CN103224631B - Carboxymethyl cellulose based reversible photochromic hydrogel and its preparation method - Google Patents
Carboxymethyl cellulose based reversible photochromic hydrogel and its preparation method Download PDFInfo
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Abstract
The invention relates to a preparation method of a carboxymethyl cellulose based reversible photochromic hydrogel. The preparation method comprises the following steps: dissolving carboxymethyl cellulose of different substitution degrees into water to prepare a carboxymethyl cellulose aqueous solution, preparing a phospho-tungstic acid aqueous solution, mixing the phospho-tungstic acid solution and the carboxymethyl cellulose aqueous solution under the condition of continuous stirring, controlling addition manner and dosage of phospho-tungstic acid, and finally stopping stirring and standing for 2h so as to obtain the carboxymethyl cellulose based hydrogel.
Description
Technical field
The present invention relates to the hydrogel that a kind of organism is matrix, relate in particular to a kind of preparation method of carboxymethyl cellulose-based ability of reverse photochromism hydrogel, belong to photochromic hydrogel field.
Background technology
Photochromic material in photochemical reaction, specific refractory power when its physical property changes, relative permittivity, oxidation-reduction potential with and geometry also change.Therefore, photochromic material has many potential Application Areass, for example: sensitometry and thermal measurement, radiation measurement, photoswitch, optical filter, indicating meter, information storage, solar energy converting, light regulation and control, optical information gene material etc., especially aspect biologic applications, photochromic material has unique advantage, because light wave can not produce damage to relatively fragile biological tissue and organ.Compared with traditional photochromic material, photochromic hydrogel has good wetting ability and biocompatibility, aspect biologic applications, (such as pharmaceutical carrier, fluorescent mark etc.) have good prospect, this is because hydrogel is by the molecular three-dimensional net structure of high score, can a large amount of moisture of swelling absorption in water, but can not dissolve, be widely used in association areas such as biological medicine, organizational project, functional materialss, as wound dressing, drug release carrier, artificial organ etc.
At present, photochromic hydrogel is generally all by matrix and photochromic material (the Fernando Pina and T. Alan Hatton. Photochromic Soft Materials:Flavylium Compounds Incorporated into Pluronic F-127 Hydrogel Matrixes that is composited, 2008,24 (6): Tan 2356-2364. Liaanjiang county, Liu Shuiping, Chen Yanmo etc. a kind of synthetic and sign [J] of photochromic hydrogel. synthetic technology and application, 2011,26 (1): 11-14.).
Having a extensive future of photochromic hydrogel, prepares photochromic hydrogel, and the selection of body material and off-color material is very important, will consider in preparation process, whether to need to use linking agent simultaneously.The selection of body material, except requiring it to have good wetting ability, also should consider the interaction of itself and off-color material.The polymer of preparing hydrogel mainly has two large classes: a class is for synthetic polymer, as vinylformic acid, acrylamide, acrylate etc.; Another kind of is natural polymer, as Lalgine, starch, Mierocrystalline cellulose, chitosan etc.Hydrogel prepared by natural polymer has the advantage (Jing Zhanxin such as good biological degradability and biocompatibility with respect to synthetic polymer, Sun Xiaofeng, Wang Haihong etc. environment sensitive type cellulose aquagel and the application aspect medicine controlled releasing [J] thereof. material Leader, 2012,26 (4): 83-88.).Wherein Mierocrystalline cellulose is the rich in natural resources of occurring in nature, by the carboxymethyl cellulose of cellulose modified preparation, in the time that its substitution value acquires a certain degree, can be dissolved in water, form the solution of clear, there is the features such as biological degradability, biocompatibility, safety non-toxic due to it, become the ideal material of preparing hydrogel.
Phospho-wolframic acid is a kind of important heteropoly compound, heteropolyacid can be used as electron acceptor(EA) and organic to body form electronics give-be subject to title complex, part can occur under ultraviolet excitation to be shifted to the electric charge of metal center, thereby show photochromic property, the combination of polyacid compound and macromolecular material is not only conducive to the workability of matrix material, make the application of such photochromic material become possibility, and can greatly improve the ability of structuring polymer participation transfer transport and transport, widen its range of application.
The mode that high-molecular gel forms generally has two kinds, i.e. chemically crosslinked and physical crosslinking.Chemical mode linking agent often has larger toxicity, and physical crosslinking gel forms by physical bond modes such as entanglement point, crystallite districts, can avoid using linking agent.The photochromic hydrogel that uses phospho-wolframic acid and carboxymethyl cellulose to be compounded to form is physical crosslinking, without adding linking agent, has avoided owing to using linking agent to introduce toxic substance.
Summary of the invention
The object of the invention is, in order to solve the problem that existing photochromic hydrogel matrix biocompatibility is poor, processing need add poisonous linking agent, provides a kind of simple cellulose base ability of reverse photochromism hydrogel and preparation method thereof.
The object of the invention is to realize by following technical proposals:
A kind of carboxymethyl cellulose-based ability of reverse photochromism hydrogel, matrix of the present invention is the carboxymethyl cellulose that utilizes different degree of substitution prepared by conventional heterogeneous method, hydrogel is to be mixed to get by carboxymethyl cellulose aqueous solution and phosphotungstic acid aqueous solution, the mode of mixing is: phosphotungstic acid aqueous solution dropwise and is slowly joined in carboxymethyl cellulose aqueous solution, mix simultaneously by magnetic agitation; The concentration of described carboxymethyl cellulose aqueous solution is between 1%-5%, and substitution value is between 0.6-1.8, and the concentration of phosphotungstic acid aqueous solution is 5%-30%.
Preparation method's concrete steps of carboxymethyl cellulose-based ability of reverse photochromism hydrogel are as follows above:
Step 2, prepare phosphotungstic acid aqueous solution, concentration is between 5%-30%.
Step 3, under the condition of magnetic agitation, the carboxymethyl cellulose aqueous solution that the phosphotungstic acid aqueous solution of step 2 gained is made with step 1 mixes; Phosphotungstic acid aqueous solution and sodium carboxymethyl cellulose solution mass ratio are between 1:1.7～2.0.
Step 4, stop stirring, leave standstill more than 2 h, can obtain carboxymethyl cellulose-based ability of reverse photochromism hydrogel.
In above step 1, the carboxymethyl cellulose substitution value range accommodation adopting is very wide, and the present invention has chosen substitution value between 0.6-1.8.Its consideration is: for using heterogeneous legal system standby carboxymethyl cellulose, if substitution value lower than 0.6, carboxymethyl cellulose solvability declines to a great extent, and can cause gel transparency variation; If substitution value higher than 1.8, needs repeatedly to alkalize and etherificate, greatly increase unnecessary cost.
The hybrid mode of the phosphotungstic acid aqueous solution described in step 3 and cmc soln must adopt phosphotungstic acid aqueous solution dropwise, slowly to join in carboxymethyl cellulose aqueous solution.If phosphotungstic acid aqueous solution is joined and changes other modes in carboxymethyl cellulose aqueous solution and as carboxymethyl cellulose aqueous solution joined in phosphotungstic acid aqueous solution or directly, a certain amount of carboxymethyl cellulose is dissolved in phosphotungstic acid aqueous solution or phospho-wolframic acid powder is directly joined in carboxymethyl cellulose aqueous solution and other conventional hybrid modes, no matter how the add-on that adds speed, phospho-wolframic acid of the substitution value of carboxymethyl cellulose and concentration, phospho-wolframic acid changes, and all can not form hydrogel.
Other modes that add can not form the reason of gel, relevant with the speed that forms gel, CMC is first dissolved in the present invention, drip again phospho-wolframic acid, control the speed that forms gel, the final webbed structure of shape, become gel, other add mode when CMC is joined in Salkowski's solution, because phospho-wolframic acid in system is more, first form layer of gel on CMC surface, in gel, comprise undissolved CMC, through stirring, inner undissolved CMC also forms gel gradually, so just form one by one independently micro-gel particles, cannot form reticulated structure, can only exist with the form of microgel.
In the present invention, must select rightly the rate of addition of phosphotungstic acid aqueous solution and the substitution value of carboxymethyl cellulose, the concentration of carboxymethyl cellulose aqueous solution and the concentration of phosphotungstic acid aqueous solution, must rational Match between them, because, applicant finds that maximum rate of addition reduces with the increase of phosphotungstic acid aqueous solution concentration under the certain condition of carboxymethyl cellulose substitution value, concentration of aqueous solution; Under the certain condition of carboxymethyl cellulose substitution value, Salkowski's solution concentration, maximum rate of addition reduces and reduces with carboxymethyl cellulose concentration; Under the constant condition of carboxymethyl cellulose aqueous solution concentration, phosphotungstic acid aqueous solution concentration, maximum rate of addition reduces with the increase of carboxymethyl cellulose substitution value.Through large quantitative analysis and research, applicant thinks, under condition of the present invention, the fastest 10s/ of being no more than that adds of phosphotungstic acid aqueous solution drips.
In the present invention, the amount that forms carboxymethyl cellulose in the required amount of phospho-wolframic acid of gel and the substitution value of carboxymethyl cellulose, solution is relevant, of the present invention most important to the formation of hydrogel with magnitude relation selection.Research through applicant obtains: if will form network structure than more complete hydrogel, the add-on of phospho-wolframic acid will be controlled within the specific limits, add-on is not enough, and system is solution state, add-on is too much, network structure is too fine and close, no longer there is the water absorbing properties of hydrogel, form hard block.Under the certain condition of cmc soln concentration, along with the rising of carboxymethyl cellulose substitution value, the ratio increase of the mole number of residual hydroxyl in the minimum mole number that forms the required phospho-wolframic acid of the comparatively complete hydrogel of network structure and carboxymethyl cellulose, the ratio increase of the mole number of residual hydroxyl in the highest mole number that forms the required phospho-wolframic acid of the comparatively complete hydrogel of network structure and carboxymethyl cellulose, but the difference of the highest mole number and minimum mole number reduces; Under the certain condition of carboxymethyl cellulose substitution value, along with the increase of carboxymethyl cellulose concentration, the ratio reduction of the mole number of residual hydroxyl in the minimum mole number that forms the required phospho-wolframic acid of the comparatively complete hydrogel of network structure and carboxymethyl cellulose, in the highest mole number that forms the required phospho-wolframic acid of the comparatively complete hydrogel of network structure and carboxymethyl cellulose, the ratio of the mole number of residual hydroxyl also reduces, but the increase of the difference of the highest mole number and minimum mole number.For example, it is 2% constant that the concentration of cmc soln remains, Salkowski's solution concentration is 10% constant, when the substitution value of carboxymethyl cellulose is during in 0.6 left and right, the ratio range that forms the mole number of residual hydroxyl in the mole number of the required phospho-wolframic acid of form hydrogel better, that network is complete and carboxymethyl cellulose is 0.02-0.06; In the time that the substitution value of carboxymethyl cellulose is 0.8 left and right, the ratio range that forms the mole number of residual hydroxyl in the mole number of the required phospho-wolframic acid of form hydrogel better, that network is complete and carboxymethyl cellulose is 0.04-0.07; In the time that the substitution value of carboxymethyl cellulose is 1.00 left and right, the ratio range that forms the mole number of residual hydroxyl in the mole number of the required phospho-wolframic acid of form hydrogel better, that network is complete and carboxymethyl cellulose is 0.06-0.08; In the time that the substitution value of carboxymethyl cellulose is 1.8 left and right, the ratio range that forms the mole number of residual hydroxyl in the mole number of the required phospho-wolframic acid of form hydrogel better, that network is complete and carboxymethyl cellulose is very little, and its ratio can only be 0.30 left and right.The product that visible the present invention obtains, by rheol sign, can prove that the carboxymethyl cellulose-based hydrogel forming has comparatively complete network structure, and its network structure is relevant with the substitution value of carboxymethyl cellulose and the add-on of phospho-wolframic acid.
In addition, when the phosphotungstic acid aqueous solution described in step 3 mixes with carboxymethyl cellulose aqueous solution, carboxymethyl cellulose aqueous solution will be placed in rapid stirring on magnetic stirring apparatus, and speed is greater than 1000rpm.
Beneficial effect of the present invention:
1, the present invention utilizes the hydroxyl on carboxymethyl cellulose surface and the phospho-wolframic acid of heteropolyanion structure easily to form the characteristic of hydrogen bond, prepared the hydrogel of physical crosslinking, avoided using poisonous linking agent, carboxymethyl cellulose-based body has nontoxic, renewable, the advantages such as good biocompatibility.Meanwhile, carboxymethyl cellulose belongs to anionic derivatived cellulose, can be used as polymer electron donor(ED), phospho-wolframic acid is a kind of heteropolyacid, can be used as electron acceptor(EA), under the irradiation of light, electric charge has been transferred on heteropolyanion from polymeric anion, form mixed-valence complex---assorted blue, make mixture present blueness, therefore, can there is photochromic reactions in the hydrogel making, preparation method is easy, and product is nontoxic.
2, the carboxymethyl cellulose hydrogel making by present method, water white transparency, light transmission is high; There is good degradability; The hydrogel that the present invention is obtained irradiates 5 h under ultraviolet lamp, and hydrogel becomes blueness, and the hydrogel of variable color is placed in to dark place 5 h, and hydrogel becomes colorless again.This hydrogel irradiates under ultraviolet lamp, can be by the colourless blueness that changes into gradually; Hydrogel is placed in to dark place for some time, and color can revert to colourless.
3, the hydrogel making is carried out to rheology test, find that the add-on of the network structure of gel and the substitution value of carboxymethyl cellulose and phospho-wolframic acid is relevant.Forming in the scope of gel, when the content of phospho-wolframic acid increases, the storage modulus increase of hydrogel, out-of-phase modulus changes and weakens, and network structure is tightr.
4, by respectively the hydrogel before and after variable color having been carried out to the detection of absorbancy and transmitance, find before hydrogel variable color, its transmitance in the scope of visible ray is very high, can reach more than 92%, and do not see through completely in the scope of UV-light, after hydrogel variable color, its transmitance in visible-range decreases, this is to cause because the gel after variable color absorbs to strengthen in visible region, gel after variable color does not still see through completely in UV-light region, illustrate that this hydrogel can issue and changes colour response and effectively intercept ultraviolet ray at high light, by ultraviolet-visible spectrophotometer, absorbancy and the transmittance of the hydrogel before and after variable color are characterized as seen, find that it is having very important application prospect aspect pre-antiultraviolet and strong illumination, can be applied to building, light splitting and other are about field.
Brief description of the drawings
Fig. 1 is a series of gels that form as 1.00 carboxymethyl celluloses as matrix taking substitution value, its storage modulus G ' and the changing conditions of out-of-phase modulus G ' ' with carboxymethyl cellulose and phospho-wolframic acid content ratio;
Fig. 2 is the comparison diagram of the hydrogel b before hydrogel a and the variable color after UV-irradiation variable color;
Fig. 3 is the transmitance comparison diagram of the hydrogel before hydrogel and the variable color after UV-irradiation variable color;
Fig. 4 is the absorbancy comparison diagram of the hydrogel before hydrogel and the variable color after UV-irradiation variable color.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Step 2, get 0.80 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
1, step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm;
After step 4, dropping finish, stop stirring, leave standstill 2 h;
Adopt above consumption and preparation method can not form hydrogel, its reason is phospho-wolframic acid add-on deficiency.
Embodiment 2
Step 2, get 0.83 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, obtain ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 3
Step 2, get 0.83 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, CMC solution is slowly added drop-wise in Salkowski's solution;
After step 4, dropping finish, stop stirring, leave standstill 2 h;
Can not form hydrogel, reason is that the mode that adds of CMC and Salkowski's solution is not right.
Embodiment 4
Step 2, the CMC that is 1.0 by 0.60g substitution value join in phosphotungstic acid aqueous solution, are stirred to dissolving;
After step 3, CMC all dissolve, stop stirring, leave standstill 2 h;
Can not form hydrogel.
Embodiment 5
Step 2, get 0.85g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 6
Step 2, get 0.90 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 7
Step 2, get 0.95 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 8
Step 2, get 1.00 g phospho-wolframic acids and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 9
Step 2, get 1.10 g phospho-wolframic acids and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution;
After step 4, dropping finish, stop stirring, leave standstill 2 h;
Can not form hydrogel, reason is that phospho-wolframic acid is excessive.
Step 2, get 0.70 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution;
After step 4, dropping finish, stop stirring, leave standstill 2 h;
Can not form hydrogel, reason is phospho-wolframic acid deficiency.
Embodiment 11
Step 2, get 0.80g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 12
Step 2, get 0.90 g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again, and its process is referring to Fig. 2, Fig. 3 and 4.
Embodiment 13
Step 2, get 1.00 g phospho-wolframic acids and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 14
Step 2, get 1.10g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 15
Step 2, get 1.15 g phospho-wolframic acids and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution;
After step 4, dropping finish, stop stirring, leave standstill 2 h;
Can not form hydrogel, reason is that phospho-wolframic acid is excessive.
Embodiment 16
Step 2, get 0.90g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, CMC solution is slowly added drop-wise in Salkowski's solution;
After step 4, dropping finish, stop stirring, leave standstill 2 h;
Can not form hydrogel.
Embodiment 17
Step 2, get 0.55g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 18
Step 2, get 1.00g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 19
Step 2, get 2.05g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Embodiment 20
Step 2, get 2.10g phospho-wolframic acid and join in 10g water, concussion is to dissolving;
Step 3, under the condition of magnetic agitation, Salkowski's solution is slowly added drop-wise in CMC solution, stirring velocity is greater than 1000rpm, Salkowski's solution is no more than 10s/ and drips;
After step 4, dropping finish, stop stirring, leave standstill 2 h, form ability of reverse photochromism hydrogel.
Gained hydrogel is irradiated under ultraviolet lamp to 5 h left and right, hydrogel becomes blueness, and the hydrogel of variable color is placed in to 5 h left and right, dark place, and hydrogel becomes colorless again.
Claims (4)
1. a carboxymethyl cellulose-based ability of reverse photochromism hydrogel, it is characterized in that: it is to be mixed to get by carboxymethyl cellulose aqueous solution and phosphotungstic acid aqueous solution, the mode of mixing is: phosphotungstic acid aqueous solution dropwise and is slowly joined in carboxymethyl cellulose aqueous solution, mix simultaneously by magnetic agitation; The concentration of described carboxymethyl cellulose aqueous solution is between 1%-5%, and substitution value is between 0.6-1.8, and the concentration of phosphotungstic acid aqueous solution is 5%-30%.
2. a preparation method for carboxymethyl cellulose-based ability of reverse photochromism hydrogel, is characterized in that: comprise the steps:
Step 1, prepare carboxymethyl cellulose aqueous solution, the concentration of carboxymethyl cellulose aqueous solution is between 1%-5%, and the substitution value of carboxymethyl cellulose is between 0.6-1.8;
Step 2, prepare phosphotungstic acid aqueous solution, concentration is 5%-30%;
Step 3, under magnetic agitation, the carboxymethyl cellulose aqueous solution that the phosphotungstic acid aqueous solution of step 2 gained is made with step 1 mixes, phosphotungstic acid aqueous solution and carboxymethyl cellulose aqueous solution mass ratio are between 1:1.7～2.0, and hybrid mode is that phosphotungstic acid aqueous solution dropwise and slowly joins in carboxymethyl cellulose aqueous solution;
Step 4, stop stirring, leave standstill more than 2 h, can obtain carboxymethyl cellulose-based ability of reverse photochromism hydrogel.
3. carboxymethyl cellulose-based ability of reverse photochromism hydrogel preparation method according to claim 2, is characterized in that: phosphotungstic acid aqueous solution drips is fastestly no more than 1/10 drop/sec of clock.
4. the carboxymethyl cellulose-based ability of reverse photochromism hydrogel of one according to claim 2 preparation method, is characterized in that: the speed of described magnetic agitation is greater than 1000rpm.
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