CN107236146A - Utilize the method for pinpointing concentration solvent exchange process preparation starch base porous aquagel - Google Patents
Utilize the method for pinpointing concentration solvent exchange process preparation starch base porous aquagel Download PDFInfo
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- CN107236146A CN107236146A CN201710554914.6A CN201710554914A CN107236146A CN 107236146 A CN107236146 A CN 107236146A CN 201710554914 A CN201710554914 A CN 201710554914A CN 107236146 A CN107236146 A CN 107236146A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
Abstract
The invention discloses a kind of using the method that concentration solvent exchange process prepares starch base porous aquagel is pinpointed, belong to technical field of polymer materials.Its preparation method is as follows：Monomer, crosslinking agent and initiator are sequentially added in starch solution, is well mixed, 50oC‑60 oCReaction obtains starch based aquagel.After the washing of obtained hydrogel with water, being swelled, it is immersed in the solution of specific composition and carries out exchange of solvent, by drying, obtain starch base porous aquagel.Starch base porous hydrogel hydrogel opening prepared by the present invention is good, three-dimensional structure is stable, it is biodegradable, preparation method is simple and efficient, only need to carry out a solvent exchange procedure, loose structure starch base porous aquagel is obtained, this method is applicable to the preparation of the starch base porous aquagel of various compositions.
Description
Technical field
The present invention relates to technical field of polymer materials, it is related to a kind of porous aquagel preparation side constituted based on starch
Method, the method for preparing starch base porous aquagel especially with fixed point concentration solvent exchange process.
Background technology
Hydrogel is a kind of with hydrophily and water insoluble high molecular polymer, can rapidly be swelling to and be swelled in water
Balance, is widely used in food processing, medicine, Material Field.Compared with traditional hydrogel, in porous aquagel
There is substantial amounts of pore structure in portion, possesses bigger space and bigger interior surface area, thus with more preferable swelling behavior, more
Fast Swelling Dynamics and to external echo faster feature.
Starch is a kind of reproducible natural resources, abundance, cheap, with resource regeneration, hypotoxicity,
Biocompatibility, biological degradability.But starch has the shortcomings that crystallinity is strong, is difficult to process and is molded, therefore, generally in itself
Starch is physically or chemically modified, to improve the structure and performance of starch, the application field of starch is widened.Starch in recent years
Deng natural polymer as renewable, sustainable development green material, obtain wider in fields such as chemical industry, medicine, environment
General and in-depth study and application.
Preparing the conventional method of porous aquagel at present has：Foaming, pore-foaming agent method, freeze-drying, exchange of solvent method.
Foaming is to react the gas produced or organic solvent gas volatilization using foaming agent, forms abscess in material internal, such as
CN103044703A prepares multihole bubble colloid by foaming agent of air, is used as the part of wound dressing；
CN102492093A、CN1264321 A、CN1757662 A、CN1488331 A、CN1763123A、CN1768920A、
CN102633956 B etc. are using carbonate or bicarbonate as foaming agent, and reaction in acid condition generates gas titanium dioxide
Loose structure is formed after carbon, volatilization.CN102702559A uses microorganism --- and dry ferment makees foaming agent, is produced by its fermentation
Gas, so as to form porous aquagel.CN102167763A makes foaming agent low temperature photopolymerization of low boiling point solvent and prepares porous water
Gel.CN101588790A, CN1527860A etc. are that the gas of generation is reacted by the use of in polymerization process as foaming agent,
Hole is left in hydrogel matrix.CN1763124A, CN102406595A use microcapsules conduct prepared by orifice coagulating bath method
Foaming agent, produces foam structure in hydrogel.Pore method is that pore former is entrained in polymer body, and polymer is placed in
In water.Pore-foaming agent is dissolved in the water and polymer is insoluble, hole will be left in polymeric inner, such as using ethanol as pore-foaming agent
Prepare polyacrylamide/potassium acrylate interpenetrating networks porous aquagel (material Leader, 2011,25 (10), 28-31).It is separated
Method is also exchange of solvent method, is not dissolved in a solvent using polymer, and polymer phase mutually produces phase separation with solvent, then dry
During dry, solvent volatilization leaves hole in polymer matrix body, and such as Zhang is mixed with sucrose solution and Isosorbide-5-Nitrae-dioxane
Close liquid be solvent prepare PNIPA hydrogels (《Macromolecular Chemistry and Physics》,2004,205(1),
107-113.).Freeze-drying is the solvent in polymer is volatilized under the conditions of cryogenic vacuum, so as to leave in the polymer
Hole《Zhongzhou Univ.'s journal》), 2016,33 (14) 113-116.)), such as CN103094596A is prepared many using freeze-drying
Hole hydrogel, is used as the carrier of proton membrane.
In the above prepares the method for porous aquagel, generally there are problems that：The gas that such as foaming agent is produced
Body rate of volatilization is very fast, and the extent of reaction and pore structure are often difficult to the materials such as control, and foaming agent, pore easily in water-setting
Remained in glue, the application to hydrogel brings potential safety hazard.Although freeze-drying need not add infusion and pore-foaming agent,
Freeze drying equipment is expensive, longevity of service, in addition, freeze-drying is limited by volume of equipment, it is impossible to meet a large amount of raw
The need for production.When volatilization or phase separation form hole, the three-dimensional structure of hydrogel would generally be destroyed, and hole
Structure, size and form be difficult to control to, opening is poor, and its three-dimensional dimension would generally before and after be swelled for porous aquagel
Occurs violent change, when the stereochemical structure for needing porous aquagel holding stable in some operating process, using just
It can be restricted.Therefore, the preparation method of simple and efficient porous aquagel is developed, increasingly causes the concern of people.
The exchange of solvent method commonly used for porous material, researcher makes improvements, in order that solvent volatilization is complete,
Do not remain, it is general many from low boiling, easy volatile solvent.But be due to water and low boiling point solvent liquid property difference it is too big,
In exchange of solvent, serious contraction can occur for the hole of hydrogel, as a result cause hydrogel inner void to diminish, or even almost
Just without pore space structure.The problem of in order to solve void collapse, the method that people develop gradient solvent exchange again, by hydrogel
It is immersed in successively in a series of mixed solution of organic solvent-water of the ascending distribution gradient of volumetric concentration, i.e., by water-setting
Glue carries out exchange of solvent successively, by the exchange of moisture being swelled in hydrogel, substitutes, then organic solvent is volatilized, you can obtain many
Pore structure.Although cumbersome, this method safe operation, conveniently, it is not necessary to heat, without being limited by instrument and equipment, no
Need to add other reagents, safe, solvent is volatile, the advantages of do not remain, therefore, it is more popular, (《Zhongzhou Univ. is learned
Report》2013,30 (5)), 126-128.) but the present inventor by long-term practice find, the polymerization common for preparing of this method
Thing porous material is highly effective, but this method does not have positive effect when preparing starch base porous aquagel.Starch base water-setting
When in gradient concentration solvent exchange of solvent occurs for glue, still can occur obvious volume contraction phenomenon, this shows, hydrogel
Pore space structure has been destroyed.
The content of the invention
It is an object of the invention to provide the porous water of starch base that a kind of easy to operate, opening is good, three-dimensional structure is stable
The preparation method of gel.
The present inventor has found that shrinkage phenomenon always occurs in the molten of a certain certain concentration in gradient solvent exchange method
Liquid.Hydrogel is carried out exchange of solvent by the present inventor in these solvents for having specific composition, finds shrinkage phenomenon almost no longer
Occur, show in the process, the empty structure of hydrogel is not collapsed, also maintain pore space structure when being swelled, Qian Houshui
The volume of gel is basically unchanged, and the composition of this specific solvent, the no obvious relation between persistence of composition with hydrogel, therefore, should
Method is applicable to the preparation of the starch base porous aquagel of various compositions.
Starch base porous aquagel preparation method of the present invention is specific as follows：Sequentially added in starch solution monomer,
Crosslinking agent and initiator, and be well mixed after the addition of each component, 50 DEG C of -60 DEG C of reactions are heated to, starch base water is obtained
Gel.After obtained starch based aquagel is soaked in water, washed, being swelled, it is dipped in the solution of specific composition and carries out
Exchange of solvent, by drying, you can obtain starch base porous aquagel.
Described starch solution is：Starch-aqueous solution or starch-dimethyl sulfoxide solution.The mass concentration of starch solution
It is preferred that 5%-8%.
Described initiator is：Ammonium persulfate-ascorbic acid.
Described monomer is：N hydroxymethyl acrylamide, acrylate, acrylic acid, acrylamide, dimethylaminoethyl acrylate methyl
One or both of amino ethyl ester.
Described crosslinking agent is：One or both of the methylene diacrylamine of N, N mono-, glutaraldehyde, epoxychloropropane.
Described starch is：Soluble starch, CMS, HES.The mass ratio of the starch and monomer
It is preferred that 1:1-8.
The solution of described specific composition is：The ethanol water and weight/mass percentage composition 85% of weight/mass percentage composition 78%
Aqueous acetone solution.Both volume ranges are 1：1.3—2.5.
The order for adding raw material is preferred：It is followed successively by starch solution, monomer, crosslinking agent and initiator.
The mass/volume (g/ml) of starch based aquagel and particular solution is than choosing：1:5-30.
Innovative point of the present invention is：Fixed point concentration solvent exchange process is proposed, solvent is carried out with the mixed solution of specific composition
Exchange, using there is similar surface tension between mixed solution and water, in solvent exchange procedure, two kinds of liquid have similar move
Speed is moved, original pore space structure will not be destroyed, three-dimensional structure intrinsic inside aquogel polymer can be kept, it is only necessary to enter
Solvent exchange procedure of row, with regard to loose structure can be obtained.
Thus bring it is an advantage of the invention that：
(1) starch polymer and polymer macromolecule are combined to form to the hydrogel of inierpeneirating network structure, can not only be changed
The performance of kind starch, and the formation of starch base porous aquagel is easier, structure is more stable.
(2) by starch based aquagel weight/mass percentage composition 75%-78% ethanol solution and weight/mass percentage composition 82%-
The mixed solution of 85% acetone soln composition carries out exchange of solvent, once completes, you can obtain starch base porous aquagel, walks
It is rapid simple, and the hydrogel is before and after being swelled, obvious change does not occur for three-dimensional structure.
(3) conventional gradient concentration exchange of solvent method needs repeatedly to carry out exchange of solvent, and process is cumbersome, easily to gel
Surface structure is damaged.In contrast, the present invention only needs an exchange of solvent to can obtain starch using fixed point strength solution
Base porous aquagel, method is easy to be quick, multi-pass operation can be avoided to damage porous aquagel.
(4) fixed point concentration solvent exchange process proposed by the present invention, for the preparation of other composition starch porous aquagels
With great reference significance.
Brief description of the drawings
Fig. 1 is starch-dimethylaminoethyl methacrylate porous aquagel section electron microscope prepared by embodiment 1.
Embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, the specific implementation to the present invention below is carried out
Describe in more detail, but the embodiment is not construed as limiting the invention.
Embodiment 1
2.00g soluble starches and 40mL distilled water are added in round-bottomed flask, is stirred, is heated to 85 DEG C, makes shallow lake
Powder is fully gelatinized, and is subsequently cooled to room temperature.Monomer methacrylic acid dimethylaminoethyl is sequentially added in starch solution
4.00g, the methylene diacrylamine 1.00g of crosslinking agent N, N mono- and glutaraldehyde 0.5g, initiator ammonium persulfate-ascorbic acid
1.0g (the two mol ratio 3:2), 50 DEG C of reaction 1h, produce starch based aquagel.Hydrogel is taken out, repeatedly with distillation water logging
Steep, be swelled, washing for several times, that is, obtaining pure hydrogel.The hydrogel being swelled is immersed in 10mL weight/mass percentage compositions 75%
Ethanol and the acetone of 20mL weight/mass percentage compositions 85% mixed solution in, immersion be hardened and then be placed on drying to gel within 2 hours
Dried in case, you can obtain starch base porous aquagel.
Embodiment 2
3.00g CMSs and 40mL distilled water are added in round-bottomed flask, is stirred, is heated to 85 DEG C, makes shallow lake
Powder is fully gelatinized, and is subsequently cooled to room temperature.Monomer butyl acrylate 2.00g, crosslinking agent N, N mono- are sequentially added in starch solution
Methylene diacrylamine 1.00g and glutaraldehyde 1.0g, initiator ammonium persulfate-ascorbic acid 10.8g (the two mol ratio 3:
2), 50 DEG C of reaction 1h, produce starch based aquagel.Produce starch based aquagel.Hydrogel is taken out, repeatedly with distillation washing
Wash, be swelled, obtaining pure hydrogel.The hydrogel being swelled is immersed into the ethanol solution+25mL85% acetone of 10mL 75%
In mixed solution, vibration is hardened for 2 hours to hydrogel, is then placed in drying box and dries, produces starch base porous aquagel.
Embodiment 3
Acrylic acid 3.0g is weighed, is added in the sodium hydroxide solution of weight/mass percentage composition 25% and acrylic acid (degree of neutralization
60%), it is cooled to room temperature.1.0g HESs, 10mL distilled water are put into beaker, 70 DEG C are heated to, 0.5h is reacted.So
Acrylic acid solution, weight/mass percentage composition 0.9%N, N- methylene bisacrylamide acyl that above-mentioned degree of neutralization is 60% are sequentially added afterwards
Amine aqueous solution (crosslinking agent) 1mL, initiator ammonium persulfate-ascorbic acid 10.8g (the two mol ratio 3:2) 60 DEG C of reactions, are heated
1.5h, produces starch based aquagel.Hydrogel is taken out, repeatedly with distilling water washing, being swelled, that is, pure hydrogel is obtained.
In the mixed solution that the hydrogel being swelled is immersed to the ethanol of 10mL 75% and the acetone of 15mL 85%, 2 hours are vibrated to hydrogel
It is hardened, is then placed in drying box and dries, produce starch base porous aquagel.
Embodiment 4
1.0g starch, 15mL dimethyl sulfoxides are put into beaker, 70 DEG C of gelatinization 0.5h are heated to.Then third is sequentially added
Olefin(e) acid and acrylamide, starch, acrylic acid, the mass ratio of acrylamide are respectively 1:2:6, add crosslinking agent glutaraldehyde 1.0g
With weight/mass percentage composition 0.9%N, N- methylene-bisacrylamide solution 1mL, initiator ammonium persulfate-ascorbic acid 10.8g
(the two mol ratio 3:2) 55 DEG C of reaction 1h, are heated, starch based aquagel is produced.Hydrogel is taken out, repeatedly with distillation washing
Wash, be swelled, that is, obtain pure hydrogel.The hydrogel being fully swelled is immersed in ethanol-acetone in the mixed solvent (10mL matter
Measure the acetone soln of ethanol solution+20mL weight/mass percentage compositions 82% of percentage composition 75%) vibrate 2 hours, after gel is hardened,
Dried in drying box, produce starch base porous aquagel.
Claims (5)
1. a kind of preparation method of starch base porous aquagel, it is characterised in that realize by the following method：
Monomer, crosslinking agent and initiator are sequentially added in starch solution, and is well mixed after the addition of each component, heating
To 50oC-60 oCReaction, obtains starch based aquagel；
After obtained starch based aquagel is soaked in water, washed, being swelled, be dipped in the solution of specific composition carry out it is molten
Agent is exchanged, by drying, you can obtain starch base porous aquagel；
Described starch solution is：Starch-aqueous solution or starch-dimethyl sulfoxide solution；
Described initiator is：Ammonium persulfate-ascorbic acid；
Described monomer is：N hydroxymethyl acrylamide, acrylate, acrylic acid, acrylamide, dimethylaminoethyl
One or both of ethyl ester；
Described crosslinking agent is：One or both of the methylene diacrylamine of N, N mono-, glutaraldehyde, epoxychloropropane；
Described starch is：Soluble starch, CMS, HES；
The solution of described specific composition is：Weight/mass percentage composition 75%-78% alcohol mixed solution and weight/mass percentage composition
82%-85% acetone mixed solution, both volume ranges are 1：1.3—2.5.
2. the preparation method of starch base porous aquagel according to claim 1, it is characterised in that：The starch solution
Mass concentration is 5%-8%.
3. the preparation method of starch base porous aquagel according to claim 1, it is characterised in that：The starch and monomer
Mass ratio be 1:1-8.
4. the preparation method of starch base porous aquagel according to claim 1, it is characterised in that：Starch based aquagel with
The mass/volume of particular solution is than choosing：1:5-30, unit g/ml.
5. the preparation method of the starch base porous aquagel according to one of claim 1-4, it is characterised in that：Add
The addition sequence of raw material is followed successively by starch solution, monomer, crosslinking agent and initiator.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109554010A (en) * | 2018-11-29 | 2019-04-02 | 河北宇达防锈科技有限公司 | The controllable gas-phase antirusting film and preparation method thereof of antirust time |
| CN112980028A (en) * | 2021-02-05 | 2021-06-18 | 浙江大学 | Polymer material with porous interface and preparation method thereof |
| CN113143851A (en) * | 2021-03-02 | 2021-07-23 | 复旦大学 | Solvent exchange-based injectable hydrogel and preparation method and application thereof |
| CN114343651A (en) * | 2021-12-09 | 2022-04-15 | 中国科学院深圳先进技术研究院 | Flexible contact with gradient porosity, gel semi-dry electrode containing flexible contact and electroencephalogram cap containing flexible contact |
| WO2023092728A1 (en) * | 2021-11-29 | 2023-06-01 | 深圳先进技术研究院 | Starch-based hydrogel and preparation method therefor, and hemostatic dressing |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554010A (en) * | 2018-11-29 | 2019-04-02 | 河北宇达防锈科技有限公司 | The controllable gas-phase antirusting film and preparation method thereof of antirust time |
| CN109554010B (en) * | 2018-11-29 | 2020-11-27 | 河北宇达防锈科技有限公司 | Gas-phase antirust film with controllable antirust time and preparation method thereof |
| CN112980028A (en) * | 2021-02-05 | 2021-06-18 | 浙江大学 | Polymer material with porous interface and preparation method thereof |
| CN112980028B (en) * | 2021-02-05 | 2022-04-29 | 浙江大学 | Polymer material with porous interface and preparation method thereof |
| CN113143851A (en) * | 2021-03-02 | 2021-07-23 | 复旦大学 | Solvent exchange-based injectable hydrogel and preparation method and application thereof |
| WO2023092728A1 (en) * | 2021-11-29 | 2023-06-01 | 深圳先进技术研究院 | Starch-based hydrogel and preparation method therefor, and hemostatic dressing |
| CN114343651A (en) * | 2021-12-09 | 2022-04-15 | 中国科学院深圳先进技术研究院 | Flexible contact with gradient porosity, gel semi-dry electrode containing flexible contact and electroencephalogram cap containing flexible contact |
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Application publication date: 20171010 |