CN103804700A - Method for preparing chemically crosslinked photonic crystal hydrogel with adjustable color - Google Patents
Method for preparing chemically crosslinked photonic crystal hydrogel with adjustable color Download PDFInfo
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- CN103804700A CN103804700A CN201410056696.XA CN201410056696A CN103804700A CN 103804700 A CN103804700 A CN 103804700A CN 201410056696 A CN201410056696 A CN 201410056696A CN 103804700 A CN103804700 A CN 103804700A
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Abstract
The invention relates to a method for preparing chemically crosslinked photonic crystal hydrogel with an adjustable color. The method comprises the following steps: (1) dissolving N-isopropylacrylamide, N-hydroxyethyl acrylamide, a cross-linking agent and an emulsifier into deionized water, stirring, warming and keeping warm under the condition at 20-25 DEG C in a nitrogen condition, and then adding an initiator to continue to react for 1-4 hours, and dialyzing, so as to obtain a colloidal crystal hydrogel solution; (2) concentrating the obtained colloidal crystal hydrogel solution, standing at room temperature, adjusting the pH by adopting an NaOH solution, adding a crosslinking agent, evenly mixing, centrifuging, and standing at room temperature after taking, so as to obtain the chemically crosslinked photonic crystal hydrogel. The method is simple in process and low in cost, and the prepared photonic crystal hydrogel has thermosensibility. In addition, the obtained photonic crystal hydrogel is good in stability, and free of hydrolysis, the problem that nano hydrogel is easily decomposed because of ester hydrolysis in 2-hydroxy ethyl acrylate is solved, and the defects of the photonic crystal hydrogel in application are compensated.
Description
Technical field
The invention belongs to photonic crystal hydrogel field, particularly the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color.
Background technology
Photonic crystal (photonic crystal) is to arrange according to certain cycle order the material with ordered structure forming in space by the two or more materials with differing dielectric constant, and its photonic band gap structure having can carry out Effective Regulation to the propagation direction of light.Wherein, colloidal crystal (colloidal crystal) refers to the two dimension or system three-dimensional order, that be similar to crystalline structure that in the solvent of low ionic strength, are made up of through specific arrangement mode the colloid micro ball of monodispersed submicron order (submicro) or nano level (nano).
Hydrogel is a kind of can swell in significantly water 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 specific character of hydrogel makes it discharge in the control of medicine, and the fields such as immobilization, feed separation and the bio-medical material of enzyme 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 is shunk-expanded occurs.
In recent years, investigators combine the characteristics such as the swell cross of colloidal photon crystal self-assembly characteristic and enviromental sensitive hydrogel, have made the gel photonic crystal material of series of new.This gellike photon crystal material can lead to the response of environmental change being made to rapid sensitive, by the contraction or expansion of hydrogel, the variation that causes photonic crystal photon band gap is subjected to displacement Bragg diffraction peak, in macroscopic view, can directly observe material color by naked eyes and change, its responsiveness is evaluated.Gel photonic crystal material has been obtained huge progress in fields such as biosensor, optical switch, bionical, paint, ceramic process and ion probes.(the Hu Z such as Hu, Lu X, Gao J, Adv.Mater.2001,13,1708-1713) by using divinylsulfone (DVS) covalent cross-linking attached gel self-assembly under alkaline condition, synthesized the opal gel with temperature-responsive to gather (NIPA-co-vinylformic acid (2-hydroxy ethyl methacrylate)) (PNIPAM-co-AA(HEAc)).This material has dazzling color as native protein stone, can substituted dyes, fluorescent agent etc. plays chromogenesis.But due to the facile hydrolysis in alkali of ester group in HEAc, the nanogel physical strength that causes NIPAM and HEAc crosslinking copolymerization to form is very poor, has limited its application.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color, 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 obtaining is fine, can not be hydrolyzed, and has solved because hydrolysis of ester group in HEAc causes the labile problem of nano-hydrogel, has made up its shortcoming in application.
Described multipolymer is to have two kinds of monomer copolymerizations of monomer structure A NIPA (N-isopropylacrylamide, NIPAM) and monomer structure B N-hydroxyethyl acrylamide (N-Hydroxyethyl acrylamide, HEAA) synthetic.
The preparation method of the photonic crystal hydrogel of the chemically crosslinked that a kind of color of the present invention is adjustable, comprising:
(1) NIPA (NIPAM), N-hydroxyethyl acrylamide (HEAA), linking agent and emulsifying agent are dissolved in deionized water, in nitrogen atmosphere, under 20～25 ℃ of conditions, stir 80～120min, be then warming up to 50-80 ℃, insulation 30～50min, then add initiator, 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, leave standstill to room temperature, adopt NaOH solution to regulate pH, add linking agent, mix, centrifugal, after taking out, under room temperature, leave standstill, obtain the photonic crystal hydrogel of the adjustable chemically crosslinked of color.
Linking agent in described step (1) is N, N '-methylene-bisacrylamide, and 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), for adopting deionized water to soak 3-7 days, is changed water every day one time; 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%.
In described step (2), regulating pH is 9～15.
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 size distribution homogeneous and particle diameter at adjustable poly-(NIPA-co-N-hydroxyethyl acrylamide) of wide range (P(NIPAM-co-HEAA)) 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) under certain pH value, it to be cross-linked, the wherein selection of comonomer HEAA, has solved the problem a little less than the nano-hydrogel physical strength causing due to hydrolysis of ester group in HEAc, has made up its shortcoming in application.The color of the photonic crystal hydrogel making can regulate by changing hydrogel particle diameter and two kinds of modes of mass concentration.
beneficial effect
Technique of the present invention 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 adjustable feature of its color; By adding of linking agent DVS, expand its using value thereby improve its mechanical strength; In addition, the introducing of comonomer HEAA, the photonic crystal hydrogel stability obtaining is fine, can not be hydrolyzed, and a little less than having solved the nano-hydrogel physical strength causing due to hydrolysis of ester group in HEAc, labile problem, has made up its shortcoming in application.
Accompanying drawing explanation
Fig. 1 is P(NIPAM-co-HEAA) colloidal crystal that is cross-linked to form by DVS in the time that concentration is 6.7wt% of nano-hydrogel (ratio of NIPAM:HEAA is 1:0.1, w/w).
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
1. the preparation of colloidal crystal hydrogel solution:
(1) get 3.7903gNIPAM, 0.3808g HEAA, 0.0725g N, 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 ℃, and is incubated 40 minutes under N2 protection;
(3) get 0.17g ammonium persulphate and add in above-mentioned solution, keep N2 atmosphere, continue reaction 4 hours;
(4) then gained reactant is soaked in deionized water and is dialysed 7 days, change water every day one time, 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 concentrated, regulating its concentration is 6.74wt%, leaves standstill to room temperature, pours in test tube, dripping NaOH solution regulation system pH is 12, drip rapidly 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 under room temperature and leave standstill 2hr, complete the crosslinking curing of colloidal crystal hydrogel.
Embodiment 2
1. the preparation of colloidal crystal hydrogel solution:
(1) get 3.7903gNIPAM, 0.3808g HEAA, 0.0725g N, 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 ℃, and is incubated 40 minutes under N2 protection;
(3) get 0.17g ammonium persulphate and add in above-mentioned solution, keep N2 atmosphere, continue reaction 4 hours;
(4) then gained reactant is soaked in deionized water and is dialysed 7 days, change water every day one time, 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 concentrated, regulating its concentration is 6.74wt%, leaves standstill to room temperature, pours in test tube, dripping NaOH solution regulation system pH is 11, drip rapidly 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 under room temperature and leave standstill 2hr, complete the crosslinking curing of colloidal crystal hydrogel.
Embodiment 3
1. the preparation of colloidal crystal hydrogel solution:
(1) get 3.7864gNIPAM, 0.3960g HEAA, 0.0701g N, 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 ℃, and is incubated 40 minutes under N2 protection;
(3) get 0.17g ammonium persulphate and add in above-mentioned solution, keep N2 atmosphere, continue reaction 4 hours;
(4) then gained reactant is soaked in deionized water and is dialysed 7 days, change water every day one time, 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 concentrated, regulating its concentration is 6.22wt%, leaves standstill to room temperature, pours in test tube, dripping NaOH solution regulation system pH is 12, drip rapidly 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 under room temperature and leave standstill 2hr, complete the crosslinking curing of colloidal crystal hydrogel.
Claims (10)
1. a preparation method for the photonic crystal hydrogel of the adjustable chemically crosslinked of color, comprising:
(1) NIPA, N-hydroxyethyl acrylamide, linking agent and emulsifying agent are dissolved in deionized water, in nitrogen atmosphere, under 20～25 ℃ of conditions, stir 80～120min, be then warming up to 50-80 ℃, insulation 30～50min, then add initiator, 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, leave standstill to room temperature, adopt NaOH solution to regulate pH, add linking agent, mix, centrifugal, after taking out, under room temperature, leave standstill, obtain the photonic crystal hydrogel of the adjustable chemically crosslinked of color.
2. the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color 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 adjustable chemically crosslinked of a kind of color 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 adjustable chemically crosslinked of a kind of color 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 adjustable chemically crosslinked of a kind of color according to claim 1, is characterized in that: the dialysis in described step (1), for adopting deionized water to soak 3-7 days, is changed water every day one time; The molecular weight cut-off of dialysis tubing used is 8000～14000.
6. the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color 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 adjustable chemically crosslinked of a kind of color according to claim 1, is characterized in that: in described step (2), regulating pH is 9～15.
8. the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color according to claim 1, it is characterized in that: the linking agent in described step (2) is divinylsulfone, add-on is 0.2%～5% of NIPA and N-hydroxyethyl acrylamide quality summation.
9. the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color according to claim 1, is characterized in that: the centrifugal speed in described step (2) is 4000r/min, and centrifugation time is 5min.
10. the preparation method of the photonic crystal hydrogel of the adjustable chemically crosslinked of a kind of color according to claim 1, is characterized in that: the time of repose in described step (2) is 20～300min.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893709A (en) * | 2015-06-09 | 2015-09-09 | 西北核技术研究所 | Surface treatment method for scintillator |
| CN105646904A (en) * | 2016-01-05 | 2016-06-08 | 东华大学 | Preparation method of conductive photon crystal aquagel |
| CN107075127A (en) * | 2014-06-04 | 2017-08-18 | 克洛克斯科技公司 | bio-photon hydrogel |
| CN107236085A (en) * | 2017-06-26 | 2017-10-10 | 北京理工大学 | A kind of method that large area quickly prepares stretching discoloration photon crystal water gel duplicature |
| CN108179640A (en) * | 2018-02-01 | 2018-06-19 | 江兵 | A kind of environmental type dyeing of superfine fiber chemical leather |
| CN108301230A (en) * | 2018-02-01 | 2018-07-20 | 江兵 | A kind of synthetic dyeing microcapsule disperse dye and preparation method thereof |
| CN110982011A (en) * | 2019-11-29 | 2020-04-10 | 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 |
| CN112521634A (en) * | 2020-12-23 | 2021-03-19 | 安徽美科迪智能微胶囊科技有限公司 | Preparation and immobilization method of temperature-responsive nano hydrogel photonic crystal |
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| US20040018160A1 (en) * | 2001-11-15 | 2004-01-29 | Zhibing Hu | Synthesis, uses and compositions of crystal hydrogels |
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Patent Citations (1)
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| US20040018160A1 (en) * | 2001-11-15 | 2004-01-29 | Zhibing Hu | Synthesis, uses and compositions of crystal hydrogels |
Non-Patent Citations (2)
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| YOUGEN CHEN ET AL.: ""Structural effect of a series of block copolymers consisting of poly(N-isopropylacrylamide) and poly(N-hydroxyethylacrylamide)on thermoresponsive behavior"", 《REACTIVE & FUNCTIONAL POLYMERS》 * |
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Cited By (14)
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| CN107075127A (en) * | 2014-06-04 | 2017-08-18 | 克洛克斯科技公司 | bio-photon hydrogel |
| EP3152250A4 (en) * | 2014-06-04 | 2018-01-03 | 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 |
| CN105646904A (en) * | 2016-01-05 | 2016-06-08 | 东华大学 | Preparation method of conductive photon crystal aquagel |
| 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 |
| CN107236085A (en) * | 2017-06-26 | 2017-10-10 | 北京理工大学 | A kind of method that large area quickly prepares stretching discoloration photon crystal water gel duplicature |
| CN108179640A (en) * | 2018-02-01 | 2018-06-19 | 江兵 | A kind of environmental type dyeing of superfine fiber chemical leather |
| CN108301230A (en) * | 2018-02-01 | 2018-07-20 | 江兵 | A kind of synthetic dyeing microcapsule disperse dye and preparation method thereof |
| 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 |
| CN110982011A (en) * | 2019-11-29 | 2020-04-10 | 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 |
| CN112521634A (en) * | 2020-12-23 | 2021-03-19 | 安徽美科迪智能微胶囊科技有限公司 | Preparation and immobilization method of temperature-responsive nano hydrogel photonic crystal |
| 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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