26 | 2019-04-16 | 北京理工大学 | A kind of method that large area quickly prepares stretching discoloration photon crystal water gel duplicature |
| CN108301230B (en) * | 2018-02-01 | 2020-08-28 | 河北三利毛纺有限公司 | Disperse dye microcapsule for dyeing synthetic fibers and preparation method thereof |
| CN108179640B (en) * | 2018-02-01 | 2020-09-08 | 义乌市赛恩斯高分子材料有限公司 | Green environment-friendly dyeing process of superfine fiber synthetic leather |
| CN110982011B (en) * | 2019-11-29 | 2021-08-03 | 河北大学 | Light-directing bending material and preparation method thereof |
| CN111548452A (en) * | 2020-04-13 | 2020-08-18 | 剑桥大学南京科技创新中心有限公司 | Preparation method of self-adaptive optical gel based on borate reversible covalent bond |
| CN112521634B (en) * | 2020-12-23 | 2023-08-29 | 安徽美科迪智能微胶囊科技有限公司 | Preparation and immobilization methods of temperature-responsive nano hydrogel photonic crystal |
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| "Hydrogel Opals";Zhibing Hu et al.;《Adv. Mater.》;20011106;第13卷(第22期);第1708–1712页 * |
| "Structural effect of a series of block copolymers consisting of poly(N-isopropylacrylamide) and poly(N-hydroxyethylacrylamide)on thermoresponsive behavior";Yougen Chen et al.;《Reactive & Functional Polymers》;20081227;第69卷;第463–469页 * |
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