CN102492153A - Preparation method of photosensitive hydrogel - Google Patents
Preparation method of photosensitive hydrogel Download PDFInfo
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- CN102492153A CN102492153A CN2011103598583A CN201110359858A CN102492153A CN 102492153 A CN102492153 A CN 102492153A CN 2011103598583 A CN2011103598583 A CN 2011103598583A CN 201110359858 A CN201110359858 A CN 201110359858A CN 102492153 A CN102492153 A CN 102492153A
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Abstract
The invention discloses a preparation method of photosensitive hydrogel. The method comprises 3 steps that: 1, modified cyclodextrin is subject to a reaction with polyacrylic acid, such that cyclodextrin-modified polyacrylic acid is obtained; 2, azobenzene substituted by monoamino is subject to a reaction with polyacrylic acid, such that azobenzene-modified polyacrylic acid is synthesized; and 3, the two polymers are mixed, such that the photosensitive hydrogel is obtained. When the photosensitive hydrogel is irradiated by using ultraviolet light with a certain wavelength, the viscosity of the photosensitive hydrogel is substantially reduced, and the photosensitive hydrogel turns into a movable solution. When irradiation is stopped, a gel state is recovered. The photosensitive hydrogel can be used for preparing light-controlled motors and light-controlled switches. The photosensitive hydrogel can also be used in light-controlled drug-releasing.
Description
Technical field
The present invention relates to a kind of intelligent polymer material technology; Be specially a kind of intelligent type macromolecule water gel of optical Response; Promptly viscosity significantly reduces to become flowable solution under the UV-irradiation of certain wavelength; Stop to be returned to original gel state fully after the illumination, belong to new material technology field.
Background technology
Progress in Intelligent Hydrogel is the hydrophilic polymer that environment (like temperature, pH value, electricity, light, magnetic field, specific biological molecules etc.) is small to external world variation or stimulation have the three-dimensional net structure of significantly replying, and has broad application prospects at aspects such as drug release, chemical separation, chemical sensor and catalyzer.Molecule with the reversible isomerizing characteristic of light can change by occurred conformation under illumination, like nitrogen benzide and verivate thereof reversible cis-trans isomerization reaction can take place under UV-irradiation, can prepare the photosensitivity hydrogel with it as the photosensitivity group.The preparation method of this kind photosensitivity hydrogel utilizes the method for homopolymerization or copolymerization that the photosensitivity group is introduced main polymer chain or side chain at present; The substituted nitrogen benzide of Zhao Yi equality people elder generation synthesis of vinyl for example, in the presence of linking agent and initiator again with acrylic amide copolymerization (one Chinese patent application number: 200610016425.7).But restive products therefrom molecular weight of the method for this copolymerization or homopolymerization and MWD, the product property difference that obtains is big, and optical Response is obvious inadequately.
The present invention adopts a kind of novel method; Be grafted to alpha-cylodextrin and the substituted nitrogen benzide of mono amino on the ROHM respectively; Then that both are composite, utilize the light sensitive characteristic of inclusion ability and the nitrogen benzide of Schardinger dextrins to prepare one type and have the novel photosensitivity aquogel system that sol-gel changes behavior mutually.The preparation method is easy to control, and optical Response is more responsive, more obvious.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of photosensitivity hydrogel, viscosity significantly reduces to become flowable solution under the UV-irradiation of certain wavelength so that reach, and stops to be returned to fully after the illumination effect of original gel state.This photosensitivity hydrogel can be applicable to light-operated motor, photoswitch and light-operated drug release etc.
A kind of preparation method of photosensitivity hydrogel comprises the steps:
(1) ROHM of preparation nitrogen benzide modification: under 60～70 ° of C, ROHM is dissolved in the N-N-methyl-2-2-pyrrolidone N-, adds the substituted nitrogen benzide of mono amino then, add dewatering agent again, stirring reaction is 48～96 hours under 60～70 ° of C; The aqueous sodium hydroxide solution of adding 30～35% must precipitate after the stirring, and suction filtration after scouring, dialysis, drying get the ROHM that the title product nitrogen benzide is modified;
Above-mentioned sedimentary treatment process can be: the N-N-methyl-2-2-pyrrolidone N-of precipitated solid with 60～70 ° of C washed 2～3 times, and each consumption is identical with the volume of aqueous sodium hydroxide solution.The gained solid is dissolved in deionized water after using methanol wash 2～3 times again, and with the deionized water dialysis, obtains title product after the freeze-drying;
The mass ratio of said ROHM and said N-N-methyl-2-2-pyrrolidone N-is 1: 25～35;
Substituted nitrogen benzide of said mono amino and said polyacrylic mass ratio are 0.2～0.5:1;
The mol ratio of substituted nitrogen benzide of said mono amino and said dewatering agent is 1:1～1.2;
Said aqueous sodium hydroxide solution and said N-N-methyl-2-2-pyrrolidone N-volume ratio are 1～1.2:1;
(2) preparation photosensitivity hydrogel: will cyclodextrin modified ROHM and the ROHM of the said nitrogen benzide modification that obtains of step (1) be dissolved in uniform mixing behind the deionized water respectively, obtain said photosensitivity hydrogel; The polyacrylic mass concentration sum of above-mentioned two kinds of modifications is 3～8%.
Wherein, the mol ratio of Schardinger dextrins group and azobenzene group is 1:3～3:1.
Said cyclodextrin modified ROHM is that the method that the Chinese invention patent application of CN101717517A is described makes according to publication number.
Said dewatering agent is N, N'-DIC, dicyclohexyl carbimide or 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide.
Said Schardinger dextrins is the a-Schardinger dextrins.
The substituted nitrogen benzide of said mono amino is that the ortho position amino replaces, a bit amino replaces or to the substituted nitrogen benzide of bit amino.
Innovative point of the present invention is, utilizes the inclusion characteristic of Schardinger dextrins and the light isomery characteristic of nitrogen benzide to prepare a kind of novel photosensitivity hydrogel, and the preparation method is easier, be easy to control.Hydrogel with this method preparation has good responsiveness to UV-light; Promptly viscosity significantly reduces to become flowable solution under the UV-irradiation of certain wavelength; Stop to be returned to original gel state fully after the illumination, and this process can be carried out repeatedly reversiblely.Photosensitivity hydrogel of the present invention is applied widely, especially is expected to be applied at aspects such as optical element such as light-operated motor, photoswitch, light-operated drug release.
The accompanying drawing instance
Fig. 1 is zero the cut viscosity variation diagram of photosensitivity hydrogel before and after UV-irradiation of embodiment 1 preparation;
Fig. 2 is zero the cut viscosity variation diagram of photosensitivity hydrogel before and after UV-irradiation of embodiment 2 preparations;
Fig. 3 is zero the cut viscosity variation diagram of photosensitivity hydrogel before and after UV-irradiation of embodiment 3 preparations.
Embodiment
Below, further specify the present invention with embodiment, but protection scope of the present invention is not limited in embodiment.The variation and the modification of other that those skilled in the art is made under the situation that does not deviate from spirit of the present invention and protection domain still are included within the protection domain of the present invention.
Step a: the mass ratio by ROHM and N-N-methyl-2-2-pyrrolidone N-is that 1:25 is dissolved in ROHM in the N-N-methyl-2-2-pyrrolidone N-under 60 ° of C; Then with P-aminoazobenzene with the ROHM mass ratio be that 0.2:1 adds; By P-aminoazobenzene and dicyclohexyl carbimide mol ratio is that 1:1 adds dewatering agent dicyclohexyl carbimide; Stirring reaction is 48 hours under 60 ° of C; In reacted material, be that 1:1 adds 30% aqueous sodium hydroxide solution by aqueous sodium hydroxide solution and N-N-methyl-2-2-pyrrolidone N-volume ratio; Must precipitate after the stirring, behind the suction filtration solid washed 2 times with 60 ° of C N-N-methyl-2-2-pyrrolidone N-s, consumption is identical with the volume of aqueous sodium hydroxide solution.The gained solid with methanol wash 3 times after, be dissolved in deionized water, and, obtain the ROHM that the title product nitrogen benzide is modified after the freeze-drying with deionized water dialysis;
Step b: getting cyclodextrin modified ROHM and making the mol ratio of Schardinger dextrins group and azobenzene group with ROHM that nitrogen benzide is modified is 1:1, is dissolved in uniform mixing behind the deionized water respectively, promptly gets said product photosensitivity hydrogel; The polyacrylic mass concentration sum of above-mentioned two kinds of modifications is 4%.
This routine product lucifuge left standstill 3 days; Using wavelength then is the UV-irradiation of 365 nanometers, becomes flowable solution, with its zero viscosity degradation about 93% of cutting of senior rotational rheometer test; Its again lucifuge left standstill 3 days; Can be returned to original gel state, this variation can be handled with UV-irradiation and lucifuge and take place repeatedly reversiblely, and is as shown in Figure 1.
Embodiment 2
Step a: the mass ratio by ROHM and N-N-methyl-2-2-pyrrolidone N-is that 1:30 is dissolved in ROHM in the N-N-methyl-2-2-pyrrolidone N-under 65 ° of C; Then with P-aminoazobenzene with the ROHM mass ratio be that 0.3:1 adds; By P-aminoazobenzene and dicyclohexyl carbimide mol ratio is that 1:1.1 adds dewatering agent dicyclohexyl carbimide; Stirring reaction is 72 hours under 65 ° of C; In reacted material, be that 1.2:1 adds 35% aqueous sodium hydroxide solution by aqueous sodium hydroxide solution and N-N-methyl-2-2-pyrrolidone N-volume ratio; Must precipitate after the stirring, behind the suction filtration solid washed 3 times with 65 ° of C N-N-methyl-2-2-pyrrolidone N-s, consumption is identical with the volume of aqueous sodium hydroxide solution.The gained solid with methanol wash 2 times after, be dissolved in deionized water, and, obtain the ROHM that the title product nitrogen benzide is modified after the freeze-drying with deionized water dialysis.
Step b: getting cyclodextrin modified ROHM and making the mol ratio of Schardinger dextrins group and azobenzene group with ROHM that nitrogen benzide is modified is 1:1, is dissolved in uniform mixing behind the deionized water respectively, promptly gets said product hydrogel; The polyacrylic mass concentration sum of above-mentioned two kinds of modifications is 6%.
This routine product lucifuge left standstill 3 days, and using wavelength then is the UV-irradiation of 365 nanometers, and viscosity degradation 96% becomes flowable solution, and lucifuge left standstill 3 days again, can be returned to original gel state.It zero cuts viscosity change with the test of senior rotational rheometer, and is as shown in Figure 2.
Step a: the mass ratio by ROHM and N-N-methyl-2-2-pyrrolidone N-is that 1:35 is dissolved in ROHM in the N-N-methyl-2-2-pyrrolidone N-under 70 ° of C; Then with P-aminoazobenzene with the ROHM mass ratio be that 0.5:1 adds; By P-aminoazobenzene and dicyclohexyl carbimide mol ratio is that 1:1.2 adds dewatering agent dicyclohexyl carbimide; Stirring reaction is 96 hours under 70 ° of C; In reacted material, be that 1.2:1 adds 35% aqueous sodium hydroxide solution by aqueous sodium hydroxide solution and N-N-methyl-2-2-pyrrolidone N-volume ratio; Must precipitate after the stirring, behind the suction filtration solid washed 2 times with 70 ° of C N-N-methyl-2-2-pyrrolidone N-s, consumption is identical with the volume of aqueous sodium hydroxide solution.The gained solid with methanol wash 3 times after, be dissolved in deionized water, and, obtain the ROHM that the title product nitrogen benzide is modified after the freeze-drying with deionized water dialysis.
Step b: getting cyclodextrin modified ROHM and making the mol ratio of Schardinger dextrins group and azobenzene group with ROHM that nitrogen benzide is modified is 1:1, is dissolved in uniform mixing behind the deionized water respectively, promptly gets said product hydrogel; The polyacrylic mass concentration sum of above-mentioned two kinds of modifications is 8%.
This routine product lucifuge left standstill 3 days, and using wavelength then is the UV-irradiation of 365 nanometers, becomes flowable solution, with the test of senior rotational rheometer its zero to cut viscosity degradation about 92%, lucifuge left standstill 3 days again, can be returned to original gel state.It zero cuts viscosity change with the test of senior rotational rheometer, and is as shown in Figure 3.
It is above-mentioned that to state cyclodextrin modified ROHM be that the method that the Chinese invention patent application of CN101717517A is described makes according to publication number.
Claims (5)
1. the preparation method of a photosensitivity hydrogel is characterized in that, comprises the steps:
(1) ROHM of preparation nitrogen benzide modification: under 60～70 ° of C, ROHM is dissolved in the N-N-methyl-2-2-pyrrolidone N-, adds the substituted nitrogen benzide of mono amino then, add dewatering agent again, stirring reaction is 48～96 hours under 60～70 ° of C; The aqueous sodium hydroxide solution of adding 30～35% must precipitate after the stirring, and suction filtration after scouring, dialysis, drying get the ROHM that the title product nitrogen benzide is modified;
The mass ratio of said ROHM and said N-N-methyl-2-2-pyrrolidone N-is 1:25～35;
Substituted nitrogen benzide of said mono amino and said polyacrylic mass ratio are 0.2～0.5:1;
The mol ratio of substituted nitrogen benzide of said mono amino and said dewatering agent is 1:1～1.2;
Said aqueous sodium hydroxide solution and said N-N-methyl-2-2-pyrrolidone N-volume ratio are 1～1.2:1;
(2) preparation photosensitivity hydrogel: will cyclodextrin modified ROHM and the ROHM of the said nitrogen benzide modification that obtains of step (1) be dissolved in uniform mixing behind the deionized water respectively, compositely obtain said photosensitivity hydrogel; The said cyclodextrin modified ROHM and the polyacrylic mass concentration sum of said nitrogen benzide modification are 3～8%; Wherein, the mol ratio of Schardinger dextrins group and azobenzene group is 1:3～3:1.
2. preparation method according to claim 1 is characterized in that, said cyclodextrin modified ROHM is that the method that the Chinese invention patent application of CN101717517A is described makes according to publication number.
3. preparation method according to claim 1 is characterized in that said dewatering agent is N, N'-DIC, dicyclohexyl carbimide or 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide.
4. preparation method according to claim 1 and 2 is characterized in that, said Schardinger dextrins is the a-Schardinger dextrins.
5. preparation method according to claim 1 is characterized in that, the substituted nitrogen benzide of said mono amino is that the ortho position amino replaces, a bit amino replaces or to the substituted nitrogen benzide of bit amino.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936826A (en) * | 2013-10-08 | 2014-07-23 | 南京大学 | Photosensitive supramolecular hydrogel forming factor, and preparation method and application thereof |
| CN104311844A (en) * | 2014-04-01 | 2015-01-28 | 东南大学 | Light-controlled hydrogel based on P(MVE-alt-MA), and preparation method thereof |
| CN106632857A (en) * | 2016-11-16 | 2017-05-10 | 宁波大学 | Self-repaired hydrogel and preparation method thereof |
| CN107384890A (en) * | 2017-09-04 | 2017-11-24 | 吉林大学 | The intelligent glutathione S-transferase constructed based on photoresponse oversubscription sub switch |
| CN109749025A (en) * | 2019-02-26 | 2019-05-14 | 哈尔滨工业大学 | A kind of 4D prints preparation and the Method of printing of self-healing hydrogel material |
| CN110372887A (en) * | 2019-07-30 | 2019-10-25 | 西安石油大学 | A kind of self-healing property photoresponse supermolecule fluorescence hydrogel and its preparation method and application |
| CN112138636A (en) * | 2020-08-19 | 2020-12-29 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
| CN112708149A (en) * | 2020-12-24 | 2021-04-27 | 山东师范大学 | Reversible photosensitive hydrogel and preparation method and application thereof |
| CN112826791A (en) * | 2021-01-13 | 2021-05-25 | 中国药科大学 | Light-controlled hydrogel microneedle array patch and preparation method thereof |
| CN114409908A (en) * | 2021-11-25 | 2022-04-29 | 山东师范大学 | Polyurethane, single-component light-sensitive reversible hydrogel, and preparation method and application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936826A (en) * | 2013-10-08 | 2014-07-23 | 南京大学 | Photosensitive supramolecular hydrogel forming factor, and preparation method and application thereof |
| CN104311844A (en) * | 2014-04-01 | 2015-01-28 | 东南大学 | Light-controlled hydrogel based on P(MVE-alt-MA), and preparation method thereof |
| CN106632857A (en) * | 2016-11-16 | 2017-05-10 | 宁波大学 | Self-repaired hydrogel and preparation method thereof |
| CN106632857B (en) * | 2016-11-16 | 2018-10-16 | 宁波大学 | A kind of selfreparing hydrogel and preparation method thereof |
| CN107384890A (en) * | 2017-09-04 | 2017-11-24 | 吉林大学 | The intelligent glutathione S-transferase constructed based on photoresponse oversubscription sub switch |
| CN107384890B (en) * | 2017-09-04 | 2020-10-13 | 吉林大学 | Intelligent glutathione-S-transferase constructed based on photoresponse supermolecule switch |
| CN109749025A (en) * | 2019-02-26 | 2019-05-14 | 哈尔滨工业大学 | A kind of 4D prints preparation and the Method of printing of self-healing hydrogel material |
| CN110372887B (en) * | 2019-07-30 | 2022-01-28 | 西安石油大学 | Self-healing photoresponse supramolecular fluorescent hydrogel and preparation method and application thereof |
| CN110372887A (en) * | 2019-07-30 | 2019-10-25 | 西安石油大学 | A kind of self-healing property photoresponse supermolecule fluorescence hydrogel and its preparation method and application |
| CN112138636A (en) * | 2020-08-19 | 2020-12-29 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
| CN112138636B (en) * | 2020-08-19 | 2023-04-07 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
| CN112708149A (en) * | 2020-12-24 | 2021-04-27 | 山东师范大学 | Reversible photosensitive hydrogel and preparation method and application thereof |
| CN112826791A (en) * | 2021-01-13 | 2021-05-25 | 中国药科大学 | Light-controlled hydrogel microneedle array patch and preparation method thereof |
| CN112826791B (en) * | 2021-01-13 | 2023-11-03 | 中国药科大学 | Light-operated hydrogel microneedle array patch and preparation method thereof |
| CN114409908A (en) * | 2021-11-25 | 2022-04-29 | 山东师范大学 | Polyurethane, single-component light-sensitive reversible hydrogel, and preparation method and application thereof |
| CN114409908B (en) * | 2021-11-25 | 2023-01-20 | 山东师范大学 | Polyurethane, single-component light-sensitive reversible hydrogel, and preparation method and application thereof |
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Application publication date: 20120613 |