CN1594385A - Biodegradable hydrogel and method for preparing same - Google Patents
Biodegradable hydrogel and method for preparing same Download PDFInfo
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- CN1594385A CN1594385A CN 200410013316 CN200410013316A CN1594385A CN 1594385 A CN1594385 A CN 1594385A CN 200410013316 CN200410013316 CN 200410013316 CN 200410013316 A CN200410013316 A CN 200410013316A CN 1594385 A CN1594385 A CN 1594385A
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Abstract
The invention discloses a biodegradable hydrogel and method for preparing same which consists of, preparing microporous konjak gluglucosan aqueous gel, preparing refined konjaku flour, dissolving in distilled water, agitating, charging inorganic solvent, adjusting pH, carrying out crossbridging under a controlled temperature and time, water scrubbing the product yield, repeated frost thawing, freeze-drying, then swelling the konjak gluglucosan gel into the aqueous solution of acroleic acid, cross linking agent, and initiating agent, carrying out polymerization under a controlled temperature and time, and water scrubbing the obtained outcome yield.
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 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 konjak gel.
The preparation method of above-mentioned macropore konjak gel 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 konjak gel 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 konjak gel, it consists of: konjaku powder 1.5g, distilled water 100mL, sodium hydroxide adjust pH are 13.
Embodiment 2: the macropore konjak gel, it consists of: konjaku powder 2.5g, distilled water 100mL, yellow soda ash adjust pH are 11.
Embodiment 3: the macropore konjak gel, it consists of: konjaku powder 3.5g, distilled water 100mL, yellow soda ash adjust pH are 9.
Embodiment 4: the macropore konjak gel, 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 konjak gel behind the multigelation 3 times.
Embodiment 5: biodegradable pH response water gel, it consists of: macropore konjak portuguese gansu polyose gel 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 konjak portuguese gansu polyose gel 1.62g, vinylformic acid 21mL, N, N '-methylene-bisacrylamide 0.05g, ammonium persulphate 0.684g, distilled water 18mL.
Embodiment 7: biodegradable pH response water gel, it consists of: macropore konjak portuguese gansu polyose gel 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 konjak gel 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 konjak portuguese gansu polyose gel 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 with freeze-drying obtains are immersed in the 5 FU 5 fluorouracil aqueous solution of 150mL 2.5%, and room temperature left standstill 48 hours, take out gel, and be surperficial with 30 ℃ of following drying under reduced pressure behind a small amount of distilled water wash.
Claims (5)
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;
Initiator 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 biodegradable hydrogel according to claim 1 is characterized in that initiator is ammonium persulphate or Potassium Persulphate.
4, 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 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 konjak gel;
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.
5, the preparation method of biodegradable hydrogel according to claim 4 is characterized in that mineral alkali is yellow soda ash or sodium hydroxide or potassium hydroxide.
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| CNB2004100133160A CN1296400C (en) | 2004-06-18 | 2004-06-18 | Biodegradable hydrogel and method for preparing same |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102876312A (en) * | 2012-09-26 | 2013-01-16 | 西南石油大学 | Acrylamide graft copolymer oil-displacing agent and preparation method thereof |
| CN106117442A (en) * | 2016-07-28 | 2016-11-16 | 关亚玲 | A kind of water-absorbing resin being applied to diaper and preparation method thereof |
| CN106187996A (en) * | 2016-07-07 | 2016-12-07 | 华南师范大学 | A kind of composite aquogel containing rare earth compounding of novel pH response and its preparation method and application |
| CN109127691A (en) * | 2016-06-18 | 2019-01-04 | 毛强平 | A kind of adsorbent for heavy-metal contaminated soil reparation |
| 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 |
| CN110437471A (en) * | 2019-07-11 | 2019-11-12 | 郑州轻工业学院 | A kind of viscosity composite hydrogel and its preparation method and application |
| 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 |
| CN113509590A (en) * | 2021-06-07 | 2021-10-19 | 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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| CN1104456C (en) * | 2000-03-16 | 2003-04-02 | 武汉大学 | Semi interpenetration polymer network material and its preparing method and use |
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Cited By (15)
| 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 |
| CN102876312A (en) * | 2012-09-26 | 2013-01-16 | 西南石油大学 | Acrylamide graft copolymer oil-displacing agent 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 |
| CN109127691A (en) * | 2016-06-18 | 2019-01-04 | 毛强平 | A kind of adsorbent for heavy-metal contaminated soil reparation |
| CN106187996A (en) * | 2016-07-07 | 2016-12-07 | 华南师范大学 | A kind of composite aquogel containing rare earth compounding of novel pH response and its preparation method and application |
| 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 |
| CN106117442A (en) * | 2016-07-28 | 2016-11-16 | 关亚玲 | A kind of water-absorbing resin being applied to diaper and preparation method thereof |
| 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 |
| CN110437471A (en) * | 2019-07-11 | 2019-11-12 | 郑州轻工业学院 | A kind of viscosity composite hydrogel and its preparation method and application |
| 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 |
| CN113509590A (en) * | 2021-06-07 | 2021-10-19 | 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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