CN104177636A - In-situ mineralized reinforced composite hydrogel and preparation method thereof - Google Patents
In-situ mineralized reinforced composite hydrogel and preparation method thereof Download PDFInfo
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- CN104177636A CN104177636A CN201310190481.2A CN201310190481A CN104177636A CN 104177636 A CN104177636 A CN 104177636A CN 201310190481 A CN201310190481 A CN 201310190481A CN 104177636 A CN104177636 A CN 104177636A
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Abstract
The invention discloses an in-situ mineralized reinforced composite gel film and a preparation method thereof, and belongs to the technical field of gel preparation. The preparation method comprises that an acrylic acid monomer and a (N-isopropyl)acrylamide monomer undergo a copolymerization reaction under the action of an initiator and are cross-linked by a cross-linking agent, simultaneously, sodium alginate is added into the reaction system, the mixture is subjected to metal ion-based chelating to form a physical cross-linked net, and the physical cross-linked net is mineralized in a gel net under the action of vapor deposition to form inorganic particles. The chemically and physically co-cross-linked gel retains the characteristics of the original gel system, and through in-situ mineralization, gel mechanical properties are improved. The preparation method has mild conditions, low energy consumption, operation easiness and good application implementation prospect.
Description
Technical field
The invention belongs to gel preparing technical field, be specifically related to a kind of composite aquogel technology of preparing of original position mineralising, the hydrogel preparation that is introduced as of physical crosslinking agent and mineralising reaction provides a kind of new method.
Background technology
Responsive gel is also referred to as intelligent gel (intelligent hydrogel), refer to its physics or chemical property with external environment as variations such as temperature, pH, ionic strength, optical, electrical fields and noticeable change.What research was more at present is the volume phase transition (volume phase transition, VPT) of gel, and the subtle change of external environment causes that the discontinuous formula of gel volume changes.Due to these peculiar character, in recent years, because intelligent aqueous gel capable is being widely used of the fields such as the control release of medicine, gene transmission, organizational project, scientific worker is very active for the research activities in this field.
According to the body material that forms hydrogel network, mainly contain synthetic macromolecule hydrogel and natural polymer hydrogel.From the research course of hydrogel, former researchist be take and synthesized high-molecular gel as main study subject, because the structure of synthetic high-molecular gel is precisely controlled with function energy, and alternative kind is a lot.Along with deepening continuously to its research, its effect has started to manifest, in medical science, field of pharmacology, show particularly outstandingly especially, but the unreacted monomer, residual initiator or catalyzer and the small molecule by-product etc. that in synthetic macromolecule hydrogel, mix are often answering Fang Erhui band in river to serve bad reaction.Natural polymer hydrogel has as features such as good biocompatibility, easily degraded, hypotoxicities, is subject to people's favor.But natural polymer hydrogel less stable, many scientists have carried out the research work of natural polymer with synthetic polymer blended hydrogel in recent years.
Through effort for many years of investigator, response speed that synthetic macromolecule hydrogel has is slow, biocompatibility is poor and the problem such as non-biodegradable has obtained the solution of certain degree; Yet mechanical property some biological hydrogel identical with water ratio of synthetic hydrogel compared still inferior a lot.
The design philosophy that utilization of the present invention is coupled hardness with softness, builds two gel (DN) systems, synthesizing, is in macromolecule network structure, introduces chemical cross-linking agent as bridge formation material, and this is rigid structure; Introduce natural polysaccharide polymeric hydantoin sodiun alginate, by divalent metal particle complexing bridging, this is flexible structure; Between these two, by being wound around kink between mutual Van der Waals force, Hyarogen-bonding, macromolecular chain, form interpenetrating polymer networks (inter penetrating polymer network, IPN).And then, by the common inductive effect of sodium alginate and PAA-PIPNIA, release of carbon dioxide or other carbon sources in system, the biotic induce mineralizations of macromole to inanimate matter such as the polysaccharide in imitated biological tissue, protein, the stacked in layers structure of formation mechanical property excellence.Utilize at present biomimetic mineralization to strengthen composite aquogel mechanical property and there is not yet report.
Summary of the invention
The present invention aims to provide a kind of composite aquogel and preparation method thereof, and technique is simple, and easy handling is easy to utilize.The present invention can improve mechanical property and the snappiness of gel, and has kept the pH responsiveness of polyacrylic acid unit and the temperature-responsive of PNIPAM.
For achieving the above object, the present invention adopts following technical scheme:
1) preparation of vinylformic acid-N-isopropylacrylamide copolymer hydrogel
Get a certain amount of Acrylic Acid Monomer, add sodium hydroxide, adjusting pH is 4-8, add NIPA monomer, add S-WAT and Potassium Persulphate, with N, N '-methylene-bisacrylamide is initiator, add a certain amount of sodium alginate, stirring reaction 5～30min at room temperature, solution is poured in prefab-form, one night of standing gelatinization reaction, the diaphragm that reaction is obtained is soaked in certain hour in deionized water, washes away residual monomer, small molecules oligopolymer and initiator etc., and this process in triplicate;
2) preparation of original position mineralising composite aquogel
The film making is soaked in ionic calcium soln, after it absorbs swelling certain hour, takes out, be placed in close drying device; In moisture eliminator, place volatile salt solid, by controlling the gas phase carbon dioxide deposition reaction time, in film, generate calcium carbonate nano particle, obtain the compound water congealing glue material that mineralising strengthens simultaneously.
Preparation method of the present invention innovates and introduces mineralising deposition as strengthening mechanical property means, and the biomineralization of matching natural tissues, makes it be converted into calcium carbonate to the calcium ion in composite gel system by Induction deposition effect;
Composite gel material prepared by the method has following characteristics:
(1) the chemical bond bridge linking effect of the chemical cross-linking agent of existing rigidity in plural gel network, also has the metal complexation of the physical crosslinking that is flexible;
(2) composite aquogel that the method is made retains pH and the temperature-responsive of former polymerized unit;
(3) preparation method that a kind of mineralising strengthens composite aquogel is proposed, by nature biotechnology mineralization is completed to the regulation and control from nucleation to crystallisation process by simple inorganic component, construction structure is accurate, the matching of the excellent organic/inorganic composite material process of mechanical property.The lifting of realization to gellifying property;
(4) mineralising depositing operation is simple, and mild condition, less energy-consumption, pollution-free, have industrializing implementation prospect.
Accompanying drawing explanation
Fig. 1 is the reaction schematic diagram that original position mineralising sedimentation is obtained plural gel.
Embodiment
Being below specific embodiments of the invention, is to further describe of the present invention.But specific embodiment does not limit the claims in the present invention.
Embodiment 1:
1) get 0.71g vinylformic acid, be dissolved in 10g water, add sodium hydroxide solution, regulating pH is 6.5, adds 0.72g acrylamide, stirs 30min, and mixed system is dissolved completely; In above system, add 2% Potassium Persulphate 3.38g and 2% S-WAT 1.58g, after stirring and dissolving, add 0.06gN, N '-methylene-bisacrylamide adds 5% sodium alginate soln 14g simultaneously, stirring reaction 30min at room temperature, solution is poured in prefab-form, standing and reacting 24h, and the diaphragm that reaction is obtained is soaked in certain hour in deionized water, wash away residual monomer, small molecules oligopolymer and initiator etc., in triplicate;
2) film making is soaked in calcium chloride solution, after it absorbs swelling certain hour, takes out, be placed in close drying device; In moisture eliminator, place volatile salt, be 16h by controlling the gas phase carbon dioxide deposition reaction time simultaneously, generates calcium carbonate particles in film, obtains the compound water congealing glue material that mineralising strengthens.
Embodiment 2:
1) get 0.71g vinylformic acid, be dissolved in 10g water, add sodium hydroxide solution, regulating pH is 6.8, adds 1.13gN-N-isopropylacrylamide, adds 14g sodium alginate soln (5% massfraction) simultaneously, stirs 30min, and mixed system is dissolved completely; In above system, add 2% potassium persulfate solution 3.38g, 2% sodium sulfite solution 3.16g, after stirring and dissolving, add 0.09gN, N '-methylene-bisacrylamide, stirring reaction 30min at room temperature, solution is poured in prefab-form, standing and reacting 24h, the diaphragm that reaction is obtained is soaked in certain hour in deionized water, washes away residual monomer, small molecules oligopolymer and initiator etc., repeats this process three times;
2) film making is soaked in calcium chloride solution, after it absorbs swelling certain hour, takes out, be placed in close drying device; In moisture eliminator, place volatile salt, be 24h by controlling the gas phase carbon dioxide deposition reaction time simultaneously, generates calcium carbonate particles in film, obtains the compound water congealing glue material that mineralising strengthens.
Claims (6)
1. original position mineralising strengthens a preparation method for composite aquogel, it is characterized in that: the mineralization points that the mechanical property of composite aquogel forms by original position on macromolecule network is enhanced.
2. a kind of original position mineralising as claimed in claim 1 strengthens a preparation method for composite aquogel, it is characterized in that described preparation method comprises the following steps:
1) get a certain amount of Acrylic Acid Monomer, add sodium hydroxide, adjusting pH is 4-8, add NIPA monomer, add S-WAT and Potassium Persulphate, with N, N '-methylene-bisacrylamide is initiator, add a certain amount of sodium alginate, stirring reaction 5～30min at room temperature, solution is poured in prefab-form, standing gelatinization reaction, the diaphragm that reaction is obtained is soaked in certain hour in deionized water, washes away residual monomer, small molecules oligopolymer and initiator etc., and this process in triplicate;
2) film making is soaked in ionic calcium soln, after it absorbs swelling certain hour, takes out, be placed in close drying device; In moisture eliminator, place volatile salt, by controlling the gas phase carbon dioxide deposition reaction time, in film, generate calcium carbonate particles, obtain the compound water congealing glue material that mineralising strengthens simultaneously.
3. the preparation method of the composite aquogel that mineralising strengthens according to claim 2, is characterized in that: step 1) described copolymer hydrogel system is temperature-pH Lazer type hydrogel.
4. the preparation method of the composite aquogel that mineralising strengthens according to claim 2, is characterized in that: step 1) acrylic acid molar fraction is 40-80% in described copolymer hydrogel system.
5. the preparation method of the composite aquogel that mineralising strengthens according to claim 2, is characterized in that: step 1) massfraction of sodium alginate is 2-20% in described physical-chemical co-crosslinking aquogel system.
6. the preparation method of the composite aquogel that mineralising strengthens according to claim 2, is characterized in that: step 2) in described copolymer hydrogel mineralising reaction the carbonic acid gas deposition reaction time be 1-24h.
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| CN201310190481.2A CN104177636A (en) | 2013-05-22 | 2013-05-22 | In-situ mineralized reinforced composite hydrogel and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107011609A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-strength chemical-physical double-network hydrogel with automatic recovery ability and preparation method and application |
| CN109529101A (en) * | 2018-12-27 | 2019-03-29 | 西北工业大学 | Toughening type hydrogel wound dressing capable of being fast degraded and preparation method thereof |
| CN109908872A (en) * | 2018-02-01 | 2019-06-21 | 常州大学 | A kind of micro-gel particles of bowl structure and its preparation method and application |
| CN110038134A (en) * | 2019-05-31 | 2019-07-23 | 南开大学 | The Nano medication transmission system and preparation method of double responsiveness carrying anti-tumor drug for oncotherapy |
| CN110960990A (en) * | 2019-12-09 | 2020-04-07 | 西安建筑科技大学 | Preparation method of inorganic nano homogeneous hybrid PVDF (polyvinylidene fluoride) super-hydrophilic ultrafiltration membrane |
| CN111777772A (en) * | 2020-06-15 | 2020-10-16 | 东南大学 | Method for improving hydrogel through microbial mineralization |
| CN113943430A (en) * | 2021-10-27 | 2022-01-18 | 中国科学院长春应用化学研究所 | In-situ mineralized hydrogel and preparation method and application thereof |
| CN114507314A (en) * | 2022-03-14 | 2022-05-17 | 北京石油化工学院 | Hydrogel sensitive to temperature and solvent concentration and preparation method thereof |
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2013
- 2013-05-22 CN CN201310190481.2A patent/CN104177636A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011609A (en) * | 2016-01-27 | 2017-08-04 | 中国科学院化学研究所 | A kind of high-strength chemical-physical double-network hydrogel with automatic recovery ability and preparation method and application |
| CN109908872A (en) * | 2018-02-01 | 2019-06-21 | 常州大学 | A kind of micro-gel particles of bowl structure and its preparation method and application |
| CN109908872B (en) * | 2018-02-01 | 2021-08-24 | 常州大学 | Microgel particles with bowl-shaped structure and preparation method and application thereof |
| CN109529101A (en) * | 2018-12-27 | 2019-03-29 | 西北工业大学 | Toughening type hydrogel wound dressing capable of being fast degraded and preparation method thereof |
| CN109529101B (en) * | 2018-12-27 | 2021-07-20 | 西北工业大学 | Tough hydrogel wound dressing capable of being rapidly degraded and preparation method thereof |
| CN110038134A (en) * | 2019-05-31 | 2019-07-23 | 南开大学 | The Nano medication transmission system and preparation method of double responsiveness carrying anti-tumor drug for oncotherapy |
| CN110038134B (en) * | 2019-05-31 | 2022-03-29 | 南开大学 | Double-response nano-drug delivery system carrying anti-tumor drug for tumor treatment and preparation method thereof |
| CN110960990A (en) * | 2019-12-09 | 2020-04-07 | 西安建筑科技大学 | Preparation method of inorganic nano homogeneous hybrid PVDF (polyvinylidene fluoride) super-hydrophilic ultrafiltration membrane |
| CN111777772A (en) * | 2020-06-15 | 2020-10-16 | 东南大学 | Method for improving hydrogel through microbial mineralization |
| CN111777772B (en) * | 2020-06-15 | 2022-11-29 | 东南大学 | Method for improving hydrogel through microbial mineralization |
| CN113943430A (en) * | 2021-10-27 | 2022-01-18 | 中国科学院长春应用化学研究所 | In-situ mineralized hydrogel and preparation method and application thereof |
| CN114507314A (en) * | 2022-03-14 | 2022-05-17 | 北京石油化工学院 | Hydrogel sensitive to temperature and solvent concentration and preparation method thereof |
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Application publication date: 20141203 |