CN107434851A - A kind of preparation method of Photosensitive hydrogel - Google Patents
A kind of preparation method of Photosensitive hydrogel Download PDFInfo
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- CN107434851A CN107434851A CN201710796219.0A CN201710796219A CN107434851A CN 107434851 A CN107434851 A CN 107434851A CN 201710796219 A CN201710796219 A CN 201710796219A CN 107434851 A CN107434851 A CN 107434851A
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C08J2305/16—Cyclodextrin; Derivatives thereof
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Abstract
The invention discloses a kind of preparation method of Photosensitive hydrogel, comprise the following steps：1) PEG is modified, prepares PEG Azo；2) PEG Azo and α CD are subjected to Supramolecular self assembly, obtain Photosensitive hydrogel.The preparation method of the present invention is simple, and the defects of Subjective and Objective material biology is incompatible be present mainly for prior art, the inventive method is during hydrogel is prepared, Subjective and Objective material used is respectively provided with good bio-compatibility, and the transformation of collosol and gel can be achieved in the hydrogel of acquisition under ultraviolet-visible.
Description
Technical field
The present invention relates to a kind of preparation method of Photosensitive hydrogel, category new function material field.
Background technology
Hydrogel is a kind of soft material of high degree of water, is widely used in the neck such as beauty, shaping, medical treatment, medical research
Domain, added value is high, causes international extensive concern with paying attention to.Wherein, there is the hydrogel (intelligence of special work(functional group
Can hydrogel) can to the change of external environment, such as temperature, light, magnetic and pH, react so as to causing gel in physics or
Change in person's chemical property.On the other hand, the self assembly of molecule can by the intermolecular forces and three-dimensional effect of its molecule come
Supermolecule of the structure with specific structure module units.
To sum up, by the functional group with optical Response, such as：Azobenzene, it is incorporated on host molecule, then in supramolecular chemistry
Driving force under with guest molecule carry out self assembly, a kind of hydrogel with light sensitivity can be prepared, with realize colloidal sol-coagulate
The transformation of glue.At present, the patent document of China's Subjective and Objective-Photosensitive hydrogel also has many reports, but its material of main part is mostly
It is that secondary high molecular polymerization (Jinze Li, Zheng Zhou, Li Ma, Guangxin Chen and are carried out to high polymer material
Qifang Li,Hierarchical assembly of amphiphilic POSS-Cyclodextrin Molecules
and Azobenzene End-Capped Polymers[J],Macromolecules,2014,47,5739-5748；Jinze
Li,Li Ma,Guangxin Chen,Zheng Zhou,and Qifang Li,High water-content and high
elastic dual-responsive polyurethane hydrogel for drug delivery[J].Journal of
Materials Chemistry B,2015,3,8401-8409).Patent 201110359858.3 be by modified cyclodextrin with
Azobenzene small molecule passes through the Photosensitive hydrogel prepared by the self assembly of Subjective and Objective.Patent 201611030280.6 is first by ring
Dextrin and epichlorohydrin reaction generation copolymer, are obtained with azobenzene acrylamide by Host guest complexation again afterwards
Crosslinking agent, finally it is copolymerized to obtain hydrogel with the water-soluble monomer such as this crosslinking agent and acrylamide.
The above article and patent have been respectively adopted different Subjective and Objective molecules and have prepared Photosensitive hydrogel, but in the presence of one
A little problems：(1) initiator is often used when synthesizing high molecular polymerization, it is difficult to be removed in last handling process, so as to
It has impact on the purity of hydrogel component.(2) the Subjective and Objective molecule for forming hydrogel all has certain biological incompatibility.
The content of the invention
The defects of Subjective and Objective material biology is incompatible be present for prior art, the present invention, which provides one kind, has bio-compatible
The Photosensitive hydrogel of property.During hydrogel is prepared, Subjective and Objective material used is respectively provided with good biological simultaneous this method
Capacitive, and under ultraviolet-visible light can be achieved sol-gel transformation.
In order to solve the above-mentioned technical problem, used scheme is the present invention：
A kind of preparation method of Photosensitive hydrogel, comprises the following steps：
1) the high polymer material PEG (polyethylene glycol) with good biological compatibility performance is modified, first synthesizes PEG-
Br macromoleculars, and 4- hydroxyl -4'- Methoxy-azobenzenes (Azo) are synthesized, PEG- is prepared using PEG-Br and Azo again as raw material
Azo；
2) PEG-Azo and α-CD is subjected to Supramolecular self assembly, obtains Photosensitive hydrogel.
In above-mentioned technical proposal, further, PEG-Br macromoleculars can be synthesized with the following method：By 2- bromine isobutyryls
The THF solution of bromine is added dropwise in the THF solution containing triethylamine and PEG, is reacted 1h at 0 DEG C and is then reacted 10h at room temperature again,
Obtain white paste product PEG-Br.
Further, Azo can be synthesized with the following method：By the aqueous solution, acetone and hydrochloric acid of P-nethoxyaniline
Solution is added drop-wise in the aqueous solution of natrium nitrosum respectively at 0 DEG C, then the aqueous solution of phenol and NaOH is respectively added to above-mentioned
In mixed liquor and continue to stir 15h, obtain khaki solid Azo.
The method for preparing PEG-Azo is specific as follows：PEG-Br is dissolved in chloroformic solution, is stirred vigorously down and adds according to this
Azo、K2CO3, using KI as catalyst, and PEG-Br, Azo, K2CO3Mol ratio be 1:1:1, flow back 50h at 60 DEG C；Reaction
After end, product fully to be washed with water, obtained organic phase obtains crude product after removing dissolution solvent by rotary evaporation,
Crude product is re-dissolved in water, is collected by filtration aqueous phase, dry product PEG-Azo.
Main body PEG-Azo and object α-CD are dissolved in water, obtain the PEG-Azo aqueous solution and the α-CD aqueous solution,
Two kinds of solution are mixed at room temperature and carry out molecular self-assembling so that PEG-Azo is 1 with α-CD mol ratios:2, stirring, obtain light
Quick type hydrogel.
The beneficial effects of the present invention are：
For the method for the present invention during hydrogel is prepared, Subjective and Objective material used is respectively provided with good bio-compatible
Property, and under ultraviolet-visible light can be achieved sol-gel transformation, obtain Photosensitive hydrogel.
Brief description of the drawings
Fig. 1 is the process chart that the present invention prepares Photosensitive water-setting gluing method；(1) synthesize PEG-Br, (2) synthesis Azo,
(3) PEG-Azo, (4) Supramolecular self assembly；
Fig. 2 is under the ultraviolet irradiation (a) of hydrogel (after dyeing) made from the embodiment of the present invention 2 and radiation of visible light (b)
Mobility photo.
Embodiment
The application is described in further detail with reference to the accompanying drawings and examples, it is to be understood that retouch in this place
The specific embodiment stated is used only for explaining related invention, rather than the restriction to the invention.It also should be noted that in order to
It is easy to describe, the part related to invention is illustrate only in accompanying drawing.
It should be noted that in the case where not conflicting, the feature in embodiment in the application can be mutually combined.Under
Face describes the application in detail by refer to the attached drawing and in conjunction with the embodiments.
1.PEG-Azo synthesis
PEG-Azo synthesis：
The THF solution of 2- bromine isobutyl acylbromides is added dropwise in the THF solution containing triethylamine and PEG, 0 DEG C react 1h with
React 10h at room temperature again afterwards, obtain white paste product PEG-Br；
The aqueous solution, acetone and hydrochloric acid solution of P-nethoxyaniline are added drop-wise to the water of natrium nitrosum respectively at 0 DEG C
In solution, then the aqueous solution of phenol and NaOH is respectively added in above-mentioned mixed liquor and continues to stir 15h, obtained khaki and consolidate
Body Azo；
PEG-Br (2.2g, 0.22mmol) is dissolved in 20mL chloroformic solution, then added according to this under vigorous stirring
Enter Azo (0.052g, 0.23mmol), K2CO3(0.03g, 0.22mmol), and a small amount of KI, flow back 50h at 60 DEG C.Reaction terminates
Afterwards, product is washed with substantial amounts of water, obtained organic phase obtains crude product after removing dissolution solvent by rotary evaporation.Slightly
Product is re-dissolved in water, is collected by filtration aqueous phase, dry product 2.0g (yields：89%).
2. the preparation of Photosensitive hydrogel
Embodiment 1：By the PEG-Azo aqueous solution and the α-CD aqueous solution at room temperature, according to mol ratio 1：1 is mixed.
Under stirring, no gel generation.Under ultraviolet irradiation, also without Sol-gel phase transition phenomenon.
Embodiment 2：By the PEG-Azo aqueous solution and the α-CD aqueous solution at room temperature, according to mol ratio 1：2 are mixed.
Under stirring, no gel generation.Then it is to be irradiated under 365nm uviol lamp exposed to wavelength by this colloidal sol, it is found that colloidal sol gradually coagulates
Admittedly being changed into gel, i.e., this example obtains Photosensitive hydrogel.
Embodiment 3：By the PEG aqueous solution and the α-CD aqueous solution at room temperature, according to mol ratio 1：3 are mixed.Stirring
Under, there is gel generation.Then it is to be irradiated under 365nm uviol lamp exposed to wavelength by this gel, it is found that phase will not occur for gel
Transformation.
Claims (7)
1. a kind of preparation method of Photosensitive hydrogel, it is characterised in that it comprises the following steps：
1) PEG is modified, prepares PEG-Azo；
2) PEG-Azo and α-CD is subjected to Supramolecular self assembly, obtains Photosensitive hydrogel.
2. the preparation method of Photosensitive hydrogel according to claim 1, it is characterised in that described step 1) is specifically wrapped
Include following steps：
1. synthesize PEG-Br macromoleculars；
2. synthesize 4- hydroxyl -4'- Methoxy-azobenzenes (Azo)；
3. synthesize PEG-Azo.
3. the preparation method of Photosensitive hydrogel according to claim 2, it is characterised in that described step is 1. as follows：
The THF solution of 2- bromine isobutyl acylbromides is added dropwise in the THF solution containing triethylamine and PEG, 1h is reacted at 0 DEG C then again
10h is reacted at room temperature, obtains white paste product PEG-Br.
4. the preparation method of Photosensitive hydrogel according to claim 2, it is characterised in that described step is 2. as follows：
The aqueous solution, acetone and hydrochloric acid solution of P-nethoxyaniline are added drop-wise to the aqueous solution of natrium nitrosum respectively at 0 DEG C
In, then the aqueous solution of phenol and NaOH is respectively added in above-mentioned mixed liquor and continues to stir 15h, obtain khaki solid
Azo。
5. the preparation method of Photosensitive hydrogel according to claim 2, it is characterised in that described step is 3. as follows：
PEG-Br is dissolved in chloroformic solution, is stirred vigorously down and adds Azo, K according to this2CO3, using KI as catalyst, and PEG-
Br、Azo、K2CO3Mol ratio be 1:1:1, flow back 50h at 60 DEG C；After reaction terminates, product is fully washed with water, obtained
The organic phase arrived obtains crude product after removing dissolution solvent by rotary evaporation, and crude product is re-dissolved in water, and water is collected by filtration
Phase, dry product PEG-Azo.
6. the preparation method of Photosensitive hydrogel according to claim 1, it is characterised in that described step 2) is included such as
Lower step：
PEG-Azo and α-CD are dissolved in water, obtain the PEG-Azo aqueous solution and the α-CD aqueous solution, at room temperature by this two
Kind solution mixing so that PEG-Azo is 1 with α-CD mol ratios:2, stirring, obtain Photosensitive hydrogel.
7. a kind of Photosensitive hydrogel, it is characterised in that be prepared using the method as described in claim any one of 1-6.
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| CN201710796219.0A CN107434851B (en) | 2017-09-06 | 2017-09-06 | Preparation method of photosensitive hydrogel |
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| CN201710796219.0A CN107434851B (en) | 2017-09-06 | 2017-09-06 | Preparation method of photosensitive hydrogel |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133596A (en) * | 2021-12-15 | 2022-03-04 | 山东理工大学 | Preparation and application of ABA type photosensitive gel |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023270A1 (en) * | 2005-08-20 | 2007-03-01 | Smart Tech Limited | Hydratable polymer materials |
| CN102268460A (en) * | 2011-07-20 | 2011-12-07 | 浙江大学 | Method for preparing photo-responsive PEGylation gene transfer system assembled on basis of subject and object |
-
2017
- 2017-09-06 CN CN201710796219.0A patent/CN107434851B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023270A1 (en) * | 2005-08-20 | 2007-03-01 | Smart Tech Limited | Hydratable polymer materials |
| CN102268460A (en) * | 2011-07-20 | 2011-12-07 | 浙江大学 | Method for preparing photo-responsive PEGylation gene transfer system assembled on basis of subject and object |
Non-Patent Citations (2)
| Title |
|---|
| 冀璐康等: "光响应的超分子水凝胶的制备及其应用研究", 《中国化学会第30届学术年会摘要集-第二十四分会：超分子组装与软物质材料》 * |
| 黄飞鹤等: "《超分子聚合物》", 30 April 2012 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114133596A (en) * | 2021-12-15 | 2022-03-04 | 山东理工大学 | Preparation and application of ABA type photosensitive gel |
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