CN102911381B - Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof - Google Patents
Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to chemical/ionic/physical compounding cross linking hydrogel and a preparation method thereof. The hydrogel is polymerized in a way that olefin monomer M1, a chemical cross-linking agent M2, multivalent ion biomacromolecule M3, an ionic cross-linking agent M4 and a physical cross-linking agent M5 are dissolved in water. The method comprises the following steps: preparing chemical/physical cross linked gel prepolymerization liquid, preparing chemical/ionic/physical cross linked gel prepolymerization liquid and preparing and purifying chemical/ionic/physical compounding cross linked gel. According to the invention, the characteristics and properties of the chemical cross-linking agent, the physical cross-linking agent and the ionic cross-linking agents are taken into consideration comprehensively, the compounding cross linking of molecular chains is realized; the prepared hydrogel is optically transparent and has higher mechanical ductility and rebound elasticity; the mechanic, optical and thermal performances and other performances can be regulated conveniently by controlling technology parameters and conditions; and the prepared hydrogel can be used in the fields such as tissue engineering, food industry, agricultural irrigation, daily chemical engineering, oil production, dye adsorption and biological medicine.
Description
Technical field
The present invention relates to macromolecular material, biological medicine and field of environment protection, be specifically related to a kind of chemistry/ion/physical compounding cross-linked hydrogel and preparation method thereof.
Background technology
Hydrogel is the polymkeric substance that a class has three-dimensional net structure, in water, can absorb large quantity of moisture and swelling, and after swelling, can continue to keep its original structure and not dissolved.Because of water suction, water conservation and the bionical characteristic of its uniqueness, hydrogel is widely used in the fields such as industry, agricultural, chemical industry, medicine and biotechnology.The three-dimensional network of macromolecule hydrogel generally forms by physical crosslinking or Chemical Crosslinking Methods.It is current main gel process for preparing that the method for employing chemosynthesis is prepared high-molecular gel.
Chemically crosslinked type hydrogel is to use the technology such as prior synthesizing method or radiation, photopolymerization, the covalent cross-linking network forming by copolymerization or polycondensation.In cross-linked phase, hydrogel reaches certain equilibrium swelling degree according to different cross-linking densities, therefore in the crosslinked low swelling of height region, form cluster structure, they are dispersed in the high swelling of low cross-linking region, because hydrophobicity gathering has caused the aggregate of high crosslink density, thereby cause the unhomogeneity of hydrogel structure.Conventional chemical cross-linking agent comprises glutaraldehyde, formaldehyde, epoxy chloropropane, diacetyl oxide, diglycidyl ether, pungent two imido acid methyl esters, Vinylstyrene, vulcabond and methylene-bisacrylamide (MBA) etc.Chinese patent CN102146200B discloses a kind of temperature-sensitive hydrogel based on chemical cross-linking gel granules and preparation method thereof.This hydrogel is a kind of nanoparticle aqueous solution of certain density chemically crosslinked, and the nanoparticle of chemically crosslinked is dispersed in water; Described nanoparticle is comprised of polyoxyethylene glycol/polyester has amphipathic segmented copolymer, introduces crosslinkable groups at two ends, water-soluble by finite concentration, the spontaneous micella that is assembled into, add initiator after initiated polymerization be cross-linked to form.Chinese patent CN100390220C discloses a kind of method of preparing hydrogel, the method comprises: after vinyl monomer, linking agent and initiator are mixed, be dissolved in solvent and make reaction system, in this reaction system, the weight ratio of each composition is: monomer: linking agent: initiator: solvent=100: 2-50: 0.2-1: 1-10.Utilize microwave or the 300MHz-300GHz variable frequency microwave that frequency is 2450MHz to carry out obtaining after irradiated heat to reaction system.
Physical crosslinking type gel refers to the network structure that polymer chain forms as molecular entanglement and ion, hydrogen bond, hydrophobic association and electrostatic interaction etc. by different interactions.Chinese patent CN200810036457.2 discloses a kind of composite aquogel and preparation method with the high clay content of critical solution temperature.Preparation method, it is characterized in that, comprise the steps: the radical polymerization of pre-polymerization liquid original position, the component of pre-polymerization liquid and parts by weight: N-isopropylacrylamide 7.5-8.2 part, linking agent 7.5-10 part, initiator 0.08-0.16 part, catalyzer 0.08-0.16 part, polyoxyethylene glycol 1.4-10 part, water 74-82 part; Linking agent is the hectorite through trisodium phosphate modification.Hectorite mainly plays the effect of physical crosslinking agent.
During the polyvalent ion bonding of polyelectrolyte and oppositely charged, formed physical crosslinking type hydrogel is called again ionomer hydrogel (Ionotropic Hydrogel).On ionomer polyampholyte hydrogel, there is the group with both positive and negative electric charge, between positive and negative charge, formed ionomer.Ionic cross-linked bond is compared with covalent linkage, belongs to weak interaction, more responsive to the variation of environment.For example,, for the ion crosslinking agent of chitosan multivalent anions normally, as SO
4 2-, tripoly phosphate sodium STPP, Trisodium Citrate etc.; Ion crosslinking agent for sodium alginate is polyvalent cation, as Ca
2+, Zn
2+deng.Even if sodium alginate aqueous solution, under room temperature and physiological pH value, runs into divalence (except magnesium ion), polyvalent metal ion, will there is gelation reaction, form the alginate hydrogel of ionomer.It has been generally acknowledged that calcium ion combines with the guluronic acid residues in sodium alginate molecule, among the encirclement of calcium ion in carboxylate radical negative ion, just as the egg in egg box, thereby be often called as " egg box " model.Chinese patent CN102086592B discloses polyalcohol hydrogel of a kind of ionomer grafting on fiber and preparation method thereof.Preparation method is: with uv-radiation grafted polyacrylic acid on fiber, with in sodium hydroxide with after obtain the fiber of grafted polyacrylic acid sodium; The fiber of grafted polyacrylic acid sodium is soaked in the aqueous solution of sodium alginate, takes out the too much viscous solution that scrapes off adhesion, put it in calcium chloride water and be cross-linked, obtain the alginate calcium hydrogel of grafting on fiber.
By upper analysis, can be found out, at present crosslinked being cross-linked mainly with unicity of gel is main, and it is also considerably less that different sorts linking agent composite prepared document or the patent of gel.All there is considerable change in swelling behavior, bore hole size, mechanical property and the respondent behavior of the gel after composite being cross-linked.The present invention has considered feature and the character of chemistry, physics and ion crosslinking agent, for different function monomers, adopt different composite linking agents, overcome that the single crosslinked gel swelling causing is low, poor mechanical property and the uneven first-class shortcoming of network structure, the composite crosslinking of realization to molecular chain, form multiple cross-linked network, effectively regulate swelling capacity, hole form and the physical strength of high-molecular gel, constantly approach the crosslinked pattern of life entity, and be applied to the fields such as organizational project, foodstuffs industry, chemical industry absorption and biological medicine.
Summary of the invention
The object of the present invention is to provide a kind of chemistry/ion/physical compounding cross-linked hydrogel and preparation method thereof, overcome the shortcoming that traditional single chemical crosslink gel lattice is inhomogeneous, single ionic cross linked gel responsiveness is low and single one physical cross linked gel comprehensive mechanical property is poor.The present invention comprehensively adopts chemistry, ion and physical crosslinking agent to be cross-linked different properties monomer, rationally regulate composition and engineering condition, parameter etc., preparation meets different service requirementss and different gel, and has potential application prospect in fields such as organizational project, foodstuffs industry, chemical industry absorption and biological medicines.The swelling capacity of the composite cross-linked hydrogel of gained, responsiveness, bore hole size, dye uptake and mechanical property can be by regulating the adjustings such as monomer concentration, feed ratio, linking agent kind and consumption, crosslinker compounding type, temperature of reaction, water content and order of addition(of ingredients).
The present invention realizes by following technical scheme.
Chemistry/ion/physical compounding cross-linked hydrogel, by olefin monomer M1, chemical cross-linking agent M2, polyvalent ion biopolymer M3, ion crosslinking agent M4 and water-soluble being polymerized of physical crosslinking agent M5.
Described olefin monomer M1 is acrylamide, Methacrylamide, NIPA, N hydroxymethyl acrylamide, 2-(dimethylamino) ethyl-Methacrylamide, 2-hydroxyethyl methacrylate, NVP, vinylformic acid, methacrylic acid, tert-butyl acrylate, sodium acrylate, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, Polyethyleneglycol methacrylate, its inorganic salt, with and composition thereof.
Described chemical cross-linking agent M2 is N, any one in N '-methylene-bisacrylamide, two (methyl) vinylformic acid glycol ester, diglycidyl ether, epoxy chloropropane and glutaraldehyde.
Described polyvalent ion biopolymer M3 is the mixture of a kind of or any two kinds of compositions in sodium alginate, chitosan, polylysine.
Described ion crosslinking agent M4 is the mixture of a kind of or any two kinds of compositions in calcium chloride, calcium carbonate, calcium sulfate, calcium lactate, calcium phosphate, bariumchloride, cupric chloride, copper sulfate, zinc chloride and zinc sulfate.
Described physical crosslinking agent M5 is any one in magnesium hectorite, hectorite, magnesium soap stone, sauconite or lithium magnesium silicate, outward appearance is white solid powder, can be dispersed after stirring in water, in water, peel off completely, its lamella diameter 25-30nm, thickness is 0.9-1nm, and sheet surfaces is with a large amount of negative charges, and edge is with negative charge.
The preparation method of the present invention's a kind of chemistry/ion/physical compounding cross-linked hydrogel, comprises the steps:
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: physical crosslinking agent M5, olefin monomer M1 and chemical cross-linking agent M2 are added in deionized water successively, be mixed with the aqueous solution that mass concentration is 8-15%, often add primary material, all stir 15~35min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ion/physical crosslinking gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, polyvalent ion biopolymer M3 is slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, adding immediately ion crosslinking agent M4 and mass concentration is 0.1% softening agent glycerine, and 3~15min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion/physics composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately initiator ammonium persulfate or Potassium Persulphate, catalyzer Tetramethyl Ethylene Diamine or S-WAT, after 5min, mixing solutions is slowly poured in the glass mold that thickness is 1~5mm, control temperature of reaction is 50-70 ℃, carries out polyreaction 1~4h;
4) purifying of chemistry/ion/physics composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 2~6 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
The mass percent of M1 in step 1~3 of the present invention: M2: M3: M4: M5 is: M1: 82-97%, M2: 0-1%, M3: 3-15%, M4: 0-2%, M5: 0-2 ‰.
Described polyreaction is any one in original position radical polymerization, microwave radiation, uv photopolymerization or atom transfer radical polymerization.
Described initiator and catalyzer are 1% and 3 ‰ of olefin monomer M1 consumptions.
Described chemistry/ion/physics composite crosslinking gel be shaped as column, taper, bar-shaped, porous spongy, fibrous, hollow form, any one in membranaceous or spherical.
Described chemistry/ion/physics composite crosslinking gel is optically transparent, have high mechanical tenacity and rebound resilience, its swelling capacity, responsiveness, bore hole size, dye uptake and mechanical property can be by regulating monomer concentration, feed ratio, linking agent kind and consumption, crosslinker compounding type, temperature of reaction, water content and order of addition(of ingredients) to regulate.
Described chemistry/ion/physics composite crosslinking gel is at least one in chemistry/ion composite crosslinking gel, ion/physics composite crosslinking gel, chemical/physical composite crosslinking gel or chemistry/ion/physics composite crosslinking gel.
Adopt chemistry/ion/physics composite crosslinking gel prepared by aforesaid method application in organizational project, foodstuffs industry, agricultural irrigation, daily-use chemical industry, oil production, dye adsorption and biomedicine field.
Principle of the present invention is: with regard to physical crosslinking effect, physical crosslinking agent M5 lamella and initiator interact and attract in M5 sheet surfaces, and initiated polymerization, one end of the molecular chain that M1 polymerization forms is fixed on M5 sheet surfaces, chainpropagation is continued in the active centre of the other end, then with multi-form, carry out chain termination, finally form physical cross-linked network.With regard to ionomer effect, polyvalent ion biopolymer M3 is comprised of D-MANNOSE aldehydic acid and 2 kinds of uronic acids of L-guluronic acid as sodium alginate, and wherein multivalent metal cation is (as Ca
2+) can displace the Na of L-guluronic acid combination
+, and form the water-insoluble gel of egg case structure.Chemically crosslinked effect is the most traditional crosslinking method, repeats no more here.
Compare with preparation method with existing gel, the present invention has the following advantages:
1. the composite crosslinking hydrogel that prepared by the present invention has organically merged the advantage of chemistry, ion and physical crosslinking agent, has overcome that traditional single chemical crosslink gel lattice is inhomogeneous, single one physical crosslinked or physical/chemical composite crosslinking gel comprehensive mechanical property poor shortcoming.
2. simple, the simple operation of preparation method of the present invention, the reaction times is short, raw material is easy to get, mild condition, on original synthesis device, can prepare.
3. according to polymerization mechanism, the present invention can be by regulating linking agent kind and composite chemistry/ion/physical compounding cross-linked hydrogel than waiting the different swelling capacity of acquisition, responsiveness, bore hole size, dye uptake and mechanical property.
4. preparation method of the present invention has versatility and universality, has set up the structure and property correlation between gel and linking agent kind, for the application of gel in the fields such as biology, chemical industry, medical science and industry laid a good foundation.
Accompanying drawing explanation
Fig. 1 is height stretching hydrogel prepared by composite crosslinking.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should understand; these embodiment are only not used in and limit the scope of the invention for the present invention is described; other any do not run counter to change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: 0.001g hectorite, 1g acrylamide and 0.001g methylene-bisacrylamide are added in deionized water successively, be mixed with mass concentration and be 10% the aqueous solution, often add primary material, all stir 20min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ion/physical crosslinking gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, 0.1g sodium alginate is slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, adding immediately 0.01g calcium sulfate and mass concentration is 0.1% softening agent glycerine, and 5min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion/physics composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately 0.1g initiator ammonium persulfate, 0.003g catalyzer Tetramethyl Ethylene Diamine, after 5min, mixing solutions is slowly poured in the bar-shaped glass mold that thickness is 2mm, controlling temperature of reaction is 60 ℃, carries out original position Raolical polymerizable 2h;
4) purifying of chemistry/ion/physics composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 4 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
Gained chemistry/ion/physics composite crosslinking gel is completely transparent, can be stretched as 12 times of former length, and can reply completely, can be used for foodstuffs industry.
Embodiment 2
1) preparation of chemically crosslinked gel pre-polymerization liquid: 2g N-isopropylacrylamide and 0.002g methylene-bisacrylamide are added in deionized water successively, be mixed with mass concentration and be 9% the aqueous solution, often add primary material, all stir 25min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ionomer gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, 0.1g sodium alginate and 0.05g chitosan are slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, adding immediately 0.02g calcium sulfate and mass concentration is 0.1% softening agent glycerine, and 7min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately 0.2g initiator potassium persulfate, 0.006g catalyzer S-WAT, after 5min, mixing solutions is slowly poured in the column glass mold that thickness is 1mm, controlling temperature of reaction is 55 ℃, carries out original position Raolical polymerizable 3h;
4) purifying of chemistry/ion composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 3 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
Gained chemistry/ion composite crosslinking gel is completely transparent, can be stretched as 10 times of former length, and can reply completely, can be used for organizational project.
Embodiment 3
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: 0.002g lithium magnesium silicate, 1g n-methylolacrylamide and 0.01g glutaraldehyde are added in deionized water successively, be mixed with mass concentration and be 11% the aqueous solution, often add primary material, all stir 20min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ion/physical crosslinking gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, 0.05g sodium alginate and 0.05g polylysine are slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, adding immediately 0.005 calcium phosphate and mass concentration is 0.1% softening agent glycerine, and 8min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion/physics composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately 0.1g initiator potassium persulfate, 0.003g catalyzer Tetramethyl Ethylene Diamine, after 5min, mixing solutions is slowly poured in the hollow form glass mold that thickness is 5mm, controlling temperature of reaction is 70 ℃, carries out microwave radiation polymerization reaction 1h;
4) purifying of chemistry/ion/physics composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 5 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
Gained chemistry/ion/physics composite crosslinking gel is completely transparent, can be stretched as 7 times of former length, and can reply completely, can be used for agricultural irrigation.
Embodiment 4
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: 0.0005g magnesium hectorite, 3g sodium acrylate and 0.004g diglycidyl ether are added in deionized water successively, be mixed with the aqueous solution that mass concentration is 13wt%, often add primary material, all stir 25min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ion/physical crosslinking gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, 0.25g sodium alginate and 0.05g chitosan are slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, adding immediately 0.02g calcium chloride and mass concentration is 0.1% softening agent glycerine, and 10min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion/physics composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately 0.3g initiator potassium persulfate, 0.009g catalyzer S-WAT, after 5min, mixing solutions is slowly poured in the globular glass mould that thickness is 4mm, controlling temperature of reaction is 60 ℃, carries out uv photopolymerization reaction 2h;
4) purifying of chemistry/ion/physics composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 5 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
Gained chemistry/ion/physics composite crosslinking gel is completely transparent, can be stretched as 6 times of former length, and can reply completely, can be used for dye adsorption.
Embodiment 5
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: 0.001g sauconite, 2g 2-(dimethylamino) ethyl-Methacrylamide and 0.002g bis-(methyl) vinylformic acid glycol ester are added in deionized water successively, be mixed with the aqueous solution that mass concentration is 10wt%, often add primary material, all stir 20min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ion/physical crosslinking gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, 0.2g sodium alginate is slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, add immediately the mixture of 0.04g calcium carbonate and zinc chloride and the softening agent glycerine that mass concentration is 0.1%, 10min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion/physics composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately 0.2g initiator ammonium persulfate, 0.006g catalyzer Tetramethyl Ethylene Diamine, after 5min, mixing solutions is slowly poured in the glass mold that thickness is 3mm, controlling temperature of reaction is 70 ℃, carries out original position Raolical polymerizable 1h;
4) purifying of chemistry/ion/physics composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 3 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
Gained chemistry/ion/physics composite crosslinking gel is completely transparent, and can be stretched as 5 times of former length, and can reply completely, after lyophilize, be porous spongy, can be used for biological medicine.
Claims (7)
1. chemistry/ion/physical compounding cross-linked hydrogel, is characterized in that by olefin monomer M1, chemical cross-linking agent M2, polyvalent ion biopolymer M3, ion crosslinking agent M4 and water-soluble being polymerized of physical crosslinking agent M5, wherein said olefin monomer M1 is acrylamide, Methacrylamide, NIPA, N hydroxymethyl acrylamide, 2-(dimethylamino) ethyl-Methacrylamide, 2-hydroxyethyl methacrylate, NVP, vinylformic acid, methacrylic acid, tert-butyl acrylate, sodium acrylate, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, Polyethyleneglycol methacrylate, with and composition thereof, described chemical cross-linking agent M2 is N, N'-methylene-bisacrylamide, two (methyl) vinylformic acid glycol ester, diglycidyl ether, any one in epoxy chloropropane and glutaraldehyde, described polyvalent ion biopolymer M3 is sodium alginate, chitosan, the mixture of a kind of or any two kinds of compositions in polylysine, described ion crosslinking agent M4 is calcium chloride, calcium carbonate, calcium sulfate, calcium lactate, calcium phosphate, bariumchloride, cupric chloride, copper sulfate, the mixture of a kind of or any two kinds of compositions in zinc chloride and zinc sulfate, described physical crosslinking agent M5 is magnesium hectorite, hectorite, magnesium soap stone, any one in sauconite or lithium magnesium silicate, outward appearance is white solid powder, can be dispersed after stirring in water, in water, peel off completely, its lamella diameter 25-30nm, thickness is 0.9-1nm, and sheet surfaces is with a large amount of negative charges, and edge is with negative charge.
2. the preparation method of a kind of chemistry/ion/physical compounding cross-linked hydrogel according to claim 1, comprises the following steps:
1) preparation of chemical/physical cross linked gel pre-polymerization liquid: physical crosslinking agent M5, olefin monomer M1 and chemical cross-linking agent M2 are added in deionized water successively, be mixed with the aqueous solution that mass concentration is 8-15%, often add primary material, all stir 15~35min, until form homogeneous pre-polymerization liquid;
2) preparation of chemistry/ion/physical crosslinking gel pre-polymerization liquid: under nitrogen protection and magnetic agitation, polyvalent ion biopolymer M3 is slowly added in the pre-polymerization liquid in step 1, after occurring without aggregate, adding immediately ion crosslinking agent M4 and mass concentration is 0.1% softening agent glycerine, and 3~15min is stirred in the slow speed of revolution;
3) preparation of chemistry/ion/physics composite crosslinking gel: the gel pre-polymerization liquid in step 2 has thick while starting to occur, add immediately initiator ammonium persulfate or Potassium Persulphate, catalyzer Tetramethyl Ethylene Diamine or S-WAT, after 5min, mixing solutions is slowly poured in the glass mold that thickness is 1~5mm, control temperature of reaction is 50-70 ℃, carries out polyreaction 1~4h;
4) purifying of chemistry/ion/physics composite crosslinking gel: the disk that reacted product is cut into diameter 10mm, be soaked in 50mL deionized water, be placed in 2~6 ℃ of refrigerators and carry out swelling, within 1 week, be placed on lyophilize in-60 ℃ of cryogenic refrigerators, obtain described dry composite crosslinking gel solid, kept dry is standby.
3. the preparation method of a kind of chemistry/ion/physical compounding cross-linked hydrogel according to claim 2, is characterized in that described polyreaction is any one in original position radical polymerization, microwave radiation, uv photopolymerization.
4. the preparation method of a kind of chemistry/ion/physical compounding cross-linked hydrogel according to claim 2, what it is characterized in that described chemistry/ion/physics composite crosslinking gel is shaped as column, taper, bar-shaped, porous spongy, fibrous, hollow form, any one in membranaceous or spherical.
5. the preparation method of a kind of chemistry/ion/physical compounding cross-linked hydrogel according to claim 2, is characterized in that described initiator and catalyzer are 1% and 3 ‰ of olefin monomer M1 consumptions.
6. the preparation method of a kind of chemistry/ion/physical compounding cross-linked hydrogel according to claim 2, it is characterized in that described chemistry/ion/physics composite crosslinking gel is optically transparent, have high mechanical tenacity and rebound resilience, its swelling capacity, responsiveness, bore hole size, dye uptake and mechanical property can be by regulating monomer concentration, feed ratio, linking agent kind and consumption, crosslinker compounding type, temperature of reaction, water content and order of addition(of ingredients) to regulate.
7. the preparation method of a kind of chemistry/ion/physical compounding cross-linked hydrogel according to claim 2, is characterized in that the application of chemistry/ion/physics composite crosslinking gel in foodstuffs industry, agricultural irrigation, daily-use chemical industry, oil production, dye adsorption and biomedicine field.
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