CN1296400C - Biodegradable hydrogel and method for preparing same - Google Patents
Biodegradable hydrogel and method for preparing same Download PDFInfo
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- CN1296400C CN1296400C CNB2004100133160A CN200410013316A CN1296400C CN 1296400 C CN1296400 C CN 1296400C CN B2004100133160 A CNB2004100133160 A CN B2004100133160A CN 200410013316 A CN200410013316 A CN 200410013316A CN 1296400 C CN1296400 C CN 1296400C
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Abstract
The present invention discloses biodegradable hydrogel and a preparation method thereof. The preparation method comprises the following steps: firstly, macropore konjac glucomannan hydrogel is prepared; fine konjaku flour is weighed, and then, the konjaku flour is dissolved in distilled water and is stirred; inorganic base is added to regulate the pH value; certain temperature and time are controlled to carry out crosslink; products are washed with water and are repeatedly frozen and thawed for several times for freeze drying; secondly, the macropore konjac glucomannan hydrogel is swelled in a water solution with certain proportion of crylic acid, a crosslinking agent and an initiating agent, and certain temperature and time are controlled for polymerization; obtained products are washed with water and are dried. The present invention has the advantages of convenience, efficiency and no use of organic solvents in reaction. Obtained hydrogel has good biodegradability and pH response performance, and can absorb or embed medicine for the controlled release of the medicine. The present invention has multiple uses in the fields of biological chemistry, medicine, agriculture, chemical industry concerned with products for daily use, etc.
Description
Technical field
The present invention relates to field of biomedical polymer materials, more specifically relate to a kind of biodegradable hydrogel, the preparation method who also relates to the biodegradable hydrogel simultaneously, it is the interpenetrating polymer networks that crosslinked by the Rhizoma amorphophalli glucomannan thermokalite, that freeze thawing treatment obtains gel and polyacrylic acid constitute.
Background technology
Macromolecule hydrogel is the network size of hydrophilic high mol, its swellable and keep large quantity of moisture and don't dissolving in water.Hydrogel has caused scientific worker's common concern in many purposes in fields such as biological chemistry, medical science, agricultural, daily-use chemical industry.Polyacrylic acid hydrogel is the very wide synthesized polymer material of a kind of application, has the pH responsiveness, on the drug oral preparation good prospects for application is arranged.But because its non-biodegradation has limited its application aspect biological medicine.
The stem tuber of konjaku is rich in Rhizoma amorphophalli glucomannan, and it is the main component of konjaku powder, account for dry product heavy 50%～60%.Rhizoma amorphophalli glucomannan has many good properties as a kind of natural macromolecule amylose, such as biocompatibility, and film-forming properties, biodegradable etc.Can be applicable to food, biochemistry, medicine and daily life all respects.Deacetylation takes place when Rhizoma amorphophalli glucomannan heats under the effect of alkali, and self-crosslinking forms the gel of heat irreversible.
Freeze-thaw technology is a kind of comparatively easy method of preparation macropore hydrogel, for example takes the method for freeze thawing to obtain the physical cross-linking hydrogel of polyvinyl alcohol, and its strength ratio not gel of freeze thawing treatment increases.Natural polymer and synthetic macromolecule form interpenetrating polymer networks (IPN), can have both characteristics concurrently, can improve the mechanical property of material simultaneously.In our the former research work, (CN 02139036.3, CN03128030.7) to have synthesized konjac glucomannan grafted co-polypropylene sour water gel.Do not see as yet up to now about adopting Interpenetrating Polymer Network Technology to prepare the report of Rhizoma amorphophalli glucomannan/polyacrylic acid hydrogel.
Summary of the invention
The objective of the invention is to be to provide a kind of biodegradable hydrogel, it has the biological degradability and the polyacrylic pH responsiveness of Rhizoma amorphophalli glucomannan simultaneously, and has uniform macroporous structure, higher physical strength, swelling behavior and sensitive pH responsiveness fast.Rhizoma amorphophalli glucomannan is from agricultural-food cheap and easy to get, and the present invention also provides an effective way for the comprehensive utilization of agricultural byproducts.
Another object of the present invention is the preparation method who is to provide a kind of biodegradable hydrogel, adopt macropore glucomannan hydrogel of konnjaku swelling in the aqueous solution that contains vinylformic acid, linking agent, initiator, to prepare interpenetrating polymer networks exactly, this method is simply effective, the reaction conditions gentleness, reaction medium is a water, do not adopt organic solvent, can be in reaction process bioactive macromolecules such as embedding protein, polypeptide, and keep active.
Realize that technical scheme of the present invention is: a kind of biodegradable hydrogel, it be by macropore glucomannan hydrogel of konnjaku swelling in the aqueous solution of vinylformic acid, linking agent, initiator, 40～60 ℃ of following polyreactions prepared in 12～24 hours.Macropore glucomannan hydrogel of konnjaku and acrylic acid ratio (sugar unit and monomeric mol ratio) are 1: 20～90; Linking agent and acrylic acid mol ratio are 1: 80～1000; Initiator and acrylic acid mol ratio are 1: 100～800.Linking agent is N, and N '-methylene-bisacrylamide or diacrylate binaryglycol ester or Ethylene glycol dimethacrylate or diethyleneglycol dimethacrylate(DEGDMA), initiator are ammonium persulphate or Potassium Persulphate.
A kind of preparation process of biodegradable hydrogel is: at first prepare the macropore glucomannan hydrogel of konnjaku, concrete steps are as follows:
A. take by weighing konjaku powder, be dissolved in the distilled water, room temperature (15～30 ℃) stirred 2-5 hour, made into even colloidal sol;
B. in even colloidal sol, add the 2-4N inorganic base aqueous solution and stir, make colloidal sol pH value be 9-13, the weight concentration of konjaku powder is 1～5%;
C. temperature is controlled at 60-100 ℃, and the reaction times is 1-5 hour, and cooling was left standstill 12-24 hour; With distilled water immersion washing, make water become neutral, gel was placed-15～-25 ℃ of freezing tanks freezing 2～6 hours, room temperature was melted 2～8 hours, and behind the multigelation 1～6 time, freeze-drying obtains the macropore glucomannan hydrogel of konnjaku.
The preparation method of above-mentioned macropore glucomannan hydrogel of konnjaku is characterized in that mineral alkali is yellow soda ash or sodium hydroxide or potassium hydroxide.
Again with macropore glucomannan hydrogel of konnjaku swelling in the aqueous solution of vinylformic acid, linking agent, initiator 4～8 hours, 40～60 ℃ of following polyreactions 12～24 hours, product with distilled water immersion, wash to water and be neutral, freeze-drying or 60 ℃ of oven dry prepare.
The present invention compared with prior art has the following advantages and effect: it has the biological degradability and the polyacrylic pH responsiveness of Rhizoma amorphophalli glucomannan simultaneously, and has uniform macroporous structure, higher physical strength, swelling behavior and sensitive temperature response fast.This method is simply effective, the reaction conditions gentleness, reaction medium is a water, does not adopt organic solvent, can be in reaction process bioactive macromolecules such as embedding protein, polypeptide, and kept activity.Rhizoma amorphophalli glucomannan is from agricultural-food cheap and easy to get, and the present invention also provides an effective way for the comprehensive utilization of agricultural byproducts.Useful as drug conlon targeting sustained release carrier behind biodegradable pH response interpenetrating polymer networks hydrogel embedding of the present invention or the absorption medicine as water-absorbing resin, also can be applicable to fields such as biological chemistry, medical science, agricultural, daily-use chemical industry.
Embodiment
The present invention adds Thermogelling by the konjak portuguese gansu polyose sugar aqueous solution under the alkali effect, obtain the macropore glucomannan hydrogel of konnjaku through freeze thawing treatment again, again with macropore glucomannan hydrogel of konnjaku swelling in the aqueous solution of vinylformic acid, linking agent, initiator, 40～60 ℃, polymerization obtained in 12～24 hours.Specific implementation method is exemplified below:
Embodiment 1: the macropore glucomannan hydrogel of konnjaku, it consists of: konjaku powder 1.5g, distilled water 100mL, sodium hydroxide adjust pH are 13.
Embodiment 2: the macropore glucomannan hydrogel of konnjaku, it consists of: konjaku powder 2.5g, distilled water 100mL, yellow soda ash adjust pH are 11.
Embodiment 3: the macropore glucomannan hydrogel of konnjaku, it consists of: konjaku powder 3.5g, distilled water 100mL, yellow soda ash adjust pH are 9.
Embodiment 4: the macropore glucomannan hydrogel of konnjaku, it consists of: konjaku powder 2g, distilled water 100mL, potassium hydroxide adjust pH are 12.
The preparation method of the foregoing description 1-4 is: take by weighing 1.5～3.5g konjaku powder, be dissolved in 80～100mL distilled water stirring at room 2～5 hours, make into even colloidal sol, adding the 3N inorganic alkali solution stirs, making Rhizoma amorphophalli glucomannan water-sol pH value is 13 or 11 or 9 or 12, in 70 ℃ the reaction 3 hours after naturally cooling left standstill 24 hours.Use distilled water immersion, repeatedly change water, make water be neutral.Gel was placed-15 ℃ of freezing tanks freezing 4 hours, room temperature was thawed 4 hours, and freeze-drying obtains the macropore glucomannan hydrogel of konnjaku behind the multigelation 3 times.
Embodiment 5: biodegradable pH response water gel, it consists of: macropore glucomannan hydrogel of konnjaku 1.62g, vinylformic acid 28mL, N, N '-methylene-bisacrylamide 0.156g, ammonium persulphate 0.228g, distilled water 22mL.
Embodiment 6: biodegradable pH response water gel, it consists of: macropore glucomannan hydrogel of konnjaku 1.62g, vinylformic acid 21mL, N, N '-methylene-bisacrylamide 0.1g, ammonium persulphate 0.684g, distilled water 18mL.
Embodiment 7: biodegradable pH response water gel, it consists of: macropore glucomannan hydrogel of konnjaku 1.62g, vinylformic acid 28mL, Ethylene glycol dimethacrylate 0.2g, Potassium Persulphate 0.27g, distilled water 25mL.
The preparation method of the foregoing description 5-7 is: with vinylformic acid, N, N '-methylene-bisacrylamide or Ethylene glycol dimethacrylate, ammonium persulphate or Potassium Persulphate are dissolved in the water, then the macropore glucomannan hydrogel of konnjaku is immersed in the mixing solutions 4～8 hours, 40～60 ℃ of reactions 12～24 hours.Product with distilled water immersion, wash to water and be neutral, freeze-drying.
Embodiment 8: the preparation of the biodegradable pH response water gel of bag medicine carrying thing
1.62g macropore glucomannan hydrogel of konnjaku is immersed in 50mL contains 28mL vinylformic acid, 0.156gN, in the aqueous solution of N '-methylene-bisacrylamide, 0.228g ammonium persulphate and 1.5g 5 FU 5 fluorouracil 4～8 hours, 40 ℃ of reactions 16 hours.Product with distilled water immersion, wash to water and be neutral, freeze-drying.
Embodiment 9: the preparation of the biodegradable pH response water gel of pastille
Vinylformic acid and Rhizoma amorphophalli glucomannan interpenetrating polymer networks 1.62g that freeze-drying is obtained, be immersed in the 150mL weight concentration and be in 2.5% the 5 FU 5 fluorouracil aqueous solution, room temperature left standstill 48 hours, took out gel, and is surperficial with 30 ℃ of following drying under reduced pressure behind a small amount of distilled water wash.
Claims (4)
1, a kind of biodegradable hydrogel, it is to be made by following molar ratio raw material:
The sugar unit of macropore glucomannan hydrogel of konnjaku and acrylic acid ratio are 1: 20～90;
Linking agent and acrylic acid ratio are 1: 80～1000;
Ammonium persulphate or Potassium Persulphate and acrylic acid ratio are 1: 100～800.
2, a kind of biodegradable hydrogel according to claim 1 is characterized in that linking agent is N, N '-methylene-bisacrylamide or diacrylate binaryglycol ester or Ethylene glycol dimethacrylate or diethyleneglycol dimethacrylate(DEGDMA).
3, a kind of preparation method who realizes the described biodegradable hydrogel of claim 1 the steps include:
A. preparing the macropore glucomannan hydrogel of konnjaku, at first is to take by weighing konjaku powder, is dissolved in the distilled water, stirring at room 2-5 hour, makes into even colloidal sol; Next is in even colloidal sol, adds the 2-4N inorganic base aqueous solution and stirs, and makes colloidal sol pH value be 9-13, and the weight concentration of konjaku powder is 1～5%; The 3rd is that temperature is controlled at 60-100 ℃, reaction times is 1-5 hour, cooling was left standstill 12-24 hour, wash with distilled water immersion then, make water become neutral, gel was placed-15～-25 ℃ of freezing tanks freezing 2～6 hours, room temperature was melted 2～8 hours, after the freeze thawing 1～6 time, freeze-drying obtains the macropore glucomannan hydrogel of konnjaku;
B. with macropore glucomannan hydrogel of konnjaku swelling in the aqueous solution of vinylformic acid, linking agent, initiator 4～8 hours, 40～60 ℃ of following polyreactions 12～24 hours, product with distilled water immersion, wash to water and be neutral, freeze-drying or 60 ℃ of oven dry.
4, the preparation method of biodegradable hydrogel according to claim 3 is characterized in that mineral alkali is yellow soda ash or sodium hydroxide or potassium hydroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108669032A (en) * | 2018-05-24 | 2018-10-19 | 西南大学 | Noctilucence device for adhering insects |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100419013C (en) * | 2005-10-18 | 2008-09-17 | 武汉大学 | Biodegradable materials, preparation method and usage |
| CN100577700C (en) * | 2007-11-27 | 2010-01-06 | 湖北省农业科学院农产品加工与核农技术研究所 | Method for preparing high water absorption konjac glucomannan crylic acid irradiation graft polymers |
| CN101168937B (en) * | 2007-11-28 | 2010-05-19 | 华南理工大学 | Guar gum-acrylic acid water absorption resin coating moisture absorbing paper and preparation method thereof |
| CN102876312B (en) * | 2012-09-26 | 2015-01-07 | 西南石油大学 | Acrylamide graft copolymer oil-displacing agent and preparation method thereof |
| CN106001090B (en) * | 2016-06-18 | 2019-02-05 | 江苏华东新能源勘探有限公司（江苏省有色金属华东地质勘查局八一三队） | A kind of absorption of heavy metal pollution of mine soil-Co-bioremediation method |
| CN106187996B (en) * | 2016-07-07 | 2018-11-09 | 华南师范大学 | A kind of composite hydrogel and its preparation method and application containing rare earth compounding of novel pH responses |
| CN106117442B (en) * | 2016-07-28 | 2018-08-03 | 汕头市集诚妇幼用品厂有限公司 | A kind of water-absorbing resin and preparation method thereof applied to diaper |
| CN109998987A (en) * | 2019-04-08 | 2019-07-12 | 上海理工大学 | A kind of composite hydrogel and its preparation method and application based on natural konjaku flour |
| CN110117383A (en) * | 2019-05-05 | 2019-08-13 | 合肥卓汇新材料科技有限公司 | A kind of high-strength gel elastomeric material |
| CN110437471B (en) * | 2019-07-11 | 2022-02-15 | 郑州轻工业学院 | Adhesive composite hydrogel and preparation method and application thereof |
| CN111742770A (en) * | 2020-07-10 | 2020-10-09 | 宜宾职业技术学院 | Full-degradable liquid agricultural stock solution and preparation method thereof |
| CN113509590B (en) * | 2021-06-07 | 2022-09-09 | 广东唯泰生物科技有限公司 | Wound dressing with exosome combined with hyaluronic acid and preparation method and application thereof |
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| CN1314427A (en) * | 2000-03-16 | 2001-09-26 | 武汉大学 | Semi interpenetration polymer network material and its preparing method and use |
| CN1480219A (en) * | 2003-05-26 | 2004-03-10 | 武汉大学 | Biodegradable multiple targeting hydrogel orientated to eolon as well as its preparation and application |
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| CN1314427A (en) * | 2000-03-16 | 2001-09-26 | 武汉大学 | Semi interpenetration polymer network material and its preparing method and use |
| CN1480219A (en) * | 2003-05-26 | 2004-03-10 | 武汉大学 | Biodegradable multiple targeting hydrogel orientated to eolon as well as its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108669032A (en) * | 2018-05-24 | 2018-10-19 | 西南大学 | Noctilucence device for adhering insects |
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